WO2018135787A1 - Copolymerized polyethylene terephthalate polymer, yarn/bcf/film comprising same, and method for producing same - Google Patents

Abstract

The present invention relates to copolymerized polyethylene terephthalate comprising polyethylene terephthalate (PET) and unidirectional end-group-modified polydimethylsiloxane (PDMS) and having improved wear resistance, which is produced by a method of directly threading the copolymerized polyethylene terephthalate, or by a method of copolymerizing a high concentration of unidirectional end-group-modified polydimethylsiloxane with polyethylene terephthalate and using same for a master batch. A polyethylene terephthalate polymer produced thereby may be used for producing a yarn, BCF for a car mat or a film having improved wear resistance or release force.

Description

Copolymerized Polyethylene Terephthalate Polymer, Yarn / BCF / Film Containing The Same And Method For Making The Same

The present invention is in addition to the existing polyethylene terephthalate bond ethylene glycol (EG, Ethyleneglycol) and terephthalic acid (TPA, Terephthalic acid) in addition to polyethylene glycol (PEG) chain number of 1 to 50 one-way end group modified PDMS The present invention relates to a copolymer of polyethylene terephthalate having improved wear resistance prepared by introducing (polydimethylsiloxane) and a medical or industrial yarn, a BCF or a film for a carpet.

Generally, polyester resins, especially polyethylene terephthalate resins, are linear polymers synthesized from dicarboxylic acids or their ester-forming derivatives and diols or their ester-forming derivatives, and are inexpensive, yet have excellent mechanical and chemical properties. In addition to excellent gas barrier properties, it is widely used in the manufacture of various containers, films, fibers and the like. On the other hand, polyester is produced by the condensation polymerization method, the equilibrium reaction according to external conditions to obtain a commercially available viscosity through the conditions of high temperature, high vacuum, wherein a certain amount of oligomers remain in the final polymer.

Conventional polyethylene terephthalate has a problem that it is difficult to apply to the field (resin injection, yarn, film, etc.) is a wear resistance is weak compared to other resins.

It is an object of the present invention to introduce copolymerized polyethylene terephthalate having improved abrasion resistance by additionally introducing a unidirectional end group-modified polydimethylsiloxane (PDMS) having 1 to 50 chains of polyethylene glycol (PEG) in the preparation of copolymerized polyethylene terephthalate. And to provide a medical or industrial yarn, a carpet for the BCF or film comprising the same.

According to one suitable embodiment of the present invention for achieving the above object, Slurrying step of ethylene glycol (EG, Ethyleneglycol) and terephthalic acid (TPA); Esterification of the slurry; And a polycondensation reaction step, wherein the polycondensation reaction comprises a general formula (I) below and has 1 to 50 chains of polyethylene glycol (PEG), and has a number average molecular weight of 800 to 50,000. Provided is a method for preparing copolymerized polyethylene terephthalate containing polydimethylsiloxane (PDMS).

   (I)

Wherein R =-(CH ₂ -CH ₂ -O) _m- , m = 1 to 50, T = hydroxyl)

According to a preferred embodiment of the present invention, the modified polydimethylsiloxane (PDMS) is added in an amount of 0.1 to 20% by weight based on the total weight of the copolymerized polyethylene terephthalate.

According to another preferred embodiment of the present invention, there is provided a polyethylene terephthalate (PET) prepared by the above production method.

According to another suitable embodiment of the present invention, polyethylene terephtalate (PET) 80 to 99.9% by weight; And 0.1 to 20% by weight of unidirectional end group-modified polydimethylsiloxane (PDMS), wherein the unidirectional end group-modified polydimethylsiloxane (PDMS) is a chain of polyethyleneglycol (PEG) of the general formula (I) Provided is a medical or industrial polyethylene terephthalate yarn having improved wear resistance, including copolymerized polyethylene terephthalate, wherein the number is 1 to 50 and the number average molecular weight is 800 to 50,000.

   (I)

Wherein R =-(CH ₂ -CH ₂ -O) _m- , m = 1 to 50, T = hydroxyl)

According to a preferred embodiment of the present invention, it is prepared by the method of direct copolymerization of the copolymerized polyethylene terephthalate and a method of copolymerizing one-way end group-modified polydimethylsiloxane (PDMS) to polyethylene terephthalate at high concentration and using it as a master batch. Provided is a medical or industrial polyethylene terephthalate yarn with improved wear resistance.

According to another preferred embodiment of the present invention, the copolymerized polyethylene teretate is a slurry (Slurry) step of ethylene glycol (EG, Ethyleneglycol) and terephthalic acid (TPA, Terephthalic acid); Esterification of the slurry; And a polycondensation reaction step, wherein the abrasion resistance is improved medical or industrial polyethylene, including copolymerized polyethylene terephthalate prepared by a method of injecting one aromatic end group-modified polydimethylsiloxane (PDMS) into the rear end of the polycondensation reaction. Provide terephthalate yarn.

According to another suitable embodiment of the present invention, Polyethylene terephtalate (PET) 80 to 99.9% by weight; And 0.1 to 20% by weight of unidirectional end-modified polydimethylsiloxane (PDMS), wherein the unidirectional end-group modified polydimethylsiloxane (PDMS) has a number of chains of polyethylene glycol (PEG) of general formula (I) Provided is a BCF for a carpet having improved abrasion resistance, including copolymerized polyethylene terephthalate, having 1 to 50 and a number average molecular weight of 800 to 50,000.

