TW200831738A - Dope dyed flame retardant polyester fiber and blackout fabric produced therefrom - Google Patents

Abstract

Provided is a flame-retardant polyester fiber comprising a phosphorus flame retardant, represented by Chemical Formula 1 below, including 500-50000 ppm of phosphorus; a manganese salt, which is used as a UV stabilizer, including 0.1-500 ppm of manganese; a phosphorus compound, which is used as a UV stabilizer, including 0.1-500 ppm of phosphorus; and 500-5000 ppm of carbon black, and to a blackout fabric produced using the flame-retardant polyester fiber, and a blackout fabric produced using the flame-retardant polyester fiber. The dope-dyed flame-retardant polyester fiber has excellent flame retardant properties, UV stability, and color fastness. The blackout fabric produced using the flame-retardant polyester fiber can simultaneously exhibit excellent flame retardant properties and light blocking properties.

Description

200831738 IX. The invention relates to a textile dyed flame retardant polyester fiber and a light-shielding fabric manufactured therefrom; and more particularly to a flame retardant polyester fiber containing the following chemical formula Phosphorus flame retardant (including 500~5 000 0 ppm of phosphorus), using manganese salt as uv stabilizer (including 〇·1~500 ppm manganese), using phosphorus compound as uv stabilizer ( It includes 〇·1 to 500 ppm of phosphorus, and 500 to 5000 ppm of carbon black; and a light-shielding fabric made of the flame retardant polyester fiber. 0 〇r1~op-ch2-ch2-co-r3 r2 Chemical Formula 1 [Prior Art] In view of the time when the flame retardant property is imparted to the fiber product, the method of imparting the flame retardant property to the fiber can be classified into the fiber produced by the post-treatment. The product is a method for imparting a flame retardant to a fiber product, a method of adding a flame retardant in a fiber spinning process, and a process of preparing a fiber polymer (mainly a polymerization process) to copolymerize a component containing a flame retardant. The monomer side = 22nd, since natural fibers cannot be imparted to the flame retardant properties during the fiber spinning process or polymerization process, they must be imparted with flame retardant properties by post-treatment methods. In contrast, synthetic fiber 5 200831738 is usually entangled in the fiber spinning process and *, , , ° to the flame retardant properties. However, in order to woven the fiber, there is a limit to the resistance of the i.,., & fiber flame retardant v cut ', ', ^ at the textile temperature must be decomposed, + decomposition, and when the flame retardant is When the swarf is not taken by q", the money material, the dispersibility is so good that it will not hinder /, the swarf has the advantage of giving the characteristics of the flame retardant can be reduced, the production is possible. The method of adding the organic material f The second method is to enter the machine material in the evening, „^ The method of the flame retardant in the material is here. As for the method of industrial fuel. ,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,, )compound of. , T, ,, and ϋ give these synergistic effects to the properties of the flame retardant. The synergistic effect between nitrogen and phosphorus and the synergistic effect between halogen ", gas or /6) and daytime are known in the art. A ruthenium-free compound is disclosed in Japanese Unexamined Patent Publication No. SHO-62-691, No. SHO-62-46398, and No. 51-28894. Here, since the bromine compound is easily heated at a high temperature, it is necessary to add a large amount of a flame retardant to obtain an effective flame retardant. As a result, there is a problem that the color tone of the polymer deteriorates, and the lightness is reduced, and a toxic gas is generated upon burning. Further, a flame retardant containing a phosphorus compound is disclosed in U.S. Patent Nos. 3,941, 752, 5, 399, 428 and 6, 2008, 317, 793, and Japanese Unexamined Patent Publication No. SHO-50-56488 and No. 52-47891. Here, when a flame retardant containing a phosphorus compound is used, no harmful substances such as dioxin, benzotrize or the like are generated during incineration. However, since the flame retardant containing a phosphorus compound has low stability against ultraviolet rays (UV), when it is exposed to the sun for a long period of time, there is a problem that the flame retardant property of the flame retardant is reduced, and the physical properties of the fiber are deteriorated. At the same time, since the polyester fiber is not easily dyed in a dark color and does not chemically bond the dye, the polyester fiber has low color fastness, and its washing durability may be problematic due to low color fastness. There is a relatively high demand for 'grey yarns' with deep black in various colors. However, it is difficult to make the polyester fiber & ice black using a general dyeing method. Therefore, the problem of the color fastness is exhibited by the formation of the fibers of the poly-g fibers in the "dope dyed filaments". The method of producing the dyed yarn is as follows. First, there are methods for injecting dyes and pigments during the polymerization process. The problem with this method is that when the spun yarn is manufactured using a batch process, it is difficult to adjust the color difference between batches, and it is difficult to manufacture different kinds of polymers in the same polymerization reactor because of polymerization. The reactor is contaminated with dyes and pigments. 7 200831738 The second 'mixing' consists of a master batch of highly concentrated pigments and dyes with polyester polymers and then spinning them. In this method, a parent batch including a large amount of carbon black can be used, particularly when the spun yarn to be produced is black. Furthermore, in this method, the parent batch including the appropriate type and content component is selected.

