KR100867196B1 - Manufacturing method of and polyester fiber having flame retardant and basic dyeable - Google Patents

Abstract

A manufacturing method of polyester fiber having basic salting and flame resisting is provided to synthesize phosphate glycol compound by reacting a phosphate flame retardant and a glycol compound at a proper reaction condition and to provide the polyester fiber including the phosphate flame retardant compound having metal sulfonate salt by synthesizing a phosphate flame retardant compound having a metal sulfonate salt having a stabilized structure through an esterification-reaction with a metal sulfonate salt. A phosphate glycol compound is manufactured by reacting a phosphate flame retardant with a glycol compound. One or more reactors selected from a group consisting of a carboxyl group or carbomethoxy are at one side of both sides of the phosphate flame retardant. A metal sulfonate salt is produced by reacting the phosphate glycol compound with the metal sulfonate salt. The flame resisting and basic salting polyester fiber is manufactured by injecting the phosphate flame retardant compound having metal sulfonate salt in the polyester fiber.

Description

FIELD OF THE INVENTION [0001] The present invention relates to a flame-retarding and basic fluorine-containing polyester fiber,

The present invention relates to a method for producing a flame retardant and basic fluorophilic polyester fiber, and more particularly, to a method for producing a flame retardant and basic fluorophilic polyester fiber having a metal sulfinate salt produced through an esterification reaction between a phosphorus glycol compound and a metal sulfinate salt, (DEG) at the same time as the flame retardancy and the basic salt addition, and to minimize the content of diethylene glycol (DEG).

Flame retardancy can be imparted from halogens and non-halogen compounds in order to impart flame retardancy to polyester. Recently, as the regulation of halogen compounds becomes more severe, there is an increasing need for environmentally friendly phosphorus flame retardants. These processes are divided into addition type and reaction type. The addition type manufacturing method is a method of manufacturing a polyester masterbatch resin containing a high-concentration flame retardant by adding the resin to a spinning process of polyester resin at a predetermined ratio. This method can vary the content of the flame retardant, but the viscosity of the masterbatch resin containing a high concentration of the flame retardant is lowered, the flame retardant can not be uniformly produced, and the pack pressure . Further, there is a problem that the flame retardancy is lowered.

On the other hand, the reaction type production method is a method in which a flame retardant capable of reacting with a polyester is added to an esterification reaction or a polycondensation reaction to copolymerize with a polyester resin. This method is characterized by excellent flame retardancy due to copolymerization of a polyester resin and a flame retardant. When such a reactive phosphorus flame retardant is used, it is prepared by adding a reactive phosphorus flame retardant to the production process of the polyester resin, and can be fiberized by melt spinning alone. In this way, Korean Patent No. 632988 discloses a method. However, when an unreacted product is present in the polyester copolymerization process of the reactive phosphorylation flame retardant, the viscosity is markedly lowered, and there is a problem that whitish foreign matter is generated in the melt spinning or fiber post treatment process.

In order to enable dyeing at normal pressure through copolymerization, a method of preparing a copolymerized material capable of reacting with a basic dye is disclosed in International Patent No. 99/09238. However, since dimethyl terminated at the terminal of the copolymer, dimethyl terephthalate (DMT ). When terephthalic acid (TPA) is used as the main raw material, the esterification reaction and the ester exchange reaction proceed simultaneously. Therefore, diethylene glycol (DEG), which is a byproduct of reaction due to unstable reaction, .

Patent patent No. 2005-0107858 and Korean Patent No. 0561083 disclose patents for manufacturing a phosphorus flame retardant and a basic saltable copolyester. Specifically, dimethyl sulfide (DMS) is dissolved in DES (diethylene glycol sulfone salt ) Is applied to prepare a polyester resin. However, this method has a problem in that the DEG, which is a side reaction, is so high that the melting temperature and the glass transition temperature are rapidly lowered and the reactivity is low. This lowers the melting temperature and can not be manufactured when the content of the flame retardant and DES is high.

The production of DEG from dimethyl sulfoxide isophthalate (DMSIP), which is a metal sulfinate salt compound, for the production of a basic fluorophilic resin by the TPA method in polyester polymerization, 7.0% by weight. Such DEG causes a problem of drastically lowering the melting temperature and the glass transition temperature of the polymer.

