A polymer starting solution suitable for use in the production of modular acrylic fibers, in which the amount of antimony-based compounds used is reduced, and a method for using this solution.

Abstract

The invention relates to a polymer starting solution used for the production of modacrylic fibers and a fiber production method using this solution. More specifically, the invention relates to the creation of an additive system that allows for a reduction in the amount of antimony-based flame retardant compounds while maintaining the flame resistance, process stability, and dyeability properties of the fiber.

Description

SUITABLE FOR USE IN THE PRODUCTION OF MODACRYLIC FIBERS. THE AMOUNT OF ANTIMONY-BASED COMPOUNDS USED HAS BEEN REDUCED. A POLYMER STARTING SOLUTION AND THIS SOLUTION A METHOD FOR ITS USE TECHNICAL FIELD The invention relates to a polymer starting solution used for the production of modacrylic fibers and This relates to a method in which this polymer starting solution is used. More specifically. The invention enables a reduction in the quantity of antimony-based flame retardant compounds. Nevertheless, modacrylic fiber has flame resistance, process stability and dyeability. It is about creating a method that preserves its characteristics. PREVIOUS TECHNIQUE Modacrylic fibers are a type of acrylonitrile-based copolymer fiber. Their structure typically consists of... Acrylonitrile units at 50% to 85% by weight (according to ISO 2076:2021 standards) It contains, the remainder being halogen-containing vinyl monomers, such as vinyl chloride. or vinylidene chloride is included. These halogenated monomers are chemically incorporated into the polymer chain. Bonding in this way gives the fiber inherently flame-retardant properties. The polymer, typically polar compounds such as N,N-dimethylacetamide (DMAc) or N,N-dimethylformamide (DMF). Dissolving in aprotic solvents to form a suitable starting solution for fiber spinning (also known as dope) (can be expressed) is transformed into this form. This polymer is formed from the starting solution in dry or Fibers are obtained through wet spinning methods. The resulting modacrylic fibers are processed at high temperatures. Thanks to their stability, non-melting properties and good elasticity, technical textiles are used in interior design. in areas requiring safety and performance such as interior furnishings and protective clothing It is widely used. The flame-retardant property of modacrylic fibers makes them suitable for a wide range of applications. This is of great importance. Especially personal protective equipment, industrial work clothes, In areas such as electrical insulation fabrics and upholstery textiles, the fabric may come into contact with flame. It must prevent the flame from continuing to burn and to stop the spread of the fire. Modacrylic 2 Polymers are resistant to oxidative degradation thanks to the halogen atoms in their structure. They become resistant. These atoms undergo free radical chain reactions during combustion. By suppressing it, it prevents the flame from continuing. It also prevents halogens from attaching to the polymer chain. The covalent bond ensures that the flame retardant effect is permanent and can be removed by washing. This makes it impossible to remove the flame. Thanks to these properties, modacrylic fibers are resistant to additional flame. Even without the addition of retarder additives, they have a certain degree of self-extinguishing capability. It shows. In current technology, the flame resistance of modacrylic fibers generally depends on halogen-antimony synergy. It is based on the combustion of halogen atoms such as chlorine or bromine present in the polymer structure. During this process, hydrogen halides (e.g., HCl or HBr) are released. Gases react with hydrogen (-H) and hydroxyl (-OH) radicals formed in the flame region. by entering the free radical chain, it interrupts the combustion reaction. It stops the presence of antimony trioxide (Sb₂O₃) or within the modacrylic fiber. Compounds such as antimony pentoxide (Sb₂O₅) react with halogenated gases to produce volatile antimony. They form halides (e.g., SbCl₃). These compounds diffuse in the gas phase, igniting the flame. It forms a radical scavenging layer on top and mixes oxygen with hydrocarbons. It interrupts the chain reactions between radicals. Thus, the antimony-halogen pair, by reducing heat transfer in the condensation phase and by capturing radicals in the gas phase. It creates a directional flame retardant mechanism. This mechanism uses modacrylic Modacrylic fibers resist combustion even at low oxygen index temperatures. It enables the fire to be extinguished. However, this method has several disadvantages. It is based on high amounts of antimony. The use of compounds causes dispersion difficulties in the production process, the solution By increasing its viscosity, antimony negatively affects the fiber drawing stability. The high density of oxides tends to precipitate within the DOP and spread throughout the fiber. This reduces the homogeneity of the additive distribution. This situation affects micron-scale distributions within the fiber cross-section. It forms particle aggregations and affects the mechanical properties of the final fiber. This creates irregularities. Furthermore, the high cost of antimony-based compounds... its existence and the environmental risks it poses from a toxicological perspective, sustainability on an industrial scale This raises concerns about flame resistance in the current technology. High performance is ensured while also guaranteeing production stability, environmental safety, and economic efficiency. Several limitations arise in terms of efficiency. 