A dyeing method involving improved surface modification

Abstract

The present invention relates to a novel dyeing method involving surface modification that enables the dyeing of acrylic fibers with anionic and cationic paints.

Description

[0001] A Dyeing Method Involving Improved Surface Modification

[0002] FIELD OF THE INVENTION

[0003] The present invention relates to a novel dyeing method involving surface modification that enables the dyeing of acrylic fibers with anionic and cationic paints.

[0004] PRIOR ART

[0005] Fiber dyeing is a basic process that dyes textile fibers in bulk, allowing dyes to penetrate into the fiber structure. This method is especially preferred for fiber types such as wool, polyamide and acrylic. During fiber dyeing, the dye is distributed homogeneously within the fibers, which ensures high color uniformity. Acrylic fiber is the type most similar to wool among artificial fibers and contains at least 85% acrylonitrile in its chemical structure. This ratio, determined by ISO (International Standards Organization) and BISFA (International Bureau for Standardization of Synthetic Fibers), is the basic defining characteristic of acrylic fiber.

[0006] Acrylic fiber production is generally carried out by methods such as wet spinning and dry spinning. During the production process, pigments are added to the fiber and coloring is achieved with the dope dyeing method or with basic dyes in gel form. This type of fiber is suitable for the production of melange yarn, both in pure form and by blending with other fibers. However, the types of dyes used in the dyeing process of acrylic fibers are quite limited. Traditionally, cationic dyes are mostly preferred due to the negative end groups in the chemical structure of these fibers.

[0007] Cationic dyes provide excellent color depth, brightness and fastness properties by forming ionic bonds with the negatively charged end groups of acrylic fibers. In dyeings made with these colorants, lightfastness and wetfastness are quite high. Additionally, the hydrophobic structure of acrylic fiber prevents moisture from being retained within the fiber, which would cause the dye to fade. However, despite the advantages offered by cationic dyes, this method offers a limited color palette and does not allow the use of different types of dyes.Reactive dyes form covalent bonds with functional groups in the fiber structure, allowing the dye molecules to bind permanently to the fiber. Reactive dyes, commonly used on fibers such as cellulose, wool and silk, offer high color fastness. However, since the chemical structure of acrylic fiber is not compatible with reactive dyes, the use of these dyes is limited. The inability of dyes to penetrate into the fiber structure makes color fastness poor.

[0008] Various modification techniques have been developed to increase the dyeing flexibility of acrylic fibers. The addition of different comonomers to the fiber during the polymerization process aimed to increase dye compatibility. However, this process increases production costs and leads to operational complexity. Alternatively, studies have been conducted to change the surface properties of the fiber by finishing processes before dyeing. However, these processes generally resulted in low efficiency and the desired color uniformity could not be achieved because the dye could not be distributed homogeneously on the fiber surface. Retarders used in dyeing processes provide a more balanced dyeing by regulating the speed at which the dye is absorbed into the fibers. Cationic retarders compete with the dye to enter the fibers, while anionic retarders neutralize the dye cations and regulate dye accumulation on the surface. However, the use of retarder complicates the dyeing process and effective results are not always achieved. In particular, it has been observed that retarders alone are not sufficient for the use of both cationic and reactive dyes on the same fiber. Dyeing acrylic fibers with traditional methods restricts color diversity due to limited dyestuff options, making it unsuitable for a wider range of applications. These methods do not enable the effective use of reactive dyes other than cationic dyes. In addition, the high energy and water consumption required for these processes negatively affects environmental sustainability. The following documents are found during the preliminary patent research made.

[0009] PCT document with application number W02009057235A1 is a method that involves treating acrylic fibers with an acylhydrazine compound and an organic compound containing primary amino groups, hydrolyzing them to form a cross-linked structure, and then dyeing them in acidic and alkaline conditions. The resulting fibers are densely and evenly dyed, provide high color fastness, and retain their moisture absorption / release, antibacterial and deodorizing properties after dyeing.The SIPO document with application number CN200510111881 includes the production process of polyacrylic fibers that can be dyed with both cationic dyes and acidic dyes. The process involves using two different polyacrylonitrile resins (Resin A and Resin B), dissolving these resins at certain ratios, producing nascent (raw) fiber, and then converting the fiber into polyacrylic fiber product through post-processing.

