KR101139848B1 - Multi filament with absorbtion, quick dry characteristic and flame retardant property - Google Patents

Abstract

The present invention is a flame-retardant polyester fiber comprising a polyester resin modified with any one or more compounds of the following Chemical Formulas 1 to 3, and has a cross-shaped cross-sectional cross-section, wherein the cross-sectional shape of the cross-sectional cross-section is two cross-sections. As a cross having a symmetry axis, the ratio of the length B of the major axis to the length A of the minor axis is 1.1 to 3.0, the ratio of the length A of the minor axis to the thickness C of the major axis is 1.4 to 5.0 and the thickness of the minor axis ( It provides a flame-retardant polyester fiber characterized in that the ratio of the length (B) of the long axis portion to D) is 1.5 to 7.0, the ratio of the thickness (D) of the short axis portion to the thickness (C) of the long axis portion is 0.25 to 4.0.

<Formula 1>

<Formula 2>

<Formula 3>

In the above formulas, R ₁ , R ₂ , R ₃ , R ₄ and R ₅ are each independently hydrogen or an alkyl group having 1 to 5 carbon atoms.

Flame retardant polyester fiber according to the present invention is excellent in sweat-absorbent quick-drying and flame retardancy, and due to this property, when used in contact with the human body, such as clothing, bedding, giving comfort and soft texture, but more safe flame retardant performance from fire To express the multifunctional fiber material characteristics.

Flame retardant, quick drying sweat, polyester, fine

Description

Flame retardant polyester fiber {Multi filament with absorbtion, quick dry characteristic and flame retardant property}

The present invention relates to a flame retardant polyester fiber, and more particularly to a flame retardant polyester fiber excellent in sweat absorption quick-drying and flame retardancy.

Polyester flame retardant fibers are mainly used for interior applications such as curtains, sofas, wallpaper, etc. The properties and varieties of flame retardant fibers have been developed for these applications. For example, in the case of sofa sheets that require friction resistance or blackout curtains that require light shielding, monofilament single yarn fineness of 1 to 3 denier levels is mainly used, and the fabric is made of high or thick fabric. On the other hand, these conventional flame retardant fibers are not suitable for use in clothing because of their high degree of texture and roughness and lack of draping, resulting in a stiff form, which is unsuitable. There have been many problems to use for dragons and acupuncture.

In recent years, the application of flame retardant fibers to clothing and bedding has increased rapidly, with increasing awareness of safety from fire hazards, especially in developed countries.

In the United States, for example, the Consumer Product Safety Commission (CPSC) mandates the use of products that exhibit permanent flame retardancy in infant pajamas imported to the United States.

16CFR 1615 is a specialized law that provides flame retardancy for pajamas for infants and children aged 0 to 6 years and 16CFR 1616 for children ages 7 to 14.

In particular, in the case of pajamas or bedding sheets by direct contact with the skin when sweat occurs quickly absorbed and discharged (fast drying) to enable a comfortable sleep. However, in order to impart the sweat-absorbing quick-drying property, it is suitable to develop and apply a product having mono monodenier or less with low single yarn fineness because the contact point with the skin may be small and irritate when the fiber of the heteromorphic cross section is used. As such, there is a growing need for developing a new flame retardant fiber product with improved sensitivity and function.

In particular, the present invention is to develop a technique for producing a novel flame retardant polyester differentiating fiber that provides more human-friendly functionality in the above use in direct contact with the skin and at the same time satisfy the flame retardant performance level required by each country. .

Korean Patent No. 0449383, a method for producing a polyester flame retardant fiber copolymerized by adding an excessive amount of a phosphorus-based flame retardant has shown a technical result with good flame retardancy and fairness. However, the short fiber denier has a problem of showing a stiff form when applied to clothing at the level of 3 denier, and the amount of phosphorus copolymer added is not enough as 1 to 4% by weight to secure the flame retardancy required for recent US baby pajamas. There is a need for new and advanced polymerisation techniques that copolymerize higher levels of phosphorus.

Looking at new technologies and patents for flame retardant fiber products, most of them are focused on interior applications such as curtains, sofas, and roll screens. For example, Korean Patent No. 0615781 describes the development of polyester products with excellent light-shielding properties and flame retardancy. For this purpose, the film is claimed for blackout paper and curtains, and in Patent No. 0737577, phosphorus-based flame retardants are used for polycondensation reactions. It contains a 0.5 to 2.5% by weight of titanium dioxide in the added poly alkylene terephthalate to manufacture a flame retardant fiber with improved UV light shielding can be regarded as a related technology for interior use.

