Dyeing and fixing one-bath high-water-bubble-fastness auxiliary agent and application thereof, and ecological leather dyeing and fixing one-bath method
By using anionic aqueous polyurethane dispersion and crosslinking agent in the dyeing and solid-solid bath high blister fastness additives in the dyeing and combining with the rolling and dyeing process with low liquid consumption, the problems of poor blister fastness and pollution of the dyeing and solid-solid bath process are solved, and efficient and environmentally friendly dyeing and color fixing effects are achieved.
Patent Information
- Application Number
- CN202510144086.3
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-02-10
- Publication Date
- 2025-04-18
AI Technical Summary
The blister fastness of the ecological skin after dyeing the acid dye is poor, resulting in severe color loss after soaking in boiling water. The existing dyeing and solid bath process consumes a large amount of liquid and has serious pollution problems. The commercially available color fixing agent and acid dye cannot bathe in the same bath, which cannot effectively improve the blister fastness.
A dye-solid-solid-bath high-fungus fastness additive is used, including anionic aqueous polyurethane dispersion and crosslinking agent, and the blister fastness is improved by bathing with acid dyes. At the same time, a rolling and dyeing process with very little liquid consumption is adopted to achieve one-step dyeing and color fixation.
The blister fastness after ecological skin dyeing is significantly improved, and there is basically no color fall after soaking in boiling water. The process is simple, the cost is low, and zero emissions are achieved, reducing pollution and production costs.
Smart Images
Figure CN119843504A_ABST
Abstract
Description
Technical Field
[0001] The invention relates to the technical field of dyeing, in particular to a dyeing-fixing-in-one-bath high blister fastness auxiliary agent and application thereof, and an ecological leather dyeing-fixing-in-one-bath method. Background Art
[0002] Eco-leather is a new type of leather material, which is made by cutting and grinding the scraps and waste leather of genuine leather into powder, and then mixing and pressing it with adhesives. It is a product between natural leather and synthetic leather. Eco-leather is widely used in home furnishing, bag making, shoe making and other fields. It is low in price, can greatly reduce production costs, and has extremely high commercial value.
[0003] The base fabric of eco-leather is microfiber non-woven fabric, which has a softer feel and greater breathability than the second-generation PU synthetic leather.
[0004] At present, acid dyes are mainly used for dyeing ecological leather. However, the blister fastness of ecological leather dyed with acid dyes is poor. After soaking in boiling water, the color fades a lot. It must undergo a subsequent color fixing process to improve the blister fastness. However, this method not only increases costs, but also causes wastewater pollution problems.
[0005] Dyeing and fixing in one bath refers to the process of fixing the color at the same time during the dyeing process. This process can save a process step and is currently one of the most effective ways to simplify the process and save costs. The current dyeing and fixing in one bath usually adopts a one-bath two-step method. The key point is to discharge a small amount of dye liquor after the end of immersion dyeing, cool it to 70-80℃, add acid dye fixing agent, and then discharge the liquid after fixing the color. However, the amount of wastewater discharged from the immersion dyeing process is huge, and most of the fixing agents currently available on the market are cationic or weak cationic fixing agents, which cannot be bathed in the same bath with acid dyes with strong anionic sulfonic acid groups. Even if anionic fixing agents can be bathed in the same bath, they have no obvious effect on improving water fastness. Summary of the invention
[0006] In view of this, the present invention provides a dye-fixing one-bath high blister fastness auxiliary agent and its application, and an ecological leather dye-fixing one-bath method. The high blister fastness auxiliary agent provided by the present invention can be used in the same bath with acid dyes, and can effectively improve the blister fastness of ecological leather after dyeing; the ecological leather dye-fixing one-bath method provided by the present invention adopts a pad dyeing process with extremely low liquid consumption, and is a one-step method, with simple process and low cost.
