KR101159839B1 - Copolyester resin composition for profile extrusion molding and articles using the same - Google Patents

Abstract

The present invention relates to a copolymerized polyester resin composition for profile extrusion molding and a molded product using the same, and is characterized by adding a zinc-based lubricant and a phosphorus-based stabilizer to a polyester resin copolymerized with 1,4-cyclohexanedimethanol.

According to the present invention, by adding a zinc-based lubricant and a phosphorus stabilizer to a polyester resin copolymerized with 1,4-cyclohexanedimethanol, a profile having a constant cross-sectional area such as a pipe or a tube is used by using the same. ) It is possible to obtain products with excellent color and dimensional stability by improving processability and transparency of products during the manufacture of extruded products and preventing yellowing.

Profile, extrusion, 1,4-cyclohexanedimethanol, polyester, ethylene glycol, terephthalic acid, zinc type lubricant, phosphorus stabilizer, profile extrusion

Description

Copolyester resin composition for profile extrusion molding and articles using the same}

1 is a view schematically showing a profile extruder used in the extrusion of a molded article according to the present invention.

[Description of Reference Numerals]

10: cutting machine 20: drawing device

30 molding machine 40 molding die

50: extrusion die 60: extruder

The present invention relates to a copolymerized polyester resin composition for profile extrusion molding and a molded article using the same. More specifically, the present invention relates to a copolymerized polyester resin composition for profile extrusion molding and a molded article using the same, which improve transparency in manufacturing a profile extrusion molded product and prevent yellowing, thereby obtaining a product having excellent color and dimensional stability. .

Commonly used polyester resins have a melt viscosity that is appropriate for injection molding and sheet forming using calender rolls, but is relatively relatively for profile molding without constant calender rolls with a constant cross-sectional area. low.

In particular, when a polyester resin copolymerized with 1,4-cyclohexanedimethanol is used, it is very difficult to obtain a product having a desired dimension due to a slow cooling rate. In addition, in the case of a polyester resin copolymerized with ethylene glycol and terephthalic acid in various glycols or dicarboxylic acids used as a sheet and a bottle, when the cooling efficiency decreases, turbidity due to crystallization occurs, transparency is required. There are disadvantages in the field of application that are difficult to apply.

For this reason, various techniques have been developed to increase the extrudability, but up to now, most of the efforts have been made to modify the resin mainly in terms of polymerization.

In this regard, US Pat. No. 5,399,595 introduces a method using copolyesters having high intrinsic viscosity (IV). The patent describes a method of polymerizing to have a high IV of 0.70 to 1.20 dl / g by adding 0.5 to 5.0 mole% of dicarboxylic acid sulfonomer, but in this case, extrusion may be possible but prevention of clouding due to crystallization Difficult to do

U.S. Patent No. 4,983,711 describes a method of increasing melt viscosity by adding an additive having trifunctional functionality in Extrusion Blow Molding. According to the method, trimellitic acid or trimellitic anhydride in a copolyester resin having 25 to 75 mol% of ethylene glycol and 25 to 75 mol% of 1,4-cyclohexanedimethanol relative to terephthalic acid ( trimellitic anhydride) is added in an amount of 0.10 to 0.25 mol%. In this case, the molecular weight is increased by branching, but the melt viscosity is increased, but the shear stress is increased due to the high melt viscosity, which causes a problem that the pressure in the molding machine increases during processing. In addition, since a melt fracture is formed in the vicinity of the extrusion die, the dimensional stability of the product is lowered, thereby adversely affecting the transparency.

U.S. Patent No. 6,100,320, on the other hand, uses a method of lowering the resistance between the product and the extrusion die by adding zinc-based lubricant in Profile Extrusion. According to the patent, copolymers having 50-85 mol% of ethylene glycol and 15-50 mol% of neopentyl glycol or 5-97 mol% of ethylene glycol and 3-95 mol% of 1,4-cyclohexanedimethanol, based on terephthalic acid Zinc-based lubricant is added to the polyester resin during processing. In this case, the zinc-based lubricant acts as an external lubricant to lower the resistance between the polymer and the die of the extruder, resulting in no irregular flow.However, due to the low thermal stability of the zinc-based lubricant, yellow discoloration occurs during processing at high temperatures. There is a problem that occurs.

Accordingly, the present invention solves the above-mentioned problems, and as a result of research and research to produce a product having properties superior to the profile extrusion molded products molded using a conventional copolymerized polyester resin, 1,4-cyclohexanedimethanol By adding a phosphorus-based stