KR101910430B1 - Composite fiber for manufacturing flame-retardant hollow fiber for car interior materals and Flame-retardant hollow fiber for car interior materals - Google Patents

Abstract

The present invention relates to a flame-retardant conjugate fiber for automobile interior materials and a flame-retardant hollow fiber for automobile interior materials using the flame-retardant conjugate fiber. More particularly, the present invention relates to a flame- Flame retardant composite fiber for an automobile interior material which can prevent and / or minimize the occurrence of flame retardancy, and further, to a hollow fiber having light weight, flame retardancy and mechanical properties as an automobile interior material.

Description

TECHNICAL FIELD [0001] The present invention relates to a composite fiber for producing a flame-retardant hollow fiber for automobile interior material, and a flame-retardant hollow fiber for automobile interior material using the same.

FIELD OF THE INVENTION The present invention relates to a flame-retardant composite fiber for an automobile interior material and a flame-retardant hollow fiber for an automobile interior material in which a core portion of the composite fiber is eluted and lightened.

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.

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 or less There is a problem that a low melting point polyester having a lower melting point can not be produced.

In recent years, light weight materials for automobiles have been reduced in order to reduce fuel consumption. Accordingly, research and development of lightweight materials for automobile interior materials have been progressing. For such automobile interior materials, high flame retardancy and mechanical properties are required. However, there are many difficulties in manufacturing a lightweight material with high compatibility while meeting these specifications.

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

SUMMARY OF THE INVENTION The present invention has been devised to solve the problems described above, and it is an object of the present invention to provide a hollow fiber for automobile interior material which satisfies physical property specifications required for an automobile interior material, The present invention has been completed. That is, the present invention relates to a flame-retardant composite fiber for automobile interior materials having an optimal composition and composition ratio capable of minimizing and / or preventing the deterioration of physical properties of the composite fiber sheath portion during the elution process while easily eluting the core portion of the composite fiber, It is an object of the present invention to provide a flame retardant hollow fiber for an automobile interior material.

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

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 at the time of losing 30 minutes may be 26% or more based on the following formula (1).

In one preferred embodiment of the present invention, the composite fiber of the present invention is a low-temperature alkali-soluble polyester resin, and the sheath portion and the core portion are co-spun at a weight ratio of 7: 3, The weight loss rate (%) obtained by reducing the aqueous sodium hydroxide solution for 100 minutes may be 25 to 33% 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 sheath portion includes at least one selected from the group consisting of PET semidull polymer, PET bright polymer, and PET superbright polymer .

In one preferred embodiment of the present invention, the sheath is a PET resin comprising a polymer obtained by polymerizing an acid component containing at least one member selected from the group consisting of terephthalic acid and isophthalic acid and a diol component; A flame retardant comprising at least one selected from a melamine-based flame retardant including P (phosphorus), a phosphorus-based flame retardant, and an inorganic-based flame retardant; And a carbon-based colorant.

In one preferred embodiment of the present invention, the diol component of the sheath may include an aliphatic diol having 2 to 20 carbon atoms.

In one preferred embodiment of the present invention, the melamine-based flame retardant including P (phosphorus) in the sheath may include at least one selected from melamine, melamine cyanurate, melamine phosphate, melamine polyphosphate, and melamine pyrophosphate.

In one preferred embodiment of the present invention, the phosphorus-based flame retardant of the sheath may include a phosphorus-based flame retardant represented by the following formula (1).

[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.

In one preferred embodiment of the present invention, the inorganic flame retardant of the sheath is selected from the group consisting of aluminum hydroxide, magnesium hydroxide, zinc borate, zinc diethyl phosphinate (C ₄ H ₁₁ O ₂ P 1 / 2Zn) Or more species.

In one preferred embodiment of the present invention, the carbon-based colorant in the sheath portion may include carbon fibers, carbon black, etc., and may be contained in the sheath portion at 15,000 to 25,000 ppm.

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.

In one preferred embodiment of the present invention, the low-temperature alkali-soluble polyester resin of the core portion contains an acid component containing an aromatic polycarboxylic acid having 6 to 14 carbon atoms and sodium 3,5-dicarbomethoxybenzenesulfonate and a diol component Reacted esterification reagent; And polyethylene glycol; and copolyesters obtained by polycondensation of polyethylene glycol.

In one preferred embodiment of the present invention, the esterification reaction product of the low temperature alkali soluble polyester resin may contain an acid component and a diol component in a molar ratio of 1: 1.1 to 2.0, as a monomer.

