High-fastness high-temperature-resistant formaldehyde-free color fixing agent and preparation method thereof

Abstract

The invention discloses a high-fastness high-temperature-resistant formaldehyde-free color fixing agent and a preparation method thereof, and belongs to the technical field of textile printing and dyeing, the color fixing agent is composed of heat-stable polyquaternium, amino silicon oil capable of being cross-linked at high temperature and self-made temperature-sensitive controlled release microspheres, temperature gradient is utilized, and in the drying stage, the microspheres release an ultraviolet light absorber to be planted in fibers; in the subsequent high-temperature baking stage of 160-210 DEG C, amino silicon oil and the fibers are cross-linked to form a firm flexible film, and final color fixation is completed at the same time; according to the invention, the contradiction between wet friction resistance and light fastness is solved, and the unification of high color fastness and excellent high temperature resistance is realized through active utilization of high temperature conditions.

Description

Technical Field

[0001] This invention relates to the field of fabric color fixing technology, and in particular to a high-fastness, high-temperature resistant, formaldehyde-free color fixing agent and its preparation method. Background Technology

[0002] With increasingly stringent environmental regulations, formaldehyde-free color-fixing agents have become the industry mainstream. However, existing formaldehyde-free color-fixing agents face a double challenge in pursuing high color fastness: First, improving wet rubbing fastness often leads to a decrease in light fastness and hardening of the hand feel; second, and more seriously, many products cannot withstand the high-temperature processes essential in dyeing and finishing. During high-temperature and high-pressure dyeing (120~135℃), hot melt pad dyeing (200~220℃), or high-temperature baking in finishing (160~210℃), traditional color-fixing agents are prone to decomposition or failure, and cannot maintain a stable color-fixing effect under high-temperature conditions, which seriously limits their application in textiles. Current technologies largely focus on resolving the conflict between colorfastness and performance, attempting to harmonize properties through the synthesis of complex polymers or simple compounding. However, directly adding hydrophobic UV absorbers can lead to difficulties in dispersion within hydrophilic systems, resulting in aggregation or premature encapsulation by components such as silicone oil. Existing solutions often exhibit color changes and colorfastness degradation after standard high-temperature processing. Therefore, there is an urgent need in this field for a color-fixing agent that can not only synergistically improve various colorfastness properties but also actively adapt to and utilize high-temperature processing conditions to achieve a balance between high colorfastness and high temperature resistance.

[0003] Therefore, this invention is proposed to solve the above-mentioned technical problems. Summary of the Invention

[0004] The primary objective of this invention is to provide a high-fastness, high-temperature resistant, formaldehyde-free color-fixing agent, comprising the following raw materials in parts by weight: 60-80 parts of basic formaldehyde-free color-fixing agent, 5-10 parts of smoothing film-forming agent, and 10-15 parts of temperature-sensitive controlled-release functional microspheres; The smoothing film-forming agent is an amino-modified silicone oil emulsion; The temperature-sensitive controlled-release functional microspheres have a core-shell structure, with the core being porous nano-silica loaded with ultraviolet absorbers and the outer shell being a phase change material with a melting point of 72~80℃.

[0005] Preferably, the basic formaldehyde-free fixing agent is a cationic polyquaternary ammonium salt aqueous solution.

[0006] Preferably, the cationic polyquaternary ammonium salt is polydimethyldiallylammonium chloride.

[0007] Preferably, the amino-modified silicone oil emulsion has an ammonia value of 0.2~0.6 mmol / g. Within this range, the amino silicone oil can maintain sufficient chemical inertness during the drying stage to avoid pre-crosslinking with fibers and interfering with the uniform distribution of ultraviolet absorbers. At the same time, it can be effectively activated in the subsequent high-temperature baking stage to form a strong flexible film layer.

[0008] Preferably, the ultraviolet absorber is a benzotriazole compound, more preferably UV-326.

[0009] Preferably, the phase change material is behenic acid, and the melting point of the phase change material is 72~80℃. This melting point range is slightly lower than the temperature of the main drying zone during the fabric drying stage, thereby ensuring that the microspheres can be precisely triggered to release during the drying stage, and that the ultraviolet absorber can quickly colonize the fabric fibers by migrating with the help of water evaporation as a large amount of water evaporates.

