A water-washing resistant chlorine-resistant fixing agent and a preparation method thereof

Abstract

The application belongs to the technical field of fabric color fixing and discloses a chlorine-resistant and washing-resistant color fixing agent, which comprises a first color fixing component and a second color fixing component, the mass ratio between the first color fixing component and the second color fixing component is 1.5-3:1, the first color fixing component is obtained by polymerization of polyethylene imine and epichlorohydrin, the second color fixing component is a polyurethane color fixing agent or is obtained by polymerization of at least two cationic color fixing agents, the cationic color fixing agent is a cationic color fixing agent containing nitrogen elements, and the polyurethane color fixing agent is a polyurethane color fixing agent with -NCO as an end-capping group. In addition, the application further discloses a preparation method for preparing the chlorine-resistant and washing-resistant color fixing agent.

Description

Technical Field

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

[0002] The presence of active chlorine in tap water is the primary cause of color changes and even fading in dyed fabrics. Currently, chlorine is widely used for tap water disinfection due to its low cost and effective sterilization, resulting in high chlorine levels in urban tap water in my country. People have observed color changes in clothes after washing them with tap water over a long period. This is because active chlorine, in addition to its oxidizing and bleaching effects, can also undergo chlorination. When textiles come into contact with tap water containing active chlorine, the dyes on the fibers readily come into contact with the active chlorine. The active chlorine directly reacts with the dyes, causing them to be oxidized or chlorinated to varying degrees, leading to color changes in the textiles. This includes direct dyes and cationic dyes, especially reactive dyes, which are easily degraded by active chlorine, resulting in color changes in clothing during washing.

[0003] With the improvement of people's living standards in China, the demand for upgraded textile consumption is becoming increasingly prominent. The poor resistance of reactive dyes to chlorine water has brought the issue of poor appearance durability of dyed fabrics to the forefront of public attention. Currently available chlorine-resistant fixing agents are mostly composed of polyethylenepolyamines and antioxidants. These fixing agent molecules are adsorbed onto the fabric surface through hydrogen bonds or van der Waals forces, and have high solubility in water. During repeated washing, they gradually dissolve in the water, leading to a decrease in chlorine fastness. Therefore, the industry's goal is to improve chlorine bleach fastness while providing excellent wash durability, ensuring that textiles maintain color consistency over time.

[0004] Chinese patent application 202210170130.4 discloses the application of an active hydrophilic formaldehyde-free color-fixing agent. The preparation steps of the color-fixing agent are as follows:

[0005] 1) Add concentrated hydrochloric acid slowly with stirring, add tertiary amine dropwise, keep the reaction at the temperature, and adjust the pH of the solution to 3-4 with tertiary amine;

[0006] 2) Heat to 45℃, slowly add epichlorohydrin, maintain the temperature at 45-55℃ for 1.0-2.5h until a homogeneous solution is obtained, then adjust the pH value and cool down to obtain the intermediate product;

[0007] 3) Add the intermediate product, polyethyleneimine, and deionized water to a reaction flask, stir, and slowly add epichlorohydrin dropwise. Maintain the reaction temperature at 20–40°C for 5–7 hours, then adjust the pH to 6–7 at 65–80°C and cool to obtain a hydrophilic fixing agent. Prepare a 2.0% fixing agent working solution by mixing the hydrophilic formaldehyde-free fixing agent with water. Then immerse the fabric to be treated in the fixing agent working solution at an immersion temperature of 40–50°C, an immersion bath ratio of 1:10, and an immersion time of 20–30 minutes. Finally, remove the fabric and dry it at an immersion temperature of 95–105°C for 1–2 minutes.

[0008] This scheme exhibits good hydrophilicity by introducing quaternary ammonium salt cationic groups and epoxy groups into the amino-containing polyethyleneimine polymer backbone.

[0009] Furthermore, because the hydrophilic formaldehyde-free fixing agent of this scheme introduces quaternary ammonium salt cationic groups, it further improves the cationicity and can react with reactive dyes to form water-insoluble salts. At the same time, it introduces reactive epoxy groups, which can further form strong chemical bonds with fibers or dyes and form a polymer film on the surface of cotton fibers, firmly encapsulating the dyes within it. Therefore, it has good wash fastness, rubbing fastness and other properties.

