KR20180038946A - Flame-retardant composite fiber with excellent dyeing properties and Flame-retardan hollow fiber with excellent dyeing properties - Google Patents

Abstract

The present invention relates to a flame-retardant composite fiber having excellent dyeing properties and to a flame-retardant hollow fiber comprising the same, and more specifically, to a flame-retardant composite fiber capable of preventing and/or minimizing adverse effects on physical properties of a sheath part when a core part for hollow formation of the composite fiber is eluted during the production of the hollow fiber, and further, to an invention capable of providing the hollow fiber ensuring not only lighter weight, flame retardancy, and mechanical properties but also bathochromic properties.

Description

Flame-retardant composite fiber having excellent dyability and flame-retardant hollow fiber containing the same

The present invention relates to a flame-retardant hollow fiber excellent in dyability and a lightweight hollow fiber obtained by eluting a core portion of the above-mentioned conjugate fiber and having excellent dyability.

In general, curtains, wallpaper, carpets, flame-retardant non-woven fabrics, and other ornaments are made into flame-retarded fabrics and non-woven fabrics for safety, in places where people are densely packed, places with plenty of electric facilities, and places with many closed spaces. Therefore, in the conventional flame retardant yarn, the synthetic fiber was melt-elongated to prepare a synthetic fiber, and then the surface of each synthetic fiber was treated with a flame retardant agent so as not to burn due to flame. In addition, in the conventional method of flame-retarding treatment, the synthetic fiber is made into a fabric by using a weaving machine or a knitting machine, and then the surface of the fabric is treated with a flame retardant so as not to be ignited by fire. However, conventionally, since a flame retardant is applied to the surface of a synthetic fiber or a fabric, a flame retardant is easily removed depending on the time of use, and the flame retardant .

Therefore, a technique for manufacturing a fire retardant by mixing flame retardant components in the production of a burner is being studied and developed. However, the polyester resin having flame retardancy has a problem that the flame retardant is dispersed and distributed uniformly in the polyester resin, but the flame retardant having limited flowability has a problem that the desired flame retardant function can not be obtained because the polyester resin can not be uniformly dispersed therein.

In addition, in the case of the flame retardant fiber, there is a tendency to be used in a vehicle interior material product. In the case of a product using a high-grade fabric, a high deliquescence property is required. In order to produce such a product, a complementary agent, a dye, / ≪ / RTI > fibers.

However, in the case of conventional flame retardant fibers and / or resins for producing the same, there is a problem that the physical properties of the flame-retardant fibers and / or fabrics produced by the additive composition for improving the color sharpness, the process and the like are reduced. For example, Korean Patent Laid-Open Publication No. 2005-0103617 discloses a flame-retardant polyester added with a complementary agent and imparted excellent color development during the dyeing process. In the dyeing process, hydrolysis of a flame- Korean Patent Laid-Open Publication No. 2003-0028022 discloses a method for producing polyester using a cacao dye. This is because pretreatment of a metal sulfonate salt for maintaining spinnability during production of a polyester resin capable of dyeing a cacao dye There is a problem in that the process cost is increased and the modifier content is increased in order to improve the sharpness of the color.

On the other hand, in general, the synthetic fiber has a high melting point and its use is often limited. Particularly, when it is used as an adhesive such as a wick in the use of a fiber or the like, or as an adhesive which is inserted between cloths on a tape to be pressure bonded, the fiber fabric itself may be thermally deteriorated by heating, It is required to easily bond the substrates by a simple simple heating press without using such special equipment.

Conventional low-melting-point polyester short fibers have been extensively used in hot melt type binder fibers for the purpose of bonding different kinds of fibers to each other in a mutual fiber structure used in a mattress, an automobile interior or various nonwoven padding applications .

Therefore, there is a high demand for a polyester resin having a low melting point, and it is used for binder fibers and adhesives. For such applications, copolyesters which are generally copolymerized are used.

For example, United States Patent No. 4,129,675 discloses a low melting polyester copolymerized with terephthalic acid (TPA) and isophthalic acid (IPA), but isophthalic acid (IPA) There is a problem that the low melting point polyester using a large amount of isophthalic acid as a material has a high production cost and low competitiveness.

Japanese Unexamined Patent Application Publication No. 10-298271 discloses a process for producing an ethylene-vinyl alcohol copolymer by using adipic acid instead of terephthalic acid and 1,4-butanediol (BD) as a diol component instead of ethylene glycol, Is used to increase the adhesiveness and to provide a fiber having a small decrease in the strength of the fiber even at a high temperature. However, the low melting point polyester produced by using adipic acid has a low melting point polyester having a melting point of 150 DEG C or less There is a problem that a low melting point polyester having a lower melting point can not be produced.

Korean Patent Publication No. 2003-0028022 (published on April 4, 2003)

SUMMARY OF THE INVENTION The present invention has been conceived in order to solve the above-mentioned problems, and it is an object of the present invention to provide a flame-retardant composite fiber capable of minimizing and / or preventing deterioration of physical properties of a sheath portion during elution of a core portion of a composite fiber for producing hollow fibers, And the composition was known, thereby completing the present invention. That is, the present invention provides a flame-retardant conjugated fiber and a flame-retardant hollow fiber prepared using the same.

In order to solve the above-described problems, the present invention provides a sheath-core type composite fiber comprising: a sheath portion including a flame-retardant polyester resin; And a core portion comprising a high-temperature hot-water-soluble polyester resin or a low-temperature hot-water-soluble polyester resin.

In one preferred embodiment of the present invention, when the core portion is a high temperature hot water-soluble polyester resin, the conjugate fiber of the present invention is subjected to composite spinning so that the sheath portion and the core portion are in a weight ratio of 7: 3, The weight loss ratio (%) of the conjugated fiber may be 27% or more based on the following formula (1).

[Equation 1]

(%) = (Weight of composite fiber before weight loss (g) - weight of composite fiber after weight reduction / weight of composite fiber core before weight loss (g)) × 100 (%)

In one preferred embodiment of the present invention, when the core portion is a low-temperature hot-water-soluble polyester resin, the conjugate fiber of the present invention is subjected to composite spinning so that the sheath portion and the core portion are in a weight ratio of 7: 3, The weight loss ratio (%) of the conjugated fiber can be 26% or more based on the following formula (1).

[Equation 1]

(%) = (Weight of composite fiber before weight loss (g) - weight of composite fiber after weight reduction / weight of composite fiber core before weight loss (g)) × 100 (%)

As a preferred embodiment of the present invention, in the conjugate fiber of the present invention, the flame-retardant polyester resin is a PET (polyethylene terephthalate) semidull polymer, a PET bright polymer, and a PET superbright polymer And the like.

