KR20150069483A - Composition of Flame retardant polyester resin, Flame retardant polyester resin having high limiting oxygen index and Polyester yarn of that - Google Patents

Abstract

The present invention relates to a flame retardant polyester resin, and a flame retardant polyester fiber using the same wherein a reaction rate between a flame retardant agent and other compositions have been increased and accordingly, a falling-off of a flame retardant agent has been prevented at the time of manufacturing and a secondary ignition phenomenon caused by an incomplete combustion has been prevented and in addition thereto, a material having mechanical properties and showing a high limiting oxygen index can be made available.

Description

FIELD OF THE INVENTION The present invention relates to a flame retardant polyester resin composition, a flame retardant polyester resin having excellent LOI using the flame retardant polyester resin, a flame retardant polyester resin having a high limiting oxygen index and a polyester yarn,

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polyester resin composition, a polyester resin produced using the same, and a polyester fiber using the same. In producing a polyester resin, the reactivity with other compositions and a flame retardant is improved, The present invention relates to a polyester resin having an improved limiting oxygen index of an injection molded article (for example, a fiber, a fire retardant or the like) using a polyester resin, and also relates to a polyester fiber using such a resin.

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 agent 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 .

A flame retardant polyester composition for calendering is disclosed in Korean Patent No. 1084423, wherein (a) is a random copolymer and has a melting point of not higher than 30 占 폚 A glass transition temperature (Tg) of at least 5 minutes, a crystallization half-life from the molten state of at least 5 minutes; (b) a plasticizer 10, based on the total amount of the polyester composition, comprising at least one aromatic ring and dissolving a 5-mil (0.127 mm) thick film of the polyester to produce a clear solution at a temperature of 160 & To 40% by weight; (c) from 5 to 40% by weight of a phosphorus-containing flame retardant selected from at least one of a monoester, a diester or a triester of phosphoric acid, which is miscible with the plasticizer plasticized with the plasticizer; And (d) an additive effective to prevent the polyester from sticking to the calender roll. Korean Patent Laid-Open No. 10-2013-0102623 discloses a technique of using an amino-terminated phosphonamide and oligomers thereof as a flame-retardant additive for various polymers for imparting flame retardancy while maintaining or improving processing characteristics and the like , The flame retardant content of the flame retardant itself is too small, and the heat resistance is insufficient. In such prior arts, a flame retardant is dispersed and distributed in the polyester resin, but the flame retardant that can not be melted is not easily dispersed evenly in the polyester resin, there is a problem.

In addition, conventional polyester fibers and the like have a problem in that a large amount of smoke is generated due to a flame-retarding action due to incomplete combustion, and a secondary ignition cause is caused by a phenomenon such as drip.

Disclosure of Invention Technical Problem [8] Accordingly, the present invention has been made keeping in mind the above problems occurring in the prior art, and it is an object of the present invention to provide a polyester resin composition which can prevent flame retardancy from deteriorating due to post- It is possible to provide a polyester resin having an optimum composition and composition ratio as well as a novel polyester resin capable of improving flame retardancy by minimizing and / or preventing secondary ignition due to development such as drip due to incomplete combustion And a polyester fiber produced using the same.

In order to solve the above-mentioned problems, the present invention relates to a flame retardant polyester resin composition for producing a flame retardant polyester resin having excellent LOI, which comprises a flame retardant polyester resin composition containing at least one selected from the group consisting of terephthalic acid and isophthalic acid Phthalic acid; Glycols containing at least one selected from ethylene glycol, diethylene glycol, propylene glycol, and butylene glycol; And an organic phosphorus flame retardant and a melamine flame retardant in a weight ratio of 4: 1 to 1: 4.

In one embodiment of the present invention, in the composition of the present invention, the organophosphorus flame retardant may include a compound 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.

As a preferred embodiment of the present invention, in the composition of the present invention, the melamine-based flame retardant includes at least one selected from melamine, melamine cyanurate, melamine phosphate, melamine polyphosphate and melamine pyrophosphate can do.