[0010] The hydrophilic formaldehyde-free color-fixing agent in this solution has both good color-fixing and hydrophilic properties. After color-fixing treatment, the hydrophilicity of the cotton fabric itself is minimally affected, which can meet the requirements of printing and dyeing plants for hydrophilic formaldehyde-free color-fixing agents.

[0011] Chinese patent application 202311391528.1 discloses a color-fixing agent for blended fabrics, obtained by free radical polymerization of the following monomers: 40-48 parts by weight of dimethyl diallyl ammonium chloride; 0.1-0.5 parts by weight of a siloxane containing unsaturated bonds; 0.5-2.0 parts by weight of an epoxy polyether containing unsaturated bonds; 1.0-3.0 parts by weight of C13-C16 acrylate or C13-C16 methacrylate; 0.5-2.0 parts by weight of sulfonic acid or sulfonate containing unsaturated bonds; and 0.5-6 parts by weight of a crosslinking monomer.

[0012] The color-fixing agent prepared by this scheme adopts the mature DMDAAC route, introducing siloxanes containing unsaturated bonds, C13-C16 acrylates, or C13-C16 methacrylates to improve the fabric hand feel, increase the fabric softness, improve color fastness, and improve the stability of free radical polymerization, ultimately obtaining a product that meets the expected indicators.

[0013] The problem this solution needs to solve is: how to provide a water-resistant and chlorine-resistant color-fixing agent. Summary of the Invention

[0014] The purpose of this invention is to provide a water-resistant and chlorine-resistant color-fixing agent;

[0015] Another object of this application is to provide a method for preparing the above-mentioned low-hydrolysis chlorine-resistant fixing agent.

[0016] To achieve the above objectives, this application discloses a water-resistant and chlorine-resistant color-fixing agent, comprising a first color-fixing component and a second color-fixing component, wherein the mass ratio between the first color-fixing component and the second color-fixing component is 1.5 to 3:1;

[0017] The first color-fixing component is obtained by polymerizing polyethyleneimine and epichlorohydrin;

[0018] The second fixing component is a polyurethane fixing agent or is obtained by polymerization of at least two cationic fixing agents;

[0019] The cationic fixing agent is a cationic fixing agent containing nitrogen.

[0020] The polyurethane fixing agent is a polyurethane fixing agent with -NCO as the end group.

[0021] Preferably, the second color-fixing component is obtained by polymerization of at least two cationic color-fixing agents.

[0022] Preferably, the cationic fixing agent is selected from diallylamine, acrylamide, dimethyldiallyl ammonium chloride, methacryloyloxyethyltrimethylammonium chloride, and acryloyloxyethyltrimethylammonium chloride;

[0023] Preferably, the second fixing agent is obtained by polymerizing diallylamine, acrylamide, and dimethyl diallyl ammonium chloride, and the molar ratio of diallylamine, acrylamide, and dimethyl diallyl ammonium chloride is 15-25:4-15:100-110.

[0024] Preferably, the water-resistant and chlorine-resistant color-fixing agent does not precipitate solid substances within 30 days at 5°C.

[0025] Furthermore, this application also discloses a method for preparing the above-mentioned water-resistant and chlorine-resistant fixing agent, characterized by comprising the following steps:

[0026] Step 1: Mix and polymerize polyethyleneimine and epichlorohydrin to obtain the first color-fixing component;

[0027] Step 2: Mix, polymerize, or weigh at least two cationic fixing agents to obtain a second fixing component;

[0028] Step 3: Mix the first fixing component and the second fixing component at a mass ratio of 1.5 to 3:1 to obtain a water-resistant and chlorine-resistant fixing agent.

[0029] Preferably, step 1 includes the following sub-steps:

[0030] Step A1: Add polyethyleneimine to the flask, and simultaneously start stirring and heating;

[0031] Step A2: Control the temperature at 20-50℃, add epichlorohydrin dropwise to polyethyleneimine, keep warm for 2-3 hours after the addition is complete, and control the temperature at 70-75℃.