In one preferred embodiment of the present invention, the flame-retardant polyester resin constituting the sheath portion is an esterification reaction product of an oligomer obtained by polymerizing phthalic acid and an aliphatic diol and dimethyl 5-sodiosulfoisophthalate; And a reaction-type phosphorus flame retardant; and a polycondensation reaction product obtained by condensation polymerization of a mixed resin.

In one preferred embodiment of the present invention, the reactive phosphorus flame retardant may include at least one compound selected from the group consisting of compounds represented by the following general formulas (1) and (2)

 [Chemical Formula 1]

In the above formula (1), R ¹ is -OH, -COOH, -CH ₂ COOH, -CH ₂ CH ₂ COOH, -CH ₂ CH ₂ CH ₂ COOH or -CH ₂ CH ₂ CH ₂ CH ₂ COOH.

(2)

In Formula 2, R ¹ and R ² are independently an alkyl group having 1 to 10 carbon atoms, an alkylene group having 2 to 5 carbon atoms, a cycloalkyl group having 5 to 6 carbon atoms, or a phenyl group.

In one preferred embodiment of the present invention, the mixed resin may further include a metal catalyst represented by the following general formula (3).

(3)

In Formula 3, R ² is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a cycloalkyl group having 5 to 6 carbon atoms, an alkoxy group having 1 to 2 carbon atoms, or a phenyl group.

In one preferred embodiment of the present invention, the high-temperature hot water-soluble polyester resin (first resin) of the core portion may include terephthalic acid, isophthalic acid, dimethyl 5-sodiosulfoisophthalate and diethylene glycol.

In one preferred embodiment of the present invention, the high-temperature hydrothermally soluble polyester resin contains 55 to 65 mol% of terephthalic acid, 10 to 25 mol% of isophthalic acid, 5 to 15 mol% of dimethyl 5-sodiumdiisulfoisophthalate, 20 mole%.

As a preferred embodiment of the present invention, a low temperature hot water soluble polyester resin (second resin) having a composition different from that of the high temperature hot water soluble polyester resin (first resin) of the core part is an aromatic polycarboxylic acid having 6 to 14 carbon atoms , An aliphatic polycarboxylic acid having 2 to 16 carbon atoms, and sodium 3,5-dicarbomethoxybenzenesulfonate; and a diol component; And a low-temperature hot water-soluble polyester resin including a copolyester obtained by polycondensing polyethylene glycol.

In one preferred embodiment of the present invention, the esterification reaction product of the low-temperature hot water-soluble polyester resin (second resin) may contain monomers and acid components and diol components in a molar ratio of 1: 1.1 to 2.0.

In one preferred embodiment of the present invention, the acid component of the low temperature hydrothermally soluble polyester resin (second resin) is at least one selected from the group consisting of terephthalic acid, dimethyl terephthalate, isophthalic acid and dimethyl isophthalate, Aromatic polycarboxylic acids; But are not limited to, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, suberic acid, citric acid, fimaric acid, azelaic acid, sebacic acid, nonanoic acid, decanoic acid, dodecanoic acid and hexanodecanoic acid At least one aliphatic polycarboxylic acid having 2 to 14 carbon atoms; And sodium 3,5-dicarbomethoxybenzenesulfonate; Or the like.

In one preferred embodiment of the present invention, the diol component of the low temperature hydrothermally soluble polyester resin (second resin) is at least one selected from the group consisting of ethylene glycol, diethylene glycol, neopentyl glycol, 1,3-propanediol, 1,6-hexanediol, and the like.

Another object of the present invention is to provide a flame-retardant hollow fiber having improved dyability and excellent color-curing property, and is provided with only the sheath portion from which the core portion of the flame-retardant composite fiber described above is eluted.

In a preferred embodiment of the present invention, the elution may be characterized in that, when the core portion comprises a high-temperature hot-water-soluble polyester resin, the core portion is eluted by performing hot water elution treatment at 90 ° C or higher.

In a preferred embodiment of the present invention, the elution may be characterized in that, when the core portion comprises a low-temperature hydrothermally soluble polyester resin, the core portion is eluted by performing a hot water elution process under a condition of 70 ° C or lower.

Another object of the present invention is to provide a flame retardant product using the flame-retardant hollow fiber.

The flame-retarded composite fiber having excellent dyability, particularly CD (Cation Dyeable) of the present invention can exfoliate the flame-retarded composite fiber to minimize flame-retardant component separation of the sheath portion generated in the production of the flame retardant hollow fiber. Further, the present invention provides a flame-retardant hollow fiber excellent in mechanical properties and excellent in lightness and deep color due to easy elution of the core portion and minimization of the influence on the sheath portion in the core portion elution treatment, .

The flame-retarded conjugate fiber having excellent dyability of the present invention is a cis-core type conjugate fiber, and the hollow fiber composed of the sheath portion can be provided by eluting the core portion. The present invention will be described specifically by dividing the sheath portion and the core portion.

[ Shebu ]

In the flame-retardant conjugate fiber of the present invention, the sheath portion includes a flame-retardant polyester resin, preferably an oligomer obtained by polymerizing phthalic acid and an aliphatic diol, and an esterification reaction product of dimethyl 5-sodiosulfoisophthalate; And a reaction-type phosphorus flame retardant; and more preferably, a flame retardant polyester resin including a polycondensation reaction product obtained by condensation polymerization of a mixed resin including a polycondensation product of an esterification reaction product of terephthalic acid and dimethyl 5-sodiosulfoisophthalate ; And a reactive phosphorus flame retardant; and a polycondensation reaction product obtained by condensation polymerization of a mixed resin containing a phosphorus-containing flame retardant and a reactive phosphorus flame retardant.

The flame retardant polyester resin is excellent in durability with dyeing agents, dyes and the like, and can be prevented from lowering the properties of flame retardant fibers by lowering the processing temperature during processing with flame retardant fibers (and / or fire retardant).

The phthalic acid may include at least one selected from the group consisting of terephthalic acid and isophthalic acid, preferably terephthalic acid.

The aliphatic diol is preferably an aliphatic diol having 2 to 20 carbon atoms and preferably an aliphatic diol having 2 to 20 carbon atoms such as ethylene glycol, diethylene glycol, propylene glycol, butylene glycol, trimethyl glycol, tetramethylene glycol, pentamethyl glycol, hexamethylene glycol, Recycled, octamethylene glycol, nonamethylene glycol, decamethylene glycol, undecamethylene glycol, dodecamethylene glycol and tridecamethylene glycol, more preferably ethylene glycol and diethylene glycol One or two of them may be used in combination.

The oligomer may be prepared by esterification using phthalic acid and the aliphatic diol at a molar ratio of 1: 1.20 to 1.50, preferably 1: 1.25 to 1.40, more preferably 1: 1.25 to 1.35 If the mole ratio of the aliphatic diol is less than 1.2, the yield of the polyester resin may be low. If the aliphatic diol is used in an amount exceeding 1.5 mole ratio, the unreacted aliphatic diol may increase the cost of treating the polyester resin. to be.

The phosphorus flame retardant may be a phosphorus flame retardant generally used in the art, but preferably one or two or more selected from the group consisting of compounds represented by the following general formulas (1) and (2) may be used in combination.

[Chemical Formula 1]

In the above formula (1), R ¹ is -OH, -COOH, -CH ₂ COOH, -CH ₂ CH ₂ COOH, -CH ₂ CH ₂ CH ₂ COOH or -CH ₂ CH ₂ CH ₂ CH ₂ COOH, R ¹ is -CH ₂ COOH, -CH ₂ CH ₂ COOH or -CH ₂ CH ₂ CH ₂ COOH.

The compound represented by the formula (1) serves to increase the flame retardancy of the polyester resin, and its amount to be used is preferably 5,000 to 7,000 ppm (based on the P content of the compound), preferably 5,200 to 6,500 ppm (Based on the P content of the compound), more preferably 5,500 to 6,300 ppm (based on the P content of the compound). If the amount of the compound represented by the formula (1) is less than 5,000 ppm (based on the P content of the compound), sufficient flame retardancy may not be secured. If the amount exceeds 7,000 ppm (based on the P content of the compound) Reactive defects may occur during the reaction and problems such as lowering of heat resistance and viscosity of the polymer chips may occur. In the final product, the reduction of the objectivity may occur, which may cause a problem of process passability due to yarn breakage in weaving and circular knitting, so it is preferable to use within the above range.

(2)

In the general formula 2, wherein R ¹ and R ² are independently a cycloalkyl group or a phenyl group having 1 to 10 carbon atoms an alkyl group, having a carbon number of 2 to 5 alkylene group, having 5 to 6, preferably R ¹ and R ² are Independently, an alkyl group having 1 to 5 carbon atoms, an alkylene group having 2 to 3 carbon atoms, or a phenyl group, and more preferably, R ¹ and R ² are independently an alkyl group having 1 to 3 carbon atoms.

The compound represented by the general formula (2) plays a role of improving the salt-forming ability so as to exhibit a clear color through ionic bonding with cations in the dye, especially in the cation dye, and the amount thereof is in the range of 3.0 to 5.0 Mol ratio, preferably 3.225 to 4.515 molar ratio, more preferably 3.5 to 4.2 molar ratio. When the amount of the compound represented by the general formula (2) is less than 3.0 mol, sufficient salt-improving ability can not be obtained. If the amount of the compound represented by the general formula (2) is more than 5.0 mol, the amount of the compound used is too large, , There may be a problem that the mechanical properties of the flame retardant fiber are lowered.

The compound represented by the formula (2) is preferably a compound represented by the following formula (2-1).

[Formula 2-1]

In Formula 2-1, R ¹ and R ² are each independently an alkyl group having 1 to 5 carbon atoms, an alkylene group having 2 to 3 carbon atoms, or a phenyl group. Preferably, R ¹ and R ² are independently an alkyl group having 1 to 3 carbon atoms And more preferably R ¹ and R ² are each independently an alkyl group having 1 to 2 carbon atoms.

The flame-retardant polyester resin constituting the sheath may contain, in addition to the esterification reaction product and the reactive phosphorus flame retardant, a metal catalyst represented by the following general formula (3), 1 (1) selected from magnesium acetate, , Preferably a metal catalyst represented by the following formula (3). When the metal catalyst is used, the amount of the metal catalyst is preferably 100 to 500 ppm, more preferably 150 to 400 ppm, based on the total weight of the flame-retardant polyester resin.

(3)

In Formula 3, R ² is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a cycloalkyl group having 5 to 6 carbon atoms, an alkoxy group having 1 to 2 carbon atoms, or a phenyl group, preferably a hydrogen atom, Or a cycloalkyl group having 5 to 6 carbon atoms, and more preferably an alkyl group having 1 to 2 carbon atoms.

Further, the flame-retardant polyester resin can be used as a heat stabilizer, a defoaming agent, an antioxidant, a lubricant, a light stabilizer, a hydrolytic stabilizer, a release agent, a pigment, an antistatic agent, a conductivity imparting agent, an EMI shielding agent, And further adding at least one additive selected from a processing aid, a metal deactivator, a suppressing agent, a fluorine-based antistatic agent, an anti-friction agent, a wear-resistant agent and a coupling agent.

In the present invention, the heat stabilizer may be a conventional heat stabilizer used in the art, preferably trimethylphosphate, triethylphosphate, tributylphosphate, tributoxy (1) selected from the group consisting of tributoxyethyl phosphate, tricresyl phosphate, triaryl phosphate isopropylated, and hydroquinone bis- (diphenyl phosphate). Or a mixture of two or more species.

The above-mentioned flame retardant polyester resin may be produced by esterifying a phthalic acid and an aliphatic diol to prepare an oligomer; Esterifying the oligomer and dimethyl 5-sodiosulfoisophthalate to prepare an esterification reaction product; Esterification Reaction Mixing the compound represented by Formula 1 and / or the compound represented by Formula 2 to prepare a mixture; And subjecting the mixture to a polymerization reaction to produce a polymer.

Further, the step of removing unreacted monomers and oligomers, that is, the step of solid-polymerizing the polymer, may be further included.

Also, it is preferable in view of the reaction that the esterification reaction in the step of preparing the oligomer is carried out at 230 ° C to 250 ° C while dehydrating the water generated during the reaction. If the esterification reaction temperature is lower than 230 ° C, the yield of the reaction product may be lowered. If the esterification reaction temperature exceeds 250 ° C, many by-products may be generated.

Polymerization in the step of producing the polymer is preferably carried out under the conditions of 270 ° C. to 290 ° C. and 1.5 torr or less, preferably 270 ° C. to 280 ° C. and 1.5 torr or less, Can be carried out under the conditions of 275 DEG C to 280 DEG C and 1.5 torr or less. If the reaction temperature is lower than 270 ° C, there may be a problem that the unit molecular weight is lowered or the reaction participation rate of the oligomer is lowered in the polymerization reaction step, so that the reaction yield may be lowered in the vacuum stage. If the temperature exceeds 290 ° C, There may be a problem that pyrolysis occurs due to lack of heat resistance and the reactivity is lowered or browning and carbonization of the flame-retardant polyester resin occurs.

Hereinafter, the core portion will be described.