SUMMARY OF THE INVENTION The present invention has been conceived to solve the problems described above, and an object of the present invention is to provide a phosphorus-based glycol compound by reacting a phosphorus flame retardant and a glycol compound under appropriate reaction conditions, The present invention also provides a method for producing a polyester fiber capable of simultaneously producing a flame retardant and a basic salt containing a phosphorus flame retardant compound having the metal sulfoneate salt by synthesizing a phosphorus flame retardant compound having a metal sulfate salt having a stable structure.

Another object of the present invention is to provide a method for producing a polyester resin composition, which comprises introducing a compound having a stable structure through the esterification reaction described above into the esterification reaction of a polyester fiber before a polycondensation reaction to adjust the content of diethylene glycol (DEG) To less than 2.5% by weight based on the weight of the fibers, thereby eliminating unstable factors such as yarn breakage caused by the unreacted phosphorus flame retardant and the metal sulfinate salt and the increase of the pack pressure in the spinning process of the melt-spun fiber, In the treatment process, the glass transition temperature due to DEG, which is a side reaction, and freezing of the fibers due to the lowering of the melting temperature, are free from the property of the fiber.

In order to accomplish the above object, the present invention provides a method of producing a flame-retardant and basic fluorophilic polyester fiber, comprising the steps of: 1) preparing a polyester fiber having at least one of a carboxyl group and a carbomethoxy group Reacting the phosphorylated flame retardant with a glycol compound to produce a phosphorylated glycol compound; 2) reacting the phosphorylated glycol compound with the metal sulfinate salt to prepare a phosphorylated flame retardant compound having a metal sulfinate salt; and 3) And introducing the phosphorus flame retardant compound having the produced metal sulfinate salt into the polyester fiber.

The phosphorus flame retardant may preferably be 3-hydroxyphenylphosphinyl propanoic acid or the like.

 The glycol compound may be at least one compound selected from the group consisting of ethylene glycol, propanediol, butanediol, neopentyl glycol, hexanediol, heptanediol, pentanediol and 1,4-cyclohexanedimethanol.

The addition ratio of the phosphorus flame retardant and the glycol compound is preferably in a molar ratio of [1: 1] to [1: 10].

Preferably, in the step 1), at least one catalyst selected from the group consisting of antimony, titanium, germanium, aluminum, zinc and manganese compounds is added in an amount of from 0.0001 to 0.1 wt% based on the weight of the total phosphorylated glycol compound Can be added.

In the step 1), the reaction is preferably carried out at a pressure of 1 to 300 mmHg at 100 to 200 ° C for 1 to 6 hours.

The phosphorylated glycol compound is preferably a compound represented by the following formula (2).

(2)

Wherein R is a straight-chain or branched alkyl group of merchants C _{2 ~ 10.}

In the step 2), the metal sulfinate salt may preferably be a sodium sulfinate salt, a lithium sulfurate salt, a potassium sulfinate salt, or the like. The phosphorus glycol compound and the metal sulfinate may be used at a ratio of [1: 0.5] to [15: ] In the reaction system.

The step 2) is preferably carried out in the presence of at least one metal acetate catalyst selected from the group consisting of zinc acetate, cobalt acetate, calcium acetate, lithium acetate, magnesium acetate, sodium acetate and manganese acetate per 100 parts by weight of the metal sulfate salt. May be added in an amount of 0.01 to 2 parts by weight.

The step 2) is preferably carried out at a pressure of 1 to 100 mmHg at 140 to 180 ° C for 2 to 8 hours.

The phosphorus flame retardant compound having the metal sulfinate salt may preferably be a compound represented by the following formula (4) or (5).

[Chemical Formula 4]

M is an alkali metal.

[Chemical Formula 5]

M is an alkali metal.

The polyester fiber in the step 3) is preferably prepared by copolymerizing dicarboxylic acid and a diol, wherein the phosphorus content of the dicarboxylic acid is 2,000 to 10,000 ppm and the molar ratio of the metal sulfanate salt is 1 to 10 mol% A phosphorus flame retardant compound having a metal sulfinate salt can be added to the flame retardant, and the phosphorus-based flame retardant compound having the metal sulfinate salt can be added after the esterification reaction of the dicarboxylic acid and the diol before the polycondensation reaction, to be.

On the other hand, it is also possible to add titanium dioxide, barium sulfate, silica, clay and an anion in an amount of 0.01 to 5 parts by weight to the copolymerization step.

The content of diethylene glycol in the flame-retardant and basic fluorophilic polyester fibers produced through the above-described production method is maintained at 2.5 wt% or less with respect to the total polyester fibers.

