KR100615779B1 - Method for Preparing Flame Retardant Polyester Gulf - Google Patents

Abstract

The present invention relates to a method for producing a flame retardant polyester powdered yarn, and more particularly, to obtain a polyester polymer comprising a flame retardant including phosphorus, a manganese salt, and a phosphorus compound; And spinning a woolen yarn from the polymer. The method of the present invention is excellent in spinning and spraying processability, and thus, the finely divided yarn manufactured through this has excellent flame retardancy and flame retardancy, and Has UV stability.

Polyester Fiber, Monofilament, Partially Threaded Yarn, Wool, Flame Retardant, Flame Retardant Durability, UV Stability

Description

Method for Preparing Flame Retardant Polyester Fibers {Method for Preparing Flame Retardant Polyester Gulf}

The present invention relates to a method for producing a flame retardant polyester powdered yarn, and more particularly, to obtain a polyester polymer comprising a flame retardant including phosphorus, a manganese salt, and a phosphorus compound; And it relates to a method for producing a flame retardant polyester fiber spun yarn comprising the step of spinning a woolen yarn from the polymer, the use of this to provide an effect having a superior flame retardancy, flame retardant durability, and UV stability while the prepared spun yarn is maintained while spraying processability Can be.

Recently, in the polyester fiber industry, interest in branched yarns has been increased in terms of development of productivity and improved productivity of differentiated materials having high added value, and researches for providing various functions to branched yarns for this purpose have been actively conducted.

Since polyester monofilaments, which generally have a fineness of about 20 to 40 d, are thin, great care is required to achieve uniform cooling and solidification during spinning, a method designed to solve this process problem. This branching yarn is used. In other words, in the spinning fiber manufacturing method, a yarn having 10 to 20 strands of fiber is manufactured in a spinning process, and then a single yarn fineness of 20 to 40 d is separated through a splitting process, respectively. to be. Such divided yarns not only improve productivity, but also have the advantage of uniformly imparting a function required for monofilament.

On the other hand, as a method of imparting flame retardancy to a conventional polyester yarn, a method of mixing and spinning by adding a non-reactive flame retardant in the pre-spinning step after polymerization, a surface treatment method to coat or impregnate the fiber surface in the post-spinning process, organic halogen or There is known a method of copolymerizing a reactive flame retardant such as an organophosphorus compound. Among these methods, the method of copolymerizing by adding a flame retardant in the manufacture of a polymer is the most advantageous in terms of excellent flame retardancy and flame retardancy durability and low physical property deterioration.

In the method of imparting flame retardancy by copolymerization, when halogen-containing flame retardant is used, halogen compounds are easily thermally decomposed at high temperature, and thus a large amount of flame retardant must be added to obtain effective flame retardancy. Will be produced. In addition, when the organophosphorus compound is used as a flame retardant, the organophosphorus compound itself does not have good thermal stability, and there is a problem that the physical properties of the polymer tend to be lowered due to its low reactivity with polyester and do not exhibit sufficient flame retardant effects. In order to solve this problem, two types of reactive phosphorus-based flame retardants are used in Japanese Patent Application Laid-Open No. 52-47891 and U.S. Patent No. 3,941,752, which are expensive and are difficult to apply commercially. Has

An object of the present invention is to solve the above problems, to prepare a flame-retardant polyester copolymer using a phosphorus-based flame retardant, from which a polyester having excellent flame retardancy, flame retardant durability, UV stability showing excellent spinning workability and spray workability It is to provide a method for producing a branched yarn.

That is, one aspect of the present invention for achieving the above object is a flame retardant containing phosphorus 500 ~ 30,000ppm based on the phosphorus atom in the polyester, manganese salt 0.1 ~ 500ppm based on the manganese atoms in the polyester, and phosphorus compounds Obtaining a polyester polymer containing in an amount of 0.1 to 500ppm based on the phosphorus atom in the polyester; And it relates to a method for producing a polyester powdered yarn comprising spinning a woolen yarn from the polymer.