[0010] PCT document with application number W02018067092A3 describes the finishing and pre-finishing application methods to enable the dyeing of acrylic and modacrylic fibers with cationic, acidic or reactive dyes. However, these methods have difficulties such as lower efficiency and inability to apply pressure during the fiber drawing process. This invention prevents fiber surface deformation and improves dyeing efficiency by applying an amine with a molecular weight of at least 1000. The chemical is applied at temperatures between 20°C and 100°C with a concentration of more than 0.1%.

[0011] SIPO document number CN103334322B contains a dyeing retarding agent used in cationic dyeing processes. The dyeing retarding agent is imidazole-based Gemini ionic liquid and its concentration is between 0.01 -0.2 mmol / L. A dyeing effect consistent with traditional processes is achieved by using imidazole Gemini ionic liquid with different hydrophobic carbon chain lengths and linkage radical lengths instead of traditional cationic dyeing retarding agents (such as 1227 and CTAB).

[0012] As a result of the research on the current state of the art, an R&D study was carried out on the state of the art and two different fiber production processes and production lines were needed to perform the dyeing process using both anionic and cationic dyes.

[0013] As a result, all abovementioned problems have made it necessary to make an improvement in the relevant technical field.

[0014] OBJECT OF THE INVENTION

[0015] The present invention aims to eliminate the abovementioned problems and to make a development in the relevant technical field.

[0016] The main object of the present invention is to present a method structure that will enable the acrylic fiber to be dyed with anionic, reactive or cationic dye as desired, by means of a surface modification process carried out after the production of acrylic fiber.Another object of the present invention is to enable the fiber containing negatively charged groups to be transformed by gaining positively charged groups thanks to the auxiliary chemicals used.

[0017] Another object of the present invention is to ensure that the mixtures formed by modified reactive and anionic dyed acrylic fiber with other reactive and anionic dyed cellulosic fibers shorten the dyeing process times compared to unmodified conventional acrylic fiber and cellulosic fiber mixtures.

[0018] Another object of the present invention is to contribute to sustainability by reducing the amount of water, electricity and steam consumed during dyeing and to increase production capacity by reducing dyeing costs.

[0019] Another object of the present invention is to enable the dyeing of newly produced acrylic and modacrylic fibers using reactive dyes, metal complex dyes and acid dyes.

[0020] Another object of the present invention is to provide process optimization in the surface modification process of modified anionic and reactive dyed fiber, to increase the dye uptake capacity during dyeing and to produce high quality dyed fiber by preserving the mechanical and handle properties of the fiber at the end of the process.

[0021] BRIEF DESCRIPTION OF THE INVENTION

[0022] In order to achieve all the objects mentioned above and which will emerge from the detailed description below, the present invention is a method of surface modification before dyeing which allows the use of anionic or cationic dyes when dyeing acrylic fibers. Accordingly, it comprises the following process steps respectively:

[0023] a) coating the fiber with negatively charged ends (1) on the acrylic surface with 0,3-1 % by weight of amine-based cationic fatty acid finishing chemicals during fiber spinning in a 2,5-6 bar pressure reactor so as to prevent dimensional changes in the fiber and softening due to the glass transition temperature and hardening after cooling during surface modification above the glass transition temperature of the fiber in the high temperature region,

[0024] b) heating operations are carried out by starting the temperature zones at an inlet temperature of 30°C and increasing the same to 100°C with an acceleration of 1°C / min, and after reaching 100°C, increasing the same to 140-160°C withan acceleration of 0.1-0.5°C / min, in order to accelerate the application of modifying amine groups (2) to the acrylic fiber with negative ends (1) located on the acrylic surface with negatively charged ions in the pressurized reactor and to provide the necessary activation,

[0025] c) keeping the same in the mentioned temperature zones for 5 to 25 minutes at 120 ° C, 5 to 25 minutes at 130 ° C and 25 to 75 minutes at 140 ° C,

[0026] d) cooling process is carried out at 80°C with a cooling acceleration of 0.1°C / min to 0.5°C / min to avoid sudden cooling and to avoid hardening of the fiber.

[0027] A preferred embodiment of the invention is to use a mixture containing acrylic fiber in a way that completes the remaining percentage to 100% and a maximum of 90% of the fiber mentioned in the method step a) from a group containing natural or synthetic fibers such as viscose, cotton, tencell, lyocell, cellulose acetate, polyamide derivative fiber, wool derivative fiber and polyester derivative fiber.