[0032] Step A3: After the heat preservation is completed, cool the sample and adjust the pH value to 6.5-7.5 using glacial acetic acid to obtain the first color-fixing component.

[0033] Preferably, step 2 specifically involves: adding at least two cationic fixing agents into a flask under a nitrogen atmosphere, adjusting the pH value to 4-5, heating to 80°C, adding initiators respectively, reacting for 2-3 hours, and cooling to obtain the second fixing component;

[0034] The initiator is an aqueous solution of ammonium persulfate and sodium bisulfite.

[0035] Preferably, step 3 specifically involves mixing the first fixing agent component and the second fixing agent component at a mass ratio of 1.5 to 3:1, stirring, and obtaining a water-resistant and chlorine-resistant fixing agent.

[0036] The beneficial effects of this application are:

[0037] 1. Polyethyleneimine has a high amine density. Therefore, the chlorine-resistant color fastener molecule of this application contains a large number of secondary amines, primary amines and other amine groups. When free active chlorine in water comes into contact with the fabric, it will preferentially react with the amines, which can more effectively block the attack of active chlorine on the dye and significantly improve the chlorine fastness of the fabric.

[0038] 2. The compounded polycationic fixing agent can cross-link into a network film on the fiber surface, which is tightly bound to the fabric. This allows the fixing agent molecules to withstand multiple washes without falling off, enabling the fabric to maintain excellent chlorine resistance and durability for a long time. Detailed Implementation

[0039] The present invention will now be clearly and completely described in conjunction with embodiments thereof. It should be noted that, unless specific conditions are specified in the embodiments, conventional conditions or conditions recommended by the manufacturer shall apply. Reagents or instruments whose manufacturers are not specified are all commercially available conventional products.

[0040] Before demonstrating the embodiments, the source information of the raw materials involved in the embodiments will be explained as necessary, as shown in Table 1:

[0041] Table 1

[0042]

[0043] Example 1

[0044] Step 1:

[0045] Step A1: Add a 50% aqueous solution of linear polyethyleneimine (molecular weight 20,000-50,000) to the flask while stirring.

[0046] Step A2: Control the temperature at 20℃, add epichlorohydrin dropwise to the polyethyleneimine aqueous solution at a mass ratio of 1:1, keep warm for 3 hours, and control the temperature at 70℃.

[0047] Step A3: After the heat preservation is completed, cool the sample and adjust the pH value to 6.75±0.25 using glacial acetic acid to obtain the first color-fixing component;

[0048] Step 2: Add diallylamine and dimethyl diallyl ammonium chloride in a molar ratio of 15:100 to a flask under a nitrogen atmosphere, then adjust the pH to 4.5±0.5, heat to 80°C, add an initiator, react for 4 hours, and cool to obtain the second color-fixing component.

[0049] The initiator is an aqueous solution prepared by dissolving sodium sulfite and ammonium persulfate in a 1:1 mass ratio, wherein the total mass fraction of sodium sulfite and ammonium persulfate in the aqueous solution is 5%.

[0050] Step 3: Mix the first fixing agent component and the second fixing agent component at a mass ratio of 1.5:1, stir, and obtain a water-resistant and chlorine-resistant fixing agent.

[0051] Example 2

[0052] Step 1:

[0053] Step A1: Add a 50% aqueous solution of linear polyethyleneimine (molecular weight 20,000-50,000) to the flask while stirring.

[0054] Step A2: Control the temperature at 50℃, add epichlorohydrin dropwise to polyethyleneimine, add epichlorohydrin dropwise to the polyethyleneimine aqueous solution at a mass ratio of 1:1, keep warm for 2 hours, and control the temperature at 75℃.

[0055] Step A3: After the heat preservation is completed, cool the sample and adjust the pH value to 6.75±0.25 using glacial acetic acid to obtain the first color-fixing component;

[0056] Step 2: Add diallylamine and dimethyl diallyl ammonium chloride in a molar ratio of 15:100 into a flask under a nitrogen atmosphere, then adjust the pH to 4.5±0.5, heat to 80°C, add an initiator, react for 5 hours, and cool to obtain the second color-fixing component.