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

The method for producing a flame-retardant and basic fluorophilic polyester fiber according to the present invention comprises the steps of: 1) reacting a phosphorylated flame retardant having at least one reactive group selected from the group consisting of a carboxyl group or a carbomethoxy group on at least one of its terminals with a glycol compound A phosphorus-based flame retardant compound having a metal sulfinate salt is prepared by reacting the phosphorus glycol compound prepared above with a metal sulfinate salt, and 3) a step of reacting the phosphorus- And adding the phosphorus flame retardant compound to the polyester fiber.

First, the first step will be described.

In the past, phosphorus flame retardants were added to the copolyester fibers without reacting with glycol compounds. As a result, phosphorus flame retardant compounds that are not involved in the reaction between the impurities contained in the phosphorus flame retardant and the phosphorus flame retardant compound or the phosphorus flame retardant compound at the ends of the reaction are severely deteriorated, and white spots are generated in the spinning or molding process .

Thus, the first step for producing the flame retardant and basic fluorophilic polyester fibers of the present invention comprises reacting a phosphorus flame retardant and a glycol compound under specific conditions to prepare a phosphorus glycol compound. This makes it possible to minimize the impurities contained in the phosphorus flame retardant and solve various problems caused by the phosphorus flame retardant not participating in the reaction.

Specifically, the phosphorus-based flame retardant which can be used in the present invention is a phosphorus-based flame retardant which can be bonded to a glycol compound, and is preferably a phosphorus-based flame retardant having at least one reactor selected from the group consisting of a carboxyl group or a carbomethoxy group on at least one of both terminals A flame retardant may be used, and most preferably, a phosphorus flame retardant used in the following formula (1) can be used.

[Chemical Formula 1]

The glycol compound that can be used in the present invention should be able to combine with a phosphorus-based flame retardant to produce a phosphorylated glycol compound, preferably HO-R _n -OH (R is an integer of 2 to 10), ethylene glycol, , 3-propanediol, 1,4-butanediol, 1,5-hexanediol, 1,6-hexanediol, 1,4-cyclohexanedimethanol, neopentyl glycol, hexanediol and octanediol.

The addition ratio of the phosphorus flame retardant and the glycol compound is preferably in a molar ratio of [1: 1] to [1: 10]. If the amount of the glycol compound to be added is less than [1: 1], there is a problem that the reaction does not occur smoothly. If the amount of the glycol compound exceeds [1: 10], there is a problem that the cost is increased due to use of an excessive glycol compound.

Meanwhile, the reaction conditions are very important for the synthesis of the phosphorylated glycol compound through the step 1) of the present invention.

First, a catalyst should be added in order to cause the reaction to take place. Preferably, 100 parts by weight of the total phosphorylated glycol compound is selected from the group consisting of antimony, titanium, germanium, aluminum, zinc and manganese compounds 0.0001 to 0.1 part by weight of at least one catalyst is further added. If the amount of the catalyst is less than 0.0001 part by weight, the glycolysis reaction does not proceed and the reaction can not be controlled due to heat degradation. If the amount of the catalyst is more than 0.1 part by weight, the reaction proceeds rapidly. However, However, there is a disadvantage in that it is difficult to adjust the intrinsic viscosity at the time of producing the copolymerized polyester due to excessive use of the catalyst.

Preferably, in the step 1), the reaction is performed at a temperature of 100 to 200 ° C. for 1 to 6 hours under a pressure of 1 to 300 mmHg. At this time, as an apparatus for reducing pressure, an air pump, a vacuum pump, a steam ejector, Rate pressure reducing equipment can be used. If the reaction temperature is less than 100 ° C, the reaction between the glycol compound and the phosphorus flame retardant hardly occurs, and if the reaction temperature exceeds 200 ° C, the glycol compound is removed by decompression. If the reaction time is less than 1 hour, a sufficient conversion of glycolysis can not be obtained, and if the reaction time exceeds 6 hours, the occurrence of side reactants becomes severe. If the pressure exceeds 300 mmHg, it is not easy to remove water and impurities generated by the reaction between the phosphorus flame retardant and the glycol compound. If the pressure is less than 1 mmHg, the reaction compound may escape due to excessive vacuum.

The phosphorus-based glycol compound produced through the above step 1) is a compound produced by combining the phosphorus flame retardant and the glycol compound described above. In the present invention, the phosphorus-based glycol compound represented by the following formula 2 can be synthesized, Do not. The compound represented by the following formula (2) is prepared by reacting the compound represented by the formula (1) and HO-R _n -OH (wherein R is an integer of 2 to 10) through the above-described method.