[0007] In order to achieve the above-mentioned object of the invention, the present invention provides the following technical solutions:
[0008] A dye-fixing one-bath high blister fastness auxiliary agent comprises auxiliary agent A and auxiliary agent B; the auxiliary agent A is an anionic waterborne polyurethane dispersion; the auxiliary agent B is a crosslinking agent; the mass ratio of the auxiliary agent A to the auxiliary agent B is 3-5:1.
[0009] Preferably, the cross-linking agent is an imidazole-terminated aliphatic isocyanate compound.
[0010] Preferably, the brand of the anionic waterborne polyurethane dispersion is FONDFOELX 320PLUS; the brand of the imidazole-terminated aliphatic isocyanate compound is HIF-LINKB214.
[0011] The present invention also provides the use of the dye-fixing in one bath high water blister fastness auxiliary agent described in the above scheme in dye-fixing in one bath with acid dyes.
[0012] The present invention also provides an ecological leather dyeing and fixing method in one bath, comprising the following steps:
[0013] The acid dye paste, the dye-fixing one-bath high water fastness auxiliary agent described in the above scheme, the penetrant and water are mixed to obtain a padding working solution;
[0014] The ecological leather is dipped in the dip working solution and then dried and baked in sequence.
[0015] Preferably, the mass fraction of the acid dye paste in the padding working solution is 2% to 10%, the mass fraction of the auxiliary agent A is 3% to 5%, the mass fraction of the auxiliary agent B is 1% to 3%, and the mass fraction of the penetrant is 1% to 3%.
[0016] Preferably, the dipping and rolling is double dipping and double rolling.
[0017] Preferably, the rolling rate of the dipping is 60% to 70%.
[0018] Preferably, the drying temperature is 100-110°C.
[0019] Preferably, the baking temperature is 150-180° C. and the baking time is 1-3 min.
[0020] The present invention provides a dye-fixing one-bath high blister fastness auxiliary agent, comprising auxiliary agent A and auxiliary agent B; the auxiliary agent A is an anionic waterborne polyurethane dispersion; the auxiliary agent B is a crosslinking agent; the mass ratio of the auxiliary agent A to the auxiliary agent B is 3 to 5:1. Eco-leather has a protein molecular structure, that is, a peptide bond amino acid molecular structure There is also a polyurethane structure Based on the reaction characteristics of the above two groups, the present invention adopts anionic waterborne polyurethane dispersion as auxiliary agent A. The molecular structure of auxiliary agent A carries a large number of amino groups, which can react chemically with substrates having hydroxyl groups, carboxyl groups and amide groups. At the same time, the network structure formed by the self-condensation reaction of auxiliary agent A can adhere to the eco-leather and acid dyes, so that the acid dyes can no longer migrate freely into the water, thereby improving the blister fastness.
[0021] At the same time, the present invention adopts a cross-linking agent as an auxiliary agent B to form cross-links between the acid dye and the eco-skin, between the acid dye and the auxiliary agent A with a network structure, and between the eco-skin and the auxiliary agent A with a network structure. The specific principle is as follows: (1) the amino group (-NH 2 ) has a weak positive charge under acidic conditions and reacts with the strong anionic sulfonic acid group (R-SO 3 Na) to form crosslinks. (2) Sulfonic acid groups on the dye (R-SO 3 Na) and polyurethane structure The NH groups on the skin form cross-links. (3) Amino acid structure on the eco-skin With the network polymer polyurethane structure It can also form cross-links. Through multiple cross-linking reactions, the bonding energy is increased, and ultimately the effect of boiling water resistance and improved blister fastness is achieved.