Sub-twisting is important because the textile properties and fiber characteristics vary with the type of base resin included in the parent batch. Third, the production of spun dyed yarn through the yarn dyeing process or post-treatment process is not commonly used because the cost of manufacturing the spun yarn is less than the productivity of the spun yarn, and the dyeing dyed by this method. Silk can't show the quality it wants. This unpublished patent publication No. 138227, contending 03-137228 - ψ 0-77523 and ping 03_131〇51 reveals that the entertainment is injected with pigments (such as carbon in the range of pigments, etc., which are commonly used pigments) In the fiber manufacturing method of spinning and lifting wood. This method is a method of manufacturing a weaving dimension to 5 insects (for example, έ ..., 罔, 罔 women's full belt nylon). This method is not directed to ^#^%, square; a method for producing a dye-resistant polyester fiber according to the present invention. [Technical Problem] Therefore, the object of the present invention is to provide a dye-dyed flame retardant polyester fiber which has permanent flame retardant properties and uv stability, and which has high black color and color fastness. Because pigments and the like are also included. Another object of the present invention is to provide a fibrous product such as a woven fabric, a light-shielding fabric or the like which comprises a dye-dyed flame retardant polyester fiber. [Technical Solution] In order to achieve the above object, an aspect of the present invention provides a textile dyed flame retardant polyester fiber comprising the phosphorus flame retardant represented by the following Chemical Formula 1 (including 500 to 5,000 ppm of phosphorus) Using a manganese salt as a UV stabilizer (including manganese in ο"~500 ρριη), using a phosphorus compound as a UV stabilizer (including 〇.丨~5 〇〇)

Phosphorus of Ppm), and carbon black of 5〇〇~5〇〇〇ppm. R1-o~p-ch2-ch2-co~r3 R ----Chemical Formula 1 wherein Ri is hydrogen or 1 to 1 〇 a hydroxyalkyl group of carbon atoms; R2 is an alkyl group of 1 to 10 carbon atoms or an aryl group of 6 to 24 carbon atoms; and R3 is hydrogen, or a alkyl or hydroxyalkane of 1 to 1 carbon atom a group, or a functional group forming an ester thereof. The invention will be described in detail below. The inventors of the present invention have tested various flame retardants to impart excellent and permanent flame retardant properties to polyester fiber 9 200831738. At present, industrial polyester fibers impart flame retardant properties to flame retardants, which may include strontium flame retardants and phosphorus flame retardants. Although it is known that the dentate flame retardant has the characteristics of different flame retardants, the specification of the use of toxic gas is increased.