3 Various technical adjustments are being made to address these shortcomings. One of these regulations is aimed at reducing the amount of antimony-based compounds. The ratio and distribution of halogenated monomers used in the polymer structure are being optimized. By increasing the proportion of monomers such as vinylidene chloride, which have a high flame-retardant effect, The same performance is achieved at low levels of antimony-based compounds. Studies are being conducted to increase the effectiveness of antimony-based compounds. Synergistic additives are used. Compounds containing phosphorus, nitrogen and silicon, as well as some... Metal oxides prevent thermal decomposition by forming a protective layer in the condensation phase. It also delays the distribution of antimony-based compounds within the fiber. Surface modification methods are applied to improve the process; antimony oxides Polymer starter by coating the surface with organosilanes or polymeric dispersion agents. A more stable and homogeneous distribution is achieved within the solution. One of these studies is the patent dated JP3525237 B2, which deals with halogen-containing polymers. The patent relates to the development of flame-retardant fibers based on halogen. Accordingly, it concerns the development of less halogen-based flame-retardant fibers. fibers with high flame resistance, soft touch and good water absorption properties due to their compound The aim is to obtain this. To achieve this, 5–30% antimony by weight must be added to the polymer. The base compound contains 1–10% by weight of zinc stanate. The polymer contains 17–70% by weight. It contains halogen-containing vinyl or vinylidene monomer and 30–70% acrylonitrile by weight. The resulting fiber is mixed with natural or synthetic fibers to form a high flame-resistant composite. Fiber material is provided. Some studies, however, aim to completely eliminate antimony-based compounds. Solutions are being developed. In this context, phosphorus-nitrogen or alternative solutions are being considered instead of halogen-antimony synergy. Silicon-nitrogen based flame retardant systems are being developed. Melamine phosphate, phosphine Compounds such as oxide or phosphorus acrylate derivatives are integrated into the polymer chain to produce gas. through radical suppression mechanisms in the condensation phase and carbonization mechanisms in the condensation phase It is working. However, such additives do not affect the solubility of modacrylic fiber. Because it can negatively affect color balance and mechanical properties, industrial The complete elimination of antimony-based compounds on a large scale remains limited. Therefore, with the current technique, reducing the content of antimony-based compounds and more additive optimization, surface modification, and in order to make it sustainable Research is being conducted towards the development of synergistic systems. 4 Another study in the technical field is the patent with publication number WO202506010 A1, concerning phosphorus. It is related to the development of a flame retardant system based on a (meth)acrylic polymer. The patent describes a product that retains its flame-retardant properties even after the first wash, meaning it has wash resistance. The aim is to obtain a high-performance phosphorus-based flame retardant. To achieve this... Specific phosphorescent (meth)acrylic monomers have been incorporated into the polymer structure. These monomers, Because it is covalently bonded to the polymer chain, it does not wash away from the surface and Flame retardant efficacy is maintained for a long time. In conclusion, in order to impart flame retardant properties to modacrylic fibers... The current formulations used are based on the high antimony content of compounds. Therefore, viscosity control, solution stability, additive homogeneity, and Various technical problems are encountered in areas such as environmental sustainability. Antimony High density and toxicity characteristics of essential compounds, process safety and the final product This creates limiting effects in terms of quality. For these reasons, the technique in question... Resolving these problems will maintain the stability of production processes and fiber performance. Alternative solutions need to be developed. The current situation involves lower antimony levels. producing balance by providing the same level of flame resistance as the content of essential compounds It necessitates the design of new systems that protect and are more environmentally safe. It makes it possible. A BRIEF DESCRIPTION OF THE INVENTION Antimony-based compounds enhance the flame-retardant properties of modacrylic fibers. It has been used as a basic additive in the production of halogenated products for many years. By exhibiting a synergistic effect with monomers, it suppresses free radicals during combustion and It enhances the self-extinguishing property of the polymer. However, high The use of large amounts of antimony-based compounds can cause viscosity imbalance in the production process. It causes various problems such as sedimentation tendency and environmental toxicity. For these reasons, in technology, tin and / or antimony-based compounds are used to reduce their quantity. New systems have been developed in which zinc-based compounds are used as synergistic additives. Tin and / or zinc-based compounds are partially replacing antimony-based compounds. They provide a similar flame retardant effect. However, these additives are polymer starting materials. by creating ionic imbalance in the solution, the affinity of the fiber for cationic dyes This reduces the dyeing depth and color homogeneity. This 5 This situation negatively affects the dyeability performance of modacrylic fibers in particular. This presents a significant technical problem. The main objective of the present invention is to develop antimony-based solutions used in the production of modacrylic fibers. reducing the amount of compounds while maintaining the flame-retardant performance of the fiber and production The aim is to increase the stability of the process. The invention improves the efficiency of the halogen-antimony system. without reducing, equivalent flame at weight ratios of lower antimony-based compounds It aims to develop synergistic additive systems that will provide durability. Furthermore, flame retardant additives homogeneously in the polymer starting solution by ensuring dispersion, solution stability, fiber drawing balance and surface smoothness The goal is to improve. Another objective of the invention is to partially replace antimony-based compounds with tin and / or zinc. ionic instability caused by essential compounds in the polymer matrix and related The goal is to overcome paintability problems. In this context, the newly developed additive... Reducing the amount of antimony-based compounds with these materials and cationic dyes The aim is to preserve the affinity of the fibers. Thus, the invention is more environmentally friendly. Safe, more stable production process and preserved paintability