A non-formaldehyde fixing agent and a preparation method thereof

Abstract

The application relates to the technical field of printing and dyeing fixing agents, and particularly discloses a formaldehyde-free fixing agent and a preparation method thereof. The formaldehyde-free fixing agent is prepared from raw materials in the following proportions by weight: dimethyl diallyl ammonium chloride 81-162 parts; acrylamide 9-18 parts; ammonium persulfate 5-7 parts; epichlorohydrin 55-105 parts; tetraethylenepentamine 9-18 parts; triethylamine 4.5-9 parts; dimethylamine 9-18 parts; water 90-120 parts; triallylamine 0.5-1 part; the dimethyl diallyl ammonium chloride, the acrylamide, the ammonium persulfate and the epichlorohydrin are used for preparing product A; the tetraethylenepentamine, the triethylamine, the dimethylamine and the epichlorohydrin are used for preparing product B; the product A, the product B, the water and the triallylamine are mixed to obtain the formaldehyde-free fixing agent. The formaldehyde-free fixing agent of the application can balance the permeability and the reaction film-forming property after application, and has excellent fixing performance.

Description

A formaldehyde-free color-fixing agent and its preparation method Technical Field

[0001] This application relates to the field of dyeing and printing fixing agents, and more specifically, it relates to a formaldehyde-free fixing agent and its preparation method. Background Technology

[0002] In traditional dyeing processes, dyes bind to the fiber surface through electrostatic interactions or physical adsorption based on their molecular structure; however, this binding is not very strong. The role of a fixing agent is to strengthen the bond between the dye and the fiber through a chemical reaction, thereby reducing the need for washing and maintaining color stability.

[0003] Formaldehyde-containing color-fixing agents can often harm the body. Therefore, in recent years, my country has successively introduced regulations to limit the formaldehyde content in textiles, leading to a continuous increase in demand for formaldehyde-free color-fixing agents. Researchers have begun developing various novel formaldehyde-free color-fixing agents. Currently, the most mainstream formaldehyde-free color-fixing agents on the market are cationic polymers. These utilize the homopolymerization and copolymerization of cationic monomers. Based on the previous preparation of epoxy-containing cationic polymer P (DMDAAC-AGE), it is used as a reactive cationic color-fixing agent for cotton fabrics. Furthermore, because formaldehyde-free color-fixing agents are more environmentally friendly and less likely to cause skin toxicity or irritation, they have broad application prospects.

[0004] Regarding the aforementioned technologies, the inventors believe that current formaldehyde-free color-fixing agents still have some shortcomings in application. For example, when formaldehyde-free color-fixing agents are used in combination with reactive dyes, due to their large differences in polymerization, it is often difficult to balance permeability and film-forming properties, resulting in poor color-fixing effect. Therefore, it is urgent to propose a solution to solve the above-mentioned technical problems. Summary of the Invention

[0005] In order to achieve the excellent effects of low residue and high color fixation after the application of formaldehyde-free color fixing agent, this application provides a formaldehyde-free color fixing agent and its preparation method.

[0006] Firstly, this application provides a formaldehyde-free color-fixing agent, employing the following technical solution:

[0007] A formaldehyde-free color-fixing agent, made from raw materials comprising the following parts by weight:

[0008] 81-162 parts of dimethyl diallyl ammonium chloride;

[0009] Acrylamide 9-18 parts;

[0010] 5-7 parts of ammonium persulfate;

[0011] 55-105 parts of epichlorohydrin;

[0012] 9-18 parts of tetraethylenepentamine;

[0013] Triethylamine 4.5-9 parts;

[0014] 9-18 parts of dimethylamine;

[0015] 90-120 parts water;

[0016] 0.5-1 part of triallylamine;

[0017] The dimethyl diallyl ammonium chloride, acrylamide, ammonium persulfate, and epichlorohydrin are used to prepare product A;

[0018] The tetraethylenepentamine, triethylamine, dimethylamine, and epichlorohydrin are used to prepare product B;

[0019] The formaldehyde-free fixing agent can be obtained by mixing product A, product B, water and triallylamine.