[ Core portion ]

Conventional conjugated fibers are typically eluted at a temperature of 90 ° C or higher at the time of the weight loss process, and at a lower temperature, the elution property is remarkably lowered, so that it is impossible to carry out the weight loss process at a low temperature. Accordingly, the weight reduction process performed at a high temperature has a problem in that it is difficult to obtain final fibers having desired physical properties by changing physical properties of the sheath such as changing the degree of surface crystallization of the sheath component contained in the composite fiber.

On the other hand, the core portion of the flame-retardant composite fiber of the present invention comprises a high-temperature hot-water-soluble polyester resin or a low-temperature hot-water-soluble polyester resin, and preferably a high-temperature hot-water-soluble polyester resin.

The thermosoluble polyester resin may include the following high-temperature hot-water-soluble polyester resin (first resin) or low-temperature hot-water-soluble polyester resin (second resin).

The high-temperature hydrothermally soluble polyester resin (first resin) may contain terephthalic acid, isophthalic acid, dimethyl 5-sodiosulfoisophthalate and diethylene glycol, preferably 55 to 65 mol% of terephthalic acid, 10 to 25 5 to 15 mol% of dimethyl 5-sodiosulfoisophthalate and 5 to 20 mol% of diethylene glycol, more preferably 57 to 63 mol% of terephthalic acid, 12 to 20 mol% of isophthalic acid, 8 to 15 mol% of diosulfo isophthalate and 7 to 16 mol% of diethylene glycol.

The high-temperature hydrothermally soluble polyester resin (first resin) may have an intrinsic viscosity (IV) of 0.750 to 0.850 dl / g, preferably 0.800 to 0.840 dl / g, and more preferably 0.810 to 0.825 dl / g. have.

Thus, when the core portion is formed of a high-temperature hot-water-soluble polyester resin (first resin), deterioration of the physical properties of the sheath due to dislocation of the flame retardant in the sheath portion can be prevented even when subjected to hot water dissolution treatment at a high temperature of 90 占 폚 or more.

Next, the low temperature hydrothermally soluble polyester resin (second resin) is obtained by reacting an aromatic polycarboxylic acid having 6 to 14 carbon atoms, an aliphatic polycarboxylic acid having 2 to 16 carbon atoms and sodium 3,5-dicarbomethoxybenzenesulfonate A reacted esterification reagent comprising an acid component and a diol component; And a low-temperature hot water-soluble polyester resin including a copolyester obtained by polycondensing polyethylene glycol.

The aromatic polycarboxylic acid having 6 to 12 carbon atoms in the acid component of the second resin may include at least one selected from terephthalic acid, dimethylterephthalate, isophthalic acid and dimethyl isophthalate, preferably terephthalic acid, It may contain isophthalic acid to improve solubility characteristics

The aliphatic polycarboxylic acid having 2 to 14 carbon atoms in the acid component of the second resin is selected from the group consisting of oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, suberic acid, citric acid, pimelic acid, Nonanoic acid, decanoic acid, dodecanoic acid, and hexanodecanoic acid, and may preferably include at least one selected from adipic acid, succinic acid, and glutaric acid , And more preferably adipic acid to further improve water availability.

The aliphatic polycarboxylic acid having 2 to 14 carbon atoms in the acid component of the second resin has an increased fluidity and a surface area to be bonded with water of the low-temperature hot water-soluble copolyester polymer chain so that the water-soluble property can be further reduced, .

In addition, the acid component of the second resin may further include sodium 3,5-dicarbomethoxybenzenesulfonate, which is a sulfonic acid metal salt capable of inducing adsorption of water molecules. Sodium 3,5-dicarbomethoxybenzenesulfonate can induce the polymer adsorption of water molecules, which further improves the water solubility, and thus may enable a weight loss process even at low temperatures. In addition to the above sodium 3,5-dicarbomethoxybenzenesulfonate, there may be used one or more selected from among lithium 3,5-dicarbomethoxybenzenesulfonate, 5-sulfoisophthalic acid monosodium salt, Sulfonic acid metal salt.

According to a preferred embodiment of the present invention, each of the monomers contained in the acid component of the second resin as described above may contain 1 to 10 mol% of an aliphatic polycarboxylic acid having 2 to 16 carbon atoms in the acid component, -Dicarbomethoxybenzenesulfonate may be contained in an amount of 5 to 12 mol%, and the balance may contain an aromatic polycarboxylic acid having 6 to 14 carbon atoms. When the aliphatic polycarboxylic acid having 2 to 16 carbon atoms in the acid component is contained in an amount of less than 1 mol%, the intended water-solubility and water-solubility characteristics are difficult to be exhibited and the elution at low temperatures may be difficult. , There is a problem that the heat resistance and the glass transition temperature of the produced copolyester are lowered, resulting in the morphological stability of the formed polymer and deterioration of the processability of the composite fiber. When sodium 3,5-dicarbomethoxybenzenesulfonate is contained in an amount of less than 5 mol% in the acid component, the desired water-solubility can not be obtained, so that the step of reducing at low temperature may be difficult and more than 12 mol% (DEG), which is a by-product of the process, and the resulting unreacted material remains in the spinning process, the process efficiency of the copolyester polymerization is remarkably lowered, the melt viscosity is increased, There is a problem of causing yarn tension and pack pressure rise.

The aromatic polycarboxylic acid having 6 to 14 carbon atoms contained as a remaining amount in the acid component of the second resin includes terephthalic acid and isophthalic acid, and may contain 5 to 25 mol% of isophthalic acid in the acidic component. If the content of isophthalic acid in the acidic component is less than 5 mol%, there is a problem in that it can not be obtained at the desired temperature and the elution at low temperature can not be achieved. If the content exceeds 25 mol%, the heat resistance There may be a problem that the fiber produced by the lowering of the temperature is changed with the lapse of time and the working of the fiber is difficult. More preferably, the acid component may include 5 to 25 mol% of isophthalic acid, 1 to 10 mol% of adipic acid, and 5 to 12 mol% of sodium 3,5-dicarbomethoxybenzenesulfonate, May contain an aromatic polycarboxylic acid having 6 to 14 carbon atoms, thereby achieving the desired remarkable water-solubility characteristics and thus excellent utilization of alkali at low temperatures.

Next, the diol component used in the synthesis of the esterification reaction product of the second resin may include at least one selected from aliphatic diols having 2 to 14 carbon atoms and polyethylene glycol. The aliphatic diol having 2 to 14 carbon atoms may be selected from the group consisting of ethylene glycol, diethylene glycol, neopentyl glycol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, propyleneglycol, trimethylglycol, tetra At least one member selected from among ethylene glycol, propylene glycol, propylene glycol, propylene glycol, propylene glycol, propylene glycol, propylene glycol, propylene glycol, And preferably at least one selected from ethylene glycol, diethylene glycol, neopentyl glycol, 1,3-propanediol, 1,4-butanediol and 1,6-hexanediol.