Patents related to flame retardant fibers that can be applied to clothing, as described in the registered patent No. 0207281, the polyester resin composition used as a fiber, film or plastic products, poly having a characteristic of improving the flame retardancy and antibacterial deodorization at the same time It was an object to provide an ester resin composition. However, it does not have the ability to absorb and release sweat and there is no technical description of the SOFTNESS texture implementation required for direct contact with the skin. At present, this patent has not been commercialized and has been extinguished.

Korean Patent Laid-Open Publication No. 2002-0071522 describes a technique for manufacturing a quick-absorbing quick-drying cross-section yarn, since single yarn fineness is 3 deniers, which does not exhibit soft texture suitable for direct contact with the skin and has no flame retardant performance. In addition, there is a burden of imparting flame retardant performance with a coating method such as posterior salt. However, due to the discoloration of the product and the stiffness of the product, the back salt coating method has been particularly difficult to apply to clothing. In addition, in the United States, non-flame retardant products are used in children's pajamas with a flame retardant copolymer having a permanent flame retardant performance.

 In order to solve this problem, the present inventors have developed a technique for producing a novel polyester fiber having excellent fine fine flame retardancy of 0.5 to 1 denier level having a single layer fineness having a sweat absorption quick-drying by a release cross section and smooth texture expression. .

It is an object of the present invention to provide a flame retardant multifunctional polyester yarn expressing a soft skin contact by a three-fiber shape of single yarn fineness of 0.5 to 1 denier while having a quick-drying function of absorbing sweat by capillary phenomenon of a heteromorphic cross section while expressing permanent and excellent flame retardant performance. By providing a different material for safer and more human-friendly bedding and clothing applications.

In addition, the melt viscosity of the flame-retardant polyester copolymer is optimized so as to achieve uniform and good physical properties without any process degradation, such as trimming, when melt spinning the yarn having such characteristics. It is to provide a fiber production technology expressing emotion.

In order to achieve the above object, the present invention is a flame-retardant polyester fiber which is composed of a polyester resin modified with any one or more compounds of the following formulas 1 to 3, and has a cross-shaped release cross-sectional shape, the release The cross section has a cross-section having two symmetry axes, wherein the ratio of the length B of the major axis to the length A of the minor axis is 1.1 to 3.0, and the ratio of the length A of the minor axis to the thickness C of the major axis is 1.4. To 5.0, the ratio of the length B of the major axis to the thickness D of the minor axis is 1.5 to 7.0, and the ratio of the thickness D of the minor axis to the thickness C of the major axis is 0.25 to 4.0. To provide ester fibers.

<Formula 1>

<Formula 2>

<Formula 3>

In the above formulas, R ₁ , R ₂ , R ₃ , R ₄ and R ₅ are each independently hydrogen or an alkyl group having 1 to 5 carbon atoms.

Preferably, the phosphorus content in the modified polyester resin is 5,000-20,000 ppm on a phosphorus atom basis.

Preferably, the intrinsic viscosity of the modified polyester resin is 0.65 to 0.75 dl / g.

Preferably, the polyester resin is at least one selected from the group consisting of polyethylene terephthalate, polybutylene terephthalate and polytrimethylene terephthalate.

Preferably, the flame-retardant polyester fiber of the present invention has a single yarn fineness of 0.5 to 1.0, and 60 or more single yarns having a total fineness of 50 to 300 deniers, preferably 60 to 600 pieces.

Flame retardant polyester fiber according to the present invention is excellent in sweat absorption quick-drying and flame retardancy. By developing these fine fiber fine fibers, it satisfies the flame retardant performance of clothes and beddings which are increasingly demanded in the world, and improves the stiffness of existing flame retardant products when the skin is touched by the soft texture of fine fibers. Because of the excellent sweat-absorbing quick-drying performance to give a comfort that was not present in the existing flame retardant products, it is possible to provide a differentiated knitted fabric that is safe against fire, especially in clothing, bedding.

Hereinafter, the present invention will be described in more detail.

The present invention is a flame-retardant polyester fiber comprising a polyester resin modified with any one or more compounds of the following Chemical Formulas 1 to 3, and has a cross-shaped cross-sectional cross-section, wherein the cross-sectional shape of the cross-sectional cross-section is two cross-sections. As a cross having a symmetry axis, the ratio of the length B of the major axis to the length A of the minor axis is 1.1 to 3.0, the ratio of the length A of the minor axis to the thickness C of the major axis is 1.4 to 5.0 and the thickness of the minor axis ( It provides a flame-retardant polyester fiber characterized in that the ratio of the length (B) of the long axis portion to D) is 1.5 to 7.0, the ratio of the thickness (D) of the short axis portion to the thickness (C) of the long axis portion is 0.25 to 4.0.