[0020] By adopting the above technical solutions, product A, prepared from dimethyl diallyl ammonium chloride, acrylamide, ammonium persulfate, and epichlorohydrin, has a small molecular weight and is easily penetrated, effectively binding with dyes and acting on fabrics. Product B, prepared from tetraethylenepentamine, triethylamine, dimethylamine, and epichlorohydrin, has a large molecular weight and good film-forming properties. It utilizes the film-forming effect of reactive groups on the fabric surface to improve the color-fixing effect and can further bind residual dyes that do not react immediately or do not react after the application of product A. The addition of triallylamine further improves the cross-linking property after the color-fixing agent binds with the dye and acts on the fabric through high-temperature setting of the fabric, forming a three-dimensional network structure and bringing a more excellent color-fixing effect. The formaldehyde-free color-fixing agent of this application, through the combination of product A, product B, and triallylamine, not only has cationic and reactive groups, but also has the superimposed reactivity between multiple components, thus taking into account both the permeability and film-forming properties after application, and exhibiting excellent color-fixing performance.

[0021] Preferably, the molar ratio of dimethyl diallyl ammonium chloride, acrylamide, and epichlorohydrin is 9:1:0.8.

[0022] By adopting the above technical solution, the product A obtained from the raw materials with the above molar ratio exhibits strong permeability and can maintain a better binding speed with the dye, thus having a better effect on printed and dyed fabrics.

[0023] Preferably, the molar ratio of tetraethylenepentamine, triethylamine, dimethane, and epichlorohydrin is 1:0.5:1:5.

[0024] By adopting the above technical solution, the product B prepared from the raw materials with the above molar ratio exhibits better film-forming properties and has a better and more stable compatibility with product A, so that the dye can be more stably bound to the fabric.

[0025] Preferably, the viscosity of product A is 600-1200 mPa·s.

[0026] By adopting the above technical solution, the product A with the above viscosity can be evenly distributed on the fabric surface, exhibiting better penetration and rapid binding with dyes. However, if the viscosity exceeds the above range, the dispersion uniformity of product A on the fabric surface will deteriorate, resulting in a loss of the actual effect of product A.

[0027] Preferably, the viscosity of product B is 18000-25000 mPa·s.

[0028] By adopting the above technical solution, the product B with the above viscosity can be evenly distributed on the fabric surface, thereby exhibiting better film-forming properties and rapid binding with residual dyes. However, if the viscosity exceeds the above range, the dispersion uniformity of product B on the fabric surface will deteriorate, resulting in a loss of the actual effect of product B application.

[0029] Preferably, the raw material of the formaldehyde-free fixing agent further contains 4-8 parts by weight of a cationic chitosan polymer, which is prepared by the following steps:

[0030] S1. N-methylethyleneamine, [(2-epoxyethylene methoxy)methyl]-phosphonate diethyl ester and paraformaldehyde are mixed and reacted in a molar ratio of 1:(1-1.2):(1-1.4) at a reaction temperature of 55-90℃ for 30-90 min. After cooling, washing and rotary evaporation, the intermediate product is obtained.

[0031] S2. The intermediate product and allyl chloride are reacted in acetone solvent at a molar ratio of 1:(1-1.2) at a reaction temperature of 40-60℃ for 5-8 hours. After cooling, washing and rotary evaporation, the functional product is obtained.

[0032] S3. Chitosan and functional products are dissolved in acetic acid solution and water at a molar ratio of 1:(4.8-5.4), respectively, and then mixed. The reaction temperature is 60-80℃ and the reaction time is 7-10h. After cooling, washing and rotary evaporation, cationic chitosan polymer is obtained.