(2)

Wherein R is a straight-chain or branched alkyl group of merchants C _{2 ~ 10.}

Next, step 2) of the present invention will be described.

The step 2) of the present invention is a step of reacting the phosphorus glycol compound prepared in the above step 1) with a metal sulfinate salt under appropriate conditions to prepare a phosphorus flame retardant compound having a metal sulfinate salt.

The metal sulfinate salt usable in the present invention is capable of producing a phosphorus flame retardant compound having a metal sulfinate salt by carrying out an ester exchange reaction with the phosphorus glycol compound, preferably sodium sulfate salt, lithium sulfurate salt, Sodium sulfate dimethyl sulfate (DMS) represented by the following formula (3) is more preferably used.

(3)

M is an alkali metal.

On the other hand, the phosphorylated glycol compound and the metal sulfinate can be reacted at a molar ratio of [1: 0.5] to [15: 1]. If the addition ratio exceeds the above-mentioned range, a problem that the reaction does not occur may occur

Meanwhile, the reaction conditions are very important for synthesizing the phosphorus-based glycol compound having the metal sulfurate salt from the phosphorus glycol compound and the metal sulfone salt through the step 2) of the present invention.

First, a catalyst should be added in order to cause the reaction to take place. Preferably, a catalyst consisting of zinc acetate, cobalt acetate, calcium acetate, lithium acetate, magnesium acetate, sodium acetate and manganese acetate is added to 100 parts by weight of the metal sulfate salt. May be added in an amount of 0.01 to 2 parts by weight based on the weight of the metal catalyst. If the added amount of the metal acetate catalyst is less than 0.02 parts by weight, the reaction proceeds slowly and the DEG reaction is increased. When the amount of the metal acetate catalyst is more than 2 parts by weight, the reaction occurs rapidly and discoloration occurs.

Also, in the step 2), the reaction is preferably performed at a pressure of 1 to 100 mmHg at 140 to 180 ° C for 2 to 8 hours. If the reaction temperature is lower than 140 ° C, the transesterification reaction time is delayed. If the reaction temperature is higher than 180 ° C, the generation of diethylene glycol (DEG) is increased. If the reaction time is shorter than 2 hours, there may be a problem that a large amount of unreacted materials are present. If the reaction time exceeds 8 hours, diethylene glycol, which is a side reaction, may occur. In addition, when the pressure is less than 1 mmHg, there is a problem that the reaction compound is released from excessive vacuum, and when the pressure exceeds 100 mmHg, the reaction effluent can not be removed.

The phosphorus flame retardant compound having the metal sulfinate salt produced through the step 2) is produced by combining the phosphorus glycol compound and the metal sulfinate salt through an esterification reaction. In the present invention, Phosphorus flame retardant compound having a metal sulfinate salt to be reacted with a phosphorus-containing flame retardant compound. The phosphorus flame retardant compound having a metal sulfinate salt represented by the following general formula (4) or (5) is prepared by reacting the compound represented by the general formula (2) and the compound represented by the general formula (3) through the method described above.

[Chemical Formula 4]

M is an alkali metal.

[Chemical Formula 5]

M is an alkali metal.

Next, step 3) will be described.

In step 3) of the present invention, the phosphorus flame retardant compound having the metal sulfinate salt prepared in the step 2) is added to the step of producing the polyester fiber. The polyester fiber used in the present invention is prepared by copolymerizing a conventional dicarboxylic acid and a diol. In the present invention, the content of phosphorus is preferably 2,000 to 10,000 ppm and the molar ratio of the metal sulfurate salt to the dicarboxylic acid If the content of phosphorus is less than 2,000 ppm, it is difficult to secure flame retardancy. If the content of phosphorus exceeds 10,000 ppm, the flame retardancy is further increased. It is difficult to expect and there is a problem that the manufacturing cost rises. When the content of the metal sulfinate salt is less than 1.0 mol% based on the dicarboxylic acid component, the basic salt is formed, but the contamination level is increased and there is a problem that the pressure is higher than the normal pressure. If the content is more than 10.0 mol% There is a disadvantage that the dyeing level of the salt is not continuously increased.