[0028] Another preferred embodiment of the invention is to apply the amine-based cationic fatty acid finishing chemical, which will consist of individuals or combinations selected from the group containing primary, secondary, tertiary and quaternary amine groups of the mixture mentioned in method step a), onto the acrylic fiber.

[0029] A preferred embodiment of the invention is that the chemical mentioned in method step b) comprises individuals or combinations selected from the group consisting of polyetheramine (jeffamine), poly allylamine, poly diamine (poly diamine) and polyethyleneimine (polyethyleneimine) compounds with a minimum molecular weight of 1.000-3.000 Da.

[0030] Another preferred embodiment of the invention is to use 100% acrylic, 100% modacrylic or any percentage of acrylic-modacrylic mixture as the fiber coated with amine-based cationic fatty acid finishing chemical during fiber drawing mentioned in method step a). A preferred embodiment of the invention is to use acrylic fiber coated with R10 touch amine based cationic fatty acid finishing chemical in method step a).BRIEF DESCRIPTION OF DRAWINGS

[0031] Figure 1 shows the molecular structure of amine groups performing surface modification by converting the negative ends on the acrylic surface into positive.

[0032] Figure 2 shows the temperature diagram at 140°C.

[0033] Figure 3 shows the temperature diagram at 130°C.

[0034] Figure 4 shows the temperature diagram at 120°C.

[0035] The figures are not required to be scaled and the details which are not necessary for understanding the present invention may be neglected. Moreover, the elements that are at least substantially identical or have at least substantially identical functions are shown by the same number.

[0036] DESCRIPTION OF THE REFERENCE NUMBERS IN FIGURES

[0037] 1. Negatively charged groups on the acrylic surface

[0038] 2. Amino groups providing surface modification

[0039] 3. Fiber obtained by applying a chemical substance containing an amine group onto the acrylic fiber

[0040] DETAILED DESCRIPTION OF THE INVENTION

[0041] In this detailed description, A Dyeing Method Involving Improved Surface Modification of the present invention is described by means of examples only for clarifying the subject matter such that no limiting effect is created.

[0042] The subject of the invention, the fiber dyeing process, which will be referred to as "acrylic fiber" in the rest of the description, is defined as a dyeing method that includes improved surface modification and is also applied in the modacrylic fiber production process with similar process steps.

[0043] Figure 1 shows the Negatively charged groups on the acrylic surface (1), the amino groups providing surface modification (2), and the fiber obtained by applying a chemical substance containing an amine group onto the acrylic fiber (3). Fiber obtained by applying a chemical substance containing an amine group onto the acrylic fiber (3) with the monomer or polymer containing a modifying amine group (2) consisting of a single component or combinations selected from primary, secondary, tertiary or quaternaryamine-containing groups applied in the pressurized reactor. With the help of the modifying amine groups (2), this fiber can also be dyed with reactive dyes.

[0044] In traditional methods, acrylic fibers are dyed only with basic dyes, which leads to limitations in responding to different color options and performance needs. Since the applicability of acidic, metal complex or reactive dyes cannot be ensured, production processes lose flexibility and fall short of meeting user demands. In addition, these methods cause problems such as high chemical consumption, energy loss and environmental impacts in the dyeing process, which both increase costs and hinder sustainability goals.

[0045] Acrylic fibers tend to show structural deterioration when exposed to high temperatures due to the thermal sensitivity of the nitrile groups in their chemical structure. Increasing temperature causes thermal degradation in polymer chains, causing breaks in the molecular structure, acceleration of oxidation processes and loss of negatively charged groups on the surface. These thermal effects negatively affect the mechanical strength of the fiber, color retention and the effectiveness of dyeing processes. Especially in traditional dyeing methods, the high temperature requirement seriously weakens the physical and chemical properties of acrylic fibers. The invention provides a surface modification method that preserves the ability to be dyed with basic dyes without making any changes in the polymerization process of the existing acrylic fiber, while optionally performing a surface modification method under appropriate reactor conditions in the finishing baths used in the finishing process or in the vat dyeing method. This method makes it possible to dye acrylic fiber with acidic, metal complex or reactive dyes. This process is compatible with existing production systems and enables the integration of primary, secondary, tertiary or quaternary amine groups onto the fiber surface as a result of the reaction of the acrylic fiber obtained by the wet spinning method with suitable chemicals in a pressurized reactor.