[0033] By employing the above technical solution, N-methylethyleneamine, [(2-epoxyethylene methoxy)methyl]-phosphonic acid diethyl ester, and paraformaldehyde are reacted to form a tertiary amine, which is then reacted with allyl chloride for quaternization treatment. Finally, the epoxy group of the functional product undergoes a ring-opening reaction with the amino group of chitosan to obtain a cationic chitosan polymer. Through the large number of hydroxyl groups on the cationic chitosan polymer, hydrogen bonds can be formed with the amino and hydroxyl groups of the dye. At the same time, the cationic active quaternary ammonium salt groups are combined with the sulfonic acid anions of the dye, thereby greatly improving the fixing effect of the formaldehyde-free fixing agent.

[0034] Secondly, this application provides a method for preparing a formaldehyde-free fixing agent, which adopts the following technical solution:

[0035] A method for preparing a formaldehyde-free color-fixing agent includes the following steps:

[0036] (1) Prepare raw materials containing dimethyl diallyl ammonium chloride, acrylamide, ammonium persulfate, epichlorohydrin, tetraethylenepentamine, triethylamine, dimethylamine, water and triallylamine according to the formula;

[0037] (2) After mixing dimethyl diallyl ammonium chloride and acrylamide in step (1) evenly, add ammonium persulfate for heating polymerization reaction. After the reaction is completed, cool and add 9.5-19.5 parts by weight of epichlorohydrin to react and obtain product A; mix tetraethylenepentamine, triethylamine and dimethylamine in step (1) evenly, add the remaining parts by weight of epichlorohydrin to react and obtain product B;

[0038] (3) Mix product A, product B, water, and triallylamine from step (2) evenly, and adjust the pH to obtain a formaldehyde-free color-fixing agent.

[0039] By adopting the above technical solution, the preparation method is simple to operate and easy to promote and apply on a large scale in industrial production. At the same time, the separate preparation of product A and product B in the process is also beneficial for quality control of the obtained product A and product B, thereby ensuring that the final formaldehyde-free fixing agent has excellent and stable quality.

[0040] Preferably, in step (2), after the dimethyl diallyl ammonium chloride and acrylamide from step (1) are mixed evenly, ammonium persulfate is added and heated to 60-90℃ for polymerization reaction for 4-6 hours. Finally, 9.5-19.5 parts by weight of epichlorohydrin are added and reacted for 1.5-2.5 hours, and then the temperature is raised to 40-60℃ and held for 3-6 hours to obtain product A.

[0041] By adopting the above technical solution and controlling the above parameters in the preparation of product A, the raw materials of each component can be fully utilized in the reaction process, thereby obtaining product A with excellent and stable quality.

[0042] Preferably, in step (2), the tetraethylenepentamine, triethylamine and dimethylamine from step (1) are mixed evenly, and the remaining weight of epichlorohydrin is added and reacted for 1.5-2.5 h. Then, the temperature is raised to 55-65℃ and kept at that temperature for 4.5-5.5 h to obtain product B.

[0043] By adopting the above technical solution and controlling the above parameters in the preparation of product B, the raw materials of each component can be stably combined during the reaction process, thereby obtaining product B with excellent and stable quality.

[0044] Preferably, in step (3), product A, product B, water, and triallylamine from step (2) are mixed evenly, and the pH is adjusted to 6-7 to obtain a formaldehyde-free fixing agent.

[0045] By adopting the above technical solution and adjusting the pH to 6-7, it is not only beneficial to maintain a relatively stable state between product A, product B, water, and triallylamine, but also to enable the formaldehyde-free fixing agent to fully cooperate with the dye and act on the fabric during application, thereby exerting excellent effects.

[0046] In summary, this application has the following beneficial effects:

[0047] 1. Because this application uses product A prepared from dimethyl diallyl ammonium chloride, acrylamide, ammonium persulfate, and epichlorohydrin as raw materials, and product B prepared from tetraethylenepentamine, triethylamine, dimethylamine, and epichlorohydrin as raw materials, and through the combination of product A, product B and triallylamine, the resulting formaldehyde-free fixing agent can exhibit excellent fixing performance after application.