[0022] The present invention also provides an ecological leather dyeing and fixing method in one bath, comprising the following steps: mixing acid dye paste, the dyeing and fixing high water blister fastness auxiliary agent in one bath described in the above scheme, a penetrant and water to obtain a padding working solution; padding the ecological leather in the padding working solution and then drying and baking in sequence. The present invention adopts a padding process with very little liquid consumption, and can achieve dyeing and fixing in one step. The process is simple, no special equipment is required, the cost is low, the dyeing and fixing effect is obvious, and no subsequent soaping process is required after dyeing, and the color can be achieved without fading in boiling water; and the method provided by the present invention can basically achieve zero emissions under the condition of recycling the padding working solution, thereby reducing pollution and reducing costs. It adheres to the concept of green development and creates a new idea for the dyeing process of ecological leather. BRIEF DESCRIPTION OF THE DRAWINGS
[0023] Figure 1 The blister fastness test results of Example 1 (left) and Comparative Example 1 (right);
[0024] Figure 2 The blister fastness test results of Example 2 (left) and Comparative Example 2 (right);
[0025] Figure 3 The blister fastness test results of Example 3 (left) and Comparative Example 3 (right);
[0026] Figure 4 The blister fastness test results of Example 4 (left) and Comparative Example 4 (right);
[0027] Figure 5 The blister fastness test results of Example 5 (left) and Comparative Example 5 (right) are shown. DETAILED DESCRIPTION
[0028] The invention provides a dye-fixing one-bath high blister fastness auxiliary agent, comprising an auxiliary agent A and an auxiliary agent B; the auxiliary agent A is an anionic waterborne polyurethane dispersion; the auxiliary agent B is a crosslinking agent; and the mass ratio of the auxiliary agent A to the auxiliary agent B is 3-5:1.
[0029] In the present invention, the cross-linking agent is an imidazole-terminated aliphatic isocyanate compound.
[0030] In the present invention, the solid content of the anionic waterborne polyurethane dispersion is 30-40wt%; the brand of the anionic waterborne polyurethane dispersion is FONDFOELX 320PLUS, and the manufacturer is Shanghai Kekai Chemical Co., Ltd.; the brand of the imidazole-terminated aliphatic isocyanate compound is HIF-LINK B214, and the manufacturer is Dongguan Enke Chemical Co., Ltd.
[0031] The present invention also provides the use of the dye-fixing bath high blister fastness auxiliary agent described in the above scheme in the dye-fixing bath of acid dyes, specifically in the dye-fixing bath of eco-leather acid dyes.
[0032] The present invention also provides an ecological leather dyeing and fixing method in one bath, comprising the following steps:
[0033] The acid dye paste, the dye-fixing one-bath high water fastness auxiliary agent described in the above scheme, the penetrant and water are mixed to obtain a padding working solution;
[0034] The ecological leather is dipped in the dip working solution and then dried and baked in sequence.
[0035] The present invention mixes acid dye paste, the dye-fixing one-bath high water blister fastness auxiliary agent described in the above scheme, a penetrant and water to obtain a padding working solution. The present invention has no special requirements for the acid dye paste, and can use the one well known to those skilled in the art, such as Meilan A801 black paste, Meilan A506 red paste, Meilan A806 navy paste, Meilan A703 blue paste or Meilan A409 brown paste.
[0036] The present invention has no special requirements on the type of the penetrant, and any penetrant known to those skilled in the art can be used. In a specific embodiment of the present invention, an environmentally friendly penetrant JFC is used.
[0037] In the present invention, the mass fraction of the acid dye paste in the padding working solution is preferably 2% to 10%, specifically 3%, 5%, 6%, 8%, 9% or 10%. In a specific embodiment of the present invention, the amount of the acid dye paste is controlled according to the color depth.
[0038] In the present invention, the mass fraction of the auxiliary agent A in the padding working solution is preferably 3% to 5%, specifically 3%, 3.5%, 4%, 4.5% or 5%. In a specific embodiment of the present invention, the amount of auxiliary agent A is controlled according to the color depth, and more auxiliary agent A is used when the color is darker.
[0039] In the present invention, the mass fraction of the auxiliary agent B in the padding working solution is preferably 1-3%, specifically 1%, 2% or 3%.