[0046] Within the scope of the invention, the existing acrylic fiber is coated with an amine-based cationic fatty acid finishing chemical and then reacted with an auxiliary chemical under pressure and temperature in a pressurized reactor to integrate the primary, secondary and quaternary amine groups onto the surface of the fiber. The basic working principle of this invention is the pressurized reactor, which is not used in the prior art, the gradual and low-acceleration temperature increase, the optimization of time and the processing of the fiber coated with the finishing chemical before modification by preserving thesoftness of the fiber form at high temperature. With these important factors, the integration of the modifying amine groups (2) into the negatively charged groups on the surface of the acrylic fiber (1) is successfully achieved. However, in the experiments conducted without these mentioned factors, the desired results in the physical properties and dyeing capacity of the fiber could not be obtained.

[0047] The chemical that ensures that the acrylic fiber has amine-based end groups must be selected from polymers containing primary, secondary, tertiary and quaternary amine groups with a maximum molecular weight of 3,000,000 Da. While the effectiveness of high molecular weight polymers decreases, the health risk increases in polymers with low molecular weight. Therefore, polymers with molecular weights between 1.000 and 3.000.000 Da constitute the most suitable options. In the preferred embodiment of the invention, polymers such as polyetheramine (Jeffamine), polyallylamine (poly allylamine), polydiamine (poly diamine) and polyethyleneimine (polyethyleneimine) are used.

[0048] The method of the present invention comprises a surface modification method applied before dyeing on acrylic / modacrylic fiber yarns in mixture with cellulosic fibers or only. In the preferred embodiment of the invention, the chemical used during the modification is selected as molecules or macromolecules such as diamine, triamine or tetraamine containing more than one amine functional group.

[0049] A surface modification before the dyeing process of the present invention that allows the use of anionic or cationic dyes when dyeing acrylic fibers, comprising the process steps of

[0050] a) coating the fiber with negatively charged ends (1) on the acrylic surface with 0,3-1 % by weight of amine-based cationic fatty acid finishing chemicals during fiber spinning in a 2,5-6 bar pressure reactor so as to prevent dimensional changes in the fiber and softening due to the glass transition temperature and hardening after cooling during surface modification above the glass transition temperature of the fiber in the high temperature region,

[0051] b) heating operations are carried out by starting the temperature zones at an inlet temperature of 30°C and increasing the same to 100°C with an acceleration of 1°C / min, and after reaching 100°C, increasing the same to 140-160°C withan acceleration of 0.1-0.5°C / min, in order to accelerate the application of modifying amine groups (2) to the acrylic fiber with negative ends (1) located on the acrylic surface with negatively charged ions in the pressurized reactor and to provide the necessary activation,

[0052] c) keeping the same in the mentioned temperature zones for 5 to 25 minutes at 120 ° C, 5 to 25 minutes at 130 ° C and 25 to 75 minutes at 140 ° C,

[0053] d) cooling process is carried out at 80°C with a cooling acceleration of 0.1°C / min to 0.5°C / min to avoid sudden cooling and to avoid hardening of the fiber.

[0054] In Figure 2 the temperature diagram of the process step b) is given; heating operations are carried out by starting the temperature zones at an inlet temperature of 30°C and increasing the same to 100°C with an acceleration of 1 °C / min, and after reaching 100°C, increasing the same to 160°C with an acceleration of 0.1-0.5°C / min, in order to accelerate the application of modifying amine groups (2) to the acrylic fiber with negative ends (1) located on the acrylic surface with negatively charged ions in the pressurized reactor and to provide the necessary activation.