Another aspect of the present invention for achieving the above object relates to a flame retardant polyester fiber thread produced using the method.

Another aspect of the present invention for achieving the above object relates to a monofilament produced by the spraying process from the flame retardant polyester fiber thread.

Another aspect of the present invention for achieving the above object relates to a fabric or fiber comprising the monofilament yarn.

Hereinafter, the present invention will be described in detail.

The first step for producing the flame retardant polyester divided yarn in accordance with the present invention is to obtain a polyester polymer to be used for spinning the divided yarn.

The polyester polymer is a flame-retardant polyester copolymer prepared by a terephthalic acid method (TPA) method using a phosphorus-based flame retardant, has excellent UV (ultra violet) stability, and has a diethylene glycol (DEG) content in the polymer. Characterized in that it is reduced.

The dicarboxylic acid or ester forming derivative thereof used to prepare the flame retardant polyester polymer may be terephthalic acid, isophthalic acid, biphenyl dicarboxylic acid, 1,4-naphthalene dicarboxylic acid, 1,5-naphthalene dicarboxylic acid Aromatic dicarboxylic acids such as acid and ester forming derivatives thereof; Alicyclic dicarboxylic acids such as 1,4-cyclohexane dicarboxylic acid; Or an alkanedicarboxylic acid having 2 to 6 carbon atoms.

Among the above monomers, in order not to significantly reduce the physical properties of the polyester while maintaining economic efficiency and flame retardancy, it is preferable that the molar ratio of terephthalic acid to the total dicarboxylic acid is 70% or more. When the molar ratio of the terephthalic acid is less than 70 mol%, the melting point or the glass transition temperature may be lowered, thereby causing moldability problems, and the manufacturing cost may be too high when some expensive copolymer monomers are used instead of the terephthalic acid.

In addition, the glycol component used to prepare the polyester polymer is ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentane Alkanediols, such as diol and 1,6-hexanediol; Alicyclic diols such as 1,4-cyclohexanediol and 1,4-cyclohexane dimethanol; Aromatic diols such as bisphenol A and bisphenol S; Ethylene oxide of this aromatic diol; Or propylene oxide adducts.

In order to express an appropriate level of polymer properties in the glycol component, it is preferable that the molar ratio of ethylene glycol in the total polymer glycol component is 70% or more. This is because molding problems may occur when used below 70%.

The flame retardant represented by the following formula (1) during the polymerization of the polyester by the TPA method can be added at any time during the direct esterification (DE) reaction or poly condensation (PC)) reaction. However, in the case of batch polymerization by the TPA method, it is added to the DE reaction tank by diethylene glycol (DEG) by dehydration of ethylene glycol (EG). Since there is a problem of promoting the production of a, for this purpose by employing a full batch system (Full batch system) or by solving the method of adding a flame retardant containing phosphorus, preferably a flame retardant represented by the formula (1) to the PC reactor The polymer may be prepared.

(Wherein R ₁ and R ₂ are each independently a hydrogen atom or a radical having a ω-hydroxy group having 2 to 4 carbon atoms, and P is an integer of 1 to 5).

On the other hand, the content of the polymer used as a flame retardant in the present invention is preferably 500 to 30,000 ppm, more preferably 1,000 to 20,000 ppm based on the phosphorus atom. If the content is less than 500ppm it is difficult to expect the desired level of flame retardant effect, if the content is more than 30,000ppm not only the problem of increasing the degree of polymerization of the polyester produced, but also the crystallinity is reduced to produce a fiber or film Difficult problems arise, which is undesirable.

Manganese phosphate used as a UV stabilizer increases the pack pressure during spinning because agglomeration occurs when a direct injection of the manganese forms a lot of foreign matter in the polymer. In addition, since the manganese compound is not dissolved in ethylene glycol which is a raw material used in the polymerization, there is a problem that it cannot be directly added. Therefore, the above problem is solved by selecting a method for producing a manganese compound in a polymerization reaction.