For this reason, the inventors of the present invention have applied a phosphorus flame retardant represented by the following chemical formula]. Depending on the phosphorus atom, the phosphorus flame retardant is a main chain flame retardant and a side chain flame retardant, showing the characteristics of the flame retardant ^ The main chain of the polyester is related. The inventors of the present invention have found that the main chain flame retardant is advantageous and has excellent flame retardant properties in terms of hydrolysis resistance and environmental affinity as compared with the side chain flame retardant. Because of the $, in the main chain flame retardant, the inventors of the present invention have adopted the F and the flammable agent having the most enthalpy, the degree of enthalpy and the reactivity with respect to ethylene glycol (eg). Depending on the molecular weight of the flame retardant, the flame retardant, including a large amount of the flame retardant, exhibits a sufficient flame retardant effect and is advantageous in terms of processing. Further, since the flame retardant has a small amount of aromatic groups, a small amount of coal ash and poison gas are generated as compared with the conventional flame retardant having a phosphorus phenanthrene group. Considering the polymerization processability and the manufacture of natural yarns, the phosphorus content of the phosphorus flame retardant for polyester polymers, regardless of its structure, can be 5〇〇~ 200831738 50,000 ppm > special i % inch can be 1000~10000 ppm . The phosphorus content of the Xingshishu flame retardant is lower than that of the ^ Η 氐 500 500 500 500 500 500 500 500 500 500 500 500 500 500 500 500 , , , , , , , 500 500 500 500 500 500 500 500 500 500 500 500 500 500 500 500 500 500 500 500 500 It is difficult to anticipate. Compared with the phase of the product, when it is more than 50 000 ppm, it will increase the degree of polymerization of the produced polyester and it is difficult to form the polyester into fiber because it is produced. The crystallinity of the polyester is extremely reduced, which is undesired.

Same as %, since most of the flame retardant products are used for shading, when they are exposed to sunlight (especially uv), the polymerization is stable, therefore, the introduction of uv stabilizer is heavy in it;: Various tests by the inventors of the present invention As a result, it was determined that manganese phosphate may be the most effective for use as a uv stabilizer. However, since manganese phosphate is insoluble in ethylene glycol, it is difficult to introduce manganese phosphate into the polymer. Therefore, the inventors of the present invention have found that the method of synthesizing manganese phosphate in the reactor is most suitable by separately introducing a phosphorus compound (e.g., manganese acetate, phosphorus) into the reactor without directly introducing the acid into the reaction. For the polyester polymer, the manganese content of the acetic acid used for the synthesis of manganese phosphate may be from 1 to 500 ppm (based on manganese), and more preferably from 0.2 to 200 ppm. When the manganese content of manganese acetate is less than 〇·1 PPm, it is difficult to obtain the desired UV stability. Compared with 11 200831738, when the amount is more than 500 ppm, there is a problem of insufficient dispersion, thereby increasing the packing pressure at the time of spinning. Further, the phosphorus content of the phosphorus compound of the polyester polymer may be from 0.1 to 500 ppm, and more preferably from 2 to 200 ppm. As long as the male compound is not problematic to react with the salt, an incremental sarcophagus compound can be added. However, when the lining content of the compound to be filled is more than 50,000 p pm, the activity of the catalyst is decreased, and thus it is difficult to produce a desired flame retardant polyester. At this time, the inventors of the present invention have conducted tests to focus on increasing the color fastness of black in the flame retardant polyester fiber. The method of producing a t-fiber by directly injecting a dye or a dye during the polymerization has a problem that the polymerization reactor is contaminated with a dye or a pigment, and it is difficult to adjust the color difference between batches.