In another preferred embodiment of the present invention, the composition of the present invention comprises at least one metal catalyst selected from the group consisting of magnesium acetate, germanium acetate and zinc acetate, And further comprising a catalyst.

(2)

In Formula 2, 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 another preferred embodiment of the present invention, the composition of the present invention may include the phthalic acid and the glycol in a molar ratio of 1: 1.2 to 1.5.

In another preferred embodiment of the present invention, the composition of the present invention is characterized in that the flame retardant is contained in an amount of 2 to 5% by weight of the total weight of the resin.

In another preferred embodiment of the present invention, the composition of the present invention may include 0.01 to 0.1% by weight of the metal catalyst.

In another preferred embodiment of the present invention, in the composition of the present invention, the phthalic acid is terephthalic acid, and the glycol is ethylene glycol.

Another aspect of the present invention relates to a flame retardant polyester resin having excellent limiting oxygen index (LOI) produced by using various compositions as described above, wherein the amount of residual inorganic material is 15 to 20% by weight when heated up to 900 캜 have.

As a preferred embodiment of the present invention, the flame-retardant polyester resin of the present invention may be characterized in that the flame retardant component content is 3,000 to 10,000 ppm%.

As a preferred embodiment of the present invention, the polyester resin of the present invention may be characterized by having an intrinsic viscosity (IV) of 0.500 to 0.750 dl / g.

As a preferred embodiment of the present invention, the molded article (or molded article) of the polyester resin of the present invention is characterized by having a limit oxygen index (LOI) of 34% to 40% measured according to KS-M ISO 4589-1 .

Another embodiment of the present invention relates to a method for producing a flame retardant polyester resin having excellent LOI using the composition described above, which comprises a step of reacting phthalic acid, a glycol, a flame retardant, and a metal catalyst represented by the following Formula 2, magnesium acetate, , Germanium acetate (Ge acetate), zinc acetate (Zn acetate), and esterification to prepare an esterification reaction product; And performing a polymerization process on the esterification reaction product to produce a flame retardant polyester resin having an excellent LOI.

(2)

In Formula 1, 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 organophosphorus flame retardant may be a compound 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.

As another preferred embodiment of the present invention, in the production method of the present invention, the melamine-based flame retardant includes at least one selected from melamine, melamine cyanurate, melamine phosphate, melamine polyphosphate and melamine pyrophosphate .

As another preferred embodiment of the present invention, in the production method of the present invention, the phthalic acid includes at least one selected from terephthalic acid and isophthalic acid, and the glycol is selected from the group consisting of ethylene glycol, diethylene glycol, propylene glycol, , And the like.

In another preferred embodiment of the present invention, the esterification reaction is carried out at 230 ° C to 250 ° C while dehydrating water generated during the reaction.

In another preferred embodiment of the present invention, in the production method of the present invention, the polymerization reaction is performed at a temperature of 260 ° C to 300 ° C and a degree of vacuum of 2.0 or less.

In another preferred embodiment of the present invention, in the method of the present invention, the step of performing the polymerizing reaction may include a step of adding a heat stabilizer to 100 parts by weight of the esterification reaction product, . ≪ / RTI >

As another preferred embodiment of the present invention, in the manufacturing method of the present invention, the step of performing the polymerizing reaction may include, in addition to the heat stabilizer, a lubricant, an antioxidant, a light stabilizer, a hydrolysis stabilizer, a releasing agent, Further comprises at least one additive selected from the group consisting of an antistatic agent, an antistatic agent, an EMI shielding agent, a magnetic property imparting agent, a mineral filler, a crosslinking agent, an antibacterial agent, a processing aid, a metal deactivating agent, .

Another aspect of the present invention relates to a polyester fiber, wherein the LOI of the present invention described above includes an excellent flame retardant polyester resin.

Another aspect of the present invention relates to an interior material, and may be characterized by including the polyester fiber.

The flame retardant polyester resin of the present invention is environmentally friendly by using a non-halogen flame retardant, and the content of the flame retardant is largely reduced while the formation of carbide is advanced, the flame retardancy is excellent, the reactivity between the flame retardant and the polyester compound is greatly improved, It is possible to provide an injection molded article excellent in mechanical properties such as strength and heat resistance, processability and moldability, which can prevent the flame retardant component from being detached from the flame retardant during the manufacturing process or during the burnishing process .