[0048] 2. This application introduces cationic chitosan polymer into the raw materials of formaldehyde-free fixing agent, which can enhance the synergistic effect between fixing agent and dye, thereby stabilizing the action on fabric and exhibiting better color fixing effect. Detailed Implementation

[0049] The present application will be further described in detail below with reference to the embodiments.

[0050] Preparation examples of raw materials and / or intermediates

[0051] Preparation Example 1

[0052] A cationic chitosan polymer is prepared by the following steps:

[0053] S1. N-methylethyleneamine, [(2-epoxyethylene methoxy)methyl]-phosphonate diethyl ester and paraformaldehyde were mixed in a molar ratio of 1:1.1:1.2 and reacted at a reaction temperature of 72.5℃ for 60 min. After cooling, washing and rotary evaporation, the intermediate product was obtained.

[0054] S2. The intermediate product and allyl chloride were reacted in acetone solvent at a molar ratio of 1:1.1 at a reaction temperature of 50°C for 6.5 h. After cooling, washing and rotary evaporation, the functional product was obtained.

[0055] S3. Chitosan and functional products were dissolved in acetic acid solution and water at a molar ratio of 1:5.1, respectively, and then mixed. The reaction temperature was 70℃ and the reaction time was 8.5h. After cooling, washing and rotary evaporation, cationic chitosan polymer was obtained.

[0056] Preparation Example 2

[0057] A cationic chitosan polymer is prepared by the following steps:

[0058] S1. N-methylethyleneamine, [(2-epoxyethylene methoxy)methyl]-phosphonic acid diethyl ester and paraformaldehyde are mixed in a molar ratio of 1:1:1 and reacted at a reaction temperature of 55℃ for 90 min. After cooling, washing and rotary evaporation, the intermediate product is obtained.

[0059] S2. The intermediate product and allyl chloride were reacted in acetone solvent at a molar ratio of 1:1. The reaction temperature was 40℃ and the reaction time was 8h. After cooling, washing and rotary evaporation, the functional product was obtained.

[0060] S3. Chitosan and functional products were dissolved in acetic acid solution and water respectively at a molar ratio of 1:4.8, and then mixed. The reaction temperature was 60℃ and the reaction time was 10h. After cooling, washing and rotary evaporation, cationic chitosan polymer was obtained.

[0061] Preparation Example 3

[0062] A cationic chitosan polymer is prepared by the following steps:

[0063] S1. N-methylethyleneamine, [(2-epoxyethylene methoxy)methyl]-phosphonate diethyl ester and paraformaldehyde were mixed in a molar ratio of 1:1.2:1.4 and reacted at a reaction temperature of 90℃ for 30 min. After cooling, washing and rotary evaporation, the intermediate product was obtained.

[0064] S2. The intermediate product and allyl chloride were reacted in acetone solvent at a molar ratio of 1:1.2 at a reaction temperature of 60℃ for 5 hours. After cooling, washing and rotary evaporation, the functional product was obtained.

[0065] S3. Chitosan and functional products were dissolved in acetic acid solution and water respectively at a molar ratio of 1:5.4, and then mixed. The reaction temperature was 80℃ and the reaction time was 7h. After cooling, washing and rotary evaporation, cationic chitosan polymer was obtained.

[0066] Example

[0067] Example 1

[0068] A formaldehyde-free color-fixing agent, the components and their corresponding weights are shown in Table 1, and it is prepared by the following steps:

[0069] (1) Prepare raw materials containing dimethyl diallyl ammonium chloride, acrylamide, ammonium persulfate, epichlorohydrin, tetraethylenepentamine, triethylamine, dimethylamine, water and triallylamine according to the formula;

[0070] (2) After mixing dimethyl diallyl ammonium chloride and acrylamide in step (1) evenly, add ammonium persulfate and heat to 75°C for polymerization reaction for 5 hours. Finally, add 9.5-19.5 parts by weight of epichlorohydrin and react for 2 hours. Then, heat to 50°C and keep warm for 4.5 hours to obtain product A. After mixing tetraethylenepentamine, triethylamine and dimethylamine in step (1) evenly, add the remaining parts by weight of epichlorohydrin and react for 2 hours. Then, heat to 60°C and keep warm for 5 hours to obtain product B.