   (I)

(Wherein, R =-(CH2-CH2-O) m-, m = 1 to 50, T = hydroxy group)

According to a preferred embodiment of the present invention, it is prepared by the method of directly copolymerizing the copolymerized polyethylene terephthalate or a method of copolymerizing unidirectional end-group-modified polydimethylsiloxane (PDMS) to polyethylene terephthalate at high concentration and using it as a master batch. Provided is a BCF for a carpet.

According to another preferred embodiment of the present invention, the copolymerized polyethylene teretate is a slurry (Slurry) step of ethylene glycol (EG, Ethyleneglycol) and terephthalic acid (TPA, Terephthalic acid); Esterification of the slurry; And a polycondensation reaction step; and a copolymer-containing BCF for a copolymer including a copolymerized polyethylene terephthalate prepared by a method of introducing one aromatic end group-modified polydimethylsiloxane (PDMS) into the rear end of the polycondensation reaction.

According to another preferred embodiment of the present invention, there is provided a polyethylene terephthalate BCF carpet with improved wear resistance prepared using the copolymerized polyethylene terephthalate.

According to another suitable embodiment of the present invention, 50 to 99.9% by weight of polyethylene terephtalate (PET); And 0.1 to 50% by weight of unidirectional end group-modified polydimethylsiloxane (PDMS), wherein the unidirectional end group-modified polydimethylsiloxane (PDMS) is a chain of polyethylene glycol (PEG) of the general formula (I) Provided is a polyethylene terephthalate film having improved wear resistance and release force, including copolymerized polyethylene terephthalate, wherein the number is 1 to 50 and the number average molecular weight is 800 to 50,000.

   (I)

(Wherein, R =-(CH2-CH2-O) m-, m = 1-50, T = hydroxy group)

According to a preferred embodiment of the present invention, it is prepared by the method of directly copolymerizing the copolymerized polyethylene terephthalate or a method of copolymerizing unidirectional end-group-modified polydimethylsiloxane (PDMS) to polyethylene terephthalate at high concentration and using it as a master batch. It provides a polyethylene terephthalate film characterized by improved wear resistance and release force.

According to another preferred embodiment of the present invention, the copolymerized polyethylene teretate is a slurry (Slurry) step of ethylene glycol (EG, Ethyleneglycol) and terephthalic acid (TPA, Terephthalic acid); Esterification of the slurry; And a polycondensation reaction step, wherein the polyethylene has improved abrasion resistance and releasing force, including copolymerized polyethylene terephthalate prepared by a method of injecting one aromatic end group-modified polydimethylsiloxane (PDMS) into the rear end of the polycondensation reaction. Provide a terephthalate film.

The present invention is a polyethylene glycol (PEG) chain number of 1 to 50, copolymerized polyethylene terephthalate with improved wear resistance by adding one-way terminal group-modified PDMS having a molecular weight of 800 to 50,000 and a medical or industrial yarn comprising the same , BCF or film for the mat.

Figure 1 shows a wear test specimen for the friction wear characteristics analysis.

Figure 2 shows the structure of the wear test apparatus for the friction wear characteristics analysis.

Method for producing a copolymerized polyethylene terephthalate according to the present invention is a slurry (Slurry) step of ethylene glycol (EG, Ethyleneglycol) and terephthalic acid (TPA, Terephthalic acid); Esterification step; And a polycondensation reaction step, wherein one side end group-modified PDMS having 1 to 50 chains of polyethylene glycol (PEG) is introduced into the rear end of the polycondensation reaction.

In the present invention, it is preferable to add the modified PDMS to the end of the polycondensation reaction in order to express the wear resistance improving effect of polyethylene terephthalate. When the modified PDMS is added after the polycondensation reaction, a binding degree of 99% or more is obtained.

Polydimethylsiloxane further added in the present invention is a compound having a structure of the following general formula (I).

   (I)

Wherein R =-(CH ₂ -CH ₂ -O) _m- , m = 1 to 50, T = hydroxyl)

The modified PDMS is composed of OH, -COOH, or NH2 in one aromatic terminal group, and in the present invention, the polymerizable polyethylene terephthalate is mainly used using OH, -COOH, and most preferably, existing diols (-OH The modified PDMS having OH is mainly used by utilizing the polymerization bond of the group).

The modified PDMS molecular weight of the present invention is preferably in the range of 800 to 50,000, more preferably 1,000 to 15,000. At this time, when the molecular weight of the modified PDMS is less than 800, the wear resistance and the release force is lowered, and when it exceeds 50,000, the polycondensation reactivity is lowered.

The number of chains of polyethylene glycol (PEG) of the modified PDMS of the present invention is preferably in the range of 1 to 50, more preferably 1 to 20. At this time, when the number of chains of polyethylene glycol (PEG) of the modified PDMS is less than one, the polycondensation reactivity is lowered, and when it exceeds 50, the wear resistance and the release force are lowered.

The present invention is characterized in that the modified PDMS is added to the rear end of the polycondensation reaction.

The modified PDMS is preferably added at the end of the polycondensation reaction in order to express the wear resistance improving effect of polyethylene terephthalate. When the modified PDMS is added after the polycondensation reaction, a binding degree of 99% or more is obtained. When introduced into the polymer when introduced in the slurrying step and the esterification step or the initial stage of the polycondensation, there is a problem that it is difficult to increase the viscosity of the polymer and low expected reaction rate of the modified PDMS. In addition, even after the polycondensation reaction, the melt viscosity increases due to the modified PDMS, and thus, polycondensation reaction conditions should be set unlike the existing polyester polymerization conditions.