Conventional extrudates and / or articles made of polyester resin using only phosphorus flame retardant are formed by the formation of polymetaphosphoric acid upon combustion and the formation of a char by dehydration of the protective layer and polymetaphosphoric acid by the phosphoric acid layer, . However, at this time, there is a problem that the amount of generated smoke is large due to the flame-retarding action due to the incomplete combustion, and the secondary firing is caused by the phenomenon of drip and the like. In order to solve such problems, the inventors of the present invention have solved these conventional problems by simultaneously applying a specific organophosphorus flame retardant and a specific melamine flame retardant in a specific ratio at the time of manufacturing a polyester resin, I have developed a technique that can be obtained. In addition, a technique for improving the reactivity between the flame retardant and the polyester component has been developed to prevent the flame retardant component from being detached during the polyester manufacturing process or the injection molding process using the same.

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

The flame retardant polyester resin of the present invention relates to an invention capable of providing molded articles or molded articles having excellent LOI (limiting oxygen index). According to KS-M ISO 4589-1, the limit oxygen index (LOI) % To 40%, and preferably the limiting oxygen index (LOI) is 34% to 38%.

The flame retardant polyester resin of the present invention may be characterized in that the amount of residual inorganic material is 15 to 20% by weight when heated up to 900 ° C., and the content of the flame retardant component is 3,000 to 10,000 ppm, And preferably 5,000 to 7,000 ppm. A flame retardant such as an inorganic flame retardant, a melamine flame retardant, and a phosphorus flame retardant is used in an amount of 30 to 40 wt%, which is about 15 wt% or more of the total weight of the resin, for the general flame retardant polymer resin (engineering plastic) When the content of the flame retardant in the polyester resin is high, the polymerization reactivity is deteriorated by the flame retardant component containing P, N or the like, and the pack pressure is generated at the time of processing or the workability such as thread trimming may be deteriorated. The flame retardant polyester resin is an invention capable of improving the LOI index while minimizing the content of the flame retardant.

The polyester resin of the present invention may be characterized by having an intrinsic viscosity (IV) of 0.500 to 0.750 dl / g, preferably an intrinsic viscosity (IV) of 0.550 to 0.700 dl / g, It is advantageous to have an intrinsic viscosity within the above range.

The method and composition for producing a flame retardant polyester resin having the LOI of the present invention will be described below.

The flame retardant polyester resin of the present invention comprises a step of esterifying a polyester resin composition to prepare an esterification reaction product; And performing a polymerization reaction on the esterification reaction product.

The polyester resin composition may include phthalic acid; Glycol; And a flame retardant containing an organic phosphorus flame retardant and a melamine flame retardant.

In the present invention, it is preferable to use the phthalic acid and the glycol in a molar ratio of 1: 1.2 to 1.5, and if the glycol is used in an amount of less than 1.2 mol, the yield of the ester reactant as a reactant may be lowered. No, it is uneconomical.

The phthalic acid may be at least one selected from terephthalic acid and isophthalic acid, and terephthalic acid may be preferably used.

The glycol may be at least one selected from the group consisting of ethylene glycol, diethylene glycol, propylene glycol and butylene glycol, and preferably at least one selected from ethylene glycol, diethylene glycol and propylene glycol, Ethylene glycol may be used.

In the present invention, the organophosphorus flame retardant among the above flame retardant components may be one containing a compound represented by the following general formula (1).

[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, Preferably -CH ₂ COOH, -CH ₂ CH ₂ COOH, or -CH ₂ CH ₂ CH ₂ COOH, more preferably -CH ₂ CH ₂ COOH.

The melamine-based flame retardant may be at least one selected from the group consisting of melamine, melamine cyanurate, melamine phosphate, melamine polyphosphate and melamine pyrophosphate, preferably at least one selected from melamine cyanurate- and melamine phosphate Or better.