[0071] (3) Mix product A, product B, water, and triallylamine from step (2) evenly, and adjust the pH to 6.5 to obtain a formaldehyde-free color-fixing agent.

[0072] Note: In this embodiment, during the preparation of product A, the weight of epichlorohydrin added is 14.5 parts; the viscosity of product A is controlled to be 900 mPa·s; and the viscosity of product B is 21500 mPa·s.

[0073] Example 2-3

[0074] A formaldehyde-free color-fixing agent, which differs from Example 1 in that the components and their corresponding weights are shown in Table 1.

[0075] Table 1. Components and their weight parts (kg / part) in Examples 1-3

[0076]

[0077] Example 4

[0078] A formaldehyde-free color-fixing agent differs from Example 1 in that, in step (2), after the dimethyl diallyl ammonium chloride and acrylamide in step (1) are mixed evenly, ammonium persulfate is added and heated to 60°C for polymerization reaction for 6 hours. Finally, 14.5 parts by weight of epichlorohydrin are added and reacted for 2.5 hours, and then the temperature is raised to 40°C and kept at that temperature for 6 hours to obtain product A.

[0079] Example 5

[0080] A formaldehyde-free color-fixing agent differs from Example 1 in that, in step (2), after the dimethyl diallyl ammonium chloride and acrylamide in step (1) are mixed evenly, ammonium persulfate is added and heated to 90°C for a polymerization reaction for 4 hours. Finally, 14.5 parts by weight of epichlorohydrin are added and reacted for 1.5 hours, and then the temperature is raised to 60°C and kept at that temperature for 3 hours to obtain product A.

[0081] Example 6

[0082] A formaldehyde-free color-fixing agent differs from Example 1 in that, in step (2), the tetraethylenepentamine, triethylamine, and dimethylamine from step (1) are mixed evenly, and the remaining weight of epichlorohydrin is added and reacted for 1.5 h. Then, the temperature is raised to 55°C and kept at that temperature for 4.5 h to obtain product B.

[0083] Example 7

[0084] A formaldehyde-free color-fixing agent differs from Example 1 in that, in step (2), the tetraethylenepentamine, triethylamine, and dimethylamine from step (1) are mixed evenly, and the remaining weight of epichlorohydrin is added and reacted for 2.5 h. Then, the temperature is raised to 65°C and kept at that temperature for 5.5 h to obtain product B.

[0085] Example 8

[0086] A formaldehyde-free color-fixing agent differs from Example 1 in that, in step (3), product A, product B, water, and triallylamine from step (2) are mixed evenly, and the pH is adjusted to 6 to obtain the formaldehyde-free color-fixing agent.

[0087] Example 9

[0088] A formaldehyde-free color-fixing agent differs from Example 1 in that, in step (3), product A, product B, water, and triallylamine from step (2) are mixed evenly, and the pH is adjusted to 7 to obtain the formaldehyde-free color-fixing agent.

[0089] Example 10

[0090] A formaldehyde-free color-fixing agent, which differs from Example 1 in that the viscosity of product A is 600 mPa·s.

[0091] Example 11

[0092] A formaldehyde-free color-fixing agent, which differs from Example 1 in that the viscosity of product A is 1200 mPa·s.

[0093] Example 12

[0094] A formaldehyde-free color-fixing agent, which differs from Example 1 in that the viscosity of product A is 550 mPa·s.

[0095] Example 13

[0096] A formaldehyde-free color-fixing agent, which differs from Example 1 in that the viscosity of product A is 1250 mPa·s.

[0097] Example 14

[0098] A formaldehyde-free color-fixing agent, which differs from Example 1 in that the viscosity of product B is 18000 mPa·s.

[0099] Example 15

[0100] A formaldehyde-free color-fixing agent, which differs from Example 1 in that the viscosity of product B is 25000 mPa·s.