[0010] This invention also provides a method for preparing a high-fastness, high-temperature resistant, formaldehyde-free color-fixing agent, comprising the following steps: S1. Preparation of temperature-sensitive controlled-release functional microspheres: Ultraviolet absorber is loaded onto porous nano-silica to obtain loaded powder. The loaded powder is dispersed in hot water containing emulsifier, and molten phase change material is added for emulsification. Then, the shell of the phase change material is solidified by cooling to obtain the temperature-sensitive controlled-release functional microspheres. S2. Compounding: Weigh the basic formaldehyde-free fixing agent, smoothing film-forming agent and temperature-sensitive controlled-release functional microspheres according to the weight parts, mix them, and stir evenly to obtain a high-fastness, high-temperature resistant formaldehyde-free fixing agent.

[0011] Preferably, step S1 specifically includes: S11, Adsorption Loading: Dissolve the ultraviolet absorber in an organic solvent, add porous nano silica, disperse and stir to ensure complete adsorption, and remove the solvent to obtain the loaded powder. S12, Phase change encapsulation: The loaded powder obtained in step S11 is dispersed in hot water containing emulsifier, and molten phase change material is added at a temperature higher than the melting point of the phase change material and high-speed shear emulsification is performed. S13. Condensation molding: The emulsion obtained in step S12 is rapidly cooled to solidify the shell of the phase change material, forming solid microspheres, which are then dispersed in water after washing for later use.

[0012] The present invention also provides the application of the high-fastness, high-temperature resistant, formaldehyde-free color-fixing agent described above in the high-temperature dyeing and finishing process of textiles.

[0013] Preferably, the high-temperature dyeing and finishing process includes a high-temperature treatment step at a temperature of 160°C or higher.

[0014] The beneficial effects of this invention are: This invention utilizes the synergistic effect of self-made temperature-sensitive microspheres and amino silicone oil to precisely match the drying-baking steps in textile color-fixing processes. During the drying stage of the dyeing process, the temperature is higher than the phase change material temperature, causing the microsphere shell to change from solid to liquid. This precisely releases ultraviolet absorbers, which migrate and penetrate to the fiber surface, forming a molecular-level photoprotective layer. Subsequently, during the baking stage (>160℃), the primary / secondary amino groups (-NH2 / -NH-) in the amino silicone oil react with the hydroxyl groups (-OH) on the fabric surface. Simultaneously, the silanol groups (Si-OH) in the amino silicone oil itself undergo condensation, generating a three-dimensional siloxane network in situ. This network encapsulates and fixes the ultraviolet absorbers onto the fibers, forming a continuous and flexible organosilicon film on the fibers. This effectively improves the durability of the color-fixing agent and actively crosslinks at high temperatures, achieving high-temperature resistance. Attached Figure Description

[0015] Figure 1 This is a graph showing the lightfastness values ​​of the present invention when using different ammonia values. Detailed Implementation

[0016] The technical solutions in the embodiments of the present invention will be clearly and completely described below. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0017] Example 1 This embodiment of a high-fastness, high-temperature resistant, formaldehyde-free color-fixing agent comprises the following raw materials in parts by weight: The basic formaldehyde-free color-fixing agent is polydimethyldiallyl ammonium chloride (60 parts), the smoothing film-forming agent is amino-modified silicone oil emulsion (5 parts), and the temperature-sensitive controlled-release functional microspheres (10 parts). The smoothing film-forming agent is an amino-modified silicone oil emulsion; The temperature-sensitive controlled-release functional microspheres have a core-shell structure. The core is porous nano-silica loaded with the ultraviolet absorber benzotriazole compound UV-326, and the outer shell is a phase change material with a melting point of 72~80℃.

[0018] The preparation method of a high-fastness, high-temperature resistant, formaldehyde-free color-fixing agent according to this embodiment includes the following steps: Raw material: Porous nano-silica (specific surface area 380m²) 2 / g), UV-326 (benzotriazole ultraviolet absorber), behenic acid (melting point 72~80℃), sodium dodecyl sulfate (SDS), acetone, 40% solid content polydimethyldiallylammonium chloride (PDMDAAC) aqueous solution, commercially available low yellowing amino silicone oil emulsion (ammonia value 0.2mmol / g, solid content 35%). S11. Adsorption loading: Weigh 5g of UV absorber UV-326 and dissolve it in 100mL of organic solvent acetone. Add 20g of porous nano silica, ultrasonically disperse and stir for 6h at 50℃ to ensure complete adsorption. Remove acetone by rotary evaporation and vacuum dry at 60℃ to obtain the loaded powder. S12, Phase change encapsulation: Dissolve 1g SDS in 200mL of hot water at 60~65℃, add all the loaded powder prepared in step S11, pre-disperse at a shear rate of 8000rpm, keep the water bath temperature constant, slowly add 15g of molten behenic acid, and continue shear emulsification for 30min after the addition is completed. S13. Cooling and solidification: The emulsion obtained in step S12 is quickly poured into 400mL of ice water to cool and solidify. The microspheres are collected by centrifugation, washed, and dispersed in water to prepare a slurry with a solid content of 30% for later use.