The composition of the present invention preferably contains 2 to 5% by weight, preferably 2.5 to 3.5% by weight, of the flame retardant in the total weight of the composition. If the content of the flame retardant is less than 2% by weight, When the content of the flame retardant is less than 5% by weight, the content of the flame retardant may be insufficient for the polyester resin prepared by the composition of the present invention. When the content exceeds 5% by weight, There is a possibility that the polymerization reactivity may be deteriorated and the properties of the produced polyester resin may be deteriorated and the yarn such as fibers made of such polyester resin may be refused.

The flame retardant is used in an amount of from 5: 1 to 1: 5 by weight, preferably from 4: 1 to 1: 4 by weight, more preferably from 2: 1 to 1: 2 by weight, based on the organophosphorus flame retardant and the melamine flame retardant. Still more preferably 1: 1 to 1.5: 1 by weight. At this time, there is a problem that the organophosphorus flame retardant and the melamine flame retardant are out of the ratio of 5: 1 to 1: 5 by weight and the LOI index is lowered when the organophosphorus flame retardant enters too much or too little. It is good.

The polyester resin composition may further contain 0.01 to 0.1% by weight, preferably 0.02 to 0.05% by weight, of the catalyst, based on the total weight of the composition for improving the esterification reaction, If the amount is less than 0.1% by weight, the esterification reaction proceeds too quickly, resulting in a large amount of by-products, which may lead to a decrease in the yield. As the catalyst, at least one selected from the group consisting of metal catalysts represented by the following general formula (2), magnesium acetate, germanium acetate and zinc acetate may be used. Preferably, magnesium acetate , Germanium acetate and zinc acetate can be used.

(2)

In Formula 2, 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.

In addition to phthalic acid, a glycol, a flame retardant, and a catalyst, the polyester resin composition may further include additives such as a crosslinking agent and a coupling agent for improving the physical properties.

In the present invention, in the step of producing an esterification reaction product, the esterification reaction is carried out by performing esterification using the polyester resin composition as described above, wherein the esterification reaction is carried out at a temperature of 230 to 250 ° C , And dehydration of the water generated during the reaction. If the esterification temperature is less than 230 ° C., the yield of the reaction product may be lowered. If the esterification reaction temperature is more than 250 ° C., the by-product may be generated.

In the present invention, the step of performing the polymerization reaction is a step of polymerizing the esterification reaction product. The reaction is carried out at a reaction temperature of 260 ° C to 300 ° C and a vacuum degree of 2.0 or lower, preferably 270 ° C to 290 ° C and a degree of vacuum of 1.5 or lower It is better to carry out the reaction. If the reaction temperature is less than 260 ° C, the unit molecular weight may be lowered or the participation rate of the oligomer may be lowered in the polymerization step, resulting in a drop in the vacuum step, resulting in a decrease in the reaction yield. There is a problem that pyrolysis occurs due to the lack of heat resistance peculiar to the flame retardant agent, which may cause a decrease in reactivity or browning and carbonization of the flame retardant polyester resin.

In the step of performing the polymerization reaction, a heat stabilizer generally used in the related art is further added in addition to the above-mentioned esterification reaction material within a range not adversely affecting the LOI index of the polyester resin as the final reactant, The reaction may be carried out.

In addition to the above-mentioned heat stabilizers, within a range that does not adversely affect the LOI index of the polyester resin, a lubricant, an antioxidant, a light stabilizer, a hydrolysis stabilizer, a releasing agent, a pigment, an antistatic agent, , The polymerizing reaction may be performed after the addition of at least one additive selected from the group consisting of a filler, a mineral filler, a crosslinking agent, an antibacterial agent, a processing aid, a metal deactivator, a suppressing agent, a fluorine- have.

The method for producing the polyester resin of the present invention may further include a step of removing unreacted monomers and oligomers from the reactants obtained by the polymerization reaction, that is, a step of solid-phase polymerizing the polymer.

As described above, using the polyester resin of the present invention thus produced, it is possible to provide an injection molded article (or a molded article) such as fibers having a very low flame retardant content and a high LOI index.