[0057] The initiator is an aqueous solution prepared by dissolving sodium sulfite and ammonium persulfate in a 1:1 mass ratio, wherein the total mass fraction of sodium sulfite and ammonium persulfate in the aqueous solution is 5%.

[0058] Step 3: Mix the first fixing agent component and the second fixing agent component at a mass ratio of 2:1 and stir to obtain a water-resistant and chlorine-resistant fixing agent.

[0059] Example 3

[0060] Step 1:

[0061] Step A1: Add a 50% aqueous solution of linear polyethyleneimine (molecular weight 20,000-50,000) to the flask while stirring.

[0062] Step A2: Control the temperature at 35℃, add epichlorohydrin dropwise to the polyethyleneimine aqueous solution at a mass ratio of 1:1, keep warm for 2.5h, and control the temperature at 72℃.

[0063] Step A3: After the heat preservation is completed, cool the sample and adjust the pH value to 6.75±0.25 using glacial acetic acid to obtain the first color-fixing component;

[0064] Step 2: Add diallylamine and dimethyl diallyl ammonium chloride in a molar ratio of 15:100 into a flask under a nitrogen atmosphere, then adjust the pH to 4-5, heat to 80°C, add an initiator, react for 4.5 hours, cool, and obtain the second color-fixing component.

[0065] The initiator is an aqueous solution prepared by dissolving sodium sulfite and ammonium persulfate in a 1:1 mass ratio, wherein the total mass fraction of sodium sulfite and ammonium persulfate in the aqueous solution is 5%.

[0066] Step 3: Mix the first fixing agent component and the second fixing agent component at a mass ratio of 3:1 and stir to obtain a water-resistant and chlorine-resistant fixing agent.

[0067] Example 4

[0068] The process is basically the same as in Example 1, except that step 2 is specifically as follows:

[0069] Diallylamine and acrylamide were added to a flask under a nitrogen atmosphere at a molar ratio of 15:4. The pH was then adjusted to 4.5±0.5, and the mixture was heated to 80°C. An initiator was added, and the mixture was reacted for 4 hours and then cooled to obtain the second color-fixing component.

[0070] Example 5

[0071] The process is basically the same as in Example 1, except that step 2 is specifically as follows:

[0072] Acrylamide and dimethyl diallyl ammonium chloride were added to a flask under a nitrogen atmosphere at a molar ratio of 4:100. The pH was then adjusted to 4.5±0.5, and the mixture was heated to 80°C. An initiator was added, and the mixture was reacted for 4 hours and then cooled to obtain the second color-fixing component.

[0073] Example 6

[0074] The process is basically the same as in Example 1, except that step 2 is specifically as follows:

[0075] Diallylamine, acrylamide, and dimethyldiallyl ammonium chloride were added to a flask under a nitrogen atmosphere in a molar ratio of 15:4:100. The pH was then adjusted to 4.5±0.5, and the mixture was heated to 80°C. An initiator was added, and the mixture was reacted for 4 hours and then cooled to obtain the second color-fixing component.

[0076] Example 7

[0077] The process is basically the same as in Example 1, except that step 2 is specifically as follows:

[0078] Diallylamine, acrylamide, and dimethyldiallyl ammonium chloride were added to a flask under a nitrogen atmosphere in a molar ratio of 20:5:103. The pH was then adjusted to 4.5±0.5, and the mixture was heated to 80°C. An initiator was added, and the mixture was reacted for 4 hours and then cooled to obtain the second color-fixing component.

[0079] Example 8

[0080] The process is basically the same as in Example 1, except that step 2 is specifically as follows:

[0081] Diallylamine, acrylamide, and dimethyldiallyl ammonium chloride were added to a flask under a nitrogen atmosphere in a molar ratio of 25:15:110. The pH was then adjusted to 4.5±0.5, and the mixture was heated to 80°C. An initiator was added, and the mixture was reacted for 4 hours and then cooled to obtain the second color-fixing component.

[0082] Example 9

[0083] It is basically the same as Example 1, except that the second color-fixing component is a commercially available polyurethane color-fixing agent.