[0019] S2. Compounding: Weigh 60 parts of the basic formaldehyde-free fixing agent PDMDAAC solution, 5 parts of the smoothing film-forming agent amino silicone oil emulsion and 10 parts of the temperature-sensitive controlled-release functional microsphere slurry according to the weight parts and mix them. Stir and mix at room temperature for 40 minutes to obtain a high-fastness, high-temperature resistant formaldehyde-free fixing agent.

[0020] Example 2 This embodiment of a high-fastness, high-temperature resistant, formaldehyde-free color-fixing agent comprises the following raw materials in parts by weight: The basic formaldehyde-free color-fixing agent is polydimethyldiallyl ammonium chloride (80 parts), the smoothing film-forming agent is amino-modified silicone oil emulsion (10 parts), and the temperature-sensitive controlled-release functional microspheres (15 parts). The smoothing film-forming agent is an amino-modified silicone oil emulsion; The temperature-sensitive controlled-release functional microspheres have a core-shell structure. The core is porous nano-silica loaded with the ultraviolet absorber benzotriazole compound UV-326, and the outer shell is a phase change material with a melting point of 72~80℃.

[0021] The preparation method of a high-fastness, high-temperature resistant, formaldehyde-free color-fixing agent according to this embodiment includes the following steps: Raw material: Porous nano-silica (specific surface area 380m²) 2 / g), UV-326 (benzotriazole ultraviolet absorber), behenic acid (melting point 72~80℃), sodium dodecyl sulfate (SDS), acetone, 40% solid content polydimethyldiallylammonium chloride (PDMDAAC) aqueous solution, commercially available low yellowing amino silicone oil emulsion (ammonia value 0.6mmol / g, solid content 35%). S11. Adsorption loading: Weigh 5g of UV absorber UV-326 and dissolve it in 100mL of organic solvent acetone. Add 20g of porous nano silica, ultrasonically disperse and stir for 6h at 50℃ to ensure complete adsorption. Remove acetone by rotary evaporation and vacuum dry at 60℃ to obtain the loaded powder. S12, Phase change encapsulation: Dissolve 1g SDS in 200mL of hot water at 60~65℃, add all the loaded powder prepared in step S11, pre-disperse at a shear rate of 8000rpm, keep the water bath temperature constant, slowly add 15g of molten behenic acid, and continue shear emulsification for 30min after the addition is completed. S13. Cooling and solidification: The emulsion obtained in step S12 is quickly poured into 400mL of ice water to cool and solidify. The microspheres are collected by centrifugation, washed, and dispersed in water to prepare a slurry with a solid content of 30% for later use.

[0022] S2. Compounding: Weigh 80 parts of the basic formaldehyde-free fixing agent PDMDAAC solution, 10 parts of the smoothing film-forming agent amino silicone oil emulsion and 15 parts of the temperature-sensitive controlled-release functional microsphere slurry according to the weight parts and mix them. Stir and mix at room temperature for 40 minutes to obtain a high-fastness, high-temperature resistant formaldehyde-free fixing agent.

[0023] Example 3 This embodiment of a high-fastness, high-temperature resistant, formaldehyde-free color-fixing agent comprises the following raw materials in parts by weight: The basic formaldehyde-free color-fixing agent is polydimethyldiallyl ammonium chloride (70 parts), the smoothing film-forming agent is amino-modified silicone oil emulsion (8 parts), and the temperature-sensitive controlled-release functional microspheres (12 parts). The smoothing film-forming agent is an amino-modified silicone oil emulsion; The temperature-sensitive controlled-release functional microspheres have a core-shell structure. The core is porous nano-silica loaded with the ultraviolet absorber benzotriazole compound UV-326, and the outer shell is a phase change material with a melting point of 72~80℃.