In the above formulas, R ₁ , R ₂ , R ₃ , R ₄ and R ₅ are each independently hydrogen or an alkyl group having 1 to 5 carbon atoms.

The present invention can be prepared by melt spinning a flame retardant polyester resin expressing a permanent flame retardant performance obtained by copolymerizing with any one or more flame retardants of the compounds of formulas (1) to (3) in the polymer backbone molecule through a three-sum heteromorphic cross-section spinneret. As a result, it is possible to provide a comfortable and soft sesame composite polyester filament having a quick drying function. That is, this invention can provide the multifilament excellent in the flame retardancy which has the sweat absorption quick-drying function by the capillary phenomenon of a heteromorphic cross section, and the outstanding softness expressed by fineness.

The flame retardant polyester fiber according to the present invention is to produce a flame retardant polymer using a more environmentally friendly non-halogen-based, phosphorus-based flame retardant in order not to have a problem when using for the purpose of using a direct contact with the skin, while requiring excellent flame retardancy, The compounds of Chemical Formulas 1 to 3 are used to impart flame retardancy, thereby modifying the polyester resin by copolymerizing the polyester resin with an esterification reaction or a transesterification reaction.

Preferably, the polyester resin may be used at least one selected from the group consisting of polyethylene terephthalate, polybutylene terephthalate and polytrimethylene terephthalate.

When the flame retardant polyester fiber is prepared using the compound of Chemical Formulas 1 to 3, the flame retardant content is 5,000 to 20,000 ppm based on phosphorus atom to express excellent flame retardancy. If it is less than 5,000 ppm, it does not pass the 6CFR 1615, the flame retardant test standard for US infant pajamas, and the test results of NFPA 701, the flame retardancy test standard of France, show poor flame retardancy of M2 level. On the other hand, due to excessive copolymerization at 20,000 ppm or more, there is a problem that process degradation may occur due to a decrease in basic physical properties of the fiber and a sudden trimming during the spinning process.

In addition, the intrinsic viscosity of the flame-retardant polyester resin is preferably 0.65 ~ 0.75dl / g so as not to decrease the physical properties and trimming during spinning the three-sum heteromorphic cross section. In general, in the present invention, since the draft is high during the melt spinning of the cross-shaped cross section having two axes of symmetry compared to the circular single yarn shape, the trimming is likely to occur, and the uniformity of the degree of release is closely related to the dyeing uniformity. In the case of the copolymerized resin having a high phosphorus content, more homogeneous and high viscosity properties are required.

In the flame-retardant polyester fiber of the present invention, when the intrinsic viscosity of the flame-retardant polyester fiber is lower than 0.65 dl / g, the heat and friction received during the staying and passing through the extruder and spin block during the spinning process Due to the IV drop, the strength of the single yarn discharged from the spinneret is very weak, which may cause a problem of breaking during spinning. On the contrary, when the intrinsic viscosity is higher than 0.75, the melt flowability of the copolymer due to the high viscosity is drastically lowered, so that ejection from the spinneret does not occur smoothly, and the drawing is poor, which may result in trimming. Therefore, it is preferable to set the intrinsic viscosity within 0.65 ~ 0.75 dl / g, more preferably it is good to design the physical properties to 0.68 ~ 0.72 dl / g.

In the present invention, the flame-retardant polyester fiber is also cross-shaped having two cross-sectional symmetry axis to express the sweat-absorbing quick-drying function, the ratio of the length (B) of the long axis to the length (A) of the short axis is 1.1 to 3.0, the thickness of the long axis ( The ratio of the length (A) of the short axis to the C) is 1.4 to 5.0, and the thickness (D) of the length (B) of the major axis to the thickness (D) of the major axis is 1.5 to 7.0, the thickness (D) of the minor axis to the thickness (C) of the major axis. Prepare the ratio of 0.25 to 4.0.

The ratio (B / A) of the length B of the major axis to the length A of the minor axis should be 1.1 to 3.0, more preferably 1.2 to 2.0, so that the degree of release becomes smaller when the A / B ratio is less than 1.1. Or four excessively protruding cross-shaped blades, resulting in poor process and physical properties. If the blade is larger than 3.0, the cross-shaped blades of the short axis are relatively too small to produce a desirable cross-section, and the deformation is rather low due to severe deformation. Loss can be counterproductive.