In one preferred embodiment of the present invention, the acid component of the low temperature alkali soluble polyester resin is an aromatic polycarboxylic acid having 6 to 12 carbon atoms selected from the group consisting of terephthalic acid, dimethylterephthalate, isophthalic acid and dimethyl isophthalate ; And sodium 3,5-dicarbomethoxybenzenesulfonate.

In one preferred embodiment of the present invention, the diol component of the low temperature alkali soluble polyester resin is selected from the group consisting of ethylene glycol, diethylene glycol, neopentyl glycol, 1,3-propanediol, 1,4-butanediol and 1,6- Diol, and the like.

Another object of the present invention is to provide a flame-retardant hollow fiber for automobile interior material, which provides a flame-retardant hollow fiber formed of 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.

In a preferred embodiment of the present invention, when the core portion comprises a low temperature alkali soluble polyester resin, the core portion may be eluted by performing an alkali elution treatment.

Another object of the present invention is to provide an automobile interior material using flame retardant hollow fiber for automobile interior material.

The flame-retarded composite fiber for automobile interior material according to the present invention is excellent in flame retardancy because it can minimize flame-retarded composite fiber and elution of the flame-retardant component of the sheath portion generated during production of the flame-retardant hollow fiber. Further, since the elution of the core portion is easy and the effect on the sheath portion is minimized during the core portion elution treatment, the reduction in the physical properties of the sheath portion can be prevented, so that the flame retardant hollow fiber for automobile interior materials can be provided have.

The flame-retardant conjugated fiber for automobile interior material of the present invention is a cis-core type conjugate fiber, and the core portion is eluted to provide a hollow fiber composed of a sheath portion. The present invention will be described in detail by dividing the sheath portion and the core portion.

[ Shebu ]

In the flame-retarded composite fiber for automobile interior material according to the present invention, the sheath portion comprises a PET resin, and preferably a PET resin selected from the group consisting of PET semidull polymer, PET bright polymer, and PET superbright polymer. A PET resin including a polymer obtained by polymerizing an acid component containing at least one member selected from the group consisting of terephthalic acid and isophthalic acid and a diol component; Flame retardant; And a carbon-based colorant.

Among the sheath components, the diol component may include an aliphatic diol having 2 to 20 carbon atoms, and preferably ethylene glycol, diethylene glycol, propylene glycol, butylene glycol, trimethyl glycol, tetramethylene glycol, pentamethyl glycol, At least one member selected from among glycol, heptamethylene glycol, octamethylene glycol, nonamethylene glycol, decamethylene glycol, undecamethylene glycol, dodecamethylene glycol and tridecamethylene glycol, more preferably ethylene glycol, diethylene glycol , Propylene glycol and butylene glycol, or a mixture of two or more thereof.

Among the sheath components, the flame retardant may include at least one member selected from the group consisting of melamine flame retardants including P (phosphorus), phosphorus flame retardants, and inorganic flame retardants, and preferably at least one member selected from among melamine- , And more preferably a melamine flame retardant containing P can be used.

The P-containing melamine flame retardant may include at least one selected from melamine, melamine cyanurate, melamine phosphate, melamine polyphosphate, and melamine pyrophosphate.

The phosphorus-based flame retardant may be a phosphorus-based flame retardant commonly used in the art, and preferably a phosphorus-based flame retardant represented by the following general formula (1).

[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.

The inorganic flame retardant may include at least one selected from aluminum hydroxide, magnesium hydroxide, zinc borate and zinc diethyl phosphinate (C ₄ H ₁₁ O ₂ P 1 / 2Zn) And the content of the inorganic flame retardant is preferably 4,500 ppm to 8,000 ppm, more preferably 5,200 to 7,800 ppm, and still more preferably 5,500 to 7,200 ppm in the cis portion. If the content of the inorganic flame retardant is less than 4,500 ppm, there may be a problem that the defective flame retardancy (carbonization distance of 20 cm or more) occurs in the evaluation of fire resistance of the final product (ASTM D 6413: 2008) There may be a problem that the yield of production such as trimming and lowering of spinning speed is decreased.