properties, flame retardant. It aims to enable the production of modacrylic fibers. DETAILED DESCRIPTION OF THE INVENTION In this detailed description, the subject of the invention is a device suitable for use in the production of modacrylic fibers. a starting polymer solution and a method for obtaining this starting polymer solution and this relates to modacrylic fibers obtained with this starting polymer solution and only with examples that will not have any limiting effect on a better understanding of the subject It is explained. The main component of the polymer starting solution within the scope of this invention is modacrylic. These are copolymers. This copolymer consists of acrylonitrile monomer with one or more halogens. It is a thermoplastic polymer obtained by copolymerization of vinyl monomer with a polymer containing vinyl monomer. This polymer, by its nature, has the polar character of the nitrile (–C≡N) groups in its chain. thanks to properties such as solubility, chemical resistance and mechanical strength. It offers this occasionally. 6 This polymer, by its nature, has the polar character of the nitrile (–C≡N) groups in its chain. thanks to properties such as solubility, chemical resistance and mechanical strength. It presents itself in between. In order to be classified as modacrylic, it must have a polymer chain. The proportion of acrylonitrile units is generally in the range of 50–85% by weight, in halogenated units. The percentage of vinyl monomers ranges from 15–50% by weight. Within the scope of the invention, the polymer starting solution contains between 15% and 25% by weight. It contains polymer solids. The polymer starting solution covered by this invention contains at least one polar aprotic It contains a solvent. This polar aprotic solvent facilitates the dissolution of the modacrylic copolymer and It is used to ensure a homogeneous distribution of the additive components. This is achieved by using a solvent with a high dielectric constant and low hydrogen bonding. It is expected to have the capacity to do so. This will enable acrylonitrile-based polymers. It is possible for them to dissolve and for inorganic additives to form a dispersion together. This invention uses N,N-dimethylacetamide (DMAc) as a suitable polar aprotic solvent. N,N-dimethylformamide (DMF), dimethyl sulfoxide (DMSO), and N-methyl-2-pyrrolidone (NMP) At least one of the options from this group can be used. The amount of the aforementioned polar aprotic solvent in this polymer starting solution is by weight. It is a value between 65% and 85%. The polymer starting solution prepared in this way contains modacrylic fibers that can be flame-retardantly treated. at least one flame retardant component to enhance its flame retardant properties It contains a flame retardant component, a halogenated compound found in the modacrylic polymer structure. Vinyl monomers release hydrogen halides during combustion, creating a free radical chain. It suppresses their reactions. To achieve this, at least one antimony component is included as a flame retardant component within the scope of the invention. Antimony-based compounds are used. More specifically, antimony-based compounds are used. at least one of the following groups: antimony trioxide, antimony pentaoxide, sodium antimonate, antimony oxychloride It is a preferable option. 7 In the current technique, antimony-based compounds are incorporated into the polymer starting solution. It is located at a value between 6% and 10% of the amount by weight. The determined Although antimony-based compounds used in these applications provide adequate flame resistance, they also protect the polymer. Increasing the viscosity of the initial solution causes the particles to settle. This is happening. Additionally, there are technical problems such as environmental concerns and rising costs. It constitutes. The primary arrangement of the present invention is antimony-based compounds, polymer starting materials. The aim is to reduce the amount of polymer present in the solutions. This invention encompasses polymers. At least one auxiliary flame retardant component is added to the starting solution. at least one of the tin and / or zinc-based compounds as an auxiliary flame retardant component is being added. More specifically, tin-based compounds such as tin oxide, tin hydroxide, and tin chloride are among the most important groups. Only a few options are available. More specifically, zinc-based compounds such as zinc oxide, zinc borate, and zinc hydroxide are among the most important. Only a few options are available. The auxiliary flame retardant components discussed here are gaseous antimony-based compounds. While maintaining the flame suppression mechanism it performs with halogens in the condensation phase This supports the thermal insulation effect in the phase. These compounds are partly antimony compounds. by replacing it, it maintains the synergistic effect and at the same time heats during thermal decomposition. Carbonization on the polymer surface by forming protective oxide layers with low conductivity. It encourages. These auxiliary flame retardant components react with oxygen at high temperatures to form a protective layer. It forms a surface film and contributes to increasing the flame retardancy properties of the polymer. They are also present. In addition, the ionic bond structures formed on the surface of these metal oxides, flame It indirectly contributes to the radical sweeping mechanism in the region. Each of the aforementioned auxiliary flame retardant components is resistant to polar aprotic solvents. Because it is compatible, it can be added directly to the solution as a dispersion. More specifically, 8 Compounds containing both tin and zinc are also used as auxiliary flame retardant components. This is possible. The most preferred application is using this compound as zinc stennate. Accordingly, in this invention, the polymer starting solution is used as an auxiliary flame retardant component. The percentage of polymer solids varies between 1% and 5% by weight. This determined value is the polymer starting solution of the auxiliary flame retardant component. maintaining dispersion stability, preventing sedimentation during fiber drawing or It is configured to avoid causing an increase in viscosity. Zinc and / or tin-based compounds, antimony-halogen as the arrangement of the invention. the delayed