KR20080109264A - Flame retardant copolyester composition containing 1,4-cyclohexanedimethanol, its preparation and products using it - Google Patents

Abstract

A polyester resin composition is provided to improve transparency, processability and fire retardancy by copolymerizing an interactive phosphate flame retardant. A polyester resin composition is copolymerized so that the sum total of the diol component is 100 mole % based on a diacid component 100 mole %. The diol component comprises 1,4- cyclohexanedimethanol 30~80 mole %; a diol component 5~69 mole % except for 1,4- cyclohexanedimethanol; and phosphate flame retardant 1~25 mole % represented by the chemical formula 1 or 2.

Description

1,4-cyclohexanedimethanol-containing copolymerized polyester resin composition having excellent flame retardancy, a method of manufacturing the same and a molded product using the same {FLAME RETARDANT COPOLYESTER COMPOSITION CONTAINING 1,4-CYCLOHEXANEDIMETHANOL, ITS PREPARATION AND PRODUCTS USING IT}

The present invention relates to a 1,4-cyclohexanedimethanol-containing copolyester polyester resin composition excellent in flame retardancy, a method for producing the same, and a molded product using the same, and more particularly, to a 1,4-cyclohexanedimethanol-containing copolyester polyester resin. By preparing a composition containing a reactive phosphorus flame retardant, a 1,4-cyclohexanedimethanol-containing copolymerized polyester resin having excellent flame retardancy without producing a transparent, low color change and yellowish color tone is prepared and used alone. Or to molded articles molded by blending with different polymers.

Recently, polyester resins are widely used in the fields of molded articles, films, and packaging materials, and have been applied to many fields because of their excellent transparency and processability. In particular, the copolymerized polyester resin composition containing 1,4-cyclohexanedimethanol which is a diol component is incorporated in a processing step of compounding with single or different types of resins to impart transparency.

In addition, in recent years, as the demand for safety increases, the demand for flame retardancy also increases in polyester resins.

In general, a method of imparting flame retardancy to a polyester resin may be classified into a method using a reactive flame retardant or an additive flame retardant.

First, a method of preparing a polyester resin using an additive flame retardant will be described. A polyester masterbatch resin containing a high concentration of flame retardant may be prepared, and the masterbatch resin may be prepared by adding a predetermined ratio to the spinning process of the polyester resin. Can be. The method using the additive-based flame retardant may contain a large amount of flame retardant, but due to the high concentration of the flame retardant, the viscosity in the manufacturing process of the master batch resin, the flame retardant is not uniformly produced, there is a problem that the flame retardancy is inferior. In addition, when a flame retardant powder or particle-shaped flame retardant component is added to the polyester resin, it is difficult to obtain fracture or uniform surface caused by the particles during the molding process.

In contrast, a method of preparing a polyester resin using a reactive flame retardant is a method in which a flame retardant capable of reacting with a polyester is copolymerized with a polyester resin by being added together in an esterification reaction or a polycondensation reaction. Since the method copolymerizes the polyester resin and the flame retardant, it can bring a uniform distribution of the flame retardant and is excellent in flame retardancy.

However, most of polyester resins excellent in transparency and processing characteristics do not have a function for flame retardancy.

As an example of a manufacturing method for the copolymer polyester resin composition excellent in transparency and processability, Korean Patent Laid-Open No. 2006-71712 is prepared by blending the copolymerized polyester copolymerized with 1,4-cyclohexane dimethanol and polycarbonate resin Although the method is described, in order to impart flame retardancy to the copolyester resin composition, an additive flame retardant is used.

Korean Patent Laid-Open Publication Nos. 2003-30726, 2004-29760 and 2004-80323 also disclose methods for preparing copolyester resins using 1,4-cyclohexanedimethanol, but are intended to impart flame retardancy. No specific method is described.

Therefore, in the conventional method, since the flame retardancy is imparted to the polyester resin, an additive flame retardant is used due to a problem in the process, and when the additive flame retardant is used, there is a problem in that viscosity and transparency deteriorate.

According to Korean Patent Laid-Open Publication No. 2005-304, in the production of a polyester resin copolymerized with 1,4-cyclohexanedimethanol, by adding and copolymerizing a polyfunctional monomer and polyethylene glycol bisphenol-A, excellent transparency and high melt viscosity and Disclosed is a method for producing a copolyester resin having a melt strength, while having excellent moldability due to low melt pressure. However, in order to impart flame retardancy in the above invention, a polyester resin copolymerized with 1,4-cyclohexanedimethanol is prepared using an additive flame retardant.

Accordingly, the present inventors have endeavored to efficiently impart flame retardancy to the 1,4-cyclohexanedimethanol-containing copolyester polyester resin having excellent transparency and processability, and as a result, have been identified in the 1,4-cyclohexanedimethanol-containing copolyester polyester resin composition. 1,4-cyclohexanedimethanol-containing copolyester polyester resin containing a reactive phosphorous flame retardant of 1,4-cyclohexanedimethanol, which is transparent, has little color change and does not exhibit a yellowish color tone, and is used alone or as a heterogeneous The present invention was completed by blending with a polymer to confirm the flame retardancy of the molded article.

An object of the present invention is to provide a 1,4-cyclohexanedimethanol-containing copolymerized polyester resin composition in which excellent flame retardancy is imparted to the 1,4-cyclohexanedimethanol-containing copolymerized polyester resin having excellent transparency and processability.

Another object of the present invention is to prepare a 1,4-cyclohexanedimethanol-containing copolymerized polyester resin composition comprising copolymerizing a 1,4-cyclohexanedimethanol-containing copolymerized polyester resin composition with a specific reactive phosphorus flame retardant. To provide.

Still another object of the present invention is to provide a molded product of which flame retardancy is secured using a 1,4-cyclohexanedimethanol-containing copolyester polyester composition having excellent flame retardancy.

In order to achieve the above object, the present invention is a polyester resin composition copolymerized by polycondensation reaction with respect to 100 mol% of the diex component, so that the sum of the diol component is 100 mol%, the diol component is 1,4- Excellent flame retardant composition consisting of 30 to 80 mol% of cyclohexanedimethanol, 5 to 69 mol% of diol components excluding 1,4-cyclohexanedimethanol and 1 to 25 mol% of phosphorus flame retardant represented by the following formula (1) or (2): 1,4-cyclohexane dimethanol containing polyester resin composition is provided.

Formula 1

Formula 2

The phosphorus flame retardant contains 1,000 to 30,000 ppm of phosphorus relative to the total polyester resin composition.

In the present invention, the diacid component is any one selected from the group consisting of terephthalic acid, isophthalic acid, phthalic acid, dimethyl terephthalate, thymethylisophthalate and phthalic anhydride, and the diol component is ethylene glycol, propylene glycol, butylene glycol, iso At least one selected from the group consisting of propylene glycol, 1-methyl propylene glycol and pentylene glycol is used.

The present invention provides a method for producing a 1,4-cyclohexanedimethanol-containing polyester resin composition imparted flame retardancy. More specifically,

1) Polycondensation reaction is carried out so that the sum of diol components is 100 mol% with respect to 100 mol% of diacids, but esterification reaction of 5-69 mol% of diol components and 30-80 mol% of 1, 4- cyclohexane dimethanol is carried out. To prepare bishydroxyterephthalate,

2) 1 to 25 mol% of a phosphorus flame retardant selected from compounds represented by Formula 1 or Formula 2 was added to the bishydroxyterephthalate, and 60 to 400 ppm of a reaction catalyst was added to the entire composition to prepare a mixture. ,

3) The mixture is subjected to a polycondensation reaction under vacuum of 1.0 Torr or less to prepare a copolyester resin having an intrinsic viscosity of 0.5 to 1.0 dl / g.

In the above production method, the reaction catalyst is used alone or mixed form selected from the group consisting of titanium compounds, antimony compounds, germanium compounds and aluminum compounds, 60 to 400 ppm of the total polyester resin composition, more preferably Preferably, the reaction catalyst contains 10 to 100 ppm of titanium compound and 50 to 300 ppm of antimony compound.

Furthermore, the present invention provides a molded article of a flame retardant polyester resin imparted with the flame retardancy is molded by blending with the 1,4-cyclohexane dimethanol-containing polyester resin composition alone or a heterogeneous polyester resin.