Among the sheath component, the carbon-based colorant may include carbon fiber, carbon black and the like, preferably carbon black. The content thereof may be 10,000 to 30,000 ppm, preferably 15,000 to 25,000 ppm, and more preferably 16,500 to 23,000 ppm in the cis portion. If the content of the carbon-based coloring agent is less than 10,000 ppm, there may be a problem that the salt deposition rate is lowered. If the content is more than 30,000 ppm, there is a problem that the fineness of the hollow fiber is increased, A problem may occur that the pack pressure rises.

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 for automobile interior according to the present invention comprises a high-temperature hot-water-soluble polyester resin, a low-temperature hot-water-soluble polyester resin or a low-temperature alkali-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 0.960 dl / g, preferably 0.800 to 0.920 dl / g, more preferably 0.850 to 0.920 dl / g have. If the intrinsic viscosity of the first resin is less than 0.750 dl / g, the deviation of the fineness of the fibers radiated during the composite spinning may become too large, which may result in poor workability and durability of the hollow fibers, and an inherent viscosity of 0.960 dl / g , The workability is significantly lowered, the deviation of the fineness is increased, and the hollow is difficult to form.

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 16 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 16 carbon atoms in the acid component of the second resin has an increased fluidity of the molecular chain of the low-temperature hot-water-soluble copolyester polymer and a surface area for bonding with water, so that the water- It can be possible.

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.

The second resin may have an intrinsic viscosity of 0.500 to 0.950 dl / g, preferably 0.650 to 0.950 dl / g, and more preferably 0.750 to 0.950 dl / g. If the intrinsic viscosity is less than 0.500 dl / g, there is a problem in that the mechanical strength of the composite fiber is remarkably weakened during the composite spinning with the fiber, and the post-processing operation becomes poor. If the intrinsic viscosity is more than 0.950 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.

Next, the low temperature alkali soluble polyester resin (third resin) as a core part component of the flame retardant composite fiber for automobile interior according to the present invention will be explained.

The low temperature alkali soluble polyester resin (the third resin) comprises an esterified reactant reacted with an acid component and a diol; And polyethylene glycol; and copolyesters obtained by polycondensation thereof.

As the esterification reactant component of the third resin, the acid component includes an aromatic polycarboxylic acid having 6 to 14 carbon atoms and sodium 3,5-dicarbomethoxybenzenesulfonate. Depending on the purpose, Alicyclic dicarboxylic acid, and the like. Non-limiting examples of the dicarboxylic acid include 2,5-furandicarboxylic acid, 2,5-cipopenedicarboxylic acid, and 2,5- And a carboxylic acid or a carboxylic acid.

The aromatic polycarboxylic acid having 6 to 14 carbon atoms may include at least one member selected from terephthalic acid, dimethyl terephthalate, isophthalic acid and dimethyl isophthalate, and preferably terephthalic acid and isophthalic acid. At this time, the content of isophthalic acid is preferably not high, and may be included in an amount of 5 to 25 mol%, preferably 8 to 20 mol%, of the acid component in a non-limiting amount.

The sodium 3,5-dicarbomethoxybenzenesulfonate induces the adsorption of the polymer to water molecules, thereby further improving the alkali-solubility and thus enabling the reduction process even at a low temperature. 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, And may further comprise a phosphonic metal salt. In the acid component, 3 to 10 mol% of sodium 3,5-dicarbomethoxybenzenesulfonate may be contained, and the remaining amount may include an aromatic polycarboxylic acid having 6 to 14 carbon atoms. If sodium 3,5-dicarbomethoxybenzenesulfonate is contained in an amount of less than 3 mol%, the intended low-temperature alkali can not be obtained, so that the step of reducing at low temperatures may be difficult, and if it exceeds 10 mol% The process efficiency in the polymerization of the copolyester is remarkably lowered, the melt viscosity is increased, the spinning workability is significantly lowered, and the excessive production of diethylene glycol (DEG), which is a by-product of the process, And there is a problem that causes the pack pressure to rise.

The diol used in the synthesis of the esterification reaction product of the third resin is an aliphatic diol having 2 to 14 carbon atoms, preferably ethylene glycol, diethylene glycol, neopentyl glycol, 1,3-propanediol, 1,4-butanediol, , Hexanediol, propylene glycol, trimethylglycol, tetramethylene glycol, pentamethylglycol, hexamethylene glycol, heptamethylene glycol, octamethylene glycol, nonamethylene glycol, decamethylene glycol, undecamethylene glycol, dodecamethylene Glycol and tridecamethylene glycol, and preferably 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 And the like.

The acid component 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.

