KR101276098B1 - Polyester Filaments Having Excellent Flame Retardancy and Method of Preparing the same - Google Patents

Abstract

The present invention is a polyester characterized in that the flame retardant compound having excellent flame retardancy, brushing processability, washing fastness through a split composite spinning step and a flammable step comprising a polyester copolymer resin copolymerized with a flame-retardant compound and an alkali-soluble copolymerized polyester resin A fiber and a method for producing the same.

Description

Polyester Filaments Having Excellent Flame Retardancy and Method of Preparing the same}

The present invention is a composite spinning of a polyester resin copolymerized or mixed with a flame-retardant compound and an alkali-soluble co-polyester resin by a split composite spinning method, and then reducing, dividing, raising and sanding the process by performing a flammable processing under specific conditions. The present invention relates to a method for producing a polyester fiber which is excellent in hair feeling and excellent in washing fastness and flame retardancy without deteriorating the physical properties of the yarn.

In interior products, flame retardancy is recognized as one of the most basic required performance. The technique of expressing such flame retardancy in the fiber is produced by adding or copolymerizing a large amount of flame retardant compound to express a permanent flame retardancy in the post-processing method and the post-processing method to treat the flame retardant on the surface of the fabric through the post-processing in a large woven or knitted fabric state It can be classified into a flame retardant fiber production method by the mixing method. However, in the case of post-processing, there are problems of hardening and discoloration of the surface of the product and uneven flame retardancy.

Japanese Patent Laid-Open No. 62-6912 and Japanese Patent Laid-Open No. 53-46398 disclose a method for producing a flame retardant fiber by using a bromine-based compound as a method for producing a flame retardant fiber by a method of incorporating in fibers. However, such bromine-based flame retardants are not only heat-resistant, but also reduce the content of the final product, and due to human hazards of gases generated during combustion, they are designated as regulated items in many countries, and therefore, they are restricted in use.

Instead of applying a bromine compound, US Patent Nos. 3,941,752, 5,399,428 and the like disclose a method for producing a flame retardant fiber in which a phosphorus compound is bonded to a polyester resin backbone, and Japanese Patent Application Laid-Open No. 52-47891, Korea Patent Publication No. 2001-0004814 discloses a flame retardant fiber production method for preparing a phosphorus-based compound in a polyester resin polycondensation reaction step. However, since the manufacturing method is specifically disclosed only for the method of preparing a flame retardant resin used in general fibers, when the thickness of the fiber is made fine, there is a problem of deterioration in flame retardancy and poor quality.

Flame retardant fibers must be managed under specific post-process conditions to maintain flame retardancy during preparation, weaving, dyeing and heat treatment, even if flame retardant compounds are copolymerized, dispersed or added to the polymer. In particular, when a softener and a preparation process are used, no matter how much the fabric is manufactured using a flame retardant fiber, the softening agent and the preparation process to improve the texture of the fabric are applied in the development of a flame retardant fiber product, because a sudden flame retardancy is reduced. This is difficult.

Therefore, in order to improve the texture of the fabric, it is preferable to reduce the Young's modulus and the bending stiffness by minimizing the thickness of the fiber rather than the post processing to soften the contact feeling. However, when the flame retardant fibers are made extremely fine using a flame retardant copolymer resin, it is difficult to commercialize because the number of trimming increases during spinning and the physical properties of the yarn are changed vulnerably.

On the other hand, as a method of making the fiber finer, a direct spinning method for producing fine fibers through spinning a nozzle having a fine diameter during spinning, spinning in island-in-sea type, and then island-in-the-sea composite spinning method in which the sea component is melted, and finely divided into spinning There is a split radiation method in which the two types of polymers are separated using compatibility or elution. Among them, the island-in-the-sea composite spinning method is disclosed in Japanese Patent Application No. 55-71817 and Japanese Patent Application No. 58-54022, which use an alkali-soluble polymer as a island component and nylon or polyester as a sea component. . These microfibers can be made of fabric and then raised to the artificial suede texture by raising hair while brushing and sanding to express a soft texture. However, the above inventions do not mention the flame retardancy, there is a problem that must be added to the flame retardancy in the coating or impregnation process and to implement a permanent flame retardant to use for interior use.

Korean Patent Publication No. 10-2004-0012126 uses a polyester resin copolymerized with phosphorus flame retardant, a phosphorus compound and manganese salt as a island component, and an island-in-the-sea composite spinning method using an alkali-soluble polyester resin as a sea component is used. Is disclosed. However, in the case of the flame-retardant islands-in-the-sea ultrafine fibers disclosed in the present invention, a sudden flame retardancy may occur during the raising and sanding process, and there is a problem in that the physical properties of the individual flame-retardant filaments become weak when raising. In addition, there is a problem in that the surface area is excessively large and the diameter of the individual single yarn fibers is small, so that dyeing is difficult to penetrate uniformly into the fibers, indicating poor washing fastness.

In order to solve the problems of the prior art, it can be said that the development of spinning and flammable technology to control the fineness and physical properties of ultra-fine flame retardant fibers. Therefore, the present invention proposes a manufacturing method for solving the above problems.

It is an object of the present invention to provide a split type composite spinning yarn having excellent flame retardancy and a method of manufacturing the same.

Another object of the present invention is to provide a super-fine polyester fiber excellent in hair feel without losing the physical properties of the yarn even after weight loss, splitting, brushing and sanding process, and washing fastness and flame retardancy according to performing the false processing under specific conditions, and a manufacturing method thereof To provide.

In order to solve the above problems, the present invention introduces the composite spinning in the elution split type composite spinning method rather than the island-in-the-sea composite spinning method to limit the optimum ratio of single yarn fineness and composite spinning of the flame retardant microfine fiber, the final yarn in the combustion process The main physical properties of the to prepare a polyester fiber excellent in hair feel, flame retardancy and washing fastness.

The polyester fibers according to the invention have excellent flame retardancy.

In addition, the polyester fiber according to the present invention has excellent flame retardancy without deterioration of physical properties after brushing or sanding process treatment by performing the combustion process of a specific condition.

In addition, the polyester fibers according to the present invention have an excellent hair feel.

In addition, the polyester fibers according to the invention have good wash fastnesses.

In addition, the polyester fibers according to the present invention have good brushing processability and uniformity of quality.

The present invention is to produce a flame-retardant polyester fiber spun two polymers in a splittable conjugate spinning, wherein one polymer is used a polyester copolymer resin copolymerized with a flame retardant compound As another polymer, a copolyester resin which is easily dissolved in an alkali is used.

Specifically, the polyester copolymer resin copolymerized with a flame retardant compound used as one kind of polymer is a 3-hydroxy phenyl propynyl propanoic acid (3-hydroxy-phenyl-propynyl) which is a phosphorus compound during a polyethylene terephthalate polycondensation reaction. -propanoic acid) is added, so that the phosphorus content is 1,000 to 20,000 ppm relative to the weight of the polyester copolymer resin copolymerized flame retardant compound. If the phosphorus content is less than 1,000 ppm relative to the weight of the polyester copolymer resin copolymerized with the flame retardant compound, the flame retardancy may not be properly expressed in the final product. On the contrary, the phosphorus content is 20,000 ppm relative to the weight of the polyester copolymer resin copolymerized with the flame retardant compound. If it is exceeded, it is difficult to raise the desired viscosity due to the copolymerization, the crystallinity is lowered, and the process defect due to pyrolysis during the spinning may be severe.

Specifically, the intrinsic viscosity of the polyester copolymer resin copolymerized with the flame retardant compound used as one kind of polymer is set to be 0.60 to 0.75. When the intrinsic viscosity of the polyester copolymer resin copolymerized with the flame retardant compound is less than 0.60, the physical properties of the individual filaments are severely deteriorated during the brushing and sanding process, so that they are easily broken or broken and lintized. If the intrinsic viscosity of the copolymer resin is greater than 0.75, the swelling property is increased during spinning, making it difficult to form a normal divided cross section.