ignition mechanism of the system occurring in the gas phase and condensation phase This supports the idea that antimony-based compounds react with halogenated gases during combustion. It enters the auxiliary flame to form volatile antimony halides (e.g., SbCl₃). Zinc and / or tin compounds used as retarders during this reaction By providing heat absorption and surface barrier formation, it ensures the thermal stability of the system. It increases. Thanks to this synergistic effect, antimony-based compounds can perform radical scavenging in the gas phase. While maintaining its function, the auxiliary flame-retardant component provides physical protection and heat retention during the condensation phase. It forms a barrier. This provides synergistic flame flammability performance. It can be provided. The invention involves the use of flame-retardant auxiliary components in the quantities specified within its scope. thanks to this, the amount of antimony-based compounds present in the polymer starting solution This has been reduced by approximately 40%. Thus, antimony-based compounds are compared to polymer solids. It can be used in concentrations ranging from 1.5% to 6% by weight. Despite these reduced amounts, The flame retardant properties of the fiber are due to the synergistic effect of the auxiliary flame retardant components. There is no decrease in performance, the system's oxygen index and The self-extinguishing properties are preserved. Studies have shown that zinc and / or tin-based compounds can be combined with antimony-based compounds. Although their combined use yields positive results in terms of flame retardant performance, this additive Technical problems due to the inclusion of these substances in modacrylic fiber products. It consists of 9. The addition of these flame-retardant compounds facilitates the use of modacrylic fibers with cationic dyes. It reduces its affinity. It also has high density and surface energy. Because of this, polymers tend to agglomerate in their starting solutions. The behavior shown in the diagram leads to defects on fiber surfaces at the micro scale and, in production, to filters and jets. This can cause blockages. In addition, a new additive is added to the polymer. Because it causes a change in the viscosity of the initial solution, the rheological aspect of the system... It disrupts the balance. Addition of auxiliary flame retardant components to the polymer starting solution, modacrylic This can negatively affect the dyeability properties of the fibers. This situation, Due to the ionic character of the additives, the electrical charge balance in the polymer matrix This is due to degradation. Modacrylic fibers contain sulfide groups in their structure. It is colored by establishing electrostatic interaction with cationic dyes. However, The presence of auxiliary flame-retardant components weakens these interactions and the fiber This causes a decrease in its affinity for dye molecules. As a result, dye adsorption decreases. The depth of coloration decreases, and the color... homogeneity is disrupted. In addition, the high surface energies of the additives, By creating strong physical interactions with polymer chains, it promotes dye diffusion. This restricts and causes irregular coloration in the inner parts of the fiber. Therefore, in order to prevent loss of dyeability, an additive that regulates the ionic balance in the solution is required. One component must be included. Accordingly, another modification made in the invention is that of these additives. In order to minimize the negative effects it may create, the polymer starting solution At least one ionic balance regulating component is added. Within the scope of this invention, colloidal silica is used as an ionic balance regulating component. It is used. As is known in the field of technology, antimony-based compounds present in the polymer starting solution, It tends to form partial ionic interactions in the environment. In contrast, the auxiliary flame Zinc and / or tin-based compounds used as retarder components, in solution They behave as non-ionizing, neutral inorganic particles. (mentioned) Zinc and / or tin-based compounds are insoluble in polar aprotic solvents and remain in suspension. 10 It is found in this form. Therefore, the polymer has a distinct ionic charge in the starting solution. No instability occurs, but there are limited adsorption interactions on the particle surface. This occurs at the end groups of modacrylic polymer chains, where sulfides are present. Their function is to electrostatically or by applying tin and / or zinc-based compound particles to the surface. It can be weakly adsorbed via coordinative bonds. This situation affects the polymer. some of the dye binding sites in the chain through surface interactions This causes the dye to become blocked. Thus, modacrylic fiber becomes completely undyeable. It does not come, but its affinity for cationic dyes decreases, resulting in limited staining behavior. It exhibits this effect. Within the scope of the invention, a polymer is used to eliminate this negative effect. Colloidal silica is added to the initial solution. The colloidal silica has a surface... Hydrogen is formed between polymer chains and additive particles via silanol (Si–OH) groups. By establishing bonding and physical adsorption interactions, it acts as a buffer at the polymer-particle interface. It forms a layer. This layer consists of tin sulfonate groups in modacrylic chains. and / or prevents zinc-based compounds from directly bonding to the surface, thus preventing the paint It ensures the protection of the active sites that remain open to the molecules. As a result, colloidal Silica additive improves the dyeability of modacrylic fiber, increasing color depth and It increases its homogeneity. Colloidal silica, acting in this way, interacts with cationic dye molecules in modacrylic fibers. Color depth and efficiency are achieved by preserving the electrostatic interaction between the polymers. It can ensure homogeneity. A preferred application is a water-based SiO2 solution as an ionic balance regulating component. 