The polyethylene glycol of the third resin may have a weight average molecular weight of 400 to 10,000. If the weight average molecular weight is less than 400, it is difficult to carry out the weight loss process at a low temperature since it can not have the desired alkali utilization property If the weight average molecular weight exceeds 10,000, the polymerization reactivity is lowered and the glass transition temperature of the copolyester formed becomes too low to cause a problem that the thermal stability is poor.

In the low temperature alkali soluble polyester resin, the esterification reaction product and the polyethylene glycol are condensed with each other. According to a preferred embodiment of the present invention, the copolyester is produced by adding 1 to 10 parts by weight of polyethylene glycol to the esterification reaction product, And preferably 1.5 to 7 parts by weight. If the amount of the polyethylene glycol is less than 1 part by weight, the desired water-solubility characteristics can not be obtained. Therefore, there is a problem that the weight loss process at low temperatures is difficult to perform. If the amount exceeds 10 parts by weight, It is too low and the thermal stability may become poor.

The third resin may have an intrinsic viscosity (IV) of 0.720 to 0.980 dl / g, preferably 0.760 to 0.960 dl / g, more preferably 0.800 to 0.930 dl / g. If the intrinsic viscosity of the first resin is less than 0.720 dl / g, the deviation of the fineness of the fibers radiated during the composite spinning may become too large, which may result in poor workability and durability of the hollow fibers, and an inherent viscosity of 0.980 dl / g , The workability is significantly lowered, the deviation of the fineness is increased, and the hollow is difficult to form.

In the flame-retardant composite fiber for automobile interior material according to 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 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 27% or more, preferably 28% to 30% based on the following formula (1).

When the core part is formed of low-temperature hot water-soluble polyester resin, the flame-retarded composite fiber for automobile interior material according to the present invention is spin-coated so that the sheath part and the core part are in 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 26.5% 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 (%)

In the flame-retardant conjugate fiber for automobile interior material according to the present invention, when the core portion is formed of a low-temperature alkali-soluble polyester resin, the sheath portion and the core portion are combined spinning so as to have a weight ratio of 7: 3, Based on the following formula (1), the weight loss rate (%) after the weight loss treatment in a 4 wt% sodium hydroxide aqueous solution for 100 minutes is 25 to 33%, preferably 26 to 32%, more preferably 27 to 30.5 %. ≪ / RTI >

[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 (%)

Further, the flame-retardant hollow fiber formed of only the sheath portion from which the core portion of the flame-retardant composite fiber for automobile interior material 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.

When the core part comprises a low temperature alkali soluble polyester resin, the core part can be eluted by performing an alkali elution treatment.

The flame retardant hollow fiber of the present invention thus fabricated is lightweight, has excellent mechanical properties and flame retardancy, and is thus suitable for application as an automobile interior material.

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 )

Terephthalic acid and ethylene glycol were mixed at a molar ratio of 1: 1.3, and the esterification reaction was carried out while removing water generated at 240 캜.

Thereafter, the esterification reaction product was subjected to a polymerization process at a temperature of 280 to 285 ° C and a vacuum degree of 1.5 torr or less to obtain a polyester resin through condensation polymerization.

Next, Zinc Diethyl phosphinate was added to the polyester resin at a concentration of 6,000 ppm based on the P content of the polyester resin to prepare P (phosphorus) and an inorganic additive type resin (sheath resin) . At this time, carbon black was added to the polyester resin together with a carbon-based colorant at a concentration of about 20,000 ppm.

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

A mixture containing 60 mol% of terephthalic acid (hereinafter referred to as PET), 20 mol% of isophthalic acid, 10 mol% of dimethyl 5-sodium diisophthalate (hereinafter referred to as DSIP) and 10 mol% of diethylene glycol To prepare a high-temperature hot-water-soluble polyester resin. At this time, the polymerization reaction time was about 100 minutes, and the intrinsic viscosity (IV) of the prepared resin was 0.890 dl / g.

(3) Cis - Fabrication of Core Composite Fiber

After the flame-retardant polyester resin and the water-receiving resin were fed into the sheath portion of the sheath-core type composite spinneret, the mixture was spin-cast at a spinning temperature of 280 DEG C and a spinning speed of 1,500 mpm, 30% by weight, and cis-70% by weight.

Example  1-2

A cis resin was prepared in the same manner as in Example 1-1 except that zinc diethylphosphinate was added at a concentration of 6,000 ppm and carbon black at a concentration of about 27,000 ppm with respect to the polyester 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.

