KR20180086321A - BCF containing polyethyleneterephthalate copolymer - Google Patents

Abstract

The present invention relates to a BCF for a car mat with improved abrasion resistance, which contains copolymerized polyethylene terephthalate (PET) including PET and a bidirectional end group modified polydimethylsiloxane (PDMS). The BCF of the present invention is prepared by a method of directly dispersing the copolymerized PET or a method of copolymerizing a bidirectional end group modified PDMS in PET at high concentration. Therefore, the BCF for a car mat having excellent abrasion resistance can be prepared and applied to a PET BCF car mat.

Description

BCF containing polyethyleneterephthalate copolymer containing BCF (copolymerized polyethylene terephthalate polymer)

The present invention relates to a bidirectional end-group modified PDMS (polyethylene terephthalate) having a chain number of polyethylene glycol (PEG) of 1 to 50 in addition to ethylene glycol (EG, Ethyleneglycol) and terephthalic acid The present invention relates to a BCF for a car mat, which comprises a copolymerized polyethylene terephthalate having improved abrasion resistance, which is produced by introducing polydimethylsiloxane.

Generally, polyester resins, especially polyethylene terephthalate resins, are linear polymers synthesized from dicarboxylic acids or ester-forming derivatives thereof and diols or ester-forming derivatives thereof, which are low in cost and excellent in mechanical properties and chemical properties But also has excellent gas barrier properties and is widely used for the production of various containers, films and fibers. On the other hand, the polyester is produced by condensation polymerization method. In the equilibrium reaction according to external conditions, a commercially available viscosity is obtained through high temperature and high vacuum conditions, and a certain amount of oligomer remains in the final polymer.

Conventional polyethylene terephthalate has a problem that it is difficult to apply it to a field (resin injection molding, yarn, film, etc.) which requires less abrasion resistance than other resins.

It is an object of the present invention to provide a method for producing a copolymerized polyethylene terephthalate which comprises copolymerizing polyethylene terephthalate (PEG) having improved abrasion resistance by further introducing a bi-directional end-group modified polydimethylsiloxane (PDMS) having 1 to 50 chains of polyethylene glycol And to provide a BCF for a car mat which is used.

According to one aspect of the present invention, there is provided a polyolefin resin composition comprising 80 to 99.9% by weight of polyethylene terephthalate (PET); Wherein the bi-directional end-group modified polydimethylsiloxane (PDMS) comprises from 0.1 to 20% by weight of bi-directional end-terminated polydimethylsiloxane (PDMS), wherein the number of chains of polyethylene glycol (PEG) To 50 carbon atoms and a molecular weight of 800 to 50,000. The BCF for a car mat having improved wear resistance is characterized by comprising a copolymerized polyethylene terephthalate.

(I)

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

T = hydrogen, a hydroxyl group or a carboxyl group or an amine group)

At this time, it is characterized in that it is produced by a method of directly yarn-co-polymerizing polyethylene terephthalate and a method of copolymerizing bidirectional end-group modified polydimethylsiloxane (PDMS) at high concentration into polyethylene terephthalate and using it as a master batch. At this time, the copolymerized polyethylene terephthalate may be prepared by slurrying ethylene glycol (EG, Ethyleneglycol) and terephthalic acid (TPA, Terephthalic acid); An esterification reaction step of the slurry; And a polycondensation reaction step in which a copolymerized polyethylene terephthalate is added to the end of the polycondensation reaction in a bidirectional end group modified polydimethylsiloxane (PDMS).

Further, there is provided a polyethylene terephthalate BCF car mat produced by using a BCF for a car mat with improved wear resistance.

The present invention relates to a method for producing BCF for car mat using copolymerized polyethylene terephthalate, which comprises copolymerized polyethylene terephthalate prepared by adding bi-directional end-group modified PDMS having 1 to 50 chains of polyethylene glycol (PEG) BCF for car mat is provided.

The method for producing a copolymerized polyethylene terephthalate according to the present invention comprises the steps of slurrying ethylene glycol (EG) and terephthalic acid (TPA); An esterification reaction step; And a polycondensation reaction step in which a bidirectional end-group modified PDMS having 1 to 50 chains of polyethylene glycol (PEG) is added to the 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 exhibit the anti-abrasion effect of polyethylene terephthalate. When the modified PDMS is introduced into the subsequent stage of the polycondensation reaction, the degree of bonding is 99% or more.