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 ]

Preparation Example  One

Terephthalic acid and ethylene glycol were mixed at a molar ratio of 1: 1.3, and then an organic phosphorus flame retardant represented by the following formula 1-1 and melamine phosphate and magnesium acetate, which are melamine flame retardants, were added and stirred at the same weight% To prepare a flame retardant polyester composition.

Next, the flame-retardant polyester composition was esterified while slowly stirring at 240 ° C. At this time, esterification reaction was performed by performing esterification while removing water generated during the reaction through a condenser facility .

Next, the esterification reaction product was polymerized at 280 ° C and a vacuum degree of 1.6 to prepare a flame retardant ester resin.

[Formula 1-1]

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

Preparation Example  2 to 6 and Example of comparison preparation  1-3

Preparation Examples 2 to 6 and Comparative Preparation Examples 1 to 3 were respectively carried out by preparing flame retardant ester resins in the same manner as in Preparation Example 1, except that flame retardant ester resins were prepared so as to have the composition and composition ratio shown in Table 1 below.

Preparation Example  7

A flame retardant polyester resin was prepared in the same manner as in Preparation Example 1 except that the organophosphorus flame retardant represented by Formula 1-2 was used instead of the organophosphorus flame retardant represented by Formula 1-1.

[Formula 1-2]

In the general formula (1), R ¹ is -CH ₂ COOH.

Preparation Example  8

A flame retardant polyester resin was prepared in the same manner as in Preparation Example 1 except that the esterification reaction was carried out at 250 ° C and the polymerisation reaction was carried out at 270 ° C.

division Terephthalic acid and ethylene glycol Organic phosphorus flame retardant Melamine flame retardant catalyst Preparation Example 1 96.95 wt% 2.4 wt% 0.6 wt% 0.05 wt% Preparation Example 2 96.95 wt% 1.5 wt% 1.5 wt% 0.05 wt% Preparation Example 3 96.95 wt% 0.6 wt% 2.4 wt% 0.05 wt% Preparation Example 4 97.25 wt% 1.1 wt% 1.6 wt% 0.05 wt% Preparation Example 5 96.45 wt% 1.5 wt% 2.0 wt% 0.05 wt% Preparation Example 6 95.55 wt% 2.2 wt% 2.2 wt% 0.05 wt% Preparation Example 7 96.95 wt% 2.4 wt% 0.6 wt% 0.05 wt% Preparation Example 8 96.95 wt% 2.4 wt% 0.6 wt% 0.05 wt% Comparative Preparation Example 1 96.95 wt% 3.0 wt% - 0.05 wt% Comparative Preparation Example 2 96.95 wt% - 3.0 wt% 0.05 wt% Comparative Preparation Example 3 92.95 wt% 3.5 wt% 3.5 wt% 0.05 wt%

Experimental Example  1: Measurement of physical properties of flame retardant polyester resin

The flame retardant content of the flame retardant polyester resin prepared in the preparation example and the comparative preparation example was measured by ASSIGN of the phosphonate ester bond contained in the main flame retardant polyester resin resin through ¹ H-NMR in the case of the phosphorus flame retardant agent , Amine groups were measured by ASSIGN for melamine flame retardants, and ICP was used for inorganic flame retardants. The results are shown in Table 2 below.

The intrinsic viscosity (IV) of the flame-retardant polyester resin was measured with a Ubbelohde viscometer, and the results are shown in Table 2 below.

division In resin
Flame retardant content Intrinsic viscosity Preparation Example 1 5,980 ppm 0.685 dl / g Preparation Example 2 5,975 ppm 0.682 dl / g Preparation Example 3 6,032 ppm 0.693 dl / g Preparation Example 4 4.598 ppm 0.688 dl / g Preparation Example 5 6,483 ppm 0.701 dl / g Preparation Example 6 7,533 ppm 0.680 dl / g Preparation Example 7 6,028 ppm 0.683 dl / g Preparation Example 8 6,102 ppm 0.679 dl / g Comparative Preparation Example 1 5,922 ppm 0.681 dl / g Comparative Preparation Example 2 5,884 ppm 0.685 dl / g Comparative Preparation Example 3 11,095 ppm 0.608 dl / g