Specifically, the alkali-soluble copolymer resin used as the other polymer is a modified polymer or dimethylformamide and formic acid to which 3 to 5 mol% of dimethyl sulfonate and 10 to 20 mol% of ethylene glycol are added during the polymerization of polyethylene terephthalate. It uses a thermoplastic polymer prepared as.

Specifically, the constituent ratio of the split-type composite spun fiber composed of the polymer is such that the polyester copolymer resin to the alkali-soluble copolymer resin copolymerized with the flame retardant compound is 50:50 to 80:20. Preferably, from 70:30 to 75:25, it is advantageous in terms of manufacturing cost, processability and cross section formation.

Specifically, the nozzle is selected so as to have a 9 to 16 pieces in the cross-sectional shape, in which case it may be used in any form such as orange or parallel.

Specifically, the spinning speed is set to 1,000 to 3,500 m / min, and wound in the form of POY (Partially Oriented Yarn) or SDY (Spin Draw Yarn) drawn in an unstretched state. If the spinning speed is discharged from the nozzle at a speed higher than 3,500 m / min, there is a high possibility that one or more filaments are temporarily disconnected, and the cross-section is poor, so only one component is radiated. It may be prepared in the form of a sole yarn.

Specifically, the spinning temperature varies slightly depending on the amount of the flame retardant compound in the polymer, the melt viscosity and the melt index (Melt Index), but is preferably set within 275 to 295 ℃. If it is less than 275 ℃, there is a problem of polymer flowability, so the irregularity of icicle-shaped surface irregular fiber is high. On the other hand, if it exceeds 295 ℃, the polymer discharged from the nozzle will be attached to the nozzle surface. Can be.

Specifically, through the spinning step, fibers composed of 9 to 16 pieces in one filament cross section are divided into 8 to 15 pieces by the elution process.

In the present invention, in order to produce a flame retardant polyester fiber, the composite yarns are spun into a composite spun section in an eluted split cross-section under specific conditions. In this case, it is important to set the flammable condition to satisfy the following false twisted yarn properties.

40% ≤ E ≤ 70% -------- (1)

1.0% ≤ C ≤ 3.0% ------ (2)

0.20 ≤ TMF ≤ 0.35 ---- (3)

15 ≤ OV ≤ 40 --------- (4)

E: Residual Elongation of Textured Yarn

C: Crimp of Textured Yarn

TMF: Thickness of Mono Filament after Splitted

OV: Optimal Value for Raising Pitch (OV = E * C * TMF)

Specifically, the value of E in the above formula is set higher than that of ordinary twisted yarn, which prevents the flame-retardant ultra-fine polyester fiber from forming long hair or breaking easily due to drawing force generated during brushing and sanding processes. To do this. When the E value is less than 40%, fibril and lint having a short fracture shape in which a fine fibrous structure is opened in the fiber axis direction during brushing and sanding processes are generated.

Specifically, the C value in the above formula is limited to a region significantly different from ordinary false twisted yarn. When the deformation and friction of the final twisted yarns are severely caused by the twisting force generated in the twisting direction and the drawing force generated in the axial direction during combustion, the flame retardant microfibers are used in the brushing and sanding process, which is the secondary friction process. This is because the probability of lintating is high. In general, the increase in the crimp at the time of flamming can be expected the quenching effect due to the multi-layered structure or the bulkyness, softness and elasticity due to the three-dimensional random crimp structure, but the split type microfine fiber like the present invention. It is difficult to expect bulky or quenching effect because the crimp level of the false twisted yarn is very low before splitting, but the crimp level becomes very low after splitting. On the other hand, as described above, if the crimp increases, the lintization probability increases, so that the crimp is preferably formed in the region defined in the above formula.

Specifically, when the TMF value is less than 0.20 in the above formula, the strength during the brushing and sanding process is weak and tends to be easily broken, resulting in poor wash fastness. On the contrary, if the TMF is more than 0.40, the pitch will be insufficient after raising.