When blending with the heterogeneous polyester resin, 5 to 30 wt% of a 1,4-cyclohexanedimethanol-containing polyester resin composition imparting flame retardancy is blended with 70 to 95 wt% of the heterogeneous polyester resin to be molded. To provide a molded product of a polyester resin imparted flame retardancy.

Hereinafter, the present invention will be described in detail.

The present invention is a polyester resin composition copolymerized by polycondensation reaction with respect to 100 mol% of the diacid component, so that the sum of the diol components is 100 mol%, wherein the diol component is 30 to 80 of 1,4-cyclohexanedimethanol 1,4-cyclohexanedi having excellent flame retardance, consisting of 5 to 69 mol% of diol components except 1,4-cyclohexanedimethanol and 1 to 25 mol% of phosphorus flame retardants represented by the following general formula (1) or (2): Provided is a methanol-containing polyester resin composition.

Formula 1

Formula 2

The present invention was prepared by adding 1,4-cyclohexanedimethanol to the esterification step as an additional diol component in the process of preparing a polyester resin prepared from a diacid component and a diol component, 1,4-cyclohexanedi The methanol copolyester resin is used.

At this time, the diexide component and the diol component may be used without limitation as long as it is used as a raw material for producing a conventional polyester resin, the diexide component is terephthalic acid, isophthalic acid, phthalic acid, dimethyl terephthalate, dimethylisophthalate and phthalate It is preferable that any one selected from the group consisting of talic anhydride is used, and the diol component is ethylene glycol, butylene glycol, isopropylene glycol, 1-methyl propylene glycol, pentylene glycol, diethylene glycol, triethylene glycol and poly At least one selected from the group consisting of alkylene glycols is used.

Thus, in the 1,4-cyclohexanedimethanol-containing polyester resin composition imparted flame retardancy of the present invention, the reaction mole of the diol compound with respect to the diexide component in the esterification reaction is preferably added in a ratio of 1.1 to 2.0 molar ratio. .

In the 1,4-cyclohexanedimethanol-containing polyester resin composition imparted flame retardancy of the present invention, by further containing a diol component of 1,4-cyclohexanedimethanol, transparency and excellent processability are imparted to ordinary copolymerized polyester. do.

At this time, 1,4-cyclohexane dimethanol contains 30-80 mol% of all diol components, and when it is less than 30 mol%, the transparency provided to the obtained copolyester is inadequate, and when it exceeds 80 mol%, phosphorus system Copolymerization with the flame retardant becomes difficult, and the price is high, which is not preferable.

In the 1,4-cyclohexanedimethanol-containing polyester resin composition imparted flame retardancy of the present invention, the phosphorus flame retardant is represented by 3- (hydroxyphenylphosphinyl) -propanoic acid represented by the formula (1) or formula (2). 3- (hydroxyphenylphosphinyl) -propanoic glycol ester can be used.

Phosphorus-based flame retardant of the present invention solves the environmental problems caused by the flame retardant containing a conventional halogen element, and when applied to polyester resins, impart a poor solubility, and at the same time yellowish the final product containing it It is a flame retardant that minimizes the problem.

Phosphorus-based flame retardant of the present invention preferably contains 1 to 25 mol% of the total diol component, in this case, less than 1 mol%, the phosphorus content in the copolyester resin is low, the flame retardant effect is insufficient, 25 mol% If exceeded, excessive phosphorus content in the copolyester resin may cause yellowshing problems.

As a result of confirming the content of each component of the 1,4-cyclohexanedimethanol-containing polyester resin composition of the present invention through a nuclear magnetic resonance analysis device, the phosphorus-based flame retardant of the present invention, the total phosphorus content of 1,000 to 30,000 ppm is contained to impart flame retardancy to the polyester resin composition. At this time, if the content of the phosphorus-based flame retardant is less than 1,000 ppm, the flame retardant effect is insufficient, if it exceeds 30,000 ppm, the price increases due to excessive reactive flame retardant, there is a disadvantage that the manufacturing process is unstable.