From the physical property measurement values in Table 2, it was confirmed that the flame retardant content of the flame-retardant polyester resin of Preparation Examples 1 to 8 was within 3,000 to 10,000 ppm, preferably within 4,000 to 7,500 ppm. The amount of the flame retardant content of the resin produced by using the same amount of the flame retardant polyester composition was found to be very small due to the elimination of some flame retardants during the esterification reaction and the polymerization reaction. In the preparation examples 1 to 8 and the comparative preparation examples 1 and 2, intrinsic viscosities were almost similar, and it was judged that the amounts of terephthalic acid and ethylene glycol used were similar. However, in Comparative Preparation Example 3, the intrinsic viscosity was low as compared with other preparation examples and the like. This is because the use amount of terephthalic acid and ethylene glycol was relatively small because the amount of the flame retardant was large.

Example  1: Production of flame retardant polyester fiber

The flame-retardant polyester resin prepared in Preparation Example 1 was preliminarily dried at 120 ° C for 4 hours, and then dried at 150 ° C for 4 hours. Then, spinning was carried out at a spinning temperature of 280 ° C and a spinning speed of 4,500 mpm Followed by spinning to produce a flame-retardant polyester fiber.

Example  2 to 8 and Comparative Example  1-3

Flame retardant polyester fibers were prepared in the same manner as in Example 1 except that each of the flame retardant polyester resins prepared in Preparation Examples 2 to 8 and Comparative Preparation Examples 1 to 3 was used in place of the flame retardant polyester resin in Preparation Example 1, To prepare a polyester fiber.

Experimental Example  2: Measurement of properties of flame retardant polyester fiber

The flame retardancy, strength, elongation, limiting oxygen index (LOI) and defective ratio of the flame retardant polyester fibers prepared in the above Examples and Comparative Examples were measured. The results are shown in Table 3 below.

(1) Measurement of flammability

The flame retardancy of the polyester fibers was measured using a UL 94-AVH chamber with the method of KS M 3305.

(2) Measurement of strength and elongation

The strength and elongation of the fibers were measured using an automatic tensile tester (Textechno) at a speed of 50 cm / m and a gripping distance of 50 cm. Strength and elongation are defined as the elongation (%) of the initial length of the elongated length as a percentage (g / de) divided by the denier when the fiber is stretched until it is cut with a constant force. Respectively.

(3) Measurement of limit oxygen index

The limit oxygen index (LOI) was measured according to KS-M ISO 4589-1.

(4) Defect rate measurement

The failure rate was measured by the frequency of fiber filament and the discoloration of fiber during the spinning. The failure rate was judged to be defective when the filament frequency was at least 1 time / 1 hr and the fiber b value (colorimetric value) 7 or more. , And it is judged that the degradation rate of the fiber is 1.0% or more after 72 hours from the spinning.

division Fineness
(de) Flammability
(UL-94V method) burglar
(g / de) Shindo
(%) Limit Oxygen Index (%) Defect rate
(%) Example 1 75 V1 4.5 26 34.2 0.61% Example 2 75 V1 4.4 27 36.9 0.64% Example 3 75 V1 4.6 28 35.0 0.57% Example 4 75 V1 4.5 25 34.8 0.52% Example 5 75 V1 4.4 26 37.8 0.55% Example 6 75 V1 4.6 30 38.4 0.60% Example 7 75 V1 4.5 26 34.3 0.37% Example 8 75 V1 4.4 28 34.6 0.46% Comparative Example 1 75 V1 4.5 26 33.3 0.75% Comparative Example 2 75 V1 4.4 28 27.2 0.62% Comparative Example 3 75 V1 2.1 15 39.2 2.3%

The results are shown in Table 1. The results are shown in Table 1. The results are shown in Table 1. The results are shown in Table 1. The results are shown in Tables 1 and 2.

However, in the case of Comparative Example 1 and Comparative Example 2, it was confirmed that the limit oxygen index was less than 34.0%, which is relatively low as compared with the Example.