The acid component of the second resin and the diol may be contained in a molar ratio of 1: 1.1 to 2.0. If the diol is contained in an amount less than 1.1 molar ratio, there is a problem that the degree of polymerization is lowered due to the lowered reactivity, and when the molar ratio exceeds 2.0 mol, adverse reaction products such as diethyl glycol may be generated, And there is a problem that excessive use of diol may increase the manufacturing cost.

If the molecular weight is less than 400, it is difficult to carry out the weight loss process at low temperature because the desired water-solubility characteristic can not be obtained. If the molecular weight exceeds 10,000, the polyethylene glycol may have a molecular weight of 400 to 10,000. There is a problem that the polymerization reactivity is lowered and the glass transition temperature of the copolyester formed becomes too low to make the thermal stability poor.

According to a preferred embodiment of the present invention, the copolyester may contain polyethylene glycol in an amount of 1 to 15 parts by weight based on the amount of the esterification reaction product, and the second resin may be a mixture of the esterification reaction product and the polyethylene glycol. . If the amount of the polyethylene glycol is less than 1 part by weight, the desired water-solubility characteristic can not be obtained. Therefore, there is a problem that the weight loss process at low temperature is difficult to perform. If the amount exceeds 15 parts by weight, It is too low and the thermal stability may become poor.

Such a second resin may have an intrinsic viscosity of 0.5 to 0.9 dl / g. If the intrinsic viscosity is less than 0.5 dl / g, there is a problem that the mechanical strength of the conjugate fiber is remarkably weakened during the composite spinning with the fiber, resulting in poor post-processing. If the intrinsic viscosity is more than 0.9 dl / g, There is a problem that elution at low temperature becomes difficult.

By forming the core portion with the low-temperature hot water-soluble polyester resin (second resin), the elution property is remarkably excellent even at a low temperature of 70 ° C or lower. Thus, the change in the fiber properties due to the change in the degree of crystallization of the fiber- And at the same time the elution is uniform so that the defective dyeing non-uniformity of the final fiber after the weight loss process is prevented. In addition, it has biodegradable properties, so it can be self-decomposed when landfill is discarded and thus environmental pollution can be further minimized.

In the flame-retarded composite fiber having excellent dyability of the present invention, when the core portion is formed of a high-temperature hot-water-soluble polyester resin, the core portion and the core portion are combined spinning so as to have a weight ratio of 7: 3, The weight loss ratio (%) of the conjugated fiber at the time of losing 30 minutes may be 27% or more, preferably 28% to 30% based on the following formula (1).

In the flame-retardant composite fiber having excellent dyeability of the present invention, when the core portion is formed of a low-temperature hot water-soluble polyester resin, the core portion and the core portion are combined and spinned to a weight ratio of 7: 3, The weight loss ratio (%) of the conjugated fiber at the time of losing 30 minutes may be 26% or more, preferably 27% to 30% based on the following formula (1).

[Equation 1]

(%) = (Weight of composite fiber before weight loss (g) - weight of composite fiber after weight reduction / weight of composite fiber core before weight loss (g)) × 100 (%)

The flame-retardant hollow fiber formed of only the sheath portion from which the core portion of the flame-retarded composite fiber of the present invention is eluted can be produced.

At this time, in the case where the core portion includes the high temperature hot water soluble polyester resin, the elution may be performed by eluting with hot water at 90 ° C or higher to elute the core portion.

When the core part comprises a low-temperature hot-water-soluble polyester resin, the core part can be eluted by conducting elution with hot water at 70 ° C or less.

The flame retardant hollow fiber of the present invention thus produced is lightweight and has excellent mechanical properties, flame retardancy, and excellent shading properties, and is therefore suitable for various interior flame retardant products such as curtains.

Hereinafter, the present invention will be described more specifically by way of examples. However, the following examples should not be construed as limiting the scope of the present invention, but should be construed to facilitate understanding of the present invention.

[ Example ]

Example  1-1: Cis - Core (high temperature Heat number  Solubility) Manufacture of Flame Retardant Composite Fiber

(1) Production of flame retardant polyester resin ( Shebu )

After the mixture of terphthalic acid and ethylene glycol was mixed at a molar ratio of 1: 1.3, an esterification reaction was carried out while water generated at 240 ° C was removed to prepare an oligomer.

Next, 98.7 mol% of the oligomer and 1.3 mol% of dimethyl 5-sodiosulfone isophthalate were mixed and esterification reaction was carried out while removing water generated at 240 DEG C to prepare an ester reactant.

Next, a mixture was prepared by adding and stirring the ester reactant, a compound represented by the following formula (1-1), a compound represented by the following formula (2-1), and a metal catalyst represented by the following formula (3). At this time, the compound represented by the formula (1) was added in an amount of 5,800 ppm based on the P content in the total weight of the mixture, and the compound represented by the formula (2-1) was added so as to be 4.0 molar ratio with respect to 1 mol of the terphthalic acid. Then, the metal catalyst was added so as to be 300 ppm in the total weight of the mixture.

Next, the mixture was subjected to a polymerization reaction at 278 ° C to 280 ° C and 1.5 torr or less to prepare a polymer to prepare a flame retardant polyester resin.

[Formula 1-1]

In Formula 1-1, R ¹ is -CH ₂ CH ₂ COOH.

[Formula 2-1]

In Formula 2-1, R ¹ and R ² are all methyl groups.

(3)

In the general formula (3), R ² is a methyl group.

(2) High temperature Heat number  Preparation of Soluble Polyester Resin ( Core portion )

A high-temperature hot water-soluble polyester resin was prepared by copolymerizing 60 mol% of terephthalic acid, 20 mol% of isophthalic acid, 10 mol% of dimethyl 5-sodium diisophthalate and 10 mol% of diethylene glycol . The resin produced had an intrinsic viscosity (IV) of 0.820 dl / g.

(3) Cis - Fabrication of Core Composite Fiber

The flame-retardant polyester resin and the releasable resin were put into a sheath portion of a sheath-core type composite spinneret and the spinning was carried out at a spinning temperature of 280 캜 and a spinning speed of 4,200 mpm to prepare a core of 30 wt% By weight based on the total weight of the cis-core conjugate fiber.

Example  1-2

Core composite fiber was prepared using the same sheathing resin as in Example 1-1 except that 63 mol% of terephthalic acid, 17 mol% of isophthalic acid, 11.2 mol of dimethyl 5-sodium diisophthalate %, And diethylene glycol (8.8 mol%) were copolymerized to prepare a high-temperature hot-water-soluble polyester resin. The intrinsic viscosity (IV) of the prepared resin was 0.812 dl / g.