Example  1-3

A sheath resin was prepared in the same manner as in Example 1-1 except that zinc diethylphosphinate was added at a concentration of 6,000 ppm and carbon black at a concentration of about 10,500 ppm with respect to the polyester 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.

Example  1-4

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 resin produced had an intrinsic viscosity (IV) of 0.857 dl / g.

Comparative Example  1-1

A sheath resin was prepared in the same manner as in Example 1-1 except that zinc diethylphosphinate was added at a concentration of 3,000 ppm to prepare P (phosphorus) and an inorganic additive type resin (sheath resin). At this time, carbon black was added to the polyester resin together with a carbon-based colorant at a concentration of about 20,000 ppm.

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

A cis resin was prepared in the same manner as in Example 1-1 except that zinc diethylphosphinate was added at a concentration of 6,000 ppm and carbon black at a concentration of about 35,000 ppm with respect to the polyester 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  1-3

A sheath resin was prepared in the same manner as in Example 1-1 except that zinc diethylphosphinate was added at a concentration of 6,000 ppm and carbon black at a concentration of about 5,000 ppm with respect to the polyester 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  1-4

The same sheath resin as in Example 1-1 was prepared.

Next, as a core part resin, a resin composition 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 Soluble thermoplastic polyester resin. In this case, the intrinsic viscosity (IV) of the resin prepared by proceeding the condensation polymerization reaction time to 60 minutes in order to shorten the polymerization reaction time and increase the productivity was 0.450 dl / g.

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 1-5

The same sheath resin as in Example 1-1 was prepared.

Next, as a core part resin, a resin composition 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 Soluble thermoplastic polyester resin. The intrinsic viscosity (IV) of the prepared resin was 1.05 dl / g, which was obtained by proceeding the condensation polymerization reaction time to 140 minutes in order to improve the melt viscosity in order to improve the radioactivity of the core part 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% To prepare a c-core conjugate fiber

division Example
1-1 Example
1-2 Example
1-3 Example
1-4 Comparative Example
1-1 Comparative Example
1-2 Comparative Example
1-3 Comparative Example
1-4 Comparative Example
1-5 Shebu Inorganic
Flame retardant
Content (ppm) 6,000 6,000 6,000 6,000 3,000 6,000 6,000 6,000 6,000 Carbon system
coloring agent
Content (ppm) 20,000 27,000 10,500 20,000 20,000 35,000 5,000 20,000 20,000 nose
uh
part
(mole%) PET ⁽¹⁾ 60 60 60 63 60 60 60 60 60 Isophthalic acid 20 20 20 17 20 20 20 20 20 DSIP ⁽²⁾ 10 10 10 11.2 10 10 10 10 10 DEG ⁽³⁾ 10 10 10 8.8 10 10 10 10 10 Intrinsic viscosity (IV, dl / g) 0.890 0.890 0.890 0.857 0.890 0.890 0.890 0.450 1.05 Of composite fibers
Sheath portion and core portion weight ratio 70:30 70:30 70:30 70:30 70:30 70:30 70:30 70:30 70:30 (1) Terephthalic acid
(2) Dimethyl 5-sodiosulfoisophthalate
(3) Diethylene glycol

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 black base flame retardant polyester hollow fiber.

Manufacturing example  1-2 to 1-4 and Comparative Manufacturing Example  1-1 to 1-5

(FW) for about 30 minutes in the same manner as in Preparation Example 1-1 to prepare hollow fibers. In Examples 1-2 to 1-4 and Comparative Examples 1-1 to 1- 5 were used to prepare hollow fibers, and Production Examples 1-2 to 1-4 and Comparative Production Examples 1-1 to 1-5 were respectively carried out.

Experimental Example 1: Measurement of physical properties of hollow fibers

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

The strength of the hollow fiber was measured after the reduction according to the ASTM D1682 method.

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

The measurement of the salt deposition rate was carried out by measuring the salt deposition rate according to the CIE 1976 standard using a colorimeter using the finished flame retardant construction (the black dyeing process using carbon black was separately removed). At this time, the appropriate salt rate is 3.15% or more.

(4) Pack pressure (kg / cm ² )

A pressure sensor was installed in the MP (Melting Pump) to measure the pack pressure of the hollow fiber after measuring the change in the pack pressure.