[0040] In the present invention, the mass fraction of the penetrant in the padding working solution is preferably 1% to 3%, specifically 1%, 1.5%, 2%, 2.5% or 3%. The amount of the penetrant is preferably controlled according to the amount of the acid dye paste. The greater the amount of the acid dye paste, the greater the amount of the penetrant.
[0041] The present invention controls the mass fractions of the acid dye paste, the auxiliary agent A, the auxiliary agent B and the penetrant within the above range, thereby ensuring the dyeing and fixing effects and improving the blister fastness of the dyed ecological leather.
[0042] In a specific embodiment of the present invention, it is preferred to firstly stir the acid dye paste and water, then add the auxiliary agent A and stir, then add the auxiliary agent B and stir, and finally add the penetrant and stir to obtain the padding working solution.
[0043] After obtaining the impregnation working solution, the present invention impregnates the ecological leather in the impregnation working solution and then dries and bakes it in sequence. In the present invention, the impregnation is preferably two impregnations and two rollings; the impregnation liquid rolling rate is preferably 60% to 70%; the drying temperature is preferably 100 to 110°C, specifically 105°C; the baking temperature is preferably 150 to 180°C, specifically 150°C, 160°C, 170°C or 175°C, and the baking time is preferably 1 to 3 minutes, specifically 1 minute, 2 minutes or 3 minutes.
[0044] The following will be combined with the embodiments of the present invention to clearly and completely describe the technical solutions of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.
[0045] The auxiliary agent A used in the following examples is FONDFOELX 320PLUS, produced by Shanghai Kekai Chemical Co., Ltd.; the auxiliary agent B is HIF-LINKB214, produced by Dongguan Enke Chemical Co., Ltd., and the penetrant is the environmentally friendly penetrant JFC, produced by Jiangsu Haian Petrochemical Plant.
[0046] Example 1
[0047] Mix Meilan 801 black color paste and water evenly, then add auxiliary agent A and mix evenly, then add auxiliary agent B and mix evenly, and finally add penetrant and mix evenly to obtain a padding working solution, in which the mass fraction of Meilan A801 black color paste is 5%, the mass fraction of auxiliary agent A is 5%, the mass fraction of auxiliary agent B is 1%, and the mass fraction of penetrant is 1%.
[0048] The ecological leather is twice dipped and twice rolled in the dipping and rolling working solution, with the rolling rate being 60%, and then dried at 105°C, and then baked at 150°C for 2 minutes before the cloth is produced.
[0049] Comparative Example 1
[0050] The other conditions were the same as those in Example 1, except that the additives A and B were not added.
[0051] Example 2
[0052] The other conditions were the same as those in Example 1, except that the black color paste of Meilan A801 was replaced by the red color paste of Meilan A506.
[0053] Comparative Example 2
[0054] The other conditions were the same as those in Example 2, except that the additives A and B were not added.
[0055] Example 3
[0056] The other conditions were the same as those in Example 1, except that the Meilan A801 black color paste was replaced with the Meilan A806 navy blue color paste.
[0057] Comparative Example 3
[0058] The other conditions were the same as those in Example 3, except that the additives A and B were not added.
[0059] Example 4
[0060] The other conditions were the same as those in Example 1, except that the black color paste of Meilan A801 was replaced by the blue color paste of Meilan A703.
[0061] Comparative Example 4
[0062] The other conditions were the same as those in Example 4, except that the additives A and B were not added.
[0063] Example 5
[0064] The other conditions were the same as those in Example 1, except that the black color paste of Meilan A801 was replaced by the brown color paste of Meilan A409.
[0065] Comparative Example 5
[0066] The other conditions were the same as those in Example 5, except that the additives A and B were not added.
[0067] Test Case
[0068] The blister fastness test was carried out on the ecological leather after dyeing and fixing in the same bath of Examples 1 to 5 and Comparative Examples 1 to 5. The specific test method is as follows: a 6cm×2cm cloth sample is added into 30mL of wastewater, immersed for 1min, and the degree of fading is observed. No fading is grade 5, slight fading is grade 4, and so on.