[0101] Example 16

[0102] A formaldehyde-free color-fixing agent, which differs from Example 1 in that the viscosity of product B is 17500 mPa·s.

[0103] Example 17

[0104] A formaldehyde-free color-fixing agent, which differs from Example 1 in that the viscosity of product B is 25500 mPa·s.

[0105] Example 18

[0106] A formaldehyde-free color-fixing agent differs from Example 1 in that the total amount of dimethyl diallyl ammonium chloride, acrylamide, and epichlorohydrin remains unchanged, and the molar ratio of the three components is adjusted to 9:1:0.8.

[0107] Example 19

[0108] A formaldehyde-free color-fixing agent differs from Example 1 in that the total amount of tetraethylenepentamine, triethylamine, dimethane, and epichlorohydrin remains unchanged, while the molar ratio between the four components is adjusted to 1:0.5:1:5.

[0109] Example 20

[0110] A formaldehyde-free fixing agent, which differs from Example 1 in that the raw materials of the formaldehyde-free fixing agent also include 6 parts by weight of cationic chitosan polymer, which was obtained in Preparation Example 1, and is added in step (3) in combination with product A, product B, water, and triallylamine.

[0111] Example 21

[0112] An aldehyde-free color-fixing agent, which differs from Example 1 in that the cationic chitosan polymer is added in 4 parts by weight.

[0113] Example 22

[0114] An aldehyde-free fixing agent, which differs from Example 1 in that the cationic chitosan polymer is added in 8 parts by weight.

[0115] Example 23

[0116] An aldehyde-free fixing agent, which differs from Example 1 in that the cationic chitosan polymer was obtained in Preparation Example 2.

[0117] Example 24

[0118] An aldehyde-free fixing agent, which differs from Example 1 in that the cationic chitosan polymer was obtained in Preparation Example 3.

[0119] Comparative Example

[0120] Comparative Example 1

[0121] A formaldehyde-free fixing agent, which differs from Example 1 in that the formaldehyde-free fixing agent does not contain product A in its components.

[0122] Comparative Example 2

[0123] A formaldehyde-free fixing agent, which differs from Example 1 in that the formaldehyde-free fixing agent does not contain product B in its components.

[0124] Comparative Example 3

[0125] A formaldehyde-free fixing agent, which differs from Example 1 in that the formaldehyde-free fixing agent does not contain product A and product B in its components.

[0126] Comparative Example 4

[0127] A formaldehyde-free fixing agent, which differs from Example 1 in that the formaldehyde-free fixing agent does not contain triallylamine in its components.

[0128] Performance testing test samples: The formaldehyde-free fixing agents obtained in Examples 1-24 were used as test samples 1-24, and the formaldehyde-free fixing agents obtained in Comparative Examples 1-4 were used as control samples 1-4.

[0129] Test method: Test samples were prepared using test samples 1-24 and control samples 1-4 according to the following steps, and subsequent tests were performed in sequence;

[0130] (1) Immerse the cotton fabric in reactive dye at a bath ratio of 1:20 at 25℃ and keep it warm for 10 minutes. The reactive dye is composed of scarlet (CI Reactive Red 195) and navy blue (CI Reactive Black 5) in a weight ratio of 5:1, and the amount of reactive dye is 4% owf (the dye is heavier than the fabric).

[0131] (2) Heat the fabric to 80°C at a rate of 2°C / min, dye it, keep it warm for 20 min, then heat it to 120°C at a rate of 2°C / min, keep it warm for 30 min, and obtain the coarsely dyed fabric.

[0132] (3) The coarsely dyed fabric was subjected to immersion and color fixing treatment, wherein the amount of color fixing agent was 0.5% owf (equivalent to 40% content, liquor ratio 1:20, temperature 50℃, time 20min), and the test sample was obtained after cold water washing, dehydration, and setting and drying at 150℃ for 90s.