[0055] The temperature profile shown in the diagram is designed to optimize the interaction between acrylic surfaces with negatively charged ions and modifying amine groups. The process begins with an initial temperature of 30°C, which is raised to 100°C at a rate of 1°C per minute. This rapid heating stage provides the basic conditions required for surface activation and establishes the starting level for the modification process. When 100°C is reached, the rate of temperature increase is slowed to 0.1 -0.5°C / minute, and the temperature is raised to 120°C at this rate. This stage allows the reaction to proceed in a more controlled manner. When 120°C is reached, the temperature is maintained for at least 10 minutes. This waiting period ensures the stabilization of the reaction and the effective bonding of the amine groups to the acrylic surface. In the next step, the temperature is increased at the same rate to 130°C and held at this temperature for at least 10 minutes. Then, the temperature reaches 140°C at a rate of 0.1-0.5°C / minute. A maximum waiting time of 120 minutes is anticipated for the reaction to complete at maximum temperature. This period aims to achieve the highest efficiency in the surface modification process. In the final stage, the temperature is gradually reduced to 80°C. This cooling process is necessary for the system to stabilize and for the stabilization of the products obtained.Figure 3 shows the temperature diagram at 130°C. The process begins by setting the initial temperature to 30°C and raising the same to 100°C at a rate of 1°C per minute. This step provides the necessary activation for the effective application of modifying amine groups to the negative end groups on the fiber surface. After reaching 100°C, the temperature increase rate is reduced and raised to 130°C at an acceleration of 0.1-0.5°C / minute. Here, the temperature is kept constant and held for 180 minutes to increase the sensitivity of the modification at high temperatures. This duration is critical to ensure the depth and homogeneity of the modification process. Subsequently, to avoid sudden cooling and prevent the fiber from hardening, the temperature is lowered to 80°C at a controlled rate of 0.1 -0.5°C / minute. This cooling stage stabilizes the physical and chemical properties of the modified fiber obtained.

[0056] Figure 4 shows the temperature diagram at 120°C. The process starts at an inlet temperature of 30°C and is raised to 100°C at a rate of 1°C / minute. This initial stage initiates the activation necessary for the amino groups to react with the negatively charged end groups on the acrylic surface. When 100°C is reached, the temperature increase rate is reduced to 0.1 -0.5°C / m inute and raised to 120°C. This temperature ensures that surface modification continues in a controlled manner. After reaching 120°C, the temperature is kept constant and held for a maximum of 180 minutes. This stage is a critical step in increasing the depth of the modification process and ensuring the homogeneity of reactions on the fiber surface. Finally, the temperature is lowered to 80°C at a rate of 0.1-0.5°C / minute, avoiding any sudden drops. This cooling process is necessary to preserve the mechanical properties of the fiber and stabilize the modification obtained.

[0057] In a pressure reactor, fiber obtained by applying a chemical substance containing an amine group to acrylic fiber (3) with primary, secondary, tertiary, or quaternary amine groups is dyed with negatively charged acid dyes, metal complex dyes that form complex structures with metals such as copper or zinc, or reactive dyes. Fiber obtained by applying a chemical substance containing an amine group to acrylic fiber (3) in this process has negatively charged end groups and, optionally, can also be dyed with positively charged basic dyes.

[0058] The method developed within the scope of the invention enables wool fibers carrying positive end groups and new modified fibers possessing both positive and negative end groups to be dyed in a single color using acidic dyes or metal complex dyes within thesame vat. Additionally, it creates melange effects using basic dyes. In this case, when basic dye is used, the wool fiber remains uncolored, while the modified new fiber changes color.

[0059] As an alternative embodiment, the fiber obtained by applying a chemical substance containing an amine group onto cellulosic fibers (3) carrying hydroxy groups and acrylic fibers containing primary, secondary, tertiary or quaternary amine groups are dyed in a single color at the same time using reactive dyes or metal complex dyes.

[0060] In the implemented embodiments of the invention, the said dyeing method is used in the form of fiber, yarn or fabric. Yarns and fabrics are made of 100% acrylic or different natural or synthetic fiber blends. These fibers include cellulose-based fibers (viscose, cotton, tencel, lyocell, cellulose acetate, etc.), polyamide derivatives (PA6, PA6.6, etc.), wool and polyester derivatives.

[0061] In the preferred embodiment of the invention, the fiber obtained by the mentioned modification methods is dyed with acidic, metal complex or reactive dyes by mixing it 100% or with different types of fibers at different rates. Accordingly;

[0062] It has been prepared from blends containing up to 90% cotton to blends containing 100% modified reactive acrylic fiber.

[0063] • Fabric samples consisting of 50% reactive-dyed acrylic fiber and 50% cotton yarn were prepared, fabric samples of 100% unmodified acrylic fiber and 50% cotton blended with unmodified acrylic fiber were prepared for the dyeing study.