At this time, 0.1-20 weight% is preferable with respect to the gross weight of copolymerized polyethylene terephthalate, and, as for the quantity of polydimethylsiloxane added, 0.5-5 weight% is more preferable. If the content of polydimethylsiloxane is less than 0.1% by weight, the amount of migration to the surface is small, and the effect of improving the wear resistance and the release force is insignificant. If the content exceeds 20% by weight, the productivity is reduced.

Hereinafter, a method for producing a yarn using the polyethylene terephthalate polymer prepared according to the present invention will be described in detail.

Meanwhile, in order to more conveniently apply polydimethylsiloxane (PDMS) to spinning of the polyethylene terephthalate polymer, a polyethylene terephthalate (PET) / polydimethylsiloxane (PDMS) masterbatch chip may be prepared.

At this time, the master batch chip uses a twin screw extruder composed of 28 or more L / D in consideration of the effectiveness of the kneading. The operating temperature of the axial extruder is 240 ° C to 250 ° C, and the mixing ratio of polyethylene terephthalate and polydimethylsiloxane (PDMS) on the master batch ranges from 5% to 50% by weight, preferably 10% to 20% by weight. It is preferable to set it as. The melt-kneaded mixture through the twin screw extruder passes through a cooling water tank maintained at 25 ° C. to 30 ° C. and is solidified into chips using a chip cutter.

The produced polyethylene terephthalate and polydimethylsiloxane (PDMS) master batch chip or the spinning by using the polyethylene terephthalate polymer, the final content of the PDMS contained in the fiberized polyethylene terephthalate is preferably 0.1 to 20% by weight, 0.5-5 weight% is more preferable. When the content of polydimethylsiloxane is less than 0.1% by weight, the amount of migration to the surface is small, so that the effect of improving wear resistance is insignificant. When the content is more than 20% by weight, the productivity is reduced.

In the present invention, the polyethylene terephthalate polymer or the masterbatch chip may be melt-spun according to a general process well known in the textile industry to prepare fibers of a desired shape. The form and production method are not particularly limited.

The master batch chip is melt-mixed at a predetermined ratio such that polyethylene terephthalate having an intrinsic viscosity of 0.6 to 1.3 and PDMS is 0.1 to 20% by weight, or copolymerized polyethylene terephthalate containing PDMS in a conventional process. The mixture is spun and stretched to produce polyethylene terephthalate yarns.

In the spinning step, the polyethylene terephthalate chip is melt-spun through a pack and a nozzle at a temperature of 280 to 310 ° C. In the present invention, it is preferable to mix the spun polymer evenly, and to increase the uniformity of melt viscosity of each polymer part. Static mixers, etc. can be installed on the top of the pack to provide this.

In the solidification cooling step of the present invention, the melt-discharge yarn produced in the spinning step is passed through the cooling zone to solidify. If necessary, a heating device may be installed at a distance from the nozzle directly to the start point of the cooling zone, that is, the length of the hood. . This zone is called delayed cooling zone or heating zone, and may have a length of 100 to 800 mm and a temperature of 300 to 400 ° C. In the cooling zone, open quenching, circular closed quenching, and radial outflow quenching may be applied depending on the method of blowing the cooling air. Does not. Subsequently, the discharged sand solidified while passing through the cooling zone may be oiled by 0.5 to 1.0% by the emulsion applying device.

In the drawing step of the present invention, the yarn that has passed through the feed roller, once the undrawn yarn is taken out and then passed through a series of drawing rollers by using a separate drawing process, or preferably by a spin draw method. The final stretched yarn is obtained by stretching, wherein the temperature of the second stage stretching is adjusted to 100 to 210 ° C. More specifically, first, 1 to 10% of free draw (free draw) is given, and then the first step stretching at 1.2 to 7 times at 80 to 200 ℃, the second step stretching at 1.2 to 2.0 times at 130 to 200 ℃ In order to increase the uniformity of high magnification stretching during the first stage stretching, the steam jet method may be applied. Then, according to a conventional method, the finished yarn can be heat set to a temperature of 200 to 260 ° C (relaxing) to 1 to 6%.

In addition, the spinning oil used in the production of the polyethylene terephthalate multifilament yarn of the present invention, it is preferable to use a spinning oil having a heating loss of 1 to 10% to 298 ℃ measured by TGA equipment in the state of removing solvent and water. . The spinning emulsion having a heating loss ratio of less than 1% up to 298 ° C. is hardly present, and when the spinning emulsion having a heating loss ratio of 10% or more is applied, the effect of improving the strong retention rate after high temperature heat treatment is not sufficient.

As described above, the polyethylene terephthalate multifilament yarn prepared according to the present invention may be used in fabrics, but not limited to seat belts, industrial webbing, ropes, and the like.

Hereinafter, a method for producing a BCF for a carpet using a polyethylene terephthalate polymer prepared according to the present invention will be described in detail.

First, the polyethylene terephthalate polymer prepared according to the present invention is melt-spun at 245 to 335 ° C. to pass a spinneret.

The polyethylene terephthalate resin underlying in the present invention contains 90 mol% or more of repeating units of ethylene terephthalate.