In the present invention, by spinning and flammable flame retardant polyester fiber that satisfies the ratio of the above length, high mold release property, good manufacturing processability and physical properties, excellent moisture absorption and quick drying performance, good uniformity can be obtained. there was.

Korean Patent No. 0829475 describes a manufacturing technique for expressing the sweat-absorbent quick-drying of the cross-sectional shape of the eight leaves. However, the hexagonal or octagonal six-lobed or eight-leaf cross-section fibers with a larger number of wings than the cross-shaped cross-sections used in the present invention are not only difficult to manufacture a spinneret, but also to produce a target cross section. The conditions are very demanding, and even if a satisfactory cross section is made, the variation of properties and fairness are very poor. In particular, the polyester polymer copolymerized with a large amount of flame retardant of the present invention is more difficult to establish physical properties and processability, so the cross-shaped four-leaf cross section is suitable for showing more stable and uniform mold release degree.

In the present invention, rather than the interior products (curtains, sofas, wallpaper, roll screens, etc.) that are mainly used for the conventional flame retardant fibers are intended to manufacture a multi-functional flame retardant fiber having excellent flame retardancy and sweat-absorbent quick-drying for clothing and bedding that is intended to directly contact the skin Sensibility and sag that you feel is very important. Accordingly, in order to produce a softer, lower Young's modulus fiber, the single yarn fineness is preferably 0.5 to 1.0 denier, the number of single yarns is 60 or more, and more preferably 60 to 600. When single yarn fineness is fiberized to more than 1 denier, it may be unpleasant due to its stiff shape and rough texture when worn in the form of fabric or knitted fabric or in contact with skin. In addition, when manufacturing less than 1 denier may have a problem in that the degree of releasing is reduced the quick drying function.

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

Example

Example  One

A 3-hydroxy phenyl phosphinyl propane acid flame retardant was added during the polycondensation reaction after esterification of terephthalic acid (TPA) and ethylene glycol (EG) to give a flame-retardant polyester polymer having an intrinsic viscosity of 0.65 dl / g and phosphorus content of 6500 ppm. Got it. Subsequently, POY (Polyester Filament Partially Oriented Yarn) of 120 denier 72 single-shot yarns was produced at room temperature 285 ° C. and GR1 speed 2,600 m / min using a four-leaf cross-shaped cross-sectional nozzle. Through the process, single-fiber fine 1-denier fine-sum fire-retardant sweat-absorbing quick-drying cross-section fibers were obtained.

Table 1 shows the flame retardancy, sweat absorption quick drying and processability of the fabric.

Example  2

A flame retardant was carried out in the same manner as in Example 1 except for using the compound represented by Formula 1 (wherein R ₃ is hydrogen).

<Formula 2>

Table 1 shows the flame retardancy, sweat absorption quick drying and processability of the fabric.

Example  3

Except for using a compound represented by the following formula 3 (However, R ₄ and R ₅ CH ₂ CH ₃ ) as a flame retardant was carried out in the same manner as in Example 1.

<Formula 3>

Table 1 shows the flame retardancy, sweat absorption quick drying and processability of the fabric.

Example  4

The polymerization was carried out with the same flame retardant as in Example 1 so as to have physical properties of 8000 ppm phosphorus content and intrinsic viscosity 0.7 dl / g during polycondensation. After the spinning and burning process was carried out in the same manner as in Example 1. In Example 4, the intrinsic viscosity of the polymer was raised to 0.7 dl / g in consideration of the spinning process by higher copolymerization of the flame retardant.

Example  5

The flame retardant polymer prepared in Example 1 was prepared through a cross spinneret such that the final single yarn fineness was 0.5 denier. POY spun at this time was 120 denier and 144 single yarns, and the room temperature was 290 ° C., which was 5 higher than that of Example 1 to compensate for the melt flow deterioration due to the fineness.

Example  6

A flame retardant polyester polymer was prepared using 3-hydroxy methyl phosphinyl propane acid. The phosphorus content of the polymer was 7000 ppm based on the phosphorus atom and the intrinsic viscosity was 0.7 dl / g. The intrinsic viscosity is increased in consideration of the spinning process for the increased phosphorus content. Spinning was such that the single fiber fineness of the final fiber was 0.5 denier as in Example 5 and the processability and physical properties are shown in Table 1.

Comparative example  One

By using the flame-retardant polyester polymer prepared in Example 6, the fiber of the single yarn fineness 3 denier level that is most applied to the interior was prepared using a general circular spinneret rather than a cross-shaped cross section. Table 2 shows the results of quick drying and soft texture evaluation according to the difference in cross section and fineness.