Comparative Example  1-1

Flame-retardant PET (manufactured by Toray Chemical Co., Ltd., trade name ESFRON) containing no dimethyl 5-sodiosulfoisophthalate was prepared as a sheath resin.

Next, by using the sheath resin and the high-temperature hot water-soluble polyester resin (core resin, first resin) of Example 1-1, a core of 30 weight%, a sheath of 70 weight% Core composite fiber was prepared.

Comparative Example  1-2

Core composite fiber composed of 30% by weight of core and 70% by weight of cis was produced by using alkali-soluble PET (manufactured by Toray Chemical Co., Ltd., trade name: ESP) as a core part resin.

Comparative Example  1-3

Cis-core conjugated fiber was produced using the same sheath resin as in Example 1-1.

However, as the core part resin, a high-temperature hot water-solubility test solution prepared by copolymerizing a mixture containing 52 mol% of terephthalic acid, 20 mol% of isophthalic acid, 18 mol% of dimethyl 5-sodium diisophthalate and 10 mol% of diethylene glycol A polyester resin was used. The intrinsic viscosity (IV) of the produced resin was 0.743 dl / g.

Comparative Example  1-4

Cis-core conjugated fiber was produced using the same sheath resin as in Example 1-1.

However, as the core part resin, a mixture of 68 mol% of terephthalic acid, 20 mol% of isophthalic acid, 2 mol% of dimethyl 5-diisosulfoisophthalate and 10 mol% of diethylene glycol, Soluble polyester resin was used. The intrinsic viscosity (IV) of the produced resin was 0.864 dl / g.

division
(mole%) Example
1-1 Example
1-2 Comparative Example
1-3 Comparative Example
1-4 Terephthalic acid 60 63 52 68 Isophthalic acid 20 17 20 20 Dimethyl 5-sodiosulfoisophthalate 10 11.2 18 2 Diethylene glycol 10 8.8 10 10 Intrinsic viscosity (IV) 0.820 0.812 0.864 0.743 Of composite fibers
Sheath portion and core portion weight ratio 7: 3 7: 3 7: 3 7: 3

Manufacturing example  1-1: Preparation of Flame Retardant Polyester-Based Hollow Fiber

The cis-core conjugate fiber prepared in Example 1-1 was circularized and then subjected to weight loss at 98 占 폚 in hot water (FW) for about 30 minutes to prepare a CD (cation dyeable) flame retardant polyester hollow fiber.

Manufacturing example  1-2 and Comparative Manufacturing Example  1-1 to 1-4

The hollow fibers were prepared in the same manner as in Preparation Example 1-1 by weight loss at 98 占 폚 in hot water (FW) for about 30 minutes. The hollow fibers were prepared in the same manner as in Production Example 1-1 except that each of the conjugated fibers of Examples 1-2 and Comparative Examples 1-1 to 1-4, To prepare hollow fibers, and Production Example 1-2 and Comparative Production Examples 1-1 to 1-4 were respectively carried out.

Comparative Manufacturing Example  1-5

The hollow fiber was prepared by proceeding with the alkali reduction (NaOH aqueous solution, concentration 5 vol%) of the cis-core conjugate fiber produced in Example 1-1 at all times.

Experimental Example  1: Measurement of physical properties of hollow fiber

The weight loss, the strength reduction rate, the salt deposition rate, the fire resistance, the workability and the durability of the hollow fibers of the above-mentioned Production Examples 1-1 to 1-2 and Comparative Production Examples 1-1 to 1-5 were measured, Respectively. At this time, the physical properties were measured by the following methods.

(1) Weight loss rate

The weight loss rate was measured according to the following equation (1).

[Equation 1]

(%) = (Weight of composite fiber before weight loss (g) - weight of composite fiber after weight reduction / weight of composite fiber core before weight loss (g)) × 100 (%)

(2) Strength reduction rate

According to ASTM D1682 method, the strength reduction ratio was measured by measuring the strength of the composite fiber before the weight loss and the weight of the hollow fiber after the reduction.

(3) Rate of salt formation (K / S, % )

The hollow fiber was subjected to salt casting for 60 minutes at a saponification temperature of 90 ° C. using a dye solution containing 10 parts by weight of a sample and 500 parts by weight of water (liquid ratio 50: 1) by volume and containing 2% by weight of a blue dye After that, the dyeing ratio was measured and measured according to CIE 1976 standard using a colorimeter.

(4) Fire resistance (carbonization distance, cm)

The degree of fire was measured by the vertical method according to KS K 0585: 2008.

(5) Operability , durability

The durability was measured on the basis of the dropout rate of the flame retardant during the weight loss and the rate of decrease in the strength of the yarn. At this time, evaluation of operability and durability was evaluated as being excellent:?, Excellent:?, Fair:?, Poor: X.

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1-5 Weight loss rate
(%) 29.96 28.12 29.59 2.07 29.98 0.75 74.52 Core portion
Weight loss rate
(%) 99.87 93.74 98.63 6.90 99.94 2.50 100 Hollow formation
Whether ○ ○ ○ X ○ X X burglar
Reduction rate ( % ) 5.23 5.12 5.05 5.28 5.27 5.18 Not measurable Rate of salt formation ( % ) 3.21 3.19 2.48 3.18 3.10 3.05 Not measurable Fire rating (cm) 14 15 15 25 16 25 Not measurable Operability ◎ ◎ ◎ ◎ X ◎ △ durability ◎ ◎ ◎ ○ ○ ○ △

As shown in the results of Table 2, in the case of Production Examples 1-1 and 1-2, the weight loss of the core was generally good and the weight loss rate was 28% or more. On the contrary, Comparative Production Examples 1-2 and Comparative Production Examples 1-4 showed a very low weight reduction rate.

In Comparative Production Example 1-1, although the weight loss rate was high and the strength reduction rate was adequate, there was a problem that the salt deposition rate was greatly decreased. In addition, in Comparative Production Examples 1-3, there was a problem that workability was poor. In Comparative Production Examples 1-5, there was a problem that not only the core portion was completely reduced but also the cis portion was reduced. This is because the Na ⁺ ion surfactant acts in the alkaline water and the sheath component is reduced.

Example  2-1: Cis - Core (low temperature Heat number  Solubility) Manufacture of Flame Retardant Composite Fiber

(1) A flame-retardant polyester resin was prepared as a sheath resin in the same manner as in Example 1 above.

(2) Low temperature Heat number  Preparation of Soluble Polyester Resin ( Core portion )

An acid component comprising 64.8 mol% of terephthalic acid, 20 mol% of isophthalic acid, 7 mol% of adipic acid and 8.2 wt% of sodium 3,5-dicarbomethoxybenzenesulfonate was prepared, and then the acid component and diol component diethylene Glycol was reacted at a molar ratio of 1: 1.3 to prepare an esterification reaction product.