The phosphorus-based flame retardant compound having the metal sulfinate salt of the present invention may be added in an amount of 0.1 to 30 parts by weight based on 100 parts by weight of the total polyester fibers. If the phosphorus flame retardant compound is added in an amount of less than 0.1 parts by weight, If the amount is more than 30 parts by weight, the flame retardancy and dyeability can not be continuously increased, and the cost may increase.

The phosphorus flame retardant compound having the metal sulfinate salt is added to the esterification reaction between the dicarboxylic acid and the diol before the polycondensation reaction to effectively suppress the side reaction. In other words, the phosphorus flame retardant compound having the metal sulfinate salt should be added before the polycondensation reaction after the esterification reaction of the dicarboxylic acid and the diol, so that the content of DEG as the minor reactant is maintained at 2.5% by weight or less based on the total polyester fiber In addition, in the spinning process of the melt-spun fiber, it is possible to eliminate unstable factors such as yarn breakage caused by unreacted phosphorus flame retardant and metal sulphonate salt and increase in packing pressure, and at the same time, It is free from heat transfer of the fibers due to the transition temperature and the lowering of the melting temperature, and it is possible to maintain the properties of the fiber with excellent properties.

On the other hand, it is also possible to add titanium dioxide, barium sulfate, silica, clay and an anion in an amount of 0.01 to 5 parts by weight to the copolymerization step in order to improve the stretchability or the weight of the spinning process.

Hereinafter, the present invention will be described in detail with reference to examples. The following examples illustrate the present invention, but the scope of the present invention is not limited to the following examples.

≪ Example 1 >

1. Take glycols Flame retardant  Compound manufacturing

The phosphorus flame retardant represented by Formula 1 and ethylene glycol were charged at a molar ratio of 1: 1, and the effluent corresponding to 1 mole of the phosphorus flame retardant was recovered through a condenser while stirring under reduced pressure of 50 mmHg at a reaction temperature of 120 ° C, 2 < / RTI > The prepared phosphorylated glycol flame retardant compound was continuously circulated in a storage container made of stainless steel at a temperature of 60 ° C to 100 ° C.

2. Phenolic glycol compounds and metals Sulfurate  Reaction of salt

DMSIP is added so that the molar ratio of the phosphorus-based glycol flame retardant compound represented by Formula 2 to the sodium sulfinate salt (DMSIP) is 3: 1, and the temperature is slowly raised to 160 ° C while stirring at 120 ° C for 30 minutes. Thereafter, the reaction was carried out at 160 ° C for 2 hours and then the temperature was raised to 180 ° C for 30 minutes. At that time, the pressure was 30 mmHg, and the methanol generated by the reaction was condensed and recovered through a condenser. The compounds represented by the above formulas (4) and (5) thus prepared were prepared. The prepared compound was continuously circulated in a storage container made of stainless steel at a temperature of 80 캜 before being put into the polyester reaction.

3. Preparation of Copolymerized Polyester Resin

86.5 parts by weight of terephthalic acid and 48.5 parts by weight of ethylene glycol were added to 100 parts by weight of BHET produced in the polymerizer, and the temperature was raised from 200 ° C to 250 ° C in the ester reactor, and the resulting water (H ₂ O) Reaction was carried out. 10 parts by weight of the phosphorus-based flame retardant compound having the metal sulfinate salt represented by the above Chemical Formulas (4) and (5) was added to 100 parts by weight of BHET which is the oligomer state obtained in the esterification reaction. At this time, the content of phosphorus was set to 6,000 ppm with respect to the content of terephthalic acid, the sodium sulfonate salt was adjusted to 2.0 mol% with respect to terephthalic acid, and 0.015 wt% of phosphoric acid compound and 0.03 wt% of antimony trioxide were added. Thereafter, the polycondensation reactor was evacuated to a vacuum degree of 0.8 torr, and the temperature was elevated to 285 DEG C to carry out a polycondensation reaction to obtain a polyester resin having an intrinsic viscosity of 0.671. The polymer was solidified by chilling at regular intervals while solidifying with cold water. The DEG produced as a byproduct of the reaction was 2.0% by weight based on the total polyester fiber, and the melting temperature was 238 캜 and the glass transition temperature was 75 캜.

4. Production of co-polyester fiber

The copolymer polyester resin obtained above was spun by using a melt extruder at a temperature of 290 캜, and the obtained yarn was stuck and dyed.

≪ Example 2 >

A copolymerized polyester fiber was produced in the same manner as in Example 1, except that 15 parts by weight of a phosphorus-containing flame retardant compound having a metal sulfinate salt was added to 100 parts by weight of the entire polyester fiber.