[0084] Example 10

[0085] The process is basically the same as in Example 1, except that step 2 is specifically as follows:

[0086] Diallylamine, acrylamide, and acryloyloxyethyltrimethylammonium chloride were added to a flask under a nitrogen atmosphere in a molar ratio of 20:5:103. The pH was then adjusted to 4.5±0.5, and the mixture was heated to 80°C. An initiator was added, and the mixture was reacted for 4 hours and then cooled to obtain the second color-fixing component.

[0087] Example 11

[0088] The process is basically the same as in Example 1, except that step 2 is specifically as follows:

[0089] Diallylamine, acrylamide, and methacryloyloxyethyltrimethylammonium chloride were added to a flask under a nitrogen atmosphere in a molar ratio of 20:5:103. The pH was then adjusted to 4.5±0.5, and the mixture was heated to 80°C. An initiator was added, and the mixture was reacted for 4 hours and then cooled to obtain the second color-fixing component.

[0090] Comparative Example 1

[0091] Step A1: Add a 50% aqueous solution of linear polyethyleneimine (molecular weight 20,000-50,000) to the flask while stirring.

[0092] Step A2: Control the temperature at 20℃, add epichlorohydrin dropwise to the polyethyleneimine aqueous solution at a mass ratio of 1:1, keep warm for 3 hours, and control the temperature at 70℃.

[0093] Step A3: After the heat preservation is completed, cool the sample and adjust the pH value to 6.75±0.25 using glacial acetic acid to obtain the color fixing agent.

[0094] Comparative Example 2

[0095] Diallylamine and dimethyldiallylammonium chloride were added to a flask under a nitrogen atmosphere at a molar ratio of 15:100. The pH was then adjusted to 4.5±0.5, and the mixture was heated to 80°C. An initiator was added, and the reaction was carried out for 4 hours. After cooling, a color-fixing agent was obtained.

[0096] Comparative Example 3

[0097] Diallylamine, acrylamide, and dimethyldiallyl ammonium chloride were added to a flask under a nitrogen atmosphere in a molar ratio of 20:5:103. The pH was then adjusted to 4.5±0.5, and the mixture was heated to 80°C. An initiator was added, and the mixture was reacted for 4 hours and then cooled to obtain the second color-fixing component.

[0098] Comparative Example 4

[0099] It is basically the same as Example 1, except that the mass ratio between the first color-fixing component and the second color-fixing component is 1:1.

[0100] Comparative Example 5

[0101] It is basically the same as Example 1, except that the mass ratio between the first color-fixing component and the second color-fixing component is 4:1.

[0102] Comparative Example 6

[0103] The process is basically the same as in Example 1, except that step 2 is specifically as follows:

[0104] Step 2: Add anionic acidic fixing agent 1 and anionic acidic fixing agent 2 to a flask under a nitrogen atmosphere at a molar ratio of 15:100. Then adjust the pH value to 4.5±0.5, heat to 80°C, add initiator, react for 4 hours, and cool to obtain the second fixing agent.

[0105] Among them, the anionic acidic fixing agent 1 is Mesitol BFN, which was purchased from Shanghai Tuona Chemical New Materials Co., Ltd.

[0106] The anionic acidic fixing agent 2 is VJ892F, purchased from Dongguan Xiangtao High-Tech Materials Technology Co., Ltd.

[0107] Test method:

[0108] The blue cotton knitted fabric (dye concentration 7%) was padded with dye, with a padding rate of 85%, and then dried at 120-160℃. The dried red cotton knitted fabric was then treated with 1%–3% (relative to fabric weight) of a fixing agent and tested according to the following standards:

[0109] 1. Wash fastness shall be tested according to GB / T420-90 (grades 1-5, grade 5 being the best);

[0110] 2. Chlorine fastness shall be tested according to AATCC 61-4A-2010 standard.

[0111] The test results are shown in Table 2:

[0112] Table 2

[0113]

[0114]

[0115] Results analysis:

[0116] 1. As can be seen from Examples 1-3, when some process parameters in the preparation of the fixing agent are changed, the chlorine fastness, soaping fastness, and chlorine fastness of the fabric samples after soaping in Examples 1-3 show a certain degree of change trend, but the overall change range is small.