Next, the esterification reaction product and polyethylene glycol having a weight average molecular weight of about 2,300 were condensation-polymerized to prepare a copolyester resin (second resin). The copolyester resin produced had an intrinsic viscosity (IV) of 0.750 dl / g.

(3) Cis - Fabrication of Core Composite Fiber

The low temperature hot water-soluble resin was added to the flame-retardant polyester resin and the core portion of the sheath portion of the sheath-core type composite spinneret, followed by spinning at a spinning temperature of 280 ° C and a spinning speed of 4,200 mpm. 70% by weight of a cis-core conjugated fiber.

Example  2-2

The esterification reaction product was prepared in the same manner as in Example 2-1 except that the composition ratio of the esterification reaction product in the preparation of the second resin as the core part was changed to a weight average molecular weight of about 2,300 (Second resin) was produced by subjecting polyethylene glycol, i.e., polyethylene glycol, to a polycondensation reaction to prepare a cis-core conjugated fiber.

Comparative Example  2-1

Flame-retardant PET (manufactured by Toray Chemical Co., Ltd., trade name ESFRON) containing no dimethyl 5-sodiosulfoisophthalate was prepared as a sheath resin.

Next, using the sheath resin and the low-temperature hot water-soluble polyester resin (core resin, second resin) of Example 2-1, 30% by weight of the core, 70% Core composite fiber was prepared.

Comparative Example  2-2

A flame-retardant PET (manufactured by Toray Chemical Co., Ltd., product name ESFRON) containing no dimethyl 5-sodiosulfoisophthalate was used as the sheath resin in the same manner as in Comparative Example 2-1.

Then, a cis-core conjugated fiber composed of 30% by weight of core and 70% by weight of cis was prepared by using alkali-soluble PET (manufactured by Toray Chemical Co., Ltd., trade name: ESP) as a core part resin.

Comparative Example  2-3 ~ 2-8

The esterification reaction product was prepared in the same manner as in Example 2-1 except that the composition ratio of the esterification reaction product in the preparation of the second resin as the core part was changed to a weight average molecular weight of about 2,300 (Second resin) was produced by subjecting polyethylene glycol, which is a polypropylene resin, to a polycondensation reaction to prepare a copolyester resin (second resin), and then a cis-core conjugated fiber was produced using the copolymer to thereby prepare Comparative Examples 2-3 to 2-8.

division
(mole%) Example
2-1 Example
2-2 Comparative Example
2-3 Comparative Example
2-4 Esterification
Reactant
Furtherance Acid component Terephthalic acid 64.8 69.8 76.8 57.6 Isophthalic acid 20 13 8 27.2 Adipic acid 7 10 7 7 Sodium 3,5-dicarbo-
Methoxybenzenesulfonate 8.2 7.2 8.2 8.2 Acid component and diol component molar ratio 1: 1.3 1: 1.3 1: 1.3 1: 1.3 The second resin intrinsic viscosity 0.750 dl / g 0.732 0.738 0.749 Of composite fibers
Sheath portion and core portion weight ratio 7: 3 7: 3 7: 3 7: 3

division
(mole%) Comparative Example
2-5 Comparative Example
2-6 Comparative Example
2-7 Comparative Example
2-8 Esterification
Reactant
Furtherance Acid component Terephthalic acid 73.5 59.8 70 58 Isophthalic acid 18 20 20 20 Adipic acid 0.3 12 7 7 Sodium 3,5-dicarbo-
Methoxybenzenesulfonate 8.2 8.2 3 15 Acid component and diol component molar ratio 1: 1.3 1: 1.3 1: 1.3 1: 1.3 The second resin intrinsic viscosity 0.749 0.730 0.721 0.792 Of composite fibers
Sheath portion and core portion weight ratio 7: 3 7: 3 7: 3 7: 3

Manufacturing example  2-1: Production of flame retardant polyester hollow fiber

The cis-core conjugate fiber prepared in Example 2-1 was circularized and then subjected to weight loss at 65 占 폚 in hot water (FW) for about 30 minutes to prepare a CD (cation dyeable) flame retardant polyester hollow fiber.

Manufacturing example  2-2 and Comparative Manufacturing Example  2-1, Comparative Manufacturing Example  2-3 ~ 2-8

(FW) for about 30 minutes in the same manner as in Production Example 2-1 to prepare hollow fibers, and each of the conjugated fibers of Example 2-2 and Comparative Examples 2-1 to 2-8, To prepare hollow fibers, and Production Example 2-2 and Comparative Production Examples 2-1 to 2-8 were respectively performed.

Comparative Manufacturing Example  2-2 and Comparative Manufacturing Example  2-9

The cis-core conjugated fiber prepared in Comparative Example 2-2 was subjected to alkali reduction (NaOH aqueous solution, concentration 5 vol%) to prepare hollow fibers, and Comparative Production Example 2-2 was carried out.

In addition, hollow fiber was produced by proceeding the alkali reduction (NaOH aqueous solution, concentration 5 vol%) of the cis-core conjugate fiber produced in Example 2-1 at all times, and Comparative Production Example 2-9 was carried out.

Experimental Example  2: Measurement of physical properties of hollow fibers

The weight loss rate, the strength reduction rate, the salt deposition rate, the degree of fire resistance, the workability and the durability of the hollow fibers in the Production Examples 2-1 to 1-2 and Comparative Production Examples 1-1 to 1-9 were measured, 5 to Table 6. At this time, the physical properties were measured in the same manner as in Experimental Example 2.

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2-4 Weight loss rate
(%) 28.91 26.31 29.04 38.51 24.29 29.21 Core portion
Weight loss rate
(%) 96.37 87.70 96.80 100 80.97 97.37 Hollow formation
Whether ○ ○ ○ ○ △ ○ burglar
Reduction rate ( % ) 5.12 7.34 4.91 14.92 5.02 5.34 Rate of salt formation ( % ) 3.19 3.17 2.51 2.86 3.18 3.15 Fire rating (cm) 15 18 14 22 21 16 Operability ◎ ◎ ◎ ◎ ◎ △ durability ◎ ◎ ◎ ○ ○ ○

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2-9 Weight loss rate
(%) 22.15 28.84 4.72 29.93 76.98 Core portion
Weight loss rate
(%) 73.84 96.14 15.73 99.75 100 Hollow formation
Whether △ ◎ × ◎ X burglar
Reduction rate ( % ) 8.99 5.24 7.35 4.90 Not measurable Rate of salt formation ( % ) 3.15 3.12 2.89 3.10 Not measurable Fire rating (cm) 22 16 24 18 Not measurable Operability ◎ △ ○ × △

The results of Tables 5 and 6 show that in Production Example 2-1 and Production Example 2-2, the rate of weight loss was 26% or more, and the rate of salt settling and the reduction in the appropriate strength were shown. On the other hand, Comparative Production Example 2-1 had a problem that the weight loss rate was excellent but the salt set rate was low.