2 It is used. The particle size distribution of this component is in the range of 20 to 100 nm. The silica used in this invention has a particle size of 40–50 nm and a high surface area. Thanks to this, it is homogeneously distributed in the solution medium, thus enabling ionic interactions. by facilitating its organization, the stability of the system and compatibility between components It increases. The polymer starting solution discussed in this invention contains colloidal components. Silica is present in the polymer solids in the range of 0.5% to 10% by weight, depending on the amount of solid material. This determined value is particularly important for ensuring ionic equilibrium in the polymer starting solution and This is critical for stabilizing the electrostatic interactions between the additives. This determined value prevents excessive increase in viscosity in the system, ensuring the polymer starts at 11. It maintains the homogeneity of the solution and the stability of the flow properties during fiber drawing. It ensures that it remains. The use of colloidal silica in this way offers multifaceted benefits to the polymer starting solution. It primarily provides colloidal silica, which increases the ionic charge in the polymer starting solution. By regulating its balance, it enables antimony-based compounds to function effectively. It recognizes this. Therefore, it requires a high amount of antimony to maintain its flame-retardant effect. There is no need to use the base compound. Thus, antimony-based compounds Although the quantity has been reduced by approximately 40% by weight, the flame resistance of the fiber... It is protected and retains its self-extinguishing property. Colloidal silica is the same. also the loss of paintability caused by auxiliary flame retardant components over time It eliminates ionic compounds in the system thanks to the silanol groups located on its surface. balancing the charge distribution and the electrostatic interaction of polymer chains with cationic dyes. It maintains its interaction. This reduces dye adsorption and preserves color. Homogeneity is ensured and the dyeability properties of the fiber are improved using the existing polymer starter. This is improved compared to previous solutions. Another important effect is the polymer starting point. It affects the physical stability of the solution. Colloidal silica, additive It adsorbs onto the surface of the particles, preventing them from clumping together. This ensures long-term stability in the polymer starting solution and in production. Viscosity changes are minimized throughout the process. The inventors achieved this by adding colloidal silica to the polymer starting solution. to reveal the technical benefits and performance effects, using different formulas polymer starting solutions were prepared and modacrylic was obtained from these solutions. The dyeability properties of the fibers were evaluated using Ksat measurements. On the other hand, it was first observed that antimony pentaoxide was combined with colloidal silica of anionic character. Its use results in a smoother and shinier structure on the modacrylic fiber surface. This is especially true for color tones that require high visibility (for example (Fluorescent yellow) offers a significant advantage in terms of dyeability. TS EN ISO According to the 20471:2013 standard, high visibility textiles require minimum brightness. The factor (β) value must be at least 70. This standard ensures that the fabric is suitable for fluorescent colors. It evaluates the reflective brightness of the material after it has been painted. Accordingly, the invention Modacrylic 12 contains a combination of antimony pentaoxide and zinc stennate. After dyeing 100% modacrylic knitwear made from fibers with fluorescent yellow, β The value was measured in the range of 70–71. These values ​​are close to the lower limit of the standard and are sufficient. However, it provides limited visibility. In contrast, the defined scope of the invention... In modacrylic fibers where antimony pentaoxide and colloidal silica are used together at these values, The β (gloss) value of 100% single-component knitwear obtained after dyeing is 74–77. Measurements were taken within this range. These results indicate a significant improvement in surface gloss and color vibrancy. This shows that it has increased in this way. Furthermore, artificial intelligence based on the ISO 105 B02 A1 standard... Polymer starters containing antimony pentaoxide and colloidal silica were also used in aging tests. The high brightness performance of modacrylic fibers obtained from these solutions has been preserved. After aging, the β value remained above 70, around 71, and the invention... The modacrylic fibers obtained within this scope have maintained their high visibility properties. On the other hand, it contains antimony pentaoxide and zinc stennate but does not contain colloidal silica. Aging of modacrylic fibers β value obtained from polymer starting solutions It subsequently dropped below 70, indicating that high visibility requirements could not be met. has shown. Antimony Zinc Silica pentaoxide stennate (polymer (polymer (polymer Ksat beginning Sample start (modacrylic) in solution fiber in solution) being amount of presence amount % % amount % D1 10 - - 1.7 D2 - - 10 1.9 6 - 1 1.78 D3 4 4 1 1.7 D4 4 4 - 1.56 D5 3 3.5 1 1.72 D6 D7 1.5 3 - 1.62 13 Table 1. Flame refractory analysis of modacrylic fiber samples obtained with polymer starting solutions. durability, thermal stability, and paintability performance. The samples in the table are antimony pentaoxide used in polymer starting solutions. It consists of different combinations of zinc stennate and silica ratios. Sample D1 Represents the reference sample in the current technique containing 10% antimony pentaoxide by weight. Sample D2 contains 10% silica by weight and is free of antimony or zinc stennate. It does not contain. Sample D3 contains 6% antimony pentaoxide by weight and 1% by weight. Silica was used together. Sample D4 contains 4% antimony pentaoxide and 4% zinc by weight. It is a polymer starting solution containing stennate and 1% silica. Sample D5 is the same as D4. A polymer that contains antimony and zinc stennate but no silica. The starting solution is discussed. Sample D6 contains antimony and zinc stennate by weight. a polymer with lower percentages (3% and 3.5%) and containing 1% silica by weight This is the starting solution. Sample D7 contains 1.5% antimony pentaoxide by weight and zinc. The stent contains 3% by weight and no silica. The product obtained in this way... polymer starting solutions, modacrylic fibers with other process