≪ Example 3 >

A copolymerized polyester fiber was prepared in the same manner as in Example 1, except that 20 parts by weight of a phosphorus-containing flame retardant compound having a metal sulfinate salt was added to 100 parts by weight of the entire polyester fiber.

<Example 4>

Terephthalic acid 86.5 parts by weight of ethylene glycol and 48.5 parts by weight of the pressure in the portion ester reactor temperature was raised from 200 ℃ to 250 ℃ and the resulting water (H ₂ O) the esterification reaction while removing the effluent was conducted groups continuous polymerization. Esterification 20 parts by weight of a phosphorus flame retardant compound having a metal sulfinate salt was added to 100 parts by weight of the total polyester fibers so that the phosphorus content was 6,000 ppm and the sodium sulfate salt was acidic Min., And 0.015% by weight of a phosphoric acid compound and 0.03% by weight of antimony trioxide were added while stirring. The above compound was supplied to the polycondensation reactor # 1 at a temperature of 270 ° C. to 280 ° C. and a degree of vacuum of 65 torr and was continuously supplied to the polycondensation reactor # 2 at a temperature of 280 ° C. and a degree of vacuum of 15 torr And then fed continuously to the finisher which is the last step of the polycondensation reactor to obtain a polyester resin having an ultimate viscosity of 0.670 at a final reaction temperature of 290 ° C and a vacuum degree of 0.8 Torr. This polymer is solidified by chilling at regular intervals while being solidified by using cold water and dried. DEG was 1.54 wt%, the melting temperature was 239 DEG C, and the glass transition temperature was 77.2 DEG C, respectively.

A polyester fiber was produced in the same manner as in Example 1 except for the above-mentioned contents.

&Lt; Example 5 >

A copolymerized polyester fiber was produced in the same manner as in Example 4, except that 15 parts by weight of a phosphorus-containing flame retardant compound having a metal sulfinate salt was added to 100 parts by weight of the total polyester fibers.

&Lt; Comparative Example 1 &

Polyester fibers were produced in the same manner as in Example 1, except that the compounds represented by Formulas (4) and (5) were added during the esterification process.

&Lt; Comparative Example 2 &

A polyester fiber was produced in the same manner as in Example 1, except that only the metal sulfate salt was added after the esterification step without using the phosphorus glycol compound.

&Lt; Comparative Example 3 &

A polyester fiber was produced in the same manner as in Example 1, except that only the phosphorylated glycol compound was added after the esterification step without using the metal sulfinate salt.

&Lt; Comparative Example 4 &

A polyester fiber was produced in the same manner as in Example 1, except that only the phosphorylated glycol compound was added to the esterification reactor (PC reactor) without using the metal sulfinate salt.

&Lt; Comparative Example 5 &

A polyester fiber was prepared in the same manner as in Example 1, except that the compound represented by the general formula (4) and the compound represented by the general formula (5) was added in the copolymerization step of the polyester fiber.

<Experimental Example>

The following properties of the polyester fibers produced in Examples 1 to 5 and Comparative Examples 1 to 5 of the present invention were evaluated, and the results are shown in Table 1.

1, intrinsic viscosity (intrinsic viscosity)

Using an Ortho-Chloro phenol as a solvent, the mixture was melted at a concentration of 2.0 g / 25 ml at 110 ° C. for 30 minutes, and then heated at 25 ° C. for 30 minutes to obtain a viscometer (CANON) Respectively.

2. Measurement of diethylene glycol (DEG) content

The content of diethylene glycol (DEG) was measured by gas chromatography (GC) and nuclear magnetic resonance (NMR). GC analysis was performed using amino ethanol or amino ethanol / benzyl alcohol as a solvent. The DEG calibration curve was used to determine the area ratio between the peak area and the standard sample. NMR analysis was performed by dissolving the copolyester in CDCl3 and comparing the integral of the DEG peak based on the integral of the terephthalic acid (TPA) peak to calculate the content.

3. Thermal Analysis (DSC)

The melting temperature and glass transition temperature were analyzed using a TA-3100 manufactured by Dupont Thermal Analyst System at a heating rate of 10 ° C / min.

4. Modifier (Phosphorus flame retardant with metal sulphonate salt Compound) content

The copolyester was dissolved in CDCl ₃ , and the integral value of the dimethylsulfone isophthalate sodium salt (DMSIP) as a modifier was compared with the glycolic acid phosphate compound as a modifier based on the integral value of the terephthalic acid (TPA) peak obtained through nuclear magnetic resonance analysis, Respectively.