Specifically, the OV value of the flame retardant ultrafine fibers subjected to brushing and sanding should be set to 15 to 40 so that the brushing property is good and the hair is long after the brushing, so that the flame retardancy is excellent. When the OV value is less than 15, the strength of individual single yarns decreases and the probability of developing an uneven hair state when raising is increased. On the other hand, when the OV value exceeds 40, the pitch feeling is not excellent. It is desirable to form an OV value in the region.

Specifically, it is important to set the value of each factor of the flammable condition within the range defined by the above formula. If the value of each factor is set outside the range defined by the above equation, even if the OV value is included in 15 to 40, poor brushability or flame retardancy is expressed.

Specifically, in order to satisfy the above properties, the flammable temperature should be set to 130 to 160 ° C., unlike 180 to 220 ° C., which is a general combustion temperature using a contact heater.

Specifically, the contact time passing through the heater is preferably 0.2 seconds or more to stabilize the crimp fastness.

Specifically, since the false draw ratio depends on the elongation of the spun yarn, the draw ratio is calculated and applied by setting the residual elongation (E) to 40 to 70% using the following equation.

In the above, K = 1.0940, POY denotes Partially Oriented Yarn, and DTY denotes Draw textured Yarn.

Specifically, it is preferable to set the twist angle to 90 to 95 degrees to satisfy the above C level, unlike 100 to 110 degrees, which are typically set as physical properties corresponding to the case of the nip belt twist flammable method. If the twist angle is set to 110 ° or more and the C level is adjusted as described above, as the deformation in the twisting direction increases during twisting, the yarn friction damage increases, and the crimp increases to increase the probability of getting out of the above level. .

Specifically, the TMF of the coarse fiber until the splitting process through the present invention becomes 0.2 to 0.35 DPF (Denier per filament) level ultrafine fiber, and when the sanding and brushed fabrics, knitted fabrics using such fibers have excellent pitch feeling It will be possible to develop microfiber fabrics.

Hereinafter, the present invention will be described in detail with reference to Examples. However, embodiments according to the present invention can be modified in many different forms, the scope of the present invention should not be construed as limited to the embodiments described below. Embodiments of the present invention are provided to more fully explain the present invention to those skilled in the art.

Example

Example  One

A 9-divided three-component spinning nozzle is used for the 8-divided position, which is a polyester resin obtained by copolymerizing 3-hydroxyphenolphosphinylpropanoic acid, and a phosphorus content of 7,000 ppm is used. ), The composite spinning was performed using an alkali-soluble resin so that the discharge ratio of 8 splits to 1 split would be 75:25. The spinning speed was discharged at 3,200 m / min, and was wound on the winder at a winding speed of 3,150 m / min without the stretching process. Spinning temperature was set so that it might be 280-285 degreeC for 8-division position polymer, and 270-285 degreeC for 1-division position polymer. Afterwards, combustion was performed using a nip twister belt and a contact 2.5 m heater. At this time, the combustion temperature was set to 150 ° C, the draw ratio was 1.55, and the twist angle was set to 95 °. After weaving the fabric using this yarn, the final fabric product is obtained by refining, weight loss, washing, raising and dyeing. At this time, by eluting the resin at the one-split position by alkali treatment, ultrafine fibers divided into eight can be obtained. The fabric was evaluated for flame retardancy, brushing fairness, and washing fastness. The final evaluation results and the strength, elongation, crimp, TMF and OV values of false twisted yarn are shown in Table 1.

Example  2

After spinning at the same spinning rate as in Example 1, a sample was prepared by setting the combustion temperature at the time of combustion to 150 ° C, the draw ratio of 1.63, and the twist angle to 95 °. The final evaluation results and the strength, elongation, crimp, TMF and OV values of false twisted yarn are shown in Table 1.

Example  3

After spinning the same spinning conditions as in Example 1 or the ratio of polyester copolymer resin to alkali-soluble copolymer resin copolymerized with a flame retardant compound at 60:40, the combustion temperature was 160 ° C., the draw ratio was 1.60, and the twist angle was Set to 100 °. After the process was carried out in the same manner as in Example 1 to prepare a sample. The final evaluation results and the elongation of the false twist, crimp, TMF and OV values are shown in Table 1.