steps known in the technique. It is brought to this state and then tested. The Ksat value is used to evaluate the dyeability performance of modacrylic fibers. It is a key parameter used, and values ​​generally accepted are between 1.6 and 1.8. This establishes the achievable performance limit. Accordingly, the results obtained in the table... Upon evaluation, sample D1 was found to be within the accepted range with a Ksat value of 1.7. However, despite its high antimony content, it did not provide an improvement in dyeability. It is observed that the Ksat values ​​in samples D2 and D3 are 1.9 and 1.78, respectively. It is located above the accepted limits, and this situation affects the dyeability of the fiber due to silica. It appears to be due to its performance-enhancing effect. Samples D4 and D6 showed 1.7– It was in the 1.72 range, yielding results quite close to ideal values. In contrast, D5 and In D7 samples, Ksat values ​​were 1.56 and 1.62, respectively, remaining below the lower limit. This situation involves modacrylic derived from silica-free polymer starting solutions. The disruption of ionic balance in the fibers results in reduced dye adsorption, and This indicates a weakening of color homogeneity. These results are consistent with colloidal silica-containing materials. Modacrylic fibers perform above accepted limits in terms of dyeability. This confirms what it has shown. 14 0 ISO 17493:2016 – 180 C Sample ISO 15025 A1 / A2 % OK -3.5 D1 OK -2.5 D2 D3 ok -3.5 D4 ok -3 D5 ok -4.5 D6 ok -3.5 ok -5 D7 Table 2. Flame retardancy and thermal stability performances for samples D1-D7. display. Other results included in the table are (ISO 15025 A1 / A2 and ISO 17493:2016 – 180 °C) Two studies evaluating the flame retardancy and thermal stability performance of modacrylic fibers It represents a different standard. These D1-D7 samples are modacrylic fibers obtained from polymer starting solutions. It is present in the range of 45% to 55% by weight and is cellulosic based (in these tests These are fabrics in which cotton fibers make up between 45% and 55% by weight. To make it clearer, D1 is a polymer starter containing 10% antimony pentoxide by weight. modacrylic fibers obtained from the solution have a value ranging from 45% to 55% by weight. It is a fabric obtained by combining cotton with other materials. ISO 15025 A1 / A2 is the standard that defines the flame-exposure behavior of these fabrics. Test A1 simulates flame contact from the surface, while test A2 simulates flame contact from the edge. The "OK" expression indicates that the fabrics tested showed no flame propagation or post-burning in either test. It does not show any signs of remaining in a glowing state, meaning it retains its ability to extinguish itself spontaneously. 15 These results indicate that the fabrics exhibit a high level of flame resistance. This shows that the ISO 17493:2016 – 180 °C test results indicate the heat resistance of the tested fabrics. This test demonstrates the dimensional stability of the fibers. In this test, the fiber samples were heated to 180 °C. rate of dimensional change (e.g., percentage shrinkage or elongation) due to exposure The values ​​of “–%” in the table indicate how much the sample has been heated. This indicates shrinkage. A lower negative value (e.g., -2.5%) indicates higher fiber shrinkage. It is more stable at higher temperatures, and higher negative values ​​(e.g., -5%) indicate more stability. This indicates a tendency towards shrinkage. When the ISO results are evaluated together, It appears that all samples passed the ISO 15025 A1 and A2 tests with an "OK" result, meaning... Modacrylic fibers retain their self-extinguishing behavior after contact with flame. In terms of thermal stability, the dimensional changes measured at 180 °C in the ISO 17493:2016 test are shown. It varies from sample to sample. The lowest shrinkage is approximately -2.5% in D2. It gives -3% in D4. Samples D1, D3 and D6 are at -3.5%. The values ​​of -4.5% for D5 and -5% for D7 indicate a more significant contraction. The general trend is for formulations containing colloidal silica to have high flame resistance while maintaining high resistance. it improves dimensional stability at high temperatures and when antimony pentaoxide levels are reduced. This demonstrates that even thermal performance can be kept in balance. In a preferred configuration of the invention, the polymer starting solution contains at least one It contains a polymeric dispersion component. The polymeric dispersion component is a polymer. the additives in the initial solution clinging to each other and forming agglomerations This prevents and contributes to the long-term stability of the system. In this way... The physical stability of the polymer starting solution is increased, and particles are improved during the production process. Sedimentation and viscosity fluctuations are prevented. Within the scope of this invention, the polymer starting solution is used as a polymeric dispersion component. polyethylene glycol, polyvinyl alcohol, polymethyl methacrylate, at least from the polyvinylpyrrolidone group It includes one. The polymeric dispersion component is present in the polymer starting solution at a concentration of 0.1% to 1% by weight. It is located within the 1% range. These determined values ​​are based on the completeness of the particle surfaces. This ensures that it is coated and that the viscosity of the system remains balanced. At low values, dispersion stability weakens, while at higher rates, the polymer... Increasing the viscosity of the initial solution negatively affects the fiber drawing performance. 