The 1,4-cyclohexanedimethanol-containing polyester resin composition of the present invention can confirm excellent flame retardancy of the V-0 level according to the UL-94V standard with little color change and without a yellowish hue.

The present invention provides a method for producing a 1,4-cyclohexanedimethanol-containing polyester resin composition imparted flame retardancy. More specifically,

1) Polycondensation reaction is carried out so that the sum of diol components is 100 mol% with respect to 100 mol% of diacids, but esterification reaction of 5-69 mol% of diol components and 30-80 mol% of 1, 4- cyclohexane dimethanol is carried out. To prepare bishydroxyterephthalate,

2) 1 to 25 mol% of a phosphorus flame retardant selected from the compounds represented by Formula 1 or Formula 2 was added to the bishydroxyterephthalate, and 60 to 400 ppm of the reaction catalyst was added to the entire composition to prepare a mixture. and,

3) The mixture is subjected to a polycondensation reaction under vacuum of 1.0 Torr or less to prepare a copolyester resin having an intrinsic viscosity of 0.5 to 1.0 dl / g.

The esterification reaction of step 1 is carried out at atmospheric pressure at a temperature of 200-250 ° C. or under a pressure of 2.0 kgf / cm ³ or less.

1,4-cyclohexanedimethanol component is added to the esterification step to prepare bishydroxyterephthalate (BHTE) prepared by esterification. At this time, the diacid component, diol component and 1,4-cyclohexanedimethanol used are the same as described above.

Of the phosphorus-based flame retardants used in step 2, 3- (hydroxyphenylphosphinyl) -propanoic acid represented by Chemical Formula 1 is slurried with a glycol compound in powder form, and 3- (hydroxy represented by Chemical Formula 2 The oxyphenylphosphinyl) -propanoic glycol ester is in liquid form and is easy to add in the polycondensation step. As for content of a phosphorus flame retardant, 1-25 mol% is preferable, and it is preferable that 1,000-30,000 ppm of phosphorus content is contained with respect to all the polyester resin compositions. At this time, if the content of the phosphorus-based flame retardant is less than 1,000 ppm, the flame retardant effect is insufficient, if it exceeds 30,000 ppm, the price is increased due to excessive reactive flame retardant, there is an unstable manufacturing process.

The reaction catalyst used in step 2 is one containing 60 to 400 ppm of single or mixed form selected from the group consisting of titanium compound, antimony compound, germanium compound and aluminum compound with respect to the total polyester resin composition.

Among the reaction catalysts, the titanium compound has a disadvantage in that the reaction is quick even when a small amount is used, but there is a disadvantage in that the color of the polyester resin becomes yellowish. In addition, the antimony compound is a typical catalyst used in the polymerization of polyester resins, but the low cost and stable reaction, but has a disadvantage in that the viscosity is sharply worse as the copolymerization content increases. Germanium and aluminum compounds can be reacted even if used in small amounts, but they are expensive.

In the present invention, in order to ensure the viscosity formation and color of the copolymer as a preferred reaction catalyst, the titanium compound and the antimony compound are carried out in combination, and the preferred amount of the reaction catalyst is in the range of 10 to 100 ppm titanium compound and 50 to 300 ppm antimony compound Use in combination. At this time, if the titanium compound is less than 10 ppm, and the antimony compound is less than 50 ppm, the viscosity is difficult to form and the color is badly changed, if the titanium compound exceeds 100 ppm, the antimony compound exceeds 300 ppm, the viscosity is easy to form This has the disadvantage of changing from color to polished.

In the polycondensation reaction of Step 2, other additives such as a heat stabilizer and a complementary agent may be used. The thermal stabilizer may be used in the content of 100 to 500 ppm, such as phosphoric acid or phosphoric acid trimethyl phosphate, triethyl phosphate, but in the present invention by containing as a phosphorus flame retardant to impart flame retardant, ultimately do not need to be added, Can be optionally used according to. In addition, a complementary agent may be used, and as the complementary agent, a cobalt compound or a dye may be used.

The polycondensation reaction of step 3 is carried out under a vacuum of 1.0 torr or less to prepare a copolymerized flame retarded polyester resin having an intrinsic viscosity of 0.5 to 1.0 dl / g.