The polyester fiber is produced through the yarn dyeing process to select the pigment or dye white having affinity for the polyester fiber: in the method of adding some resin to the polyester fiber per: hardening to increase the fixing strength of the pigment or dye Found that the fiber has hardened, not softened, and its flame retardant "-under-manufactured flame retardant is concentrated in the mother batch of resin. Therefore, the present invention uses the method of using the mother batch of rayon fiber, and finds the choice It is important to include 200831738 main agent. Even when the resin main agent is mixed with the flame retardant polyester polymer, the amount of the main resin used is small, and when the compatibility therebetween is low, a color difference occurs between the produced polyester fibers. Further, it has been found that when the difference in heat resistance is large, the quality of the product during the fiber manufacturing process and the post-treatment process is lowered. In order to obtain excellent processability in the weaving process, the melting point of the master batch must conform to the following formula 1, and the resin base agent contained in the master batch which is compatible with the flame retardant polyester polymer used in the present invention must meet the following Mathematical Formula 2 〇TFR - 20 ° C < TB S TFr + 20〇C ... Mathematical Formula 1 wherein TFR is the melting point of the flame retardant polyester polymer, and τ Β is the melting point of the resin base agent contained in the master batch. 220〇C < Tm < 250〇C -----------Formula 2 _ where T m is the melting point of the manufactured polyester fiber, and does not include two or more The melting point of the peak. The above melting point was analyzed using DSC 7 manufactured by Perkin Elmer Corp.

When TB is lower than TFR - 20 ° C, the melting point of the resin base agent is much lower than the melting point of the flame retardant polyester polymer, and thus it is difficult to uniformly spread the master batch. In contrast, when TB is higher than Tfr + 20 ° C 13 200831738, the operability is reduced due to the resin main agent and the flame retardant oligomeric polymer, and the 70 king is unevenly performed or The resin main agent acts as an impurity to deteriorate the fiber quality of the coat. Further, when the melting point of the fiber to be produced is 220 ° C, the enthalpy resistance is reduced by a decrease, and thus the produced fiber is liable to be melt-bonded and twisted. In comparison, when the velvet is at 25 CTC, it is difficult to obtain a star-like material due to the phase separation. Another melting peak is produced because of uniform color: uniform material properties of the fiber and manufacturing can be used in the present invention + ^ Not included in the mother batch of the resin can be free of polyethylene to the stupid acid and vinegar, including u ... % to the stupid. Or a group of benzoic polyethylene to benzoic acid, and a group consisting of m 〇 〇 〇 〇 or 之间 之间 共 共. Amethyst 色素 The pigments and dyes used in the present invention must have heat resistance, * for use in high temperature polyester polymerization and to evaluate industrial 俨 &amp; fly over 轾. Comparing the ginseng, Lu 1 mountain, mussel 0 and its performance results, it was determined that the inorganic color 匕 quot 石 stone anti-black is a suitable pigment for use in the present invention. a dyes for polyester fibers, pylons of about 280 300 c, 200831738 and therefore their color changes, making them difficult to use. Further, for the flame retardant polyester fiber, the content of carbon black may be from 5 〇 0 to 5000 ppm. When the carbon black content is less than 500 ppm, it is difficult to expect a desired color and uniformly mixed, and thus the flame retardant polyester fiber may be poorly dyed. In contrast, when the content is still 5 〇〇〇 ppm, the amount of carbon black added is extremely increased, and thus the price of the flame retardant polyester fiber produced is increased and the textile processability is decreased. The flame retardant polyester fiber of the present invention can be stretched or false twisted after being spun in a spinning process or after preparing a partial alignment yarn (P 0 Y ). The woven or shade fabric of the present invention comprises a flame retardant polyester fiber. Fabrics include woven fabrics and woven fabrics. Φ [Embodiment] Hereinafter, the present invention will be described in more detail with reference to the embodiments. However, the invention is not limited to these embodiments. (Examples) Before describing the examples, the evaluation methods for the properties of the polymers and fibers provided in the test should be described. 1. Resin main agent-PET: Polyethylene terephthalate 15 200831738 He-PBT · Polybutylene terephthalate --CoPET: PET and 2·5 m〇l〇/0 of ruthenium acid copolymerization 2 · Master batch content · · Master batch weight % when mixed (Master batch weight / (mother batch weight + flame retardant polyester polymer weight) 00) σ 3. Melting point (Tm): Tm It is measured by DSC7) manufactured by WinEhnerCorp with a differential sweeping measuring instrument and can appear 2 peaks in DSc chart. 4. Textile operability: the number of damages in textile operation is 5 or less, Shi, X, X X Chemical, textile can be transported, when the number of wire damage is 5 to ◎ table ^ ^ 乂上日守' textile can be expressed from α X, and because of the single wire loss, the nature of the performance is expressed separately.运 5 ·Staining affinity: private 丨ru • The fiber made by the yoke is fine, - (hose-knitted) is 1 〇 隹 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 衣 衣 衣 衣 衣 衣 衣 衣 衣 衣 衣 衣 衣 衣 衣 衣When the difference is evaluated by the naked eye, the dyed sigmoid woven fabric is dyed with more than one ring-shaped woven fabric I, and when one or the force is represented by X. There are „, dyeing affinity dyeing affinity respectively. When dyeing spots, 16 200831738 : According to Korean Standard (KS Μ 3 03 2), and thus the limit oxygen index value is evaluated <Examples 1 to 4, ah Comparative Examples 1 to 3> Using a half batch method (semi-batch method) esterification of a slurry prepared with 1300 g of TPA and 560 g of EG. Made with the same composition