16 In a preferred application, the polymeric dispersion component contains additives that are not yet present. It is added to the solvent before the dispersion agent is added. This process sequence determines the dispersion agent's contribution. ensuring full contact with the particles and even surface coating. This ensures that antimony, tin and / or other substances present in the polymer starting solution are removed. Zinc-based compounds and colloidal silica in a single-phase, long-term stable dispersion. It constitutes. The method described in the invention is the characterization of the polymer starting solution. The invention concerns the method for obtaining modacrylic fibers using a specific technique. It is compatible with existing production lines. High antimony based production lines in existing technology. the use of compounds can lead to problems such as ionic instability and loss of dyeability. This can be achieved using the method described in this invention. The method involves polymer starting materials. preparation of the solution, making this solution suitable for fiber drawing, then the fiber This includes process steps such as creating the form. In the polymer starting solution preparation step, N,N- is used as a polar aprotic solvent. dimethylacetamide (DMAc), N,N-dimethylformamide (DMF), dimethyl sulfoxide (DMSO) and N- It contains at least one methyl-2-pyrrolidone (NMP) group. This polymer is the starting material. In the solution, the aforementioned polar aprotic solvent is present in a value ranging from 60% to 85%. It is receiving. In the next processing step, at least one antimony-based compound and at least one auxiliary compound are added to the solution. A flame-retardant component, colloidal silica, is added. With the addition of these additives... Mixing operations are necessary to restore the solution to a homogeneous phase. This is carried out while the temperature of the solution during this mixing process is between 20 and 60 °C. It is a value within this range. On the other hand, the solution contains 1.5% to 6% by weight of polymer solid. an antimony-based compound with a value in the range of 0.5% to 5%, at least one auxiliary flame retardant component and colloidal silica in a value ranging from 1% to 10%. is being added. The solution, without the addition of any additives, may contain at least one polymeric component, if preferred. It contains a dispersion component. It is based on the polymer starting solution and the polymer solid. A polymeric dispersion component is added in an amount ranging from 0.1% to 1% by weight. 17 In a preferred application, this polymer starting solution obtained consists of particles and It can undergo filtration processes to remove undissolved residues. Alternatively, if preferred, this polymer can trap gas in the starting solution. Degassing processes can be carried out to remove particles. This gas The removal processes are more specifically carried out under vacuum. The resulting polymer starting solution is then applied to the production line using wet or dry shooting. It is converted into fiber form using one of the methods. If the dry spinning method is preferred, the polymer starting solution is used in the technique. It is desiccated by a stream of air at a known temperature and then formed into fibers. If the wet spinning method is preferred, the prepared polymer starting solution They are ensured to undergo coagulation bath treatments at least once. After solvent removal is complete by applying these process steps, the fibers The solvent is processed by first subjecting it to washing and then neutralization baths. It is being cleaned of its remnants. After washing, the resulting modacrylic fibers are subjected to stretching processes. This ensures the orientation of the molecular chains in the fiber. Stretching As is known in post-processing technology, modacrylic fibers undergo fixation treatments. This can be accomplished. The final stages involve drying the fibers. The process involves achieving the target thickness and performing the cutting operations. The parameters in these process steps are the same as those used in the technique for obtaining modacrylic fiber. These are the values. These process steps and the parameters used provide protection for the subject matter of the invention. It is not included within the scope. The method described in the invention involves the preparation of a polymer starting solution containing colloidal silica. By using it, the amount of antimony is reduced, and the flame resistance of the fiber is preserved. This allows for improved paintability properties and increased production stability. This provides functional and aesthetic appeal. Thus, the resulting modacrylic fibers are excellent. It is performing at a high level. 18 Within the scope of this invention, the ksat value of modacrylic fibers obtained by the method is between 1.7 and 1.9. It is a value within this range. These values ​​are above the accepted range of 1.6-1.8. This The situation is that the addition of colloidal silica regulates the ionic balance of the dye. It has been shown to increase adsorption and improve color homogeneity. The fabrics obtained within the scope of the invention have flame-retardant and heat-resistant properties. and / or in the production of protective textile products due to their high visibility properties. These fabrics can be used especially in situations involving high temperatures, sparks, flames, or electricity. It is preferred for safety purposes in industrial environments where risks such as arc flash exist. The modacrylic fibers obtained within the scope of the invention have a high self-extinguishing property. high temperature resistant materials such as aramid, polybenzimidazole (PBI), polyphenylene sulfide (PPS) or PEEK When combined with strong fibers, the level of thermal protection is increased. On the other hand, Modacrylic fiber together with cellulosic-based fibers (cotton, viscose, modal, lyocell) Its use improves the fabric's comfort, moisture absorption, and breathability properties. This ensures long-term wearing comfort. The fabrics covered by this invention, Industrial workwear, welder and electrician uniforms, used in the petrochemical industry. personal protective gear such as overalls, reflective vests, jackets, pants, gloves, and hoods It can be used in the production of protective equipment. It also has high visibility properties. thanks to this, it is also used in traffic safety, construction, mining, logistics and emergency response equipment. is preferred. In addition, the flame-retardant properties of the fabric ensure indoor safety. In this respect, it can also be used in curtains, seat upholstery or in-car textile products. It provides. The scope of protection of the invention is specified in the claims attached hereto, and these details are strictly adhered to. The explanation cannot be limited to those given for illustrative purposes. Because a technically skilled person... the person, without deviating from the main theme of the invention, in light of what has been described above, similar It is clear that these structures can emerge.