[0064] In order to understand the differences and optimization related to the embodiment of the invention, the color changes in the samples in some experimental results are given in Table 1.Examples Delta E Delta L Delta A Delta B Control group 1 73,77 50,77 -53,49 -1 ,58 Control group 2 17,54 6,31 -15,68 -4,67 Trial 1 7,59 -3,12 -6,87 0,77 Trial 2 11 ,87 5,08 -9,96 -4,52 Trial 3 13,68 11 ,28 -10,41 -4,89 Trial 4 20,65 15,23 -17,74 -8,47 Trial 5 1 ,14 1 ,01 -0,14 0,19

[0065]

[0066] Table 1

[0067] As control group 1 , the dyeing recipe was applied to the fabric consisting of 10 g of unmodified acrylic fiber. Then, as control group 2, the dyeing recipe was applied to the fabric consisting of 50% unmodified acrylic fiber and 50% cotton.

[0068] According to the table results, the modification process has significantly increased the color matching of acrylic fiber with cotton. While Delta E indicates the total difference between the two colors, the high value of 73,77 in Control Group 1 reveals that the unmodified acrylic fiber is quite different in color from the cotton. In Control Group 2, this difference decreased to 17,54, but full compliance was not achieved. In T rial 5, the Delta E value decreased to 1,14, showing that the modified acrylic fiber was dyed almost the same color as cotton. In addition, Delta L, Delta A and Delta B values were quite low in Trial 5, and great harmony was achieved with cotton in the brightness and color axes. These results prove that the modification process applied within the scope of the invention is extremely effective in increasing the color compatibility of acrylic fiber with cotton.

[0069] The dyeing method developed within the scope of the invention is applied by methods such as vat dyeing, ilma dyeing, hank dyeing or bobbin dyeing.Dyeing Recipe

[0070] Group Material Basic Basic Stock Amount Amount unit Solution to be Put (g) Concentration in the (g / L) Tube (mL / g) or (g) 1 Sunfix 0,45 % 1 45,00 mL Yellow

[0071] SPR

[0072] 2 Sunfix Red 0,15 % 1 15,00 mL SPR

[0073] 3 Sunfix Blue 0,25 % 1 25,00 mL SPR

[0074] 4 Akwet 0,50 % 5 10,00 mL 5 Ggfix 0,40 % 10 4,00 mL 6 NaCI 28,00 g / L Directly 0,28 7 Na2CO3 20, g / L Directly 0,20 8 Acetic acid 0,80 g / L Directly 0,08 9 Akwash SR 0,15 g / L Directly 0,015 g

[0075]

[0076] Table 2

[0077] Amount of Material to be Painted [A]: 10 g

[0078] Bath Ratio [B]: 1 :15

[0079] Total Dyeing Bath Amount [C] = [A+B]: 150 mL

[0080] The dyeing process in Table 2 was carried out step by step as follows:

[0081] a) Solutions are prepared from the stock solution according to the concentrations of the materials specified in the recipe, as specified in the Stock Solution Concentration (g / L) column.b) The dyestuffs and chemicals in the first group of the recipe are pipetted into the 200 mL volume tube of the dyeing machine in the amounts calculated in the Amount to be Put into the Tube (mL / g) or (g) column.

[0082] c) Distilled water is added until the total bath volume in the dyeing tube reaches the amount calculated in line C.

[0083] d) The pH value of the bath in the dyeing tube is measured and, if necessary, adjusted to a pH value of 6.5 using acetic acid. The cap of the tube is closed and placed in the dyeing machine.

[0084] e) The amount of distilled water calculated in line C is poured into the reference tube, the cap is closed and placed in the machine.

[0085] f) The dyeing machine is set to 30°C and run for 20 minutes. Then the temperature is increased to 60°C at a rate of 2°C / min and waited at 60°C for 20 minutes. The machine is stopped.

[0086] g) The dyeing tube is removed from the machine and its cap is opened. Na2CO3is added in the amount specified in the 2nd group of the prescription and calculated in the Amount to be Put into the Tube (mL / g) or (g) column. The cap of the tube is closed and placed in the dyeing machine again.

[0087] h) The machine temperature is set to 60°C and waited at this temperature for 30 minutes. i) The tube is removed from the machine, the cap is opened and the material is rinsed in cold running water.

[0088] e) The amount of distilled water calculated in line C is poured into the reference tube, the cap is closed and placed in the machine.