At this time, if the produced intrinsic viscosity is less than 0.5 dl / g, the viscosity of the resin is too low to have the desired physical properties, if it exceeds 1.0 dl / g, the polymerization process is long, the color of the resin is bad.

Furthermore, the present invention provides a molded article of a flame retardant polyester resin imparted with the flame retardancy is molded by blending with the 1,4-cyclohexane dimethanol-containing polyester resin composition alone or a heterogeneous polyester resin.

When blending with the heterogeneous polyester resin, 5 to 30 wt% of the flame retardant 1,4-cyclohexanedimethanol-containing polyester resin composition and 70 to 95 wt% of the heterogeneous polyester resin are blended. It is to provide a molded product of a molded, flame retardant polyester resin imparted.

In the present invention, the molded product may include a shape that is molded in a field in which a conventional polyester resin may be used, and more specifically, an extruded blow molded product such as a film, a sheet, a tube, a bottle, and a release extrusion Include molded products. The present invention also includes an injection or extrusion molded product which improves flame retardancy and processability without affecting the inherent physical properties of the resin blended with the 1,4-cyclohexanedimethanol-containing polyester resin composition having the flame retardancy.

The molded article of the flame-retardant polyester resin of the present invention contains the flame-retardant 1,4-cyclohexanedimethanol-containing polyester resin composition, thereby maintaining transparency, V-0 according to the UL-94V standard Excellent level of flame retardancy is provided.

Particularly, in the case of a molded article molded by blending with a heterogeneous polyester resin, UL-94V is contained by containing 5 to 30% by weight of the flame retardant 1,4-cyclohexanedimethanol-containing polyester resin composition. Excellent flame retardancy of V-0 level is given by the standard.

At this time, if the 1,4-cyclohexane dimethanol-containing polyester resin composition imparted flame retardancy of the present invention is contained in less than 5% by weight, the expected flame retardancy level does not reach, if it is contained in excess of 30% by weight, the price is There is a problem of increasing and compatibility with the resin to be blended is poor.

Hereinafter, the present invention will be described in more detail with reference to Examples.

This embodiment is specifically described based on the most preferred embodiment of the present invention, the scope of the present invention is not limited to these examples.

<Example 1>

Using the equipment consisting of an esterification reactor and a polycondensation reactor, bishydroxy terephthalate (BHTE) was prepared by adding 648 g of terephthalic acid, 119 g of ethylene glycol, and 337 g of 1,4-cyclohexanedimethanol to a 2 L esterification reactor. After that, 42 g of phosphorus-based flame retardant was added to the polycondensation reactor, and 20 ppm and 200 ppm of titanium and antimony compounds as reaction catalysts were added to the entire polymer, respectively. Cobalt acetate was added with 150 ppm of cobalt acetate as a complementary agent, and reacted until the intrinsic viscosity was 0.65 dl / g at 1.0 Torr or less under vacuum. The copolyester containing 1,4-cyclohexanedimethanol was prepared by discharging onto a chip.

<Example 2>

Using a facility consisting of an esterification reactor and a polycondensation reactor, 583 g of terephthalic acid, 106 g of ethylene glycol, and 304 g of 1,4-cyclohexanedimethanol were added to a 2 L esterification reactor to prepare BHET, and then sent to a polycondensation reactor. 111 g of a phosphorus flame retardant was added, and 15 ppm and 250 ppm of titanium and antimony compounds as reaction catalysts were added to the total weight of the polymer, respectively. Cobalt acetate was added with 150 ppm of a complementary colorant, and reacted until the intrinsic viscosity was 0.68 dl / g under vacuum 1.0 Torr and discharged onto a chip to prepare a copolyester containing 1,4-cyclohexanedimethanol.

Comparative Example 1

Co-polyester was prepared in the same manner as in Example 1 except that BHET was prepared by the esterification reaction, except that no phosphorus-based flame retardant was added thereto.

Comparative Example 2

A copolyester was prepared in the same manner as in Example 1 except that 5 ppm titanium and 150 ppm antimony were added as a reaction catalyst. At this time, the intrinsic viscosity increased the reaction time, but was 0.45 dl / g.