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

(I)

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

T = hydrogen, a hydroxyl group or a carboxyl group or an amine group)

Modified PDMS is composed of OH, -COOH and NH2 in the short-term end. In the present invention, the main object is to polymerize with polyethylene terephthalate using OH and -COOH, And the modified PDMS having an OH group utilizing the polymerisation of the group.

The molecular weight of the modified PDMS of the present invention is preferably in the range of 800 to 50,000, more preferably 1,000 to 15,000. If the molecular weight of the modified PDMS is less than 800, the abrasion resistance is deteriorated. If the molecular weight exceeds 50,000, the polycondensation reactivity is deteriorated.

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

The present invention is characterized in that denatured PDMS is introduced into the latter stage of the polycondensation reaction.

It is preferable that the modified PDMS is introduced into the latter stage of the polycondensation reaction in order to exhibit the anti-wear effect of the polyethylene terephthalate. When the modified PDMS is introduced into the subsequent stage of the polycondensation reaction, the degree of bonding is 99% or more. It is difficult to increase the viscosity of the polymer and the reaction rate of the modified PDMS is low when it is added in the slurrying step and the esterification reaction step or the initial stage of the polycondensation. Also, when the post-polycondensation reaction is carried out, there is a problem that the melt viscosity of the modified PDMS is increased. Therefore, polycondensation reaction conditions should be set differently from the conventional polyester polymerization conditions.

The amount of the polydimethylsiloxane to be added is preferably 0.1 to 20% by weight, more preferably 0.5 to 5% by weight, based on the total weight of the copolymerized polyethylene terephthalate. When the content of the polydimethylsiloxane is less than 0.1% by weight, the amount migrated to the surface is small and the effect of improving the abrasion resistance is insignificant. When the content exceeds 20% by weight, the productivity is decreased.

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

First, the polyethylene terephthalate polymer produced according to the present invention is melt-spun at 245 to 335 DEG C and passed through a spinneret.

The polyethylene terephthalate resin which is the basis of the present invention contains at least 90 mol% of repeating units of ethylene terephthalate.

Thereafter, it is cooled in the cooling zone with air at a speed of 0.2 to 1.0 m / sec. At this time, the cooling temperature is controlled at 10 to 35 ° C. If the cooling air speed is less than 0.2 m / sec, the cooling effect is insufficient. If the cooling air speed is more than 1.0 m / sec, the shaking of the yarn is excessive, which causes a problem in the radiation workability. If the cooling temperature is lower than 10 ° C, it is economically disadvantageous, and if it exceeds 35 ° C, the cooling effect is lowered.

After finishing the spin finish with oiling after cooling, the finishing applicator can be oiled by using the first and second two stages of neat type or water-soluble emulsion, Increase.

The filament is then fed to the stretching roller at a speed of 100 to 1,000 m / min, preferably 400 to 800 m / min, on the feed roller, wherein the stretching roller has a temperature of 100 to 230 캜 and a feed roller speed of 2.5 to 6.0 Preferably 3.5 to 5.0 times. If the stretching speed is less than 2.5 times, the stretching can not be performed sufficiently. If the stretching speed is more than 6.0 times, the polyethylene terephthalate material can not withstand the stretching due to the nature of the material.

The filaments passed through the stretching roller pass through a texturing unit with a texturing nozzle to impart balancing properties. At this time, a heating fluid of 150 to 270 DEG C is injected at a pressure of 3 to 10 kg / cm < 2 > , And the crimp ratio at this time is 3 to 50%.

In this case, the temperature of the heating fluid is preferably 150 to 270 DEG C, which is less effective at lowering the texturing effect at 150 DEG C, and causing damage to the filament at more than 270 DEG C. The heating fluid pressure is preferably 3 to 10 kg / cm 2, which is less effective at less than 3 kg / cm 2 and less than 10 kg / cm 2.

The filaments passing through the texturing unit cool down through the cooling section and pass through the entanglement machine. In this part, a slight twist and a knot are given at a pressure of 2.0 to 8.0 kg / m 2 in order to improve the fastening speed of the yarn, and it is given in the range of 0 to 40 times / m, preferably 10 to 25 times. In case of exceeding 40 times of interlocking, even after dyeing and finishing, the state of untwisted state is maintained and the appearance of the carpet is damaged.

Thereafter, the sheet is passed through a relax roller at a speed of 0.65 to 0.95 times the drawing roller speed to give a relaxation rate of 5 to 35%, and then the sheet is wound up in a final winding machine. The speed of the winder is usually controlled so that the tension of the yarn is in the range of 50 to 350 g. If the tension is less than 50 g, winding can not be performed. If the weight is more than 350 g, the warpage is decreased and the contraction of the yarn is largely caused and high tension is generated. If the speed of the relax roller is less than 0.65 times the speed of the stretching roller, it is not wound. If the relax roller is more than 0.95 times the speed of the roller is reduced, the shrinkage of the yarn is greatly increased and high tension is generated.

The above method relates to a BCF produced only from a polyethylene terephthalate resin, and the stepwise process is the same as that described above in the case of producing a raw cotton according to the use of a carpet. However, it is also possible to manufacture a seamless yarn by feeding a certain amount of coloring agent into the base chip input amount for spinning the raw material.

As described above, the polyethylene terephthalate multifilament produced according to the present invention is manufactured as a carpet after a post-process. Carpets made from the BCF yarns of the present invention can be made in any manner known to those skilled in the art. Preferably, a plurality of BCF yarns are cabled together and heat set together, followed by weaving with a primary backing. The latex adhesive and the secondary backing are then applied. A cut file style carpet or a loop file style carpet having a file height of approximately 2 to 20 mm can be manufactured.

Hereinafter, the present invention will be described in more detail with reference to the following examples. However, the following examples are intended to illustrate the present invention and are not to be construed as limiting the scope of the present invention. The properties of the yarns prepared in Examples and Comparative Examples of the present invention were evaluated in the following manner.

1. How to measure the strength of yarn

The yarn is allowed to stand in a standard temperature condition, that is, in a constant temperature and humidity room at a temperature of 25 ° C and a relative humidity of 65% RH for 24 hours, and then the sample is measured by a tensile tester by ASTM 2256 method.

2. Crimp rate and standard deviation

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

3. Wear resistance evaluation method of car mat

The abrasion resistance of the car mat was measured under the following conditions. The number of abrasion resistance of the car mat was evaluated based on the number of final abrasions at the time of exposure of the car mat bottom at the level of 2.5 Respectively.

Related test method Specification: ASTM D3884

Test method: Hyundai Motor MS300-35

Test equipment: Taber abrasion tester

Sample size: 130mm diameter Circular sample

Exam conditions

1) Wear wheel: H-18

2) Rotation speed: 70 times / minute

3) Load: 1000g

4) Evaluation method: Appearance evaluation 1st to 5th grade (Passed grade 3 or higher (3,4,5 grade) of MS343-15 of Hyundai Motor Company)

5) Evaluation criteria: No grade 5 abrasion at all

              Quadruple wear is slightly visible or almost invisible

              There is a third degree of wear but a little

              Second grade wear is slightly severe

              Level 1 fairly severe

Example  One

50 parts by weight of ethylene glycol was added to the esterification reactor to 100 parts by weight of terephthalic acid and the esterification reaction was carried out while allowing water to flow out of the reactor at 250 DEG C for 4 hours to obtain bis (2-hydroxyethyl) terephthalate [bis (2-hydroxyethyl) terephthalate]. At this time, 300 ppm of a phosphorus-based heat stabilizer was added at the end of the esterification reaction. Thereafter, 300 ppm of an antimony catalyst as a polymerization catalyst was added at the initial stage of the polycondensation reaction, the temperature was raised from 250 ° C. to 285 ° C. at 60 ° C./hr, the pressure was reduced to 0.1 torr to conduct a polycondensation reaction, After the reaction, 1.0 wt% of bidirectional end-group modified PDMS (Dow, BY16-201) having a hydroxyl group at the terminal and a chain number of polyethylene glycol (PEG) at 1 level was added to proceed a polycondensation reaction to prepare a polymer .