[0117] 2. Further observation of Examples 1 and 4-5 shows that when the second color-fixing component prepared by diallylamine and acrylamide or the second color-fixing component prepared by acrylamide and dimethyl diallyl chloride is used to replace the second color-fixing component prepared by diallylamine and dimethyl diallyl chloride in Example 1, the chlorine fastness, soaping fastness, and chlorine fastness of the fabric sample after soaping in Examples 4 and 5 show a certain degree of change. However, Examples 4-5 have advantages and disadvantages over Example 1 in the three test directions of chlorine fastness, soaping fastness, and chlorine fastness of the fabric sample after soaping, and the difference is small. It can be seen that the overall color-fixing effect obtained by Examples 4-5 is comparable to that of Example 1.

[0118] 3. Further observation of Examples 6-8 shows that when the second color-fixing component was prepared by compounding diallylamine, acrylamide, and dimethyl diallyl ammonium chloride in Examples 6-8, even though the color-fixing effect of Example 6 was relatively poor, the chlorine fastness and soap fastness of the fabric sample after soaping were significantly improved compared to Example 1, while the chlorine fastness was the same.

[0119] It is evident that when diallylamine, acrylamide, and dimethyl diallyl ammonium chloride are combined, the color-fixing effect of the fixing agent can be significantly improved.

[0120] Further observation of Examples 6 and 1, 4, and 5 reveals that when Examples 1, 4, and 5 use diallylamine and dimethyl diallyl chloride; diallylamine and acrylamide; and acrylamide and dimethyl diallyl chloride in pairs to prepare the second color-fixing component, the performance difference between the three is not significant. Therefore, theoretically, when Example 6 uses a combination of diallylamine, acrylamide, and dimethyl diallyl chloride, its color-fixing effect should be comparable to that of Examples 1, 4, and 5.

[0121] However, as can be seen from Table 2, the color-fixing effect is significantly better than that of Examples 1, 4, and 5. The reason for this phenomenon may be that diallylamine, acrylamide, and dimethyldiallyl ammonium chloride produce a synergistic effect when used together, which causes the color-fixing agent to cross-link into a network film on the fabric surface and bond tightly with the fabric. On the one hand, this enhances the adhesion of the color-fixing agent to the fabric surface, thereby improving the fastness to soaping and chlorine. On the other hand, it also provides excellent durability for the fabric to resist the erosion of active chlorine.

[0122] Meanwhile, observations of Examples 6-8 show that when the molar ratio of diallylamine, acrylamide, and dimethyldiallyl ammonium chloride is 20:5:103, the washing fastness and chlorine fastness of the fabric sample after washing are improved in Example 7 compared to Examples 6 and 8. This indicates that when the molar ratio of diallylamine, acrylamide, and dimethyldiallyl ammonium chloride is 20:5:103, the adhesion of the mesh film formed by the fixing agent on the fabric surface to the fabric is stronger.

[0123] 4. As can be seen from Examples 1 and 9, when polyurethane is used as the second color-fixing component, the difference between Example 9 and Example 1 is not significant. Further observation of Examples 10-11 shows that when diallylamine, acrylamide, and methacryloyloxyethyltrimethylammonium chloride are used as the second color-fixing component, or diallylamine, acrylamide, and methacryloyloxyethyltrimethylammonium chloride are used as the second color-fixing component, Examples 10-11 show a certain degree of improvement compared to Example 1, but the improvement is far less than that of any of Examples 6-8.

[0124] 5. As can be seen from Example 1 and Comparative Examples 1-3, when the color-fixing agent consists only of the first color-fixing component or only of the second color-fixing component, the chlorine fastness, soaping fastness, and chlorine fastness of the fabric samples after soaping in Comparative Examples 1-3 all show a significant downward trend compared to Example 1. It can be seen that when only the first color-fixing component or only the second color-fixing component is used, the color-fixing agent is difficult to generate a cross-linked network structure on the fabric surface, and it is difficult to significantly improve the color-fixing effect.