Experimental Example 1 Intrinsic Viscosity Measurement

The copolyesters prepared in Examples 1 and 2 and Comparative Examples 1 and 2 were melted in an ortho -chloro phenol solvent at a temperature of 2.0 g / 25 ml at 110 ° C. for 30 minutes, and then 25 It was measured by using an automatic viscosity measuring device connected to a CANON viscometer by incubating at 30 ° C. for 30 minutes.

Experimental Example 2 Color Measurement of Resin

The co-polyesters prepared in Examples 1 and 2 and Comparative Examples 1 and 2 were measured using the ZE-2000 color meter of Nippon Densoki for color (L, a, b).

Experimental Example 3 Component Analysis of Resin

For the copolyesters prepared in Examples 1 and 2 and Comparative Examples 1 and 2, using a ¹ H-nuclear magnetic resonance (Nuclear Magnetic Resonance), the molar component ratio of the diexide, diol and phosphorus-based flame retardant component is confirmed It was.

Experimental Example 4 Flame Retardant UL-94V Test

Standard test specimens were prepared and the specimens were held vertically, flames were burned at the bottom of the burner for 10 seconds, the flames were removed, and the time when the fires ignited on the specimens was measured. Next, when the test piece went out of fire, contacting was started again for 10 seconds, and the same time as above, the fire was removed and the time for the ignition of the fire was repeated.

Moreover, it evaluated simultaneously whether the lower surface of a test piece was ignited by falling embers.

The flame retardancy was evaluated by classifying V-0, V-1 and V-2 according to the UL-94V standard. At this time, when V-0, it means the highest flame retardancy.

In addition, for the copolyesters prepared in Examples 1 and 2 and Comparative Examples 1 and 2, the test was also performed on the oxygen index.

The oxygen index was tested to see how much combustion was achieved by igniting the tip of the sample while placing a rod-shaped plastic specimen in a combustion cylinder and sending a mixed gas of oxygen and nitrogen from the bottom. The oxygen index was calculated by the following equation.

(In the above, OI (Oxygen Index) is the oxygen index, [O ₂ ] is the oxygen flow rate (l / min), [N ₂ ] is nitrogen flow rate (l / min).)

Intrinsic viscosity, color, content of each component, and flame retardancy test results for the copolymerized polyesters prepared in Examples 1 and 2 and Comparative Examples 1 and 2 are shown in Table 2 below.

As shown in Table 2, the copolyesters prepared in Examples 1 to 2 had little color change and did not have a yellowish hue, and in particular, the flame retardancy of V-0 level was confirmed by the UL-94V standard.

Specifically, when compared with the copolyester of Comparative Example 1 prepared without the addition of a phosphorus-based flame retardant, the copolyester prepared in Example 1 was low in brightness and did not have a large color difference and showed excellent flame retardancy.

In addition, when comparing the copolyester prepared in Example 2 and Comparative Example 3 according to the content of the titanium catalyst and the antimony catalyst as the reaction catalyst, there is no difference in flame retardancy, but due to a large color change, it may cause a color defect of the final product have.

In addition, the copolyester prepared with increasing phosphorus content has a high oxygen index, and thus supports excellent flame retardancy.

<Example 3>

In order to impart flame retardance to the polycarbonate, which is a dissimilar resin, 85% by weight of a vacuum dried polycarbonate (manufactured by Samyang) for 4 hours at 130 ° C. and 15% by weight of the flame retardant copolymerized polyester resin prepared in Example 2 were blended. By extrusion molding in a conventional manner, a sheet of polycarbonate was prepared. The prepared specimens were evaluated for flame retardancy test and are shown in Table 3 below.

Comparative Example 3

The flame retardance test was performed on the polycarbonate (manufactured by Samyang Corporation) in the state where no flame-retardant co-polyester resin was added, and the results are shown in Table 3.

As shown in Table 3, by containing the flame-retardant co-polyester of the present invention, while maintaining transparency, the flame retardancy is significantly improved than the polycarbonate of Comparative Example 3 not containing, V-0 level according to the UL-94V standard Showed flame retardancy.