The prepared oligomer was used as a slurry, stirred in an esterification reactor, and the temperature of the deuteration reactor was maintained at a temperature of 250 〜 = 〇 C. The mud is then completely introduced into the esterification reactor' and then the additional west t! # - 曰化30 knives | Li Ri inch, the esterification ratio of the mud is 97%. In the spring polymer of the wisdom supply, 1 · 5 tons of the oligomer remain in the ... and the remaining oligomers are transferred to the DE-2

6. Flame retardant properties Fiber (LOI) manufactured by the test. reactor. First, 68 kg of a flame retardant represented by the chemical formula i (wherein R 丨 = H, r 2 = phenyl; and R 3 = h) is introduced into the esterification reaction with 68 kg of the reaction product. Therefore, it will be used: 3% by weight of titanium dioxide (based on the amount of the polymer) is added as a deodorant, and then stirred at a temperature of 260 °C. All oligomers stored in the DE-2 reactor were transferred to the polymerization and condensation reactor with =. Then, a 2 〇〇 g antimony trioxide solution which was dissolved in EG at a concentration of 2% by weight was introduced into the polymerization and condensation reactor, and then the polymerization and condensation reactor 17 200831738 was evacuated. The resultant is then polymerized and condensed by a general polyester polymerization method, thereby preparing a flame retardant polyester polymer. The master batch was prepared using a twin extruder with a polymer shown in Table 1 to a carbon black content of 30% by weight. Finally, the flame retardant polyester polymer prepared in the same composition as in Table 1 and the prepared master batch were woven and formed into yarns, thereby producing a spun flame retardant polyester fiber. <Comparative Example 4> Comparative Example 4 was carried out by the same method as in Example 1 except that the phosphorus content of the flame retardant polyester polymer was 400 ppm. [Table 1] Classification Example 1 Example 2 Example 3 Example 4 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Resin main agent PET CoPE T PBT PET PP Ny PET PET TB (°〇 253 251 227 254 166 230 268 253 Master batch content 4 4 4 4 4 4 1 4 Carbon black content (PPm) 1200 1200 1200 1200 1200 1200 300 1200 Phosphorus (P) content (ppm) 6500 6500 6500 6500 6500 6500 6500 400 18 200831738