Claims

1. It is a polymer starting solution suitable for use in the production of modacrylic fibers, its feature; it contains, It must contain at least one modacrylic-based copolymer and the dissolution of the modacrylic-based copolymer in question and the additives to ensure homogeneous distribution, at least one polar aprotic solvent, To ensure the flame-retardant property of modacrylic fiber, at least one antimony-based Despite reducing the amount of the compound and antimony-based compounds, the flame to ensure the preservation of its durability, at least one auxiliary flame retardant component, tin and / or zinc based as the aforementioned auxiliary flame retardant component compound, Correction of ionic balance in the polymer starting solution, viscosity control, and It contains colloidal silica to preserve dyeability.

2. A polymer starting solution conforming to claim 1, with the property of being an antimony-based compound. as antimony trioxide, antimony pentaoxide, sodium antimonate, or antimony It must contain at least one of the oxychloride groups.

3. A polymer starting solution that conforms to one of the previous requirements, and whose characteristic is; The amount of antimony-based compound produced is relative to the polymer solid in the solution. It should be between 1.5% and 6% by weight.

4. A polymer starting solution that conforms to one of the previous requirements, and whose characteristic is; Zinc stennate, zinc borate, and tin are tin and / or zinc-based compounds obtained. It must contain at least one of the following groups: oxide, tin hydroxide, or tin chloride.

5. A polymer starting solution that conforms to one of the previous requirements, and whose properties are: The amount of auxiliary flame retardant component depends on the polymer solid in the solution. It should be between 1% and 5% by weight.

6. A polymer starting solution that conforms to one of the previous requirements, and whose characteristic is; The particle size distribution of the obtained colloidal silica is in the range of 20 to 100 nm. It is of value. 35 20 7. A polymer starting solution that conforms to one of the previous requirements, and whose properties are: The amount of colloidal silica in the solution ranges from 0.5% to 1% by weight of the polymer solid. It should be in the 10% range.

8. A polymer starting solution that conforms to one of the previous requirements, and whose properties include at least: It contains a polymeric dispersion component.

9. A polymer starting solution conforming to claim 8, with the property of being a polymeric dispersion. as components: polyvinylpyrrolidone, polyethylene glycol, polyvinyl alcohol, polymethyl It must contain at least one component from the methacrylate group.

10. A polymer starting solution conforming to claim 8 or 9, whose properties are polymeric. The amount of dispersion component is 0.1% by weight of the polymer solid in the solution. It should be between 1% and 2%.

11. A method for obtaining a polymer starting solution in accordance with Claim 1, Its feature is that it includes the following steps: - at least one modacrylic-based copolymer in at least one polar aprotic solvent dissolution, - The amount of modacrylic-based copolymer in the solution is between 15% and 15% by weight. A value in the 25% range, - After the dissolution process is complete, the temperature of the solution should be between 20 and 60 °C. kept within the range - the resulting solution contains between 1.5% and 6% by weight of polymer solid. at least one antimony-based compound with a certain valence as an auxiliary flame retardant Tin and / or zinc-based compounds in a value ranging from 1% to 5% by weight. colloidal silica in amounts ranging from 0.5% to 10% by weight, respectively addition, - mixing to ensure additives form a homogeneous phase. Obtaining the solution by continuing the process.

12. A method conforming to claim 11, characterized by the presence of an antimony-based compound in the solution. as antimony trioxide, antimony pentaoxide, sodium antimonate, or antimony This means that at least one of the 35 oxychloride groups is added. 21 13. A method conforming to claim 11 or 12, characterized by the presence of tin in the solution. and / or zinc-based compounds such as zinc stennate, zinc borate, tin oxide, tin This means that at least one of the hydroxide or tin chloride groups is added.

14. A method conforming to one of the claims 11-13, characterized by the addition of additives to the solution. This means that at least one polymeric dispersion component must be added before the other two components are added.

15. A method conforming to claim 14, characterized by its polymeric dispersion component. polyvinylpyrrolidone, polyethylene glycol, polyvinyl alcohol, polymethyl methacrylate group at least one of them is being added.

16. A method conforming to one of claims 11-15, characterized by the additives. the solution obtained after addition contains particles and undissolved residues This means that a filtration process is applied to purify it.

17. A method that conforms to one of claims 11-16, characterized by the fact that the additives This involves applying a gas removal process under vacuum after the addition of gas.

18. Polymer starter obtained by a method conforming to one of claims 11-17. modacrylic fiber obtained from the solution has a value in the range of 1.7 to 1.9 ksat. It is the fact that.

19. A modacrylic fiber conforming to claim 18, an aramid-based fiber, polymenzimidazole, Polyphenylene sulfide is a fabric in which at least one element from the PEEK group is present.

20. A modacrylic fiber conforming to Claim 18, together with at least one cellulose-based fiber. a fabric in which it is located.

21. A fabric conforming to claim 20, characterized by its composition of 30% to 70% by weight. modacrylic fiber in a value between 70% and 30% by weight. It contains cellulosic-based fibers of a certain value.

22. A fabric conforming to claim 20 or 21, characterized by being a cellulosic-based fiber. It may contain at least one of the following materials: cotton, viscose, modal, or lyocell. 35 22 23. The fabric conforms to one of the requirements 20-22, and its characteristics are: ISO 17493:2016 – 180 °C According to the standard, it has a dimensional change value between -3% and -3.5%. It is the fact that.

24. A fabric conforming to one of the requirements 19-23 shall be used for industrial workwear, protective jackets, trousers, overalls, reflective vests, gloves, hats, curtains, upholstery textile products It is the use of.