[0133] The following tests were performed on the test samples:

[0134] Residual liquid after color fixation: Compare the residual liquid after color fixation. The lighter the color, the higher the color fastness (using 1 to 5 to represent the lightness and darkness, with 1 being the best and 5 being the worst).

[0135] Residual liquid after washing: Take the test sample and cut it into 10cm×4cm pieces and mark them. Prepare 200ml of 2.0g / L laundry detergent solution, put the test sample into it, and heat it at 100℃ for 5min. Observe the residual liquid. The lighter the color, the higher the color fastness (1 to 5 represent the lightness grade, with grade 1 being the best and grade 5 being the worst).

[0136] Rubbing fastness test: HGT 4268-2011 "Determination of color-fixing effect of color-fixing agent for cotton in textile dyeing and finishing auxiliaries".

[0137] Wash fastness test: HGT 4268-2011 "Determination of color-fixing effect of color-fixing agent for cotton in textile dyeing and finishing auxiliaries".

[0138] Table 2 Test results of test samples 1-24 and control samples 1-4

[0139]

[0140]

[0141] Based on Examples 1-3 and Comparative Examples 1-4, and in conjunction with Table 2, it can be seen that the combination of Product A, Product B, and triallylamine enables the formaldehyde-free fixing agent to exhibit excellent fixing performance after application. However, if either Product A or Product B is combined with triallylamine, or if only Product A or Product B is used, the tested residual liquid after fixing, residual liquid after washing, rubbing fastness, and washing fastness are all poor, far inferior to the excellent effect brought by the combination of Product A, Product B, and triallylamine.

[0142] Referring to Examples 1 and 10-13, and Table 2, it can be seen that the viscosity of product A is 600-1200 mPa·s, which ensures the stable performance of the formaldehyde-free fixing agent. Viscosities exceeding this range result in poor residue and reduced fixing effect. Referring to Examples 1 and 14-17, and Table 2, it can be seen that the viscosity of product B is 18000-25000 mPa·s, which also ensures the stable performance of the formaldehyde-free fixing agent. Viscosities exceeding this range result in poor residue and reduced fixing effect.

[0143] Combining Examples 1-3 and Example 18 with Table 2, it can be seen that a molar ratio of dimethyl diallyl ammonium chloride, acrylamide, and epichlorohydrin of 9:1:0.8 yields product A, which is of excellent quality and stable performance. This results in a formaldehyde-free fixing agent exhibiting superior application effects and outstanding fixing properties. Similarly, combining Examples 1-3 and Example 19 with Table 2, it can be seen that a molar ratio of tetraethylenepentamine, triethylamine, dimethane, and epichlorohydrin of 1:0.5:1:5 yields product B, which is of excellent quality and stable performance. This also results in a formaldehyde-free fixing agent exhibiting superior application effects and outstanding fixing properties.

[0144] As can be seen from Examples 1 and 20-24 and Table 2, introducing cationic chitosan polymers into the raw materials of formaldehyde-free fixing agents can further improve the low residue and high fixing performance. This is because cationic chitosan polymers can enhance the synergistic effect between fixing agents and dyes.

[0145] This specific embodiment is merely an explanation of this application and is not intended to limit it. After reading this specification, those skilled in the art can make modifications to this embodiment without contributing any inventive step, but such modifications are protected by patent law as long as they fall within the scope of the claims of this application.