Comparative example  One

After spinning under the same spinning conditions as in Example 1, the combustion temperature was set to 190 ° C, the draw ratio was 1.75, and the twist angle was set to 110 °. After the process was carried out in the same manner as in Example 1 to prepare a sample. The final evaluation results and the strength, elongation, crimp, TMF and OV values of false twisted yarn are shown in Table 1.

Comparative Example 2

After spinning under the same spinning conditions as in Example 1, the combustion temperature was set to 180 ° C, the draw ratio was 1.85, and the twist angle was set to 110 °. After the process was carried out in the same manner as in Example 1 to prepare a sample. The final evaluation results and the strength, elongation, crimp, TMF and OV values of false twisted yarn are shown in Table 1.

Comparative Example 3

The discharge amount was set to the same spinning and burning condition as in Example 1, but TMF was 0.1 after the burning and elution separation. After the process was carried out in the same manner as in Example 1 to prepare a sample. The final evaluation results and the strength, elongation, crimp, TMF and OV values of false twisted yarn are shown in Table 1.

Comparative example  4

As the island-in-the-sea composite spinning mode, an alkali-soluble resin was used as a sea component, and a polyester copolymer resin copolymerized with the same flame retardant compound as Example 1 was used as a sea component. At this time, the component ratio of sea component to island component was set to 70:30. The combustion temperature was set at 175 ° C, the draw ratio of 1.84 and the twist angle to 110 °. After the process was the same as in Example 1 to prepare a sample. The final evaluation results and the strength, elongation, crimp, TMF and OV values of false twisted yarn are shown in Table 1.

How to measure

-E (Residual Elongation of Textured Yarn): Using a USTER TENSION METER, measured with a dependent cut-off of 50 mm grip and 50 ± 3 cm / min tensile speed.

C (Crimp of Textured Yarn): Take a sample to 3,000 De 'by using a reel, weigh 600 g and measure the length to L0, and 30 in boiling water. After heat treatment for min, extract and leave for 4 hours. Thereafter, after weighing 600 g weight and leaving it for 1 minute, L2 was measured. After removing 600 g weight and leaving it for 5 minutes, L3 was measured. The false twist crimp is obtained by the following formula.

(L2-L3) / L0 * 100

TMF (Thickness of Mono Filament after Splitted): The final fineness is determined by the diameter and area of the fiber using an image analyzer as the fineness of the final individual filaments after splitting or elution.

-OV (Optimum Value for Raising Pitch): OV = E * C * TMF, the value within the area that satisfies each factor needs to be set, the final fabric raising fairness, It is used as a factor that affects the feeling of pitch and flame retardancy.

-Flame retardancy: evaluated by carrying out French NFP 92-503, 504, 505, the interior draper flame retardant test criteria.

-Wash fastness: The softness of the final fabric and the length and uniformity of the hair were measured by sensory evaluation by five experts.

division Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Radial 9 divisions 9 divisions 9 divisions 9 divisions 9 divisions 9 minutes 36 degrees Phosphorus content
(8 split or island component, ppm) 7000 7000 7000 7000 7000 7000 7000 Combustion temperature (℃) 150 150 160 190 180 150 175 Combustible draw ratio 1.55 1.63 1.60 1.75 1.85 1.63 1.84 Twist angle (°) 95 95 100 110 110 110 110 E (%) 44 55 50 30 30 47 35 C (%) 1.5 2.1 2.5 7.4 4.5 2.8 3.0 TMF 0.25 0.23 0.20 0.35 0.27 0.1 0.01 OV 16.5 26.5 33.7 77.7 36.4 22.3 1.05 Flammability Pass (M1) Pass (M1) Pass (M1) Fail (M2) Fail (M2) Pass (M1) Fail (M2) Fairness ◎ ○ ~ ◎ ◎ X X X XX Wash fastness 4.0 4.5 4.5 4.5 4.0 3.0 2.0