[0125] 6. As can be seen from Examples 1 and Comparative Examples 4-6, on the one hand, when the ratio between the first and second color-fixing components changes significantly, the chlorine fastness, soaping fastness, and chlorine fastness of the fabric sample after soaping in Comparative Examples 4-5 all show a significant downward trend compared to Example 1. This indicates that when the first and second color-fixing components are significantly changed, the cross-linked network structure that should have been attached to the fabric surface is destroyed, resulting in a decrease in the color-fixing effect. On the other hand, when Comparative Example 6 uses a second color-fixing component made with an anionic color-fixing agent, the chlorine fastness, soaping fastness, and chlorine fastness of the fabric sample after soaping in Comparative Example 6 show a more significant difference compared to Example 1. This indicates that the second color-fixing component made with an anionic color-fixing agent is difficult to form a cross-linked network structure on the fabric surface together with the first color-fixing component.

[0126] The above embodiments are preferred embodiments of the present invention, but the embodiments of the present invention are not limited to the above embodiments. Any changes, modifications, substitutions, combinations, or simplifications made without departing from the spirit and principle of the present invention shall be considered equivalent substitutions and shall be included within the protection scope of the present invention.

Claims

1. A wash-durable, chlorine-resistant fixing agent, characterized by comprising: The first fixing component and the second fixing component are mixed in a mass ratio of 1.5-3:1 to obtain the chlorine-resistant fixing agent which is resistant to washing; The first fixing component is obtained by polymerization of polyethylene imine and epichlorohydrin; The preparation method of the first fixing component specifically comprises the following steps: Step A1: polyethylene imine is put into a flask, stirring is started and heating is performed at the same time; Step A2: the temperature is controlled at 20-50 DEG C, epichlorohydrin is added dropwise into the polyethylene imine, 2-3 h of preservation is performed after the dropwise addition is completed, and the temperature is controlled at 70-75 DEG C; Step A3: cooling is performed after the preservation is completed, and the pH value is adjusted to 6.5-7.5 by using glacial acetic acid, so that the first fixing component is obtained; The second fixing component is obtained by polymerization of diallylamine, acrylamide and dimethyldiallylammonium chloride, and the molar ratio of diallylamine, acrylamide and dimethyldiallylammonium chloride is 15-25:4-15:100-110.

2. The wash-durable, chlorine-resistant fixing agent according to claim 1, characterized in that, The chlorine-resistant fixing agent which is resistant to washing does not precipitate solid substances within 30 days under the environment of 5 DEG C.

3. A process for preparing the wash- and chlorine-resistant fixing agent according to any one of claims 1 to 2, characterized in that, The method comprises the following steps: Step 1: polyethylene imine and epichlorohydrin are mixed and polymerized to obtain the first fixing component; Step 2: diallylamine, acrylamide and dimethyldiallylammonium chloride are polymerized to obtain the second fixing component; Step 3: the first fixing component and the second fixing component are mixed in a mass ratio of 1.5-3:1 to obtain the chlorine-resistant fixing agent which is resistant to washing.

4. The method of preparing a wash-durable, chlorine-resistant fixing agent according to claim 3, characterized in that, The step 1 comprises the following steps: Step A1: polyethylene imine is put into a flask, stirring is started and heating is performed at the same time; Step A2: the temperature is controlled at 20-50 DEG C, epichlorohydrin is added dropwise into the polyethylene imine, 2-3 h of preservation is performed after the dropwise addition is completed, and the temperature is controlled at 70-75 DEG C; Step A3: cooling is performed after the preservation is completed, and the pH value is adjusted to 6.5-7.5 by using glacial acetic acid, so that the first fixing component is obtained.

5. The method of preparing a wash-durable, chlorine-resistant fixer according to claim 3, wherein The step 2 is specifically that diallylamine, acrylamide and dimethyldiallylammonium chloride are put into a flask in a nitrogen atmosphere, the pH value is then adjusted to 4-5, heating is performed to 80 DEG C, an initiator is added, reaction is performed for 2-3 h, and cooling is performed, so that the second fixing component is obtained; The initiator is an aqueous solution of ammonium persulfate and sodium bisulfite.

6. The method of preparing a wash-durable, chlorine-resistant fixative according to claim 3, wherein The step 3 is specifically that the first fixing agent component and the second fixing agent component are mixed in a mass ratio of 1.5-3:1, stirring is performed, and the chlorine-resistant fixing agent which is resistant to washing is obtained.

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