(5) Fire resistance (carbonization distance, cm)

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

(6) 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.

division Manufacturing example
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1-2 Manufacturing example
1-3 Manufacturing example
1-4 compare
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1-5 Weight loss rate
(%) 29.68 29.66 29.54 29.38 29.54 29.04 29.44 30.05 11.98 Core portion
Weight loss rate
(%) 98.93 98.86 98.46 97.93 98.47 96.80 98.13 100 39.93 Hollow formation
Whether ○ ○ ○ ○ ○ ○ ○ ○ X Fiber section formation normal normal normal normal normal Fineness
Deviation normal Fineness
Deviation Fineness
Deviation Pack pressure
(kg / cm ² ) 120 ~
140 170-190 120 to 140 115-135 120 ~
140 180 ~
200 115 ~
135 80 ~
100 160 ~
180 Strength (g / d) 4.5 4.0 4.6 3.8 4.2 3.5 4.8 2.6 4.3 Rate of salt formation ( % ) 3.21 4.42 2.23 3.19 3.31 4.73 1.88 3.21 3.21 Fire rating (cm) 11 13 14 12 24 14 13 14 14 Operability ◎ ◎ ◎ ◎ ◎ △ ◎ △ △ durability ◎ ◎ ◎ ◎ ◎ ◎ ◎ △ ○

In Comparative Experimental Example 1 in which the composite fiber containing 3,000 ppm of the inorganic flame retardant was used, the flame retardancy defect (carbonization distance 24 cm) was evaluated in the evaluation of the fire resistance of the final product (ASTM D 6413: 2008) There was a problem that occurred.

The hollow fiber of Comparative Production Example 2 in which the carbon-based coloring agent was used in an amount exceeding 30,000 ppm produced a deviation in fineness and the productivity was inferior. The composite fiber produced using the carbon-based coloring agent in an amount of less than 10,000 ppm There was a problem that the hollow fiber of Comparative Production Example 3 had a too low salt deposition rate.

In addition, the hollow fiber of Comparative Production Example 4, which was made of conjugate fiber having an intrinsic viscosity of 0.450 dl / g as the core resin, and the core resin were made of a conjugate fiber having an intrinsic viscosity as high as 1.05 dl / g In the case of the hollow fiber of Comparative Production Example 5, there was a problem that the fineness of the hollow fiber was large and the workability was poor and the durability of the hollow fiber was poor, and the weight loss rate was not very good.

On the other hand, in the case of Production Examples 1-1 to 1-2, the product showed a high weight loss rate of 29% or more and exhibited excellent physical properties as a whole.

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 containing 65.8 mol% of terephthalic acid, 19 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 the diol component diethylene Glycol was reacted at a molar ratio of 1: 1.25 to prepare an esterification reaction product.

Next, the esterification reaction product and polyethylene glycol having a weight average molecular weight of about 2,400 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 flame-retardant polyester resin and the water-receiving resin were put into a sheath portion of a sheath-core type composite spinneret and then spun at a spinning temperature of 280 DEG C and a spinning speed of 1,600 mpm, followed by stretching at a draw ratio of 3.2, 30% by weight, and cis-70% by weight.

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

Core resin (second resin) having the composition shown in Table 3 below was prepared as a core-part resin, using the same sheathing resin as in Example 1-1. Next, the second resin was fed to the sheath portion and the core portion of the sheath portion of the sheath-core type composite spinneret, followed by spinning at a spinning temperature of 280 占 폚 and a spinning speed of 1,600 mpm, followed by stretching at a stretching ratio of 3.2 Core composite fiber composed of 30% by weight of core and 70% by weight of sheath, respectively, and Example 2-2 and Comparative Examples 2-1 to 2-4 were respectively conducted.

division
(mole%) Example
2-1 Example
2-2 Comparative Example
2-1 Comparative Example
2-2 Comparative Example
2-3 Comparative Example
2-4 Esterification
Reactant
Furtherance Acid component Terephthalic acid 65.8 69.8 76.8 57.6 73.5 59.8 Isophthalic acid 19 13 8 27.2 18 20 Adipic acid 7 10 7 7 0.3 12 Sodium 3,5-dicarbo-
Methoxybenzenesulfonate 8.2 7.2 8.2 8.2 8.2 8.2 Acid component and diol component molar ratio 1: 1.25 1: 1.25 1: 1.25 1: 1.25 1: 1.25 1: 1.25 The second resin intrinsic viscosity (dl / g) 0.812 0.808 0.821 0.790 0.822 0.795 Of composite fibers
Sheath portion and core portion weight ratio 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 black base flame retardant polyester hollow fiber.