In the above table, in the case of Comparative Example 1 in which the E, C, and OV values are outside the range defined by the present invention, and in the Comparative Example 2 in which the E and C values are outside the range defined by the present invention, flame retardancy and brushing fairness are poor. , In case of Comparative Examples 3 and 4 where the TMF value is outside the range defined by the present invention, and the brushing fairness and washing fastness are poor, and in the case of the Comparative Example 4 where the E, TMF and OV values are outside the range defined by the present invention, flame retardancy and brushing It can be seen that the processability and washing fastness are poor.

In particular, it can be seen that the TMF value is related to the laundry fastness because the TMF value is poor in the laundry fastnesses of Comparative Examples 3 and 4 outside the range defined by the present invention.

In the case of Comparative Examples 1, 2 and 4 where the E value is outside the range defined by the present invention, the flame retardancy is lowered. The fiber is easily detached during combustion due to the damage of the fiber during brushing and sanding, and the surface tarification rate of polyphosphoric acid This is because the effect of blocking oxygen is lowered.

As a result, it can be seen that the flame retardancy, brushing processability and washing fastness are remarkably inferior when each factor of the flammable condition is outside the range defined in the present invention.

Claims (9)

Flame retardant polyester flame retardant fiber satisfying the following formula comprising a polyester copolymer resin copolymerized with a flame retardant compound and an alkali-soluble copolymer polyester resin
40% ≤ E ≤ 70% -------- (1)
1.0% ≤ C ≤ 3.0% ------ (2)
0.20 ≤ TMF ≤ 0.35 ---- (3)
15 ≤ OV ≤ 40 --------- (4)
Where E is Residual Elongation of Textured Yarn, C is Crimp of Textured Yarn, TMF is Thickness of Mono Filament after Splitted, and OV is optimal pitch expression Value (Optimum Value for Raising Pitch, OV = E * C * TMF).
[Claim 2] The flame-retardant poly-polymer according to claim 1, wherein the polyester copolymer resin copolymerized with the flame-retardant compound is prepared by adding 3-hydroxy phenyl propynyl propanoic acid which is a phosphorus compound during polyethylene terephthalate polycondensation reaction. Ester combustible fiber.
The flame retardant polyester flame retardant fiber according to claim 2, wherein the phosphorus content of the polyester copolymer resin copolymerized with the flame retardant compound is 1,000 to 20,000 ppm based on the weight of the polyester copolymer resin copolymerized with the flame retardant compound.
The method of claim 1, wherein the alkali-soluble copolyester resin is prepared from modified polymer or dimethylformamide and formic acid to which 3 to 5 mol% of dimethyl sulfonate and 10 to 20 mol% of ethylene glycol are added during the polymerization of polyethylene terephthalate. A flame retardant polyester flammable fiber characterized by using a thermoplastic polymer.
The flame retardant polyester flame retardant fiber as claimed in claim 1, wherein the composition ratio of the polyester copolymer resin copolymerized with the flame retardant compound to the alkali-soluble copolymer polyester resin is 50:50 to 80:20.
The flame retardant polyester flame retardant fiber as claimed in claim 1, wherein the intrinsic viscosity of the polyester copolymer resin copolymerized with the flame retardant compound is 0.60 to 0.75 dl / g.
The flame retardant polyester combustible fiber as claimed in claim 1, wherein the flame retardant polyester combustible fiber is composed of 9 to 16 pieces in one filament cross section and is divided into 8 to 15 pieces by friction and dissolution.
Preparing a spinning polymer resin including a polyester copolymer resin copolymerized with a flame retardant compound and an alkali-soluble copolymer polyester resin; Composite spinning the spinning polymer resin using a two-component spinning nozzle; And combustible stage,
The flame retardant step is a method of producing a flame retardant polyester fiber, characterized in that the combustion temperature is 130 to 170 ℃ and twist angle 90 to 100 °.
10. The method of claim 8, wherein the spinning step is an eluted split composite spinning.