Therefore, in the method of the present invention, a manganese salt and a phosphorus compound, preferably a phosphorus material represented by the following Chemical Formula 2 are separately added.

(Wherein, R ₃ is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.)

The content of the manganese salt is preferably 0.1 to 500 ppm, more preferably 0.2 to 200 ppm in terms of manganese atoms in the polymer. If the content is less than 0.1ppm it may be difficult to obtain the desired UV stability, if it exceeds 500ppm because the dispersibility is lowered, resulting in problems such as a pack pressure increase during spinning.

The content of the phosphorus compound represented by Formula 2 is preferably in the range of 0.1 to 500 ppm based on the phosphorus atom in the polymer. More preferably, the range of 0.2-200 ppm is good.

The content of the phosphorus compound is not a problem even if a large amount is added, as long as the reaction with manganese salt is not a problem, but if it exceeds 500ppm, it may be difficult to prepare the desired flame retardant polyester by lowering the activity of the catalyst.

When a polyester polymer is obtained including the phosphorus-based flame retardant, the manganese salt, and the phosphorus-based compound as described above, a subsequent process of injecting it into the spinning and spraying process follows.

In comparison with the conventional spinning, much attention is paid to the maintenance of the cooling uniformity and the physical property uniformity between the filaments when spinning the divided yarn. Furthermore, when spinning a polyester copolymer containing a phosphorus compound, factors such as a decrease in melt viscosity due to thermal stability and an increase in non-filament non-uniformity need to be considered. This is because these factors cause tension unevenness in the spraying operation, which is likely to lead to trimming. In consideration of the above problems and the like, the spinning temperature, cold wind speed, and spinning speed are adjusted.

Specifically, since the polyester polymer used in the production method of the present invention has lower thermal stability than the normal spinning process and the viscosity is lowered, it is preferable to reduce the spinning temperature by about 5 to 10 ° C. compared with the general spinning thread spinning. That is, it is more preferable that the temperature range is 280-290 degreeC. This is because when the spinning temperature is high, there is a problem in spraying and single yarn fineness, and when the spinning temperature is too low, deterioration of spinning workability may occur.

It is also desirable to correct the lowered viscosity value by reducing the spinning speed by 100 to 1,000 m / min. That is, it is effective to adjust in the range of 3,000 ~ 4,000 m / min, because the lower the spinning speed, the lower the workability occurs, the higher the spinning speed can be difficult to spray.

In the method of the present invention, the spinning method is not particularly limited, and as long as it maintains excellent spinning workability, spin drawing, stretching after production of undrawn yarn (POY-DT), and the like are all possible.

The injection process of the divided thread by the method of the present invention is carried out using a conventional injector. After spraying, the fineness of the final monofilament is preferably maintained at 20-40den, because if the fineness is less than 20den, it is difficult to work, and if it is more than 40den, cooling becomes difficult, which may cause problems.

In addition, in the divided yarn of the present invention, the number of monofilaments is preferably about 6-20 in terms of both spinnability and sprayability, and the fineness of the divided yarn is 120-800den.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the following Examples are for illustrative purposes only and should not be construed as limiting the scope of the present invention.

In the following Examples, the physical properties of each were measured by the following method.

1) Evaluation of radio workability (no-running rate / day)

   No mortality rate exceeded 95% / day ⇒ Radio workability ○

   No trimming rate 70 ~ 95% / day ⇒ Radio workability △

   No mortality rate less than 70% / day ⇒ Radiation workability ×

   Cannot work ⇒ No radiation × ×

2) The injection workability evaluation indicated the number of yarns (%) that the injection was completed by no yarn during complete spraying. For example, when spraying 100 simulations, when 90 were sprayed by perfection, the spraying workability was expressed as 90%.