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

(FW) for about 30 minutes in the same manner as in Preparation Example 2-1 to prepare hollow fibers. The hollow fibers were prepared in the same manner as in Production Example 2-1, except that the conjugated fibers of Example 2-2 and Comparative Examples 2-1 to 2-4 To prepare hollow fibers, and Production Example 2-2 and Comparative Production Examples 2-1 to 2-4 were respectively carried out.

Experimental Example  2: Measurement of physical properties of hollow fibers

The weight loss rate, strength, salt deposition rate, fire resistance, workability and durability of the hollow fibers of Production Examples 2-1 to 2-2 and Comparative Production Examples 2-1 to 2-4 were measured, Respectively. At this time, the physical properties were measured in the same manner as in Experimental Example 1.

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2-4 Weight loss rate
(%) 28.98 27.39 27.98 28.82 25.05 29.22 Core portion
Weight loss rate
(%) 96.60 91.30 93.27 96.07 83.50 97.40 Hollow formation
Whether ○ ○ ○ ○ △ ○ Fiber section formation normal normal normal normal Bad normal Pack pressure
(kg / cm ² ) 120 ~
140 115-135 125-145 105 ~ 125 120 to 140 110 ~ 130 Strength (g / d) 4.2 4.2 4.0 3.2 4.4 3.7 Rate of salt formation ( % ) 3.19 3.15 3.13 3.09 3.08 3.17 Fire rating (cm) 10 14 15 11 22 14 Operability ◎ ◎ ◎ △ ○ △ durability ◎ ◎ ◎ △ ○ △

In the results of Table 4, in the case of Production Examples 2-1 to 2-2 and Comparative Production Example 2-1, a high weight loss rate of 27% or more was achieved, and overall properties were excellent.

On the contrary, in Comparative Production Example 2-2, the strength of the hollow fiber was relatively low, Comparative Production Example 2-3 had poor hollow formation, Comparative Production Example 2-4 had low strength , Workability and durability are poor.

Example  3-1: Cis - Manufacture of Core (Low Temperature Alkali Soluble) 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) Production of Low Temperature Alkali Soluble Polyester Resin ( Core portion )

An acid component containing 82.2% by mole of terephthalic acid, 10.5% by mole of isophthalic acid, and 7.3% by mole of sodium 3,5-dicarbomethoxybenzenesulfonate was prepared. The acid component and the diol component diethylene glycol were mixed at a molar ratio of 1: 1.35 To prepare an esterification reaction product.

Next, 5.5 parts by weight of polyethylene glycol having a weight average molecular weight of about 2,400 was subjected to polycondensation reaction with respect to 100 parts by weight of the esterification reaction product to prepare a copolyester resin (third resin). The copolyester resin produced had an intrinsic viscosity (IV) of 0.860 dl / g.

(3) Cis - Fabrication of Core Composite Fiber

After the flame retardant polyester resin and the third resin were put into the sheath portion of the sheath-core type composite spinneret, the spinning was conducted at a spinning temperature of 280 DEG C and a spinning speed of 1,600 mpm, 30% by weight, and cis-70% by weight.

Example  3-2 and Comparative Example  3-1 to 3-4

Core resin (third resin) having the composition shown in Table 5 below was prepared as a core-part resin, using the same sheathing resin as in Example 1-1. Next, the second resin was fed to the sheath portion and the core portion of the sheath portion of the sheath-core type composite spinneret, followed by spinning at a spinning temperature of 280 DEG C and a spinning speed of 1,600 mpm, followed by drawing at a draw ratio of 3.2 Core composite fiber composed of 30% by weight of core and 70% by weight of sheath, respectively, to obtain Example 3-2 and Comparative Examples 3-1 to 3-4.

division
Example
3-1 Example
3-2 Comparative Example
3-1 Comparative Example
3-2 Comparative Example
3-3 Comparative Example
3-4 Esterification
Reactant
Furtherance Acid component
(mole%) Terephthalic acid 82.2 75.5 89.0 64.0 88.0 76.5 Isophthalic acid 10.5 15.5 3.5 28.5 10.5 10.5 Sodium 3,5-dicarbo-
Methoxybenzenesulfonate 7.3 9 7.5 7.5 1.5 13 Acid component and diol component molar ratio 1: 1.35 1: 1.35 1: 1.35 1: 1.35 1: 1.35 1: 1.35 Polyethylene glycol (parts by weight) 5.5 2.3 0.5 12 5.5 5.5 The third resin intrinsic viscosity (dl / g) 0.860 0.805 0.845 0.792 0.782 0.895 Of composite fibers
Sheath portion and core portion weight ratio 7: 3