Comparative example  2

A flame retardant polyester copolymer having a phosphorus content of 3,000 ppm and an intrinsic viscosity of 0.55 dl / g was prepared using the 3-hydroxy phenyl phosphinyl propane acid flame retardant used in Example 1. Afterwards, cross-shaped spinnerets in the form of cross-sections were used to produce fine-fiber yarns with a final denier fineness of 1 denier, and to evaluate other major physical properties including flame retardancy.

Comparative example  3

In the same manner as in Comparative Example 2, the polymerization conditions were set such that the phosphorus content was 4,000 ppm and the intrinsic viscosity was 0.55 dl / g when the flame retardant polyester polymer was prepared. Thereafter, the yarns of the final single yarn fineness of 2 denier levels were prepared by using the 8-lobed heteromorphic nozzle instead of the 4-lobed used in the spinning process. After that, the cross-sectional four-leaf heteromorphic fiber was compared with processability and texture.

Table 1 and Table 2 show the results of evaluation of physical properties, functionality and flame retardancy according to the manufacturing conditions of the Examples and Comparative Examples.

1) intrinsic viscosity (extreme viscosity)

Ortho-Chloro phenol (ortho-Chloro phenol) as a solvent for 30 minutes at a concentration of 110 ℃, 2.0g / 25ml, and then incubated for 30 minutes at 25 ℃ through an automatic viscosity measuring device connected to a Canon viscosity meter Analyzed.

2) strength, elongation of fiber

It was measured according to KS K 0412 using Instron's UTM.

3) Radiation Fairness

 Full package rate during 72 hours spinning was measured.

4) Flame retardant

The French flame retardant test criteria NFP 92-503, 504 and 505, the world's most widely used flame retardant certification methods, were evaluated.

5) Absorption distance (absorbency)

KS K 0815.5.27 method was measured by the Biking method (Wicking Test). Samples were prepared by using a flame retardant polyester sesame release cross section yarn of the present invention in a 32 gauge interlock double-sided circular knitting machine, and then sampling them at a width of 2.5 cm and a length of 20 cm. One part of the fabric sample was immersed in water for 2.5 cm and left for 10 minutes, and the average value was obtained by measuring the height of moisture absorbed in the fabric three times.

6) Drying time (fast drying)

Samples were prepared by using a flame retardant polyester sesame release cross section yarn of the present invention in a 32 gauge interlock double-sided circular knitting machine, and then sampling them in a width of 20 cm x 20 cm. After dropping 0.05 ml of water to each fabric sample, the time required for complete drying was measured and set as the drying speed. The temperature-humidity air-conditioning condition at this time was made into 20 degreeC 65% RH.

7) SOFTNESS

Five experts performed a relatively sensory evaluation of touch

As shown in Table 1, the flame-retardant copolymer having a phosphorus content of 5000 ppm or more and an intrinsic viscosity of 0.6 dl / g or more is radiated and combusted in the form of a cross-shaped heteromorphic cross section with a single yarn fineness of 0.5 to 1 denier, which is not present in existing flame retardant products. Excellent moisture absorption quick drying, flame retardancy and smooth texture was obtained.

Claims (5)

A flame retardant polyester fiber comprising a polyester resin modified with any one or more compounds of the following Chemical Formulas 1 to 3, and having a cross-shaped cross-sectional shape, Phosphorus content in the modified polyester resin is 5,000 to 20,000 ppm phosphorus atom, The shape of the cross section is a cross having two axes of symmetry, wherein the ratio of the length B of the major axis to the length A of the minor axis is 1.1 to 3.0 and the length A of the minor axis to the thickness C of the major axis. The ratio of ratio 1.4-5.0 of the length B of the major axis to the thickness D of the minor axis is 1.5-7.0, and the ratio of the thickness D of the minor axis to the thickness C of the major axis is 0.25-4.0 Polyester fiber: <Formula 1>

<Formula 2>

<Formula 3>

In the above formulas, R ₁ , R ₂ , R ₃ , R ₄ and R ₅ are each independently hydrogen or an alkyl group having 1 to 5 carbon atoms. delete The flame retardant polyester fiber according to claim 1, wherein the intrinsic viscosity of the modified polyester resin is 0.65 to 0.75 dl / g. The flame retardant polyester fiber according to claim 1, wherein the polyester resin is at least one selected from the group consisting of polyethylene terephthalate, polybutylene terephthalate and polytrimethylene terephthalate. The flame retardant polyester fiber of claim 1, wherein the single yarn fineness is 0.5 to 1.0 and the total fineness is 50 to 300 denier.