Textile condition GR1 speed (m/mi η) 1400 1400 1400 3290 1400 1400 1400 1400 GR1 temperature (°C) 80 80 80 80 80 80 80 GR2 speed (m/mi η) 4150 4150 4150 3300 4150 4150 4150 4150 GR2 temperature ( °C) 125 125 125 125 125 125 125 Physical properties of natural yarns > Strength (g/d) 4.42 4.22 4.23 2.25 4.25 4.31 4.30 4.25 Length ratio (%) 34 32 33 147 34 33 32 30 Tm (°C) 242 239 239 241 2 Peak 2 Peak 241 241 Textile operability ◎ ◎ ◎ ◎ XX ◎ ◎ False 捻 condition DR 1.7 DY 1.9 False 捻 temperature (°C) 170 19 200831738 False yam strength _ 3.76 Physical property elongation ratio (% 20 Dyeing characteristics ◎ ◎ ◎ ◎ X-stained spots X ◎ Flame retardant properties (LOI) 39 38 38 38 37 37 38 22 &lt;Example 5 &gt;

Using the Example 4, a spun dyed polyester false twisted yarn was produced as a weft yarn, and a SDM 1 50/144 manufactured by Hy0sung Corp. (which is a flame retardant polyester false twisted yarn as a warp yarn and a woven 7 double-faced pile) was used. The velvet properties of the shading fabric were subsequently evaluated. The resistance of the shading fabric was evaluated according to the American standard NFPA 701.

_ Fuel characteristics and pass the test. According to the Japanese standard jl§ L 1 0 5 5 ping fabric shading performance, and its shading rate is 99.8% 有利 [Advantageous effect] The spun dyed polyester fiber according to the present invention has a flame retardant Agent characteristics, XJV stability and color fastness.封 Blocking is the use of the flame retardant polyester fiber of the present invention to produce an optical fabric capable of exhibiting both excellent flame retardant properties and light-shielding properties. 20 200831738 [Simple diagram description] [Major component symbol description]

Claims (1)

200831738 X. Patent application scope: 1 · A textile dyed flame retardant polyester fiber containing the phosphorus flame retardant represented by the following Chemical Formula 1 (including 500 to 50000 ppm of phosphorus), and a manganese salt used as a UV stabilizer ( Including 0 · 1~500 ppm I), using phosphorus compounds as UV stabilizer (including 0·1~500 ppm), and 5000 to 5000 ppm carbon black; 0 0 r1-op -ch2-ch2-co-r3 as in Formula 1 wherein R! is hydrogen or a hydroxyalkyl group of 1 to 10 carbon atoms; R2 is hydrogen, an alkyl group of 1 to 10 carbon atoms or 6 to 24 carbons An aryl group of an atom; and R3 is hydrogen, an alkyl group of 1 to 10 carbon atoms or a hydroxyalkyl group, or a functional group forming an ester thereof. 2. The textile dyed flame retardant polyester fiber according to claim 1, wherein the carbon black is introduced into the master batch, and the resin base (baseresi η) contained in the parent batch is in accordance with The polyester polymer of the following Mathematical Formula 1, and the spun dyed polyester fiber satisfy the following formula 2: TFR - 20 ° CS TB $ TFR + 20 ° C ... Mathematical Formula 1 wherein TFR is a polyester polymer The melting point, and τΒ is the melting point of the resin base agent containing 22 200831738 in the parent batch; 220〇C &lt; Tm &lt; 250〇C .............. Mathematical formula 2 wherein Tm is The melting point of the manufactured spun dyed flame retardant polyester fiber. 3 · As in the patented scope 2 of the textile dyed flame retardant polyester fiber, the resin base agent contained in the mother batch is selected from polyethylene terephthalate, polybutylene terephthalate a package comprising 12-mole or less of a copolymerized polyethylene terephthalic acid of benzoic acid, and a copolymerized polybutylene comprising 1 2 m ο 1 % or less of benzoic acid A group consisting of p-benzoic acid g. A fabric comprising a spun dyed flame retardant polyester fiber according to claim 1 or 2. A light-shielding fabric comprising a spun dyed polyester fiber as claimed in claim 1 or 2. 23 200831738 VII. Designation of representative representatives: (1) The representative representative of the case is: no picture. (2) A brief description of the symbol of the representative figure: 8. If there is a chemical formula in this case, please reveal the chemical formula that best shows the characteristics of the invention.