Manufacturing example  3-1 to 3-2 and Comparative Manufacturing Example  3-1 ~ 3-4: Preparation of flame retardant polyester hollow fiber

The sheath-core conjugate fibers prepared in Examples 3-1 to 3-2 and Comparative Preparative Examples 3-1 to 3-2 were circularized and then subjected to weight loss in an aqueous solution of sodium hydroxide at 55 占 폚 and 4 weight% Respectively, and Production Examples 3-1 to 3-2 and Comparative Production Examples 3-1 to 3-2 were respectively carried out.

Experimental Example  3: Measurement of physical properties of hollow fibers

The weight loss, strength, salt deposition rate, fire resistance, workability and durability of the hollow fibers of the Production Examples 3-1 to 3-2 and Comparative Production Examples 3-1 to 3-4 were measured, Respectively. At this time, the physical properties were measured in the same manner as in Experimental Example 1.

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3-4 Weight loss rate
(%) 28.91 29.15 24.83 29.52 4.52 29.67 Core portion
Weight loss rate
(%) 96.37 97.17 82.77 98.40 15.07 98.90 Hollow formation
Whether ○ ○ △ ○ × ○ Fiber section formation normal normal Bad normal Bad Bad
(Deviation of fineness) Pack pressure
(kg / cm ² ) 120 ~
140 110 ~ 130 125-145 100-120 115-135 140-170 Strength (g / d) 4.2 3.6 4.3 3.2 4.0 2.9 Rate of salt formation ( % ) 3.25 3.07 3.01 3.08 3.01 2.85 Fire rating (cm) 12 13 18 16 23 27 Operability ◎ ◎ ○ △ ◎ × durability ◎ ◎ △ △ ◎ △

The results of Table 6 show that the production rates of the preparation examples 3-1 to 3-2, the comparative preparation examples 3-2 and 3-4 were 28% or higher, And Comparative Production Example 3-4 showed low strength of the hollow fiber, poor workability and durability. In Comparative Production Example 3-1, there was a problem that the hollow fiber formation was not good and the fiber cross-section was poor. In Comparative Production Example 3-3, the weight loss rate was not very good.

The flame-retarded conjugate fiber according to the present invention can be easily and easily lost under high-temperature hot water and / or low-temperature hot water under low-temperature alkaline conditions as well as excellent flame retardancy and salt- It was confirmed that it has strength.

Through the use of the flame-retardant conjugate fiber of the present invention, hollow fibers having excellent lightness, flame retardancy and mechanical properties as well as deep-seated color and application products using the same, preferably automobile interior materials, can be provided.

Claims (14)

As sheath-core type conjugated fibers,
A sheath portion including a PET resin; And a core portion comprising a high-temperature hot water-soluble polyester resin,
The sheath is a PET resin comprising a polymer obtained by polymerizing a diol component comprising an acid component containing at least one member selected from terephthalic acid and isophthalic acid and an aliphatic diol having 2 to 20 carbon atoms; An inorganic flame retardant including zinc diethylphosphinate; And a carbon-based coloring agent,
The sheath portion contains 5,200 to 7,800 ppm of the inorganic flame retardant and 10,000 to 30,000 ppm of the carbon-based colorant based on P (phosphorus) content,
The high-temperature hot-water-soluble polyester resin has an intrinsic viscosity (IV) of 0.800 to 0.920 dl / g,
Soluble thermoplastic polyester resin is obtained by copolymerizing a mixture of 57 to 63 mol% of terephthalic acid, 12 to 20 mol% of isophthalic acid, 8 to 15 mol% of dimethyl 5-sodium diisophthalate and 7 to 16 mol% of diethylene glycol Wherein the composite fiber is made of a synthetic 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 (%)
delete delete delete delete delete delete delete delete delete A flame-retardant hollow fiber for automobile interiors produced by eluting a core portion of the composite fiber of any one of claims 1 to 3.
delete An automobile interior material comprising the flame retardant hollow fiber for automobile interior material of claim 12.