Further, in Comparative Production Example 2-2 and Comparative Production Example 2-9, there was a problem that the amount of the core portion was reduced, but the amount was reduced to the cis portion.

In Comparative Preparation Example 2-3 in which the content of isophthalic acid was less than 5 mol% and Comparative Preparation Example 2-5 in which the content of adisic acid was less than 1 mol%, the weight loss rate was decreased and the result showed that the hole forming ability was poor.

In Comparative Production Example 2-4 in which the content of isophthalic acid exceeded 25 mol%, the strength was increased rather than before the weight loss, but there was a problem that the productivity was deteriorated due to the lack of heat resistance and the viscosity of the polymer at the time of high-temperature spinning.

In Comparative Production Example 2-6 in which the adipic acid content was more than 10 mol%, there was a problem that the productivity was poor due to the lack of heat resistance and the decrease of the viscosity of the polymer upon high-temperature spinning.

In Comparative Preparation Example 2-7 in which the sulfonate content was less than 5 mol%, the weight loss rate was so low that hollow formation was not obtained, and in Comparative Production Example 2-8 in which the sulfonate content exceeded 12 mol% There is a problem that the packing pressure is increased in the spin beam during the spinning process due to the excessive amount of the sulfonate and the operation is poor due to the occurrence of the fineness deviation and the partial trimming during the winding.

Through the above Examples and Experimental Examples, it can be seen that the flame-retarded conjugate fiber according to the present invention has a good flame retardancy and a high salt-setting rate as well as an appropriate strength since the core portion can be easily lost at high temperature hot water and / there was.

By using the flame-retardant composite fiber of the present invention, it was confirmed that hollow fiber having excellent lightness, flame retardancy and mechanical properties as well as excellent coloration and an application product using the same can be provided.

Claims (11)

As sheath-core type conjugated fibers,
A sheath portion including a flame-retardant polyester resin; And
And a core portion comprising a high temperature hot water soluble polyester resin or a low temperature hot water soluble polyester resin.
The method according to claim 1,
When the core part is a high temperature hot water soluble polyester resin, the sheath part and the core part are combined so as to have a weight ratio of 7: 3, Based on the following formula (1): 27% or more based on the following formula (1).
[Equation 1]
(%) = (Weight of composite fiber before weight loss (g) - weight of composite fiber after weight reduction / weight of composite fiber core before weight loss (g)) × 100 (%)
The method according to claim 1,
When the core part is a low temperature hot water soluble polyester resin, the sheath part and the core part are combined so as to have a weight ratio of 7: 3, A flame-retardant conjugate fiber excellent in dyeability characterized by being 26% or more based on the following formula (1).
[Equation 1]
(%) = (Weight of composite fiber before weight loss (g) - weight of composite fiber after weight reduction / weight of composite fiber core before weight loss (g)) × 100 (%)
The flame-retardant polyester resin composition according to claim 1, wherein the flame-
An esterification reaction product of an oligomer obtained by polymerizing phthalic acid and an aliphatic diol and dimethyl 5-sodiosulfoisophthalate; And a reaction-type phosphorus flame retardant. The flame-retardant conjugate fiber according to claim 1,
The method of claim 1, wherein the reactive phosphorus flame retardant
A flame-retardant conjugate fiber excellent in dyability, which comprises at least one member selected from the group consisting of compounds represented by the following general formula (1) and compounds represented by the following general formula (2);
[Chemical Formula 1]

Wherein R ¹ is -OH, -COOH, -CH ₂ COOH, -CH ₂ CH ₂ COOH, -CH ₂ CH ₂ CH ₂ COOH or -CH ₂ CH ₂ CH ₂ CH ₂ COOH,
(2)

In Formula 2, R ¹ and R ² are independently an alkyl group having 1 to 10 carbon atoms, an alkylene group having 2 to 5 carbon atoms, a cycloalkyl group having 5 to 6 carbon atoms, or a phenyl group.
The flame-retarded composite fiber according to claim 1, wherein the high-temperature hydrothermally soluble polyester resin comprises terephthalic acid, isophthalic acid, dimethyl 5-sodiosulfoisophthalate, and diethylene glycol.
The high temperature hydrothermally soluble polyester resin according to claim 6, wherein the high-temperature hydrothermally soluble polyester resin comprises 55 to 65 mol% of terephthalic acid, 10 to 25 mol% of isophthalic acid, 5 to 15 mol% of dimethyl 5-diisocyanurate isophthalate and 5 to 20 mol% The flame-retardant composite fiber according to claim 1,
The low-temperature hydrothermally soluble polyester resin according to claim 1, wherein the low-
An esterified reactant reacted with an acid component containing an aromatic polycarboxylic acid having 6 to 14 carbon atoms, an aliphatic polycarboxylic acid having 2 to 16 carbon atoms and sodium 3,5-dicarbomethoxybenzenesulfonate, and a diol component; And polyglycol; and copolyester obtained by polycondensation of polyethylene glycol.
9. The method of claim 8,
Wherein the esterification reaction product is a monomer comprising an acid component and a diol component in a molar ratio of 1: 1.1 to 2.0,
The acid component may be at least one selected from the group consisting of aromatic polycarboxylic acids having 6 to 12 carbon atoms selected from the group consisting of terephthalic acid, dimethyl terephthalate, isophthalic acid and dimethyl isophthalate; oxalic acid, malonic acid, succinic acid, glutaric acid, At least one aliphatic polyvalent carboxylic acid having 2 to 14 carbon atoms selected from the group consisting of an acid, a hydroperoxide, an acid, a suberic acid, citric acid, fimaric acid, azelaic acid, sebacic acid, nonanoic acid, decanoic acid, dodecanoic acid and hexanodecanoic acid Bicic acid; And sodium 3,5-dicarbomethoxybenzenesulfonate; , ≪ / RTI >
Wherein the diol component comprises at least one selected from the group consisting of ethylene glycol, diethylene glycol, neopentyl glycol, 1,3-propanediol, 1,4-butanediol, and 1,6-hexanediol Flame retardant composite fiber excellent in dyability.
A flame-retardant hollow fiber excellent in dyability produced by eluting a core portion of a flame-retardant conjugated fiber according to any one of claims 1 to 9.
A flame retardant article comprising the flame retardant hollow fiber of claim 10.