Claims

1. A formaldehyde-free color-fixing agent, characterized in that, It is made from raw materials comprising the following parts by weight: 81-162 parts dimethyl diallyl ammonium chloride; 9-18 parts acrylamide; 5-7 parts ammonium persulfate; 55-105 parts epichlorohydrin; 9-18 parts tetraethylenepentamine; 4.5-9 parts triethylamine; 9-18 parts dimethylamine; 90-120 parts water; 0.5-1 part triallylamine; 4-8 parts cationic chitosan polymer; after uniformly mixing dimethyl diallyl ammonium chloride and acrylamide, the persulfate is added. Ammonium sulfate undergoes a heated polymerization reaction. After the reaction solidifies and is cooled, 9.5-19.5 parts by weight of epichlorohydrin are added to react and yield product A. Tetraethylenepentamine, triethylamine, and dimethylamine are mixed evenly, and the remaining parts by weight of epichlorohydrin are added to react and yield product B. Product A, product B, water, triallylamine, and cationic chitosan polymer are mixed to obtain a formaldehyde-free fixing agent. The viscosity of product A is 600-1200 mPa·s; the viscosity of product B is... 18000-25000 mPa·s; The cationic chitosan polymer is prepared by the following steps: S1, N-methylethyleneamine, [(2-epoxyethylene methoxy)methyl]-phosphonate diethyl ester and paraformaldehyde are mixed and reacted in a molar ratio of 1:(1-1.2):(1-1.4) at a reaction temperature of 55-90℃ for 30-90 min. After cooling, washing and rotary evaporation, an intermediate product is obtained; S2, the intermediate product, chloropropane... The alkene was reacted in acetone solvent at a molar ratio of 1:(1-1.2) at a reaction temperature of 40-60℃ for 5-8 hours. After cooling, washing, and rotary evaporation, the functional product was obtained. S3. Chitosan and the functional product were dissolved in acetic acid solution and water at a molar ratio of 1:(4.8-5.4), respectively, and then mixed. The reaction temperature was 60-80℃ for 7-10 hours. After cooling, washing, and rotary evaporation, the cationic chitosan polymer was obtained.

2. The formaldehyde-free fixing agent according to claim 1, characterized in that: The molar ratio of dimethyl diallyl ammonium chloride, acrylamide, and epichlorohydrin is 9:1:0.

8.

3. The formaldehyde-free fixing agent according to claim 1, characterized in that: The molar ratio of tetraethylenepentamine, triethylamine, dimethyl methacrylate, and epichlorohydrin is 1:0.5:1:

5.

4. The method for preparing the formaldehyde-free fixing agent according to claim 1, characterized in that: Includes the following steps: (1) Prepare raw materials containing dimethyl diallyl ammonium chloride, acrylamide, ammonium persulfate, epichlorohydrin, tetraethylenepentamine, triethylamine, dimethylamine, water, triallylamine and cationic chitosan polymer according to the formula; (2) After mixing dimethyl diallyl ammonium chloride and acrylamide in step (1) evenly, add ammonium persulfate for heating polymerization reaction, and after the reaction is completed, cool and add 9.5-19.5 parts by weight of epichlorohydrin to react and obtain product A; mix tetraethylenepentamine, triethylamine and dimethylamine in step (1) evenly, add the remaining parts by weight of epichlorohydrin to react and obtain product B; (3) Mix product A, product B and water, triallylamine and cationic chitosan polymer in step (2) evenly, adjust pH and obtain formaldehyde-free fixing agent.

5. The method for preparing the formaldehyde-free fixing agent according to claim 4, characterized in that: In step (2), after the dimethyl diallyl ammonium chloride and acrylamide from step (1) are mixed evenly, ammonium persulfate is added and heated to 60-90℃ for polymerization reaction for 4-6 hours. Finally, 9.5-19.5 parts by weight of epichlorohydrin are added and reacted for 1.5-2.5 hours. Then, the temperature is raised to 40-60℃ and kept at that temperature for 3-6 hours to obtain product A.

6. The method for preparing the formaldehyde-free fixing agent according to claim 4, characterized in that: In step (2), the tetraethylenepentamine, triethylamine and dimethylamine from step (1) are mixed evenly, and the remaining weight of epichlorohydrin is added. After reacting for 1.5-2.5 h, the temperature is raised to 55-65℃ and kept at that temperature for 4.5-5.5 h to obtain product B.

7. The method for preparing the formaldehyde-free fixing agent according to claim 4, characterized in that: In step (3), product A and product B from step (2) are mixed evenly with water, triallylamine, and cationic chitosan polymer, and the pH is adjusted to 6-7 to obtain a formaldehyde-free fixing agent.

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