After cooling in the cooling zone with air at a speed of 0.2 ~ 1.0m / sec. At this time, the cooling temperature is adjusted to 10 ~ 35 ℃. At this time, if the speed of the cooling air is less than 0.2m / sec, the cooling effect is insufficient, if it exceeds 1.0m / sec, the shaking of the yarn is excessive, which is a problem in the spinning workability. In addition, if the cooling temperature is less than 10 ℃ economically disadvantageous, if it exceeds 35 ℃ cooling effect is inferior.

After cooling, it goes through a spin finish step of oiling. In the finish applicator, the first and second stages are oiled using neat or water-soluble emulsions to improve the cohesion, lubricity and smoothness of the yarn. Increase it.

Thereafter, the feed roller is supplied to the stretching roller at a speed of 100 to 1,000 m / min, preferably 400 to 800 m / min, wherein the stretching roller is at a temperature of 100 to 230 ° C. and 2.5 to 6.0 of the feed roller speed. At a rate of fold, stretching is preferably from 3.5 to 5.0 fold. When the stretching speed is less than 2.5 times, it is not stretched sufficiently, and when the stretching speed is greater than 6.0 times, the polyethylene terephthalate material is not able to withstand the stretching and is trimmed.

The filament passed through the stretching roller passes through a texturing unit with a texturing nozzle to impart bulkiness.In this case, the filament is irregularly formed by spraying a heating fluid of 150 to 270 ° C at a pressure of 3 to 10 kg / cm2 inside the texturing unit. It is crimped to a dimension and the crimp rate at this time is 3 to 50%.

At this time, the temperature of the heating fluid is preferably 150 ~ 270 ℃, which is less than 150 ℃ texturing effect and exceeds 270 ℃ causes damage to the filament. In addition, the pressure of the heating fluid is preferably 3 to 10 kg / cm 2, which is less than the texture effect of less than 3 kg / cm 2 and causes damage to the filament exceeds 10 kg / cm 2.

After passing through the texturing unit, the filament is cooled while passing through the cooling section. In this part, in order to improve the focusing force of the yarn, a slight twist and a knot are applied at a pressure of 2.0 to 8.0 kg / m 2. The range is 0 to 40 times / m, preferably 10 to 25 times. When the entanglement is given more than 40 times, the entanglement of the entanglement remains unchanged even after dyeing and post-processing.

Thereafter, the rollers are passed through at a speed of 0.65 to 0.95 times the speed of the stretching roller to give a relaxation rate of 5 to 35%, and then wound up at the final winding machine. The speed of the winder is usually adjusted so that the tension of the thread is in the range of 50 to 350 g. At this time, if the tension in the winding machine is less than 50g, the winding is impossible, and if it exceeds 350g, the bulkiness is reduced, the yarn shrinks greatly and causes high tension, which causes trouble in the work. In addition, if the speed of the relaxation roller is less than 0.65 times of the stretching roller speed, it is not wound, and if it exceeds 0.95 times, the bulkiness is decreased, the yarn shrinks greatly, and high tension causes the work.

The method relates to a BCF made of polyethylene terephthalate resin only, the step-by-step process is the same as above when producing the primary yarn according to the carpet application. However, in the raw material supply, it is also possible to prepare the yarn by adding a predetermined amount of colorant to the base chip input amount.

The polyethylene terephthalate multifilament prepared according to the present invention as described above is produced into a carpet through a post-process. Carpets made with the BCF company of the present invention can be produced in any manner known to those skilled in the art. Preferably a plurality of BCF yarns are cable twisted and heat set together and then weave to the primary back side. The latex adhesive and the secondary backside are then applied. Cut pile style carpets or loop pile style carpets with pile heights of approximately 2-20 mm can be made.

On the other hand, the method for producing a film using the polyethylene terephthalate polymer prepared according to the present invention will be described in detail.

The film produced according to the present invention contains inorganic particles comprising silica beads having a methyl group on the surface. Silica beads generally have a hydroxy group (OH) having a hydrophilicity on the surface. According to the present invention, silica beads in which the hydroxy group on the surface is substituted with a methyl group (CH3) play a lubricating role in the film to effectively reduce the coefficient of friction of the film. . As the inorganic particles contained in the base layer, calcium carbonate, colloidal silica or a mixture thereof may be used in addition to silica beads having a methyl group.

As silica beads having a methyl group, those having a particle diameter of 2 m or less, preferably 1 m or less are used. The more the silica beads are used, the less the coefficient of friction of the release film, but the silica beads have a problem that the surface of the substrate layer is too rough when the particle size is large, so that the silica bead is excessively added.

Calcium carbonate is preferred as inorganic particles other than silica beads having a methyl group. Calcium carbonate with a particle diameter of 2 μm or less, preferably 1 μm or less and 0.4 to 0.8 μm is used, but a small particle size can be obtained and it is considered to be good for preventing blocking. However, calcium carbonate alone is not effective and uniform in process. It is also not easy to disperse.

According to the present invention, the above inorganic particles are preferably contained within the range of 1,000 to 3,000 ppm in the base layer. When included in less than 1,000ppm it is difficult to implement the physical properties required by the present invention, when included in excess of 3,000ppm inorganic particles are agglomerated to cause a process difficulty.

On the other hand, the mixing ratio between the inorganic particles, calcium carbonate and silica beads are preferably mixed in a ratio of 1: 0.3 to 1: 0.6.