[0024] The preparation method of a high-fastness, high-temperature resistant, formaldehyde-free color-fixing agent according to this embodiment includes the following steps: Raw material: Porous nano-silica (specific surface area 380m²) 2 / g), UV-326 (benzotriazole ultraviolet absorber), behenic acid (melting point 72~80℃), sodium dodecyl sulfate (SDS), acetone, 40% solid content polydimethyldiallylammonium chloride (PDMDAAC) aqueous solution, commercially available low yellowing amino silicone oil emulsion (ammonia value 0.4mmol / g, solid content 35%). S11. Adsorption loading: Weigh 5g of UV absorber UV-326 and dissolve it in 100mL of organic solvent acetone. Add 20g of porous nano silica, ultrasonically disperse and stir for 6h at 50℃ to ensure complete adsorption. Remove acetone by rotary evaporation and vacuum dry at 60℃ to obtain the loaded powder. S12, Phase change encapsulation: Dissolve 1g SDS in 200mL of hot water at 60~65℃, add all the loaded powder prepared in step S11, pre-disperse at a shear rate of 8000rpm, keep the water bath temperature constant, slowly add 15g of molten behenic acid, and continue shear emulsification for 30min after the addition is completed. S13. Cooling and solidification: The emulsion obtained in step S12 is quickly poured into 400mL of ice water to cool and solidify. The microspheres are collected by centrifugation, washed, and dispersed in water to prepare a slurry with a solid content of 30% for later use.

[0025] S2. Compounding: Weigh 70 parts of basic formaldehyde-free fixing agent PDMDAAC solution, 8 parts of smoothing film-forming agent amino silicone oil emulsion and 12 parts of temperature-sensitive controlled-release functional microsphere slurry according to the weight parts and mix them. Stir and mix at room temperature for 40 minutes to obtain a high-fastness, high-temperature resistant formaldehyde-free fixing agent.

[0026] Comparative Example 1 The difference between this comparative example and Example 3 is that the basic formaldehyde-free fixing agent polydimethyldiallyl ammonium chloride, the smoothing film-forming agent amino-modified silicone oil emulsion, the ultraviolet absorber UV-326, and porous nano-silica are directly mixed without microsphere preparation. Comparative Example 2 The difference between this comparative example and Example 3 is that the amino silicone oil has an ammonia value of 0.1 mmol / g.

[0027] Comparative Example 3 The difference between this comparative example and Example 3 is that the amino silicone oil in this example has an ammonia value of 0.7 mmol / g.

[0028] Actual test Test method: Black knitted fabric was dyed with reactive dyes on 32-count combed cotton; Process: Two dips and two rolls (75% roll-off) - pre-drying (110℃, 2 minutes) - high-temperature baking (180℃, 90 seconds) - washing and drying.

[0029] The following standard shall be used for testing: Color fastness to wet rubbing GB / T3920-2008; Lightfastness to sunlight (GB / T8427-2019); Wash fastness (color change) GB / T3921-2008; Color difference (ΔE) of fabric after baking at 180℃ GB / T8427-2019; The feel of the material was assessed by five experienced evaluators in a blind review (1-5 points, with 5 points being the best). Liquid stability testing involved placing all test samples in a 50°C constant temperature oven for 7 days to simulate accelerated storage. The test results are shown in the table below: Table 1 As can be seen from the table, Examples 1-3 exhibited excellent durability, high-temperature resistance, and a good hand feel. In contrast, the direct mixing in Comparative Example 1 resulted in a significant decrease in performance. This is because the UV absorber was not coated with a core-shell structure, and it was encapsulated by silicone oil and other substances in the early stages of processing, leading to its failure and inability to form an effective protective layer on the fiber. Furthermore, it can be seen that Comparative Example 2, using low-ammonia-value silicone oil, did not adequately improve wet friction resistance. This is because the low ammonia value resulted in insufficient active amino groups, leading to insufficient cross-linking density with the fiber at high temperatures, thus failing to form a strong protective film. Comparative Example 3, using high-ammonia-value silicone oil, had excessively high reactivity, causing partial cross-linking during the drying stage, hindering the uniform distribution of the UV absorber. Additionally, the excessive amino groups were easily oxidized at high temperatures, causing the fabric to yellow. Figure 1 The lightfastness values ​​obtained by using amino silicone oils with different ammonia values ​​in this invention can be determined by the fact that increasing the ammonia value can lead to excessively high reactivity, causing partial cross-linking during the drying stage and affecting the uniform distribution of the ultraviolet absorber. Therefore, 0.2~0.6 mmol / g is preferred. Furthermore, the embodiments exhibit excellent high-temperature resistance, which is due to the synergistic effect of core-shell slow release and ammonia value. During the drying stage, at a temperature of 100~120℃, the released ultraviolet absorber molecules migrate uniformly with the evaporated water and penetrate the fiber surface, forming a molecular-level protective layer. When the baking temperature reaches 160~210℃, the active amino groups in the amino silicone oil undergo a dehydration condensation reaction with the hydroxyl groups on the surface of the fabric fibers. Accompanied by the condensation between the silanol groups of the amino silicone oil itself, a three-dimensional siloxane network is generated, effectively forming a continuous and flexible film.

[0030] The above description is only a preferred embodiment of the present invention, but the scope of protection of the present invention is not limited thereto. Any equivalent substitutions or modifications made by those skilled in the art within the scope of the technology disclosed in the present invention, based on the technical solution and inventive concept of the present invention, should be covered within the scope of protection of the present invention.

Claims

1. A high-fastness, high-temperature resistant, formaldehyde-free color-fixing agent, characterized in that, Including the following parts by weight of raw materials: 60-80 parts of basic formaldehyde-free color-fixing agent, 5-10 parts of smoothing film-forming agent, and 10-15 parts of temperature-sensitive controlled-release functional microspheres; The smoothing film-forming agent is an amino-modified silicone oil emulsion; The temperature-sensitive controlled-release functional microspheres have a core-shell structure, with the core being porous nano-silica loaded with ultraviolet absorbers and the outer shell being a phase change material with a melting point of 72~80℃.

2. The high-fastness, high-temperature resistant, formaldehyde-free color-fixing agent according to claim 1, characterized in that, The basic formaldehyde-free fixing agent is a cationic polyquaternary ammonium salt aqueous solution.

3. The high-fastness, high-temperature resistant, formaldehyde-free color-fixing agent according to claim 2, characterized in that, The cationic polyquaternary ammonium salt is polydimethyldiallylammonium chloride.

4. The high-fastness, high-temperature resistant, formaldehyde-free color-fixing agent according to claim 1, characterized in that, The amino-modified silicone oil emulsion has an ammonia value of 0.2~0.6 mmol / g.

5. The high-fastness, high-temperature resistant, formaldehyde-free color-fixing agent according to claim 1, characterized in that, The ultraviolet absorber is a benzotriazole compound.

6. The high-fastness, high-temperature resistant, formaldehyde-free color-fixing agent according to claim 1, characterized in that, The phase change material is behenic acid.

7. A method for preparing a high-fastness, high-temperature resistant, formaldehyde-free color-fixing agent as described in any one of claims 1 to 6, characterized in that, Includes the following steps: S1. Preparation of temperature-sensitive controlled-release functional microspheres: Ultraviolet absorber is loaded onto porous nano-silica to obtain loaded powder. The loaded powder is dispersed in hot water containing emulsifier, and molten phase change material is added for emulsification. Then, the shell of the phase change material is solidified by cooling to obtain the temperature-sensitive controlled-release functional microspheres. S2. Compounding: Weigh the basic formaldehyde-free fixing agent, smoothing film-forming agent and temperature-sensitive controlled-release functional microspheres according to the weight parts, mix them, and stir evenly to obtain a high-fastness, high-temperature resistant formaldehyde-free fixing agent.

8. The preparation method according to claim 7, characterized in that, The S1 step specifically includes: S11, Adsorption Loading: Dissolve the ultraviolet absorber in an organic solvent, add porous nano silica, disperse and stir to ensure complete adsorption, and remove the solvent to obtain the loaded powder. S12, Phase change encapsulation: The loaded powder obtained in step S11 is dispersed in hot water containing emulsifier, and molten phase change material is added at a temperature higher than the melting point of the phase change material and high-speed shear emulsification is performed. S13. Condensation molding: The emulsion obtained in step S12 is rapidly cooled to solidify the shell of the phase change material, forming solid microspheres, which are then dispersed in water after washing for later use.

9. The application of the high-fastness, high-temperature resistant, formaldehyde-free color-fixing agent according to any one of claims 1 to 6 in the high-temperature dyeing and finishing process of textiles.

10. The application according to claim 9, characterized in that, The high-temperature dyeing and finishing process includes a high-temperature treatment step at 160°C or higher.

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