3) UV stability was evaluated as the ultimate viscosity retention rate by measuring the intrinsic viscosity after the polymer was molded into a film by hot press and then irradiated with UV lamp for 20 hours.

4) The flame retardance was tested by the KS M 3032 standard of Korea to evaluate the LOI (Limited Oxygen Index).

Example 1

After transferring the prepolymer reacted using only terephthalic acid (TPA) and ethylene glycol (EG) to the second DE reactor, 9,10-dihydro dissolved in 400 ppm by weight of EG, 50 ppm by weight of antimony trioxide, was used as a catalyst. -9-oxa-10- (2,3-dicarboxylpropyl) -10-phosphapefenylene-10-oxide (9,10-dihydro-9-oxa-10- (2,3-dicarboxypropyl) -10- phosphaphenathrene -10-oxide, in Formula 1, wherein p is 1 and both R ₁ and R ₂ are hydrogen), reacted by adding phosphate standard content of 6,000 ppm to the polymer, and then transferring to a polycondensation reactor. 100 ppm of acetate was used as a manganese atom relative to the polymer, 15 ppm to phosphorus atoms relative to the polymer, and 0.4 wt% of titanium dioxide was added as a quencher to the polymer to give a polymer having an ultimate viscosity of 0.642 dl / g. The polymer thus obtained was dried and spun at a spinning temperature of 285 ° C. with a first roller roller having a surface temperature of 90 ° C. and a rotating speed of 2,000 m / min, and a second roller having a surface temperature of 125 ° C. and a rotating speed of 4,000 m / min. After spin-draw and sacrifice, the spraying process was performed. The results are shown in Table 1.

Example 2

 The same procedure as in Example 1 was carried out except that 9,10-dihydro-9-oxa-10- (2,3-dicarboxypropyl) -10-phosphapefenylene-10-oxide was used in an amount of 3000 ppm. The yarn was obtained and the results are shown in Table 1.

Comparative Example 1

Except that the flame retardant, manganese acetate, and phosphoric acid was not added was carried out in the same manner as in Example 1, the results are shown in Table 1.

Comparative Example 2

A flame retardant was added in the same manner as in Example 1 except that the phosphorus reference content was 70,000 ppm, and the results are shown in Table 1.

Comparative Example 3

Manganese acetate was carried out in the same manner as in Example 2 except that polycondensation was performed by adding 0.05 ppm of manganese atoms, and the results are shown in Table 1.

Comparative Example 4

Manganese acetate was carried out in the same manner as in Example 2 except that the polycondensation by adding 2,000ppm on the basis of manganese atoms, the results are shown in Table 1.

※ Fineness, uniformity and flame retardancy are expressed as average / standard deviation of the property value of monofilament.

The manufacturing method of the present invention maintains excellent spinning workability and spraying workability, and the polyester powder spun yarn prepared using the same has permanent flame retardancy, excellent flame retardancy durability, and UV stability.

Claims (7)

500 to 30,000 ppm of phosphorus-containing flame retardant based on phosphorus in polyester, 0.1 to 500 ppm of manganese salt based on manganese atoms in polyester, and 0.1 to 500 ppm of phosphorus compounds based on phosphorus atoms in polyester Obtaining a polyester polymer; And spinning a single yarn having a single yarn fineness of 20 to 40 denier and having 6-20 single yarns from the polymer. The method of claim 1, wherein the flame retardant containing phosphorus is a compound represented by Formula 1, and the phosphorus compound is a compound represented by Formula 2 below. [Formula 1]

(R ₁ and R ₂ are each independently a hydrogen atom or a radical having a ω-hydroxy group having 2 to 4 carbon atoms, P is an integer of 1 to 5), [Formula 2]

(Wherein, R ₃ is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.) Flame retardant polyester fiber yarn produced by the method of claim 1 or 2. Monofilament manufactured by the spraying process from the flame retardant polyester powder yarn of claim 3. delete delete Textile or textile article comprising the monofilament according to claim 4.