When calcium carbonate is mixed higher than the above ratio, the effect of reducing the friction coefficient is small and the effect of preventing foreign matter mixing or scratching is small. In addition, when the silica beads are mixed higher than the above ratio, the friction coefficient reduction effect is large and foreign matter mixing or scratch reduction effect is large, but the surface roughness of the film is excessively high.

In the film of the present invention, a copolymerized polyethylene terephthalate and inorganic particles are mixed to obtain a composition, and the composition is melted, coextruded, cooled in casting, stretched 3.2 times in the longitudinal direction, and stretched 3.2 times in the width direction to 188 탆. It is made of a film of.

Hereinafter, the present invention will be described in more detail based on the following examples. However, the following examples are not intended to limit the present invention, but are not limited thereto. The physical properties of the resins, yarns, and films prepared in Examples and Comparative Examples of the present invention were evaluated by the following methods.

1. Evaluation of wear resistance of resin (tribology characteristics measurement)

1 shows a wear test specimen, and FIG. 2 shows a wear test apparatus structure.

Physical properties were measured according to the JIS K7218 method.

In other words, the frictional wear characteristics were analyzed by evaluating how much force was applied and the amount of wear when a ring-shaped specimen was mounted on the tester, and a constant load and speed were selected and rotated. Ring-shaped specimens are made of plastics and metals (S45C, copper, SUS, etc.) and other materials can be manufactured as needed. The load was measured in the range of 0.1 kgf to 500 kgf, the speed of 1 mm / sec to 1000 mm / sec and the wear distance in the range of 1 to 10 km.

1) Ring-on-ring evaluation condition: counterpart = metal (S45C), load = 11.8 kgf, speed = 300mm / s, time = 120min

2) Pin-on-disk evaluation condition: counterpart = same resin, load = 2kgf, speed = 2Hz, time = 30min

2. Wear resistance of yarn

Standard wear test method NO. The test was carried out 300 or 400 times with CS-10 to visually observe the weight loss and abrasion appearance before and after the test.

3. How to evaluate the wear resistance of the mat

The wear resistance of the mat was measured under the following conditions, and the wear resistance of the mat was evaluated based on the number of wears at the time when the surface of the mat was exposed at the level equivalent to the grade 2.5 of external appearance. It was.

Related Test Method Standard: ASTM D3884

Test method: Hyundai Motor MS300-35

Test equipment: Taber wear tester

Sample size: 130mm diameter round sample

Exam conditions

1) Abrasion Wheel: H-18

2) Speed: 70 times / min

3) Load: 1000g

4) Evaluation Method: Appearance Evaluation Grades 1-5 (Hyundai Motors MS343-15 Standard 3 or above (3, 4, 5) Pass

5) Evaluation criteria: No grade 5 wear

              Slight or almost inconspicuous class 4 wear

              Some grade 3 wear but visible

              Slightly severe class 2 wear

              Class 1 quite severe

4. How to measure the elongation of yarn

After the yarns are left in a constant temperature and humidity room at a standard condition, that is, a temperature of 25 ° C. and a relative humidity of 65% RH, the samples are measured by a tensile tester using the ASTM 2256 method.

5. Friction fastness of yarn

Using a friction tester manufactured by TORAY (model YF-850), the interfiber static friction coefficient F / F μs was measured by rubbing yarns at a speed of 3 cm / min.

6. Crimp rate and standard deviation

Measured by TYT-EW (Textured Yarn Tester) measuring device, measuring length is 5 times at 20m and 2m intervals. Temperature of heating zone is 130 ℃ and measuring speed is 20m / min.

7. Friction coefficient of film

The static and dynamic friction values were measured by the frictional force between the contact surfaces of two objects and the pressure ratio in the normal direction acting between them. The analysis was performed at 23 ° C. and 50% RH.

Static friction: Static Coefficient of Friction that must be overcome by the threshold value at the start of the sliding motion

Dynamic friction: Kinetic Coefficient of Friction during a sliding motion at a given speed

-Coefficient of friction = (generated load-applied load at friction) / applied load

8. Release force (peeling force)

According to the FINAT test method-10, a release force evaluation sample was prepared, and Nitto31B Tape of Nitto was used as a reference adhesive tape for measurement, and the release force was measured through a Peel Tester (Chem Instruments, AR-1000). Measured by 180 degree Peel method, the peeling rate is carried out at 300mpm (meters per minute).

Example  One

50 parts by weight of ethylene glycol was added to the esterification reactor with respect to 100 parts by weight of terephthalic acid, and the esterification reaction was carried out while flowing water out of the reactor at 250 ° C. for 4 hours to give bis (2-hydroxyethyl) terephthalate [bis (2-hydroxyethyl) terephthalate] was prepared. At this time, 300 ppm of the phosphorus heat stabilizer was added at the end of the esterification reaction. Thereafter, 300 ppm of the antimony catalyst was initially added as a polymerization catalyst, the temperature was raised from 250 ° C to 285 ° C to 60 ° C / hr, and the pressure was reduced to 0.1torr to carry out the polycondensation reaction. At the end of the reaction, 0.5% by weight of one-way terminal group-modified PDMS having a hydroxyl group, one polyethylene glycol (PEG) chain, and a molecular weight of 5,000 was added to carry out a polycondensation reaction to prepare a polymer. In the above example, FMNC-21 product of JNC was applied.

The prepared polymer was obtained by blending pellets at 260 ° C. using an extruder. The pellets were sufficiently dried at 105 ° C. for at least 4 hours, and then a test piece was prepared at 250 ° C. using an injection machine.