In the case of Comparative Example 3, the properties such as the flame retardancy and the limiting oxygen index were excellent, but the strength, elongation and defect rate were not good. This is because the flame retardant content in the resin is as high as 10,000 ppm or more, The polymerization reactivity was lowered due to the flame retardant component, and it was judged that the physical properties of the fiber thus produced adversely affected.

Through the above Examples and Experimental Examples, it was confirmed that the flame-retardant polyester resin composition of the present invention and the flame-retardant polyester resin produced by the production method of the present invention and the molded article thereof are excellent in physical properties. It is expected that the present invention can be applied to a wide range of applications such as textiles, fabrics and interior materials.

Claims (15)

Phthalic acid containing at least one selected from terephthalic acid and isophthalic acid;
Glycols containing at least one selected from ethylene glycol, diethylene glycol, propylene glycol, and butylene glycol; And
An organophosphorus flame retardant and a melamine flame retardant in a weight ratio of 4: 1 to 1: 4,
The organic phosphorus flame retardant includes a compound represented by the following formula (1)
Wherein the melamine-based flame retardant comprises at least one selected from the group consisting of melamine, melamine cyanurate, melamine phosphate, melamine polyphosphate, and melamine pyrophosphate.
[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 catalyst according to claim 1, further comprising at least one catalyst selected from the group consisting of a metal catalyst represented by the following general formula (2), Mg acetate, Ge acetate and Zn acetate. An ester resin composition;
(2)

In Formula 2, 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.
The flame-retardant polyester resin composition according to claim 1, wherein the phthalic acid and the glycol are contained in a ratio of 1: 1.2 to 1.5 molar ratio, and the flame retardant is contained in an amount of 2 to 5 wt% of the total weight of the composition.
The flame-retardant polyester resin composition according to claim 2, wherein the metal catalyst is contained in an amount of 0.01 to 0.1% by weight.
The flame-retardant polyester resin composition according to claim 1, wherein the phthalic acid is terephthalic acid, and the glycol is ethylene glycol.
(LOI) characterized by comprising a polyester resin which is a reaction product of the composition of any one of claims 1 to 5, wherein the reactant has an inorganic residual amount of 15 to 20 wt% Excellent flame retardant polyester resin.
The flame retardant polyester resin according to claim 6, wherein the content of the flame retardant component in the polyester resin is 3,000 to 10,000 ppm.
The flame retardant polyester resin according to claim 6, wherein the polyester resin has an intrinsic viscosity (IV) of 0.500 to 0.750 dl / g.
The injection molding of polyester resin according to claim 6, wherein the molded article of the polyester resin has a limit oxygen index (LOI) of 34% to 40% as measured according to KS-M ISO 4589-1, wherein the LOI is an excellent flame retardant polyester resin .
(1), a catalyst selected from the group consisting of phthalic acid, glycol, a flame retardant, and a metal catalyst represented by the following general formula (2), Mg acetate, Ge acetate and Zn acetate, (esterification) to produce an esterification reaction product; And
And performing a polymerization reaction on the esterification reaction product,
Wherein the flame retardant comprises an organic phosphorus flame retardant and a melamine flame retardant in a weight ratio of 4: 1 to 1: 4,
The organic phosphorus flame retardant includes a compound represented by the following formula (1)
Wherein the melamine-based flame retardant comprises at least one selected from the group consisting of melamine, melamine cyanurate, melamine phosphate, melamine polyphosphate, and melamine pyrophosphate;
[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 1, 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.
11. The method according to claim 10, wherein the phthalic acid comprises at least one selected from terephthalic acid and isophthalic acid,
Wherein the glycol comprises at least one member selected from ethylene glycol, diethylene glycol, propylene glycol, and butylene glycol.
The method according to claim 10, wherein the esterification reaction is carried out at 230 ° C to 250 ° C while dehydration of water occurs during the reaction.
11. The method according to claim 10, wherein the polymerization reaction is carried out at a temperature of from 260 DEG C to 300 DEG C and a vacuum degree of 2.0 or less.
A flame retardant polyester fiber characterized by comprising the flame retardant polyester resin of claim 6.
An interior material comprising the flame retardant polyester fiber of claim 14.