[0089] k) Distilled water in the amount calculated in row C is added to the painting tube, along with acetic acid in the amount specified in the third group and calculated in the Amount to be Added to the Tube (mL / g) or (g) column. The material is placed in this bath, the tube is capped and placed in the machine. The machine is heated to 70°C as quickly as possible and neutralization is achieved by waiting for 10 minutes.

[0090] l) The tube is removed from the machine, the cap is opened and the material is rinsed in cold running water.m) The amount of distilled water calculated in line C is poured into the reference tube, the cap is closed and placed in the machine.

[0091] n) Distilled water in the amount calculated in row C is added to the painting tube, along with soap in the amount specified in the fourth group and calculated in the Amount to be Added to the Tube (mL / g) or (g) column. The material is placed in this bath, the tube is capped and placed in the machine. The machine is heated to 95°C as quickly as possible and left for 10 minutes. The machine is then cooled down as quickly as possible to 70°C. o) If the recipe includes a second soaping process as the 5th group, steps I, m and n are repeated.

[0092] p) The tube is removed from the machine, the cap is opened and the material is rinsed in cold running water.

[0093] r) After the rinsed material is squeezed, it is dried in an oven heated to 50°C.

[0094] These method steps were applied to each sample under the same prescription conditions. While dyeing was achieved with basic dyes in previous techniques, the desired results could not be achieved with reactive dyes. The following experiments were carried out to observe the effectiveness of reactive dyes and obtain clearer results.

[0095] Trial 1

[0096] The unmodified acrylic fiber in control group 1 was treated with 1% amine-based cationic fatty acid finishing chemical by weight based on the fiber weight in a pressurized reactor using the 4 method steps mentioned above, at least 10 minutes at 120°C, at least 10 minutes at 130°C, at most 120 minutes at 140°C, and in a 2,5-6 bar pressure reactor for a total of 100 minutes.

[0097] Trial 2

[0098] The unmodified acrylic fiber in control group 1 was treated with 0,5% amine-based cationic fatty acid finishing chemical by weight based on the fiber weight in a pressure reactor using the 4 method steps mentioned above, at least 10 minutes at 120 °C, at least 10 minutes at 130 °C, at most 120 minutes at 140 °C, and in a 2,5-6 bar pressure reactor for a total of 100 minutes.

[0099] Trial 3The unmodified acrylic fiber in control group 1 was treated with the above-mentioned 4 method steps in a pressure reactor with 1 % by weight of amine-based cationic fatty acid finishing chemical based on the fiber weight, at 130 ° C for a maximum of 180 minutes and in a 2,5-6 bar pressure reactor for a total of 100 minutes.

[0100] Trial 4

[0101] The unmodified acrylic fiber in control group 1 was treated with the above-mentioned 4 method steps in a pressure reactor with 1 % by weight of amine-based cationic fatty acid finishing chemical based on the fiber weight, at 120 °C for a maximum of 180 minutes and in a 2,5-6 bar pressure reactor for a total of 100 minutes.

[0102] Trial 5

[0103] The fabric version of the yarn made by mixing 50% of the fiber and 50% of the cotton obtained in Trial 1 was dyed with the dyeing recipe after applying the processes specified in Control Group 2.

[0104] Table 1 shows the measurement results of color changes on the CIELAB scale. Delta E, Delta L, Delta A and Delta B values express the deviations from the reactive staining results in the negative or positive direction. T rial 1 , T rial 2, T rial 3 and T rial 4 were carried out using 100% acrylic fiber, while Trial 5 refers to the dyeing of a reactively dyed acrylic fiber and cotton blend. In this regard, the most suitable results were obtained with the method steps applied in the Trial 1 procedure in fabrics dyed using 100% acrylic fiber. The main reason for this is that the surface modification efficiency increases with increasing temperature under pressurized conditions. In addition, when the specified method steps are applied at a temperature of 140 °C under pressure, the preservation of the physical properties of the fiber is directly related to the use of fibers coated with an amine-based cationic fatty acid finishing chemical. On the other hand, dyeing performed on the cotton blended fabric sample as in Trial 5 gives the best result with the dyeing performed with the optimized modified acrylic fiber in Trial 1. Here it is clearly seen that the deviation obtained is minimal and the desired color matching is technically achieved.