As described above, the present invention

First, 1,4-cyclohexanedimethanol-containing copolyester polyester resin having excellent transparency and processability has a V-0 level of flame retardancy conforming to the UL-94V standard. Provided,

Second, the 1,4-cyclohexane dimethanol-containing copolymerized polyester resin composition prepared by adding a reactive phosphorous flame retardant to the esterification or polycondensation reaction step to the 1,4-cyclohexane dimethanol-containing copolymerized polyester resin composition Providing a manufacturing method of

Third, there was provided a molded product having flame retardancy secured using a 1,4-cyclohexanedimethanol-containing copolyester polyester resin composition excellent in flame retardancy.

Although the present invention has been described in detail only with respect to the embodiments described, it will be apparent to those skilled in the art that various modifications and variations are possible within the technical spirit of the present invention, and such modifications and variations belong to the appended claims. .

Claims (9)

To 100 mol% of the diex component, a polycondensation reaction is carried out so that the sum of the diol components is 100 mol%, and the copolymerized polyester resin composition, wherein the diol component is 30 to 80 mol% of 1,4-cyclohexanedimethanol, 1,4-cyclohexane imparted with flame retardancy, comprising 5 to 69 mol% of diol components except 1,4-cyclohexane dimethanol and 1 to 25 mol% of phosphorus flame retardants represented by the following general formula (1) or (2): Diethanol-containing polyester resin composition. Formula 1

Formula 2

The polyester flame retardant 1,4-cyclohexanedimethanol-containing polyester resin composition according to claim 1, wherein the phosphorus flame retardant has a phosphorus content of 1,000 to 30,000 ppm relative to the polyester resin composition. According to claim 1, wherein the diacid component is any one selected from the group consisting of terephthalic acid, isophthalic acid, phthalic acid, dimethyl terephthalate, dimethyl isophthalate and phthalic anhydride 1, 4-cyclohexanedimethanol containing polyester resin composition. The flame retardancy is imparted according to claim 1, wherein the diol component is at least one member selected from the group consisting of ethylene glycol, propylene glycol, butylene glycol, isopropylene glycol, 1-methyl propylene glycol, and pentylene glycol. 1,4-cyclohexanedimethanol containing polyester resin composition. 1) Polycondensation reaction is carried out so that the sum of diol components is 100 mol% with respect to 100 mol% of diacids, but esterification reaction of 5-69 mol% of diol components and 30-80 mol% of 1, 4- cyclohexane dimethanol is carried out. To prepare bishydroxyterephthalate, 2) 1 to 25 mol% of a phosphorus flame retardant selected from compounds represented by the following general formula (1) or (2) is added to the bishydroxyterephthalate, and 60 to 400 ppm of the reaction catalyst is added to the entire composition to prepare a mixture. and, 3) 1,4-cyclohexanedimethanol imparting flame retardancy, characterized in that the polycondensation reaction of the mixture under vacuum of 1.0 Torr or less to prepare a copolyester resin having an intrinsic viscosity of 0.5 to 1.0 dl / g. The manufacturing method of containing polyester resin composition. Formula 1

Formula 2

The method according to claim 5, wherein the reaction catalyst is a single or mixed form selected from the group consisting of titanium compounds, antimony compounds, germanium compounds and aluminum compounds, 60 to 400 ppm of the total polyester resin composition, characterized in that Method for producing a 1,4-cyclohexane dimethanol-containing polyester resin composition. The method for producing the 1,4-cyclohexanedimethanol-containing polyester resin composition according to claim 5, wherein the reaction catalyst contains 10 to 100 ppm of titanium compound and 50 to 300 ppm of antimony compound. A 1,4-cyclohexanedimethanol-containing polyester resin composition imparted with flame retardancy according to claim 1 or a molded product of a flame-retardant polyester resin imparted with a flame retardancy, characterized in that it is molded by blending with a heterogeneous polyester resin. The method according to claim 8, wherein 5 to 30% by weight of the flame retardant imparted 1,4-cyclohexanedimethanol-containing polyester resin composition is blended and molded into 70 to 95% by weight of heterogeneous polyester resin. A molded product of the polyester resin imparted with the flame retardancy.