[0069] The test results are shown in Table 1.
[0070] Table 1 Water fastness test results
[0071] project Water fastness Example 1 Level 4.5 Comparative Example 1 Level 2 Example 2 Level 4.5 Comparative Example 2 Level 2 Example 3 Level 4.5 Comparative Example 3 Level 2 Example 4 Level 4.5 Comparative Example 4 Level 2 Example 5 Level 4.5 Comparative Example 5 Level 2
[0072] Figure 1 The blister fastness test results of Example 1 (left) and Comparative Example 1 (right); Figure 2 The blister fastness test results of Example 2 (left) and Comparative Example 2 (right); Figure 3 The blister fastness test results of Example 3 (left) and Comparative Example 3 (right); Figure 4 The blister fastness test results of Example 4 (left) and Comparative Example 4 (right); Figure 5 The blister fastness test results of Example 5 (left) and Comparative Example 5 (right) are shown.
[0073] According to Table 1 and Figure 1 to Figure 5 It can be seen that in comparative examples 1 to 5, no auxiliary agent was added during dyeing, and the color faded significantly after immersion in boiling water. After adding the high blister fastness auxiliary agent of the present invention, the blister fastness of the ecological leather after dyeing was greatly increased, and there was basically no fading after immersion in boiling water.
[0074] The above is only a preferred embodiment of the present invention. It should be pointed out that for ordinary technicians in this technical field, several improvements and modifications can be made without departing from the principle of the present invention. These improvements and modifications should also be regarded as the scope of protection of the present invention.
Claims
1. A dye-fixing one-bath high blister fastness auxiliary agent, characterized in that: The invention comprises an auxiliary agent A and an auxiliary agent B; the auxiliary agent A is an anionic waterborne polyurethane dispersion; the auxiliary agent B is a crosslinking agent; and the mass ratio of the auxiliary agent A to the auxiliary agent B is 3-5:
1.
2. The dye-fixing one-bath high blister fastness auxiliary according to claim 1, characterized in that: The cross-linking agent is an imidazole-terminated aliphatic isocyanate compound.
3. The dye-fixing one-bath high blister fastness auxiliary agent according to claim 2, characterized in that: The brand of the anionic waterborne polyurethane dispersion is FONDFOELX 320PLUS; the brand of the imidazole-terminated aliphatic isocyanate compound is HIF-LINKB214.
4. Use of the high water fastness auxiliary agent for dyeing and fixing in one bath as claimed in any one of claims 1 to 3 in dyeing and fixing in one bath with acid dyes.
5. An ecological leather dyeing and fixing method in one bath, characterized in that: The following steps are involved: The acid dye paste, the dye-fixing one-bath high water fastness auxiliary agent according to any one of claims 1 to 3, a penetrant and water are mixed to obtain a padding working solution; The ecological leather is dipped in the dip working solution and then dried and baked in sequence.
6. The ecological leather dyeing and fixing method according to claim 5, characterized in that: The mass fraction of the acid dye paste in the padding working solution is 2% to 10%, the mass fraction of the auxiliary agent A is 3% to 5%, the mass fraction of the auxiliary agent B is 1% to 3%, and the mass fraction of the penetrant is 1% to 3%.
7. The ecological leather dyeing and fixing method according to claim 5, characterized in that: The dipping and rolling is two dipping and two rolling.
8. The ecological leather dyeing and fixing in one bath method according to claim 5, characterized in that: The rolling liquid rate is 60% to 70%.
9. The ecological leather dyeing and fixing in one bath method according to claim 5, characterized in that: The drying temperature is 100-110°C.
10. The ecological leather dyeing and fixing method in one bath according to claim 5, characterized in that: The baking temperature is 150-180° C. and the baking time is 1-3 minutes.