5. Pack pressure measurement

The gauge of the pack pressure gauge was evaluated as "good" and "bad" from the difference between the value of the SD sample and the value to be measured in a melt emitter which is reduced by 1/10 of the equipment size of the yarn manufacturing process . "Good" means that there is no difference between the packed pressure gauge value of SD and the packed pressure gauge of the sample to be measured, and "Bad" means that the packed pressure gauge of the sample to be measured is sharply increased I say things.

6. Dyeability

The knitted fabric was knitted using a circular knitting machine, and dyeability was evaluated by using a basic dye, which was uniformly dyed, with no good dyeing.

7. Flammability (UL-94V)

Standard test specimens were prepared and the specimens were held vertically, and the flame was removed after the flame of the burner was applied to the bottom for 10 seconds, and the time for ignition of the ignited flame was measured. Next, at the same time as the fire was turned off, the second settling was started for 10 seconds, and the time when the ignited fire was turned off was measured in the same manner as the first. It was also evaluated whether or not the lower surface of the test specimen was ignited by falling drops. The flame retardancy was evaluated using the above-mentioned combustion time and the rank of being ignited on the lower surface as V-0, V-1 and V-2 according to the UL-94V standard. V-0 is the highest flame retardancy, and lower flame retardancy means lower. Further, the oxygen index was also tested.

[Table 1]

Example 1 Example 2 Example 3 Example 4 Example 5 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Raw material, polymerization method TPA, Batchi TPA, Batchi TPA, Batchi TPA, continuous TPA, continuous TPA, Batchi TPA, Batchi TPA, Batchi TPA, Batchi TPA, Batchi Injection position of phosphorus flame retardant etc. PC reactor PC reactor PC reactor BHT Reactor BHT Reactor ES reactor ES reactor ES reactor PC reactor - Intrinsic viscosity? 0.671 0.675 0.685 0.670 0.670 0.673 0.671 0.671 0.675 0.675 By-products (DEG), wt% 2.00 1.85 1.83 1.54 1.52 4.30 3.80 1.89 1.87 1.43 The melting temperature (Tm) 237.0 236.5 234.2 239.0 239.4 224.5 226.5 241.0 247.0 252 The glass transition temperature (Tg) 75.6 76.7 75 77.2 76.5 65.7 67.5 77.2 77.2 82.4 Pack pressure Good Good Good Good Good Good Good Good Good Good Fiber strength (g / de) 4.5 4.44 4.3 4.39 4.45 4.23 4.4 4.45 4.43 4.5 Fiber elongation, (%) 35 34 32 30 34 38 33 35 30 30 Dyeability Good Good Good Good Good Good Good radish radish radish Flammability (LOI) 32 31 32 32 31 32 22 32 22 22 Flammability UL-94V V-0 V-0 V-0 V-0 V-0 V-0 ND V-0 ND ND

* ES Reactor: Esterification Reactor

* PC reactor: polycondensation reactor

* BHT Reactor: Bishydroxyterephthalic ester (BHT)

As can be seen from the above Table 1, the polyester fibers of Examples 1 to 5 of the present invention have excellent physical properties in dyeability, glass transition temperature, flame retardancy, and content of byproducts as compared with the polyester fibers of Comparative Examples 1 to 5.

As described above, the polyester fiber containing the phosphorus-based flame retardant compound having the metal sulfinate salt of the present invention has flame retardancy and basic phoshorus at the same time, and has a high reactivity, so that stable spinning and molding processes can be maintained. In addition, the phosphorylated flame retardant is converted into a phosphorylated glycol compound through glycolysis to remove impurities to increase the reactivity with the copolyester, thereby ensuring flame retardancy and providing a stable spinning and molding process. Furthermore, in order to improve the dyeability, the melting temperature and the glass transition temperature of the copolymerized polyester resin are lowered due to the excessive occurrence of DEG as a byproduct in the polymerization process of the metal sulfinate salt to be added, so that the phosphorus flame retardant and the metal sulfinate salt are esterified The reaction can be carried out, and it is possible to minimize the generation of side reactants by introducing it in a specific step in the production process of the copolymerized polyester. This makes it possible to prevent the generation of heat of the fiber due to the heat treatment during the production of the polyester fiber.