[0105] As a result, the invention enables the use of reactive dyes in dyeing acrylic fibers, yarns and fabrics produced from acrylic fibers, and mixtures of acrylic fibers with reactively dyed cellulosic fibers, by converting acrylic fibers with negatively charged groups intopositively charged groups. This transformation makes acrylic fibers more efficient and compatible with a variety of reactive dyes compared to traditional dyeing methods. In Trial 4, the fabric composed of 50% acrylic fiber and 50% cotton yarn was dyed, but color deviations were visible in this trial. However, the results obtained after implementing the invention in Trial 5 show significantly lower deviations. The method introduced by the invention enables more consistent and homogeneous color results to be obtained by providing a significant change in the chemical structure of the fiber during the dyeing process by converting negative end groups into positive ends.

[0106] Compared to cases where the invention is not applied, the differences in the method steps directly affect the effectiveness of the dyeing process and the chemical interactions of the fiber. These differences improve the color fixation rate and texture properties, especially by increasing the adhesion capacity of reactive dyes to the fiber. This allows for more homogeneous colour distribution and reduced colour deviation, especially when dyeing acrylic fibre and cotton blends. In conclusion, the invention offers significant improvement potential in industrial dyeing processes by enabling the effective use of acrylic fibers in reactive dyeing systems.

[0107] Although different dyeing recipes are applied within the scope of the protection of the invention, the environmental conditions change depending on the way the recipe is applied. This situation does not constitute an obstacle to the application of the method which is the subject of the invention.

[0108] The protection scope of the invention is specified in the claims and cannot be limited to the description made for illustrative purposes in this brief and detailed description. It is clear that a person skilled in the art can present similar embodiments in the light of the above descriptions without departing from the main theme of the invention.

Claims

CLAIMS1. A surface modification before the dyeing process that allows the use of anionic or cationic dyes when dyeing acrylic fibers, characterized by comprising the process steps respectivelya) coating the fiber with negatively charged ends (1) on the acrylic surface with 0,3-1 % by weight of amine-based cationic fatty acid finishing chemicals during fiber spinning in a 2,5-6 bar pressure reactor so as to prevent dimensional changes in the fiber and softening due to the glass transition temperature and hardening after cooling during surface modification above the glass transition temperature of the fiber in the high temperature region,b) heating operations are carried out by starting the temperature zones at an inlet temperature of 30°C and increasing the same to 100°C with an acceleration of 1°C / min, and after reaching 100°C, increasing the same to 140-160°C with an acceleration of 0.1-0.5°C / min, in order to accelerate the application of modifying amine groups (2) to the acrylic fiber with negative ends (1) located on the acrylic surface with negatively charged ions in the pressurized reactor and to provide the necessary activation,c) keeping the same in the mentioned temperature zones for 5 to 25 minutes at 120 ° C, 5 to 25 minutes at 130 ° C and 25 to 75 minutes at 140 ° C,d) cooling process is carried out at 80°C with a cooling acceleration of 0.1°C / min to 0.5°C / min to avoid sudden cooling and to avoid hardening of the fiber.

2. Surface modification method before the dyeing process that allows the use of anionic or cationic dyes when dyeing acrylic fibers according to claim 1 , characterized by using a mixture containing acrylic fiber in a way that completes the remaining percentage to 100% and a maximum of 90% of the fiber mentioned in the method step a) from a group containing natural or synthetic fibers such as viscose, cotton, tencell, lyocell, cellulose acetate, polyamide derivative fiber, wool derivative fiber and polyester derivative fiber.

3. Method according to claim 1 , characterized by applying the amine-based cationic fatty acid finishing chemical, which will consist of individuals orcombinations selected from the group containing primary, secondary, tertiary and quaternary amine groups of the mixture mentioned in method step a), onto the acrylic fiber.

4. Method according to claim 1 , characterized by comprising in process step b) individuals or combinations selected from the group consisting of polyetheramine (jeffamine), poly allylamine, poly diamine (poly diamine) and polyethyleneimine (polyethyleneimine) compounds with a minimum molecular weight of 1.000-3.000 Da.

5. Method according to any of the preceding claims, characterized by using 100% acrylic, 100% modacrylic or any percentage of acrylic-modacrylic mixture as the fiber coated with amine-based cationic fatty acid finishing chemical during fiber drawing mentioned in method step a).

6. Method according to claim 1 , characterized by using acrylic fiber coated with R10 touch amine based cationic fatty acid finishing chemical in method step a).

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