The polyethylene terephthalate polymer produced through the spinneret having 128 holes and a Y-shaped cross-section is melt-spun at 290 ° C. The polymer exiting the spinneret is cooled by cooling air at 20 ° C at a rate of 0.5 m / s below the nozzle, and then passes through the emulsion feeder. The yarn to which the emulsion has been applied is fed at a feed speed of 598 m / min, which is maintained at a temperature of 90 DEG C, and then is drawn at a speed of 2,840 m / min at 190 DEG C on a drawing roller. The yarn passed through the stretching roller passes through the texturing nozzle and is given a crimp. At this time, the hot air temperature is 200 ° C, the pressure is 7 kg / cm 2, and the back pressure is 5 kg / cm 2. After cooling by the cooling water, the entanglement is given 20 times / m at a pressure of 4.0 kg / m 2. The relaxed roller is passed at 2250 m / min, relaxed about 21%, and wound in a winding machine. The strength, elongation and crimp value of the polyethylene terephthalate BCF yarn produced by this process were measured and are shown in Table 1 below.

A car mat was manufactured using the polyethylene terephthalate BCF yarn thus produced, and the abrasion resistance was measured. The results are shown in Table 1 below.

Example  2

Example 1 was repeated except that a bidirectional end-group modified PDMS (Dow, BY16-201) having a hydroxyl group at the terminal group and a chain number of polyethylene glycol (PEG) was added to the end of the 5.0 wt% polycondensation reaction. BCF yarn and car mat were prepared in the same manner.

Example  3

Example 1 was repeated except that a bidirectional end group modified PDMS (Dow, SF-8427) having a hydroxyl group at the terminal group and 20 chains of polyethylene glycol (PEG) was added to the end of the 5.0 wt% polycondensation reaction. BCF yarn and car mat were prepared in the same manner.

Comparative Example  One

BCF yarn and car mat were prepared in the same manner as in Example 1, except that denatured PDMS was not added.

Comparative Example 1 Example 1 Example 2 Example 3 Strength (g / d) 4.9 4.8 4.7 4.3 Shinto (%) 37.7 33.9 37.9 34.8 Car mat break
Number of wear (water supply) 300 (Level 2) 500 (third grade) 550 (fourth grade) 400 (grade 3)

As shown in Table 1, when the bi-directional end-group modified PDMS having 1 to 20 chains of polyethylene glycol (PEG) represented by the general formula (I) was added to the post-polycondensation stage, The wear resistance and the coefficient of friction were improved.

While the present invention has been particularly shown and described with reference to exemplary embodiments thereof, it is to be understood that the invention is not limited to the disclosed embodiments, but, on the contrary, Will be apparent to those skilled in the art. Accordingly, the scope of protection of the present invention should be defined in the appended claims and their equivalents.

Claims (4)

80 to 99.9% by weight of polyethylene terephthalate (PET, polyethylene terephthalate); And
From 0.1 to 20% by weight of bi-directional end-modified polydimethylsiloxane (PDMS)
Wherein the bi-directional end-stage modified polydimethylsiloxane (PDMS) comprises a copolymerized polyethylene terephthalate having a number of chains of polyethylene glycol (PEG) of the general formula (I) BCF for.
(I)

(Wherein R = - (CH2-CH2-O) m-, m = 1 to 50,
T = hydrogen, a hydroxyl group or a carboxyl group or an amine group)
The method according to claim 1,
Characterized in that the BCF for car mat is manufactured by a method of directly yarn-casting the copolymerized polyethylene terephthalate or a method of copolymerizing bidirectional end-group modified polydimethylsiloxane (PDMS) with polyethylene terephthalate at a high concentration and using it as a master batch.
3. The method of claim 2,
The copolymerized polyethylene terephthalate may be prepared by slurrying ethylene glycol (EG) and terephthalic acid (TPA) into a slurry;
An esterification reaction step of the slurry; And
A polycondensation reaction step,
And BCF for a car mat is produced by introducing copolymerized polyethylene terephthalate into a bidirectional end group modified polydimethylsiloxane (PDMS) after the polycondensation reaction.
A polyethylene terephthalate BCF car mat produced by using the BCF for a car mat improved in abrasion resistance produced by the method of claim 1.