While the present invention has been particularly shown and described with reference to exemplary embodiments thereof, it will be understood by those skilled in the art that various changes and modifications may be made without departing from the spirit and scope of the invention as defined in the appended claims. .

Claims (19)

1) reacting a phosphorylated flame retardant having at least one reactive group selected from the group consisting of a carboxyl group or a carbomethoxy group on at least one of its terminals with a glycol compound to prepare a phosphorylated glycol compound; 2) reacting the prepared phosphorus glycol compound with a metal sulfinate salt to prepare a phosphorus flame retardant compound having a metal sulfinate salt; And 3) introducing the phosphorus-based flame retardant compound having the metal sulfanate salt into the polyester fiber. The method according to claim 1, wherein the phosphorus flame retardant is 3-hydroxyphenylphosphinyl propanoic acid. The method according to claim 1, wherein the glycol compound is at least one compound selected from the group consisting of ethylene glycol, propanediol, butanediol, neopentyl glycol, hexanediol, heptanediol, pentanediol and 1,4-cyclohexanedimethanol Wherein the flame-retarding and basic fluorophilic polyester fibers are obtained by a method comprising the steps of: The method according to claim 1, wherein the phosphorus flame retardant and the glycol compound are reacted at a molar ratio of [1: 1] to [1: 10]. The method according to claim 1, wherein, in step 1), at least one catalyst selected from the group consisting of antimony, titanium, germanium, aluminum, zinc and manganese compounds is added to 100 parts by weight of the total phosphorylated flame- Is added in an amount of 0.0001 to 0.1 part by weight per 100 parts by weight of the flame retardant. The method according to claim 1, wherein the reaction is carried out at 100 to 200 ° C for 1 to 6 hours in step 1). The method according to claim 1, wherein the step 1) is performed at a pressure of 1 to 300 mmHg. The method for producing a flame-retarded and basic fluorophilic polyester fiber according to claim 1, wherein the phosphorus glycol compound is a compound represented by the following formula (2). (2)

Wherein R is a straight-chain or branched alkyl group of merchants C _{2 ~ 10.} The flame-retarded and basic fluorophilic polyester fiber according to claim 1, wherein the metal sulfinate salt is at least one selected from the group consisting of a sodium sulfinate salt, a lithium sulfinate salt, and a potassium sulfinate salt. Way. The method for producing a flame-retarded and basic fluorophilic polyester fiber according to claim 1, wherein the phosphoric acid glycol compound and the metal sulfinate are reacted in a molar ratio of [1: 0.5] to [15: 1] . The method according to claim 1, wherein the step 2) is a step of dissolving at least one selected from the group consisting of zinc acetate, cobalt acetate, calcium acetate, lithium acetate, magnesium acetate, sodium acetate and manganese acetate Wherein the metal acetate catalyst is further added in an amount of 0.01 to 2 parts by weight based on the total weight of the flame-retarded and basic fluorophilic polyester fibers. The method according to claim 1, wherein the reaction is carried out at 140 to 180 ° C for 2 to 8 hours. The method according to claim 1, wherein the step 2) is carried out at a pressure of 1 to 100 mmHg. The method for producing a flame retardant and basic fluorophilic polyester fiber according to claim 1, wherein the phosphorus flame retardant compound having the metal sulfinate salt is a compound represented by Chemical Formula 4 or Chemical Formula 5. [Chemical Formula 4]

M is an alkali metal. [Chemical Formula 5]

M is an alkali metal. The polyester fiber according to claim 1, wherein the polyester fiber in step 3) is prepared by copolymerizing dicarboxylic acid and a diol, wherein the content of phosphorus is 2,000 to 10,000 ppm and the amount of the metal sulfinate is 1 to 10 mol% Wherein the phosphorus-based flame retardant compound having the metal sulfate salt is added to the flame retardant. 16. The method according to claim 15, wherein the phosphorus-containing flame retardant compound having the metal sulfinate salt is introduced before the polycondensation reaction after the esterification reaction of the dicarboxylic acid and the diol.  16. The method according to claim 15, wherein 0.01 to 5 parts by weight of titanium dioxide, barium sulfate, silica, clay and an anion are further added to the copolymerization step. A flame-retarded and basic fluorophilic polyester fiber produced by the method of any one of claims 1 to 17. The polyester fiber according to claim 18, wherein the content of diethylene glycol in the flame-retardant and basic fluorophilic polyester fibers is 2.5% by weight or less based on the total polyester fibers.