Example  2

A polymer was prepared in the same manner as in Example 1, except that 5 wt% of the aromatic terminal group-modified PDMS having a terminal group having a hydroxyl group and a molecular weight of 5,000 was added at the end of the polycondensation reaction.

Example  3

5 wt% of the aromatic terminal group-modified PDMS having a terminal group having a hydroxyl group and a molecular weight of 15,000 was added to the rear stage of the polycondensation reaction to carry out a polycondensation reaction, to prepare a polymer in the same manner as in Example 1. In the above example, FMNC-26 product of JNC was applied.

Comparative example  One

A polymer was prepared in the same manner as in Example 1 except that no modified PDMS was added.

division	Denatured PDMS input and input	Ring-on-ring type		pin-on-disk type
		Dynamic friction coefficient	Non-wear amount (㎣ / ㎏fkm)	Dynamic friction coefficient	Non-wear amount (㎣ / ㎏fkm)
Example 1	Oil / 0.5 wt%	0.15	0.03	0.13	4.3
Example 2	5% by weight	0.08	0.01	0.08	2.8
Example 3	5% by weight	0.04	0.01	0.03	1.9
Comparative Example 1	radish	0.41	0.53	0.52	7.2

As shown in Table 1, when the number of chains of the polyethylene glycol (PEG) of the general formula (I) is 1 to 20 and the molecular weight is 5,000 to 15,000 unidirectional end-group-modified PDMS is added to the rear end of the polycondensation, It was confirmed that the wear resistance is very improved compared to the comparative example without the PDMS.

Example  4

50 parts by weight of ethylene glycol was added to the esterification reactor with respect to 100 parts by weight of terephthalic acid, and the esterification reaction was carried out while flowing water out of the reactor at 250 ° C. for 4 hours to give bis (2-hydroxyethyl) terephthalate [bis (2-hydroxyethyl) terephthalate] was prepared. At this time, 300 ppm of the phosphorus heat stabilizer was added at the end of the esterification reaction. Thereafter, 300 ppm of the antimony catalyst was initially added as a polymerization catalyst, the temperature was raised from 250 ° C to 285 ° C to 60 ° C / hr, and the pressure was reduced to 0.1torr to carry out the polycondensation reaction. At the end of the reaction, 0.5% by weight of one-way terminal group-modified PDMS (JNC, FMDA-21) having a hydroxyl group, one polyethylene glycol (PEG) chain and a molecular weight of 5,000 was added, followed by a polycondensation reaction. The polymer was prepared.

The polyethylene terephthalate polymer was spun by using a 36-hole nozzle, and 75 denier / 36 filament yarns were manufactured under spinning conditions in which strength 4.8 gf / denier was expressed through a stretching step.

At this time, in order to avoid excessive heat setting during the spinning process, the temperature of the high roller 4 was produced at 220 ° C.

Example  5

Same as Example 4 except that 1.0% by weight of one-way terminal group-modified PDMS (JNC, FMDA-21) having a terminal group of hydroxyl group, one polyethylene glycol (PEG) and a molecular weight of 5,000 was added. The polymer was prepared by the method.

Example  6

Same as Example 4, except that 1.0% by weight of one-way terminal group-modified PDMS (JNC, FMDA-26) having a molecular weight of 15,000 and one chain having a hydroxyl group and one polyethylene glycol (PEG). The polymer was prepared by the method.

Comparative example  2

Polymerization was prepared in the same manner as in Example 4 except that no modified PDMS was added.

	Comparative Example 2	Example 4	Example 5	Example 6
MV	162	263	208	193
IV (dl / g)	0.68	0.80	0.80	0.77
Strength (g / d) / Elongation (%)	4.8 / 38	4.9 / 36	4.7 / 37	4.6 / 37
Wear resistance (300 times / 400 times)	X / X	O / O	O / O	O / O
Static friction coefficient	0.466	0.364	0.302	0.299

As shown in Table 2, when the number of chains of the polyethylene glycol (PEG) of the general formula (I) is 1 to 20 and the molecular weight is 5,000 to 15,000 unidirectional end group-modified PDMS is added to the rear end of the polycondensation, It was confirmed that the wear resistance and the coefficient of friction were improved while maintaining the strength / elongation compared to the comparative example without the PDMS.

Example  7

50 parts by weight of ethylene glycol was added to the esterification reactor with respect to 100 parts by weight of terephthalic acid, and the esterification reaction was carried out while flowing water out of the reactor at 250 ° C. for 4 hours to give bis (2-hydroxyethyl) terephthalate [bis (2-hydroxyethyl) terephthalate] was prepared. At this time, 300 ppm of the phosphorus heat stabilizer was added at the end of the esterification reaction. Thereafter, 300 ppm of the antimony catalyst was initially added as a polymerization catalyst, the temperature was raised from 250 ° C to 285 ° C to 60 ° C / hr, and the pressure was reduced to 0.1torr to carry out the polycondensation reaction. At the end of the reaction, 0.5% by weight of one-way terminal group-modified PDMS having a hydroxyl group, one polyethylene glycol (PEG) chain, and a molecular weight of 5,000 was added to carry out a polycondensation reaction to prepare a polymer. In the above example, FMNC-21 product of JNC was applied.

The polyethylene terephthalate polymer produced through spinneret having 128 holes and having a Y-shaped cross section is melt-spun at 290 ° C. The polymer exiting the spinneret is cooled by 0.5 m / s at 20 ° C. cooling air at the bottom of the nozzle and then passed through the emulsion feeder. The emulsified yarn is subjected to a feed roller maintained at 90 ° C. at a speed of 598 m / min, and then drawn at a speed of 190 ° C. and 2,840 m / min in a drawing roller. The yarn passed through the stretching roller passes through the texturing nozzle and is crimped. At this time, the hot air temperature is 200 ℃, the pressure is 7kg / cm2 and the back pressure is 5kg / cm2. Afterwards, 20 times / m of entanglement is applied at a pressure of 4.0 kg / m2 in the post-concentrator cooled by cooling water. It passes through the relaxation roller at 2250m / min and is relaxed by 21% and then wound up on a winding machine. The strength, elongation, wear resistance, and coefficient of static friction of the polyethylene terephthalate BCF yarn prepared by this process were measured and shown in Table 3 below.

Carpets were prepared using the prepared polyethylene terephthalate BCF yarn to measure wear resistance, and the results are shown in Table 3 below.

Example  8

A polymer was prepared in the same manner as in Example 7, except that 1.0 wt% of the aromatic terminal group-modified PDMS having a terminal group of hydroxyl group and molecular weight of 5,000 was added to the rear stage of the polycondensation reaction.

Example  9

One-way terminal group-modified PDMS having a terminal group having a hydroxyl group and a molecular weight of 15,000 was added to the rear end of the polycondensation reaction to carry out a polycondensation reaction, to prepare a polymer in the same manner as in Example 7. In the above example, FMNC-26 product of JNC was applied.

Comparative example  3

A polymer was prepared in the same manner as in Example 7, except that no modified PDMS was added.

	Comparative Example 3	Example 7	Example 8	Example 9
Strength (g / d)	4.9	4.9	4.7	4.5
Elongation (%)	37.7	35.6	36.9	36.6
Carpet fracture wear water (water supply)	300 (Level 2)	600 (Level 4)	650 (Level 4)	550 (Level 3)

As shown in Table 3, when the number of chains of the polyethylene glycol (PEG) of the general formula (I) is 1 to 20 and the molecular weight is 5,000 to 15,000 unidirectional end group-modified PDMS is added to the rear end of the polycondensation, It was confirmed that the wear resistance is very improved compared to the comparative example without the PDMS.

Example  10

50 parts by weight of ethylene glycol was added to the esterification reactor with respect to 100 parts by weight of terephthalic acid, and the esterification reaction was carried out while flowing water out of the reactor at 250 ° C. for 4 hours to give bis (2-hydroxyethyl) terephthalate [bis (2-hydroxyethyl) terephthalate] was prepared. At this time, 300 ppm of the phosphorus heat stabilizer was added at the end of the esterification reaction. Thereafter, 300 ppm of the antimony catalyst was initially added as a polymerization catalyst, the temperature was raised from 250 ° C to 285 ° C to 60 ° C / hr, and the pressure was reduced to 0.1torr to carry out the polycondensation reaction. At the end of the reaction, a polymer was prepared by carrying out a polycondensation reaction by adding 5.0% by weight of one-way terminal group-modified PDMS having a hydroxyl group, a chain number of polyethylene glycol (PEG) and a molecular weight of 5,000. In this example, FMNC-21 product from JNC was prepared.

The bidirectional end group-modified PDMS copolymerized polyethylene terephthalate polymer and 1.0 μm of silica particles were added to the extruder in the content of Table 4 and melt-extruded. The melt was coextruded and then cooled in a 40 ° C. casting roll to prepare an unstretched film. The unstretched film was stretched 3.2 times in the machine direction (MD) and then stretched 3.2 times in the longitudinal direction (TD) to prepare a multilayer film having a total thickness of 25 μm.

Example  11

Example 10 except that the polymer was prepared by a polycondensation reaction by adding 10.0% by weight of one-way terminal group-modified PDMS having a hydroxyl group, a polyethylene glycol (PEG) chain, and a molecular weight of 5,000. A polymer was prepared in the same manner as in the following.

Example  12

10.0% by weight of one-way end group-modified PDMS (JNC, FMDA-26) having a molecular weight of 15,000 and a chain of one hydroxyl group and one polyethylene glycol (PEG) was added to carry out a polycondensation reaction to prepare a polymer. A polymer was prepared in the same manner as in Example 10, except that one was prepared.

Comparative example  4

A polymer was prepared in the same manner as in Example 10 except that no modified PDMS was added.

	Comparative Example 4	Example 10	Example 11	Example 12
Coefficient of friction	0.8	0.8	0.2	0.
Release force (gf / inch)	97.3	28.9	17.8	20.8

As shown in Table 4, when the number of chains of the polyethylene glycol (PEG) of the general formula (I) is 1 to 20 and the molecular weight is 5,000 to 15,000 unidirectional end group-modified PDMS is added to the rear end of the polycondensation, It was confirmed that the friction coefficient of the film is reduced and the releasing force is improved compared to the comparative example without the PDMS.

Although the preferred embodiments of the present invention have been described in detail above, the present invention is not limited to the above-described embodiments, and the fact that the present invention can be variously changed and modified without departing from the spirit or scope of the present invention. It will be apparent to those skilled in the art. Therefore, the protection scope of the present invention should be defined in the appended claims and equivalents thereof.

Claims (13)

1. Slurrying step of ethylene glycol (EG, Ethyleneglycol) and terephthalic acid (TPA);

   Esterification of the slurry; And

   A polycondensation reaction step;

   One-way end group-modified polydimethylsiloxane (PDMS) composed of the following general formula (I) at the end of the polycondensation reaction, having 1 to 50 chains of polyethylene glycol (PEG) and having a number average molecular weight of 800 to 50,000 Method of producing a copolymerized polyethylene terephthalate is added.

      (I)

   

   Wherein R =-(CH ₂ -CH ₂ -O) _m- , m = 1 to 50, T = hydroxyl)
2. The method of claim 1,

   The modified polydimethylsiloxane (PDMS) is a method for producing copolymerized polyethylene terephthalate, characterized in that the input of 0.1 to 20% by weight relative to the total weight of the copolymerized polyethylene terephthalate.
3. Copolymerized polyethylene terephthalate (PET) prepared by the method of claim 1.
4. 80 to 99.9% by weight of polyethylene terephtalate (PET); And

   0.1-20% by weight of unidirectional end group-modified polydimethylsiloxane (PDMS)

   Including,

   The unidirectional end group-modified polydimethylsiloxane (PDMS) is a polyethylene glycol (PEG) of the general formula (I) of 1 to 50 chain number, copolymer number, characterized in that the number average molecular weight is 800 to 50,000 Medical or industrial polyethylene terephthalate yarn with improved abrasion resistance, including terephthalate.

      (I)

   

   Wherein R =-(CH ₂ -CH ₂ -O) _m- , m = 1 to 50, T = hydroxyl)
5. The method of claim 4, wherein

   Copolymerized polyethylene terephthalate, characterized in that the method of direct yarn and copolymerized polyethylene terephthalate unidirectional terminal group modified polydimethylsiloxane (PDMS) to a high concentration copolymerized to polyethylene terephthalate prepared by using a master batch Medical or industrial polyethylene terephthalate yarns with improved wear resistance.
6. The method of claim 5,

   The copolymerized polyethylene terephthalate is

   Slurrying step of ethylene glycol (EG, Ethyleneglycol) and terephthalic acid (TPA);

   Esterification of the slurry; And

   A polycondensation reaction step;

   Medical or industrial polyethylene terephthalate yarn with improved abrasion resistance comprising a copolymerized polyethylene terephthalate prepared by a method of injecting a single aromatic group modified polydimethylsiloxane (PDMS) to the rear end of the polycondensation reaction.
7. 80 to 99.9% by weight of polyethylene terephtalate (PET); And

   0.1-20% by weight of unidirectional terminal modified polydimethylsiloxane (PDMS)

   Including,

   The unidirectional end group-modified polydimethylsiloxane (PDMS) is a polyethylene glycol (PEG) of the general formula (I) of 1 to 50 chain number, copolymer number, characterized in that the number average molecular weight is 800 to 50,000 BCF for a carmat with improved abrasion resistance including terephthalate.

      (I)

   

   (Wherein, R =-(CH2-CH2-O) m-, m = 1 to 50, T = hydroxy group)
8. The method of claim 7, wherein

   It includes a copolymerized polyethylene terephthalate which is prepared by a method of directly directing the copolymerized polyethylene terephthalate or a method of copolymerizing unidirectional end-group-modified polydimethylsiloxane (PDMS) to polyethylene terephthalate at high concentration and using it as a master batch. BCF for the carmat with improved wear resistance.
9. The method of claim 8,

   The copolymerized polyethylene teretate is

   Slurrying step of ethylene glycol (EG, Ethyleneglycol) and terephthalic acid (TPA);

   Esterification of the slurry; And

   A polycondensation reaction step;

   BCF for a carpet improved improved wear resistance comprising a copolymerized polyethylene terephthalate prepared by a method of injecting a one-way end group-modified polydimethylsiloxane (PDMS) to the rear end of the polycondensation reaction.
10. Polyethylene terephthalate BCF carpet with improved wear resistance prepared using the copolymerized polyethylene terephthalate of claim 7.
11. 50 to 99.9% by weight of polyethylene terephtalate (PET); And

    0.1-50% by weight of unidirectional end group-modified polydimethylsiloxane (PDMS)

    Including,

    The unidirectional end group-modified polydimethylsiloxane (PDMS) is a copolymer number of 1 to 50 chains of polyethylene glycol (PEG) of the general formula (I), the number average molecular weight is 800 to 50,000 Polyethylene terephthalate film with improved wear resistance and release force, including terephthalate.

       (I)

    

    (Wherein, R =-(CH2-CH2-O) m-, m = 1-50, T = hydroxy group)
12. The method of claim 11,

    It includes a copolymerized polyethylene terephthalate which is prepared by a method of directly directing the copolymerized polyethylene terephthalate or a method of copolymerizing unidirectional end-group-modified polydimethylsiloxane (PDMS) to polyethylene terephthalate at high concentration and using it as a master batch. Polyethylene terephthalate film with improved wear resistance and release force.
13. The method of claim 12,

    The copolymerized polyethylene teretate is

    Slurrying step of ethylene glycol (EG, Ethyleneglycol) and terephthalic acid (TPA);

    Esterification of the slurry; And

    A polycondensation reaction step;

    A polyethylene terephthalate film having improved abrasion resistance and release force, including a copolymerized polyethylene terephthalate prepared by a method of injecting one aromatic end group-modified polydimethylsiloxane (PDMS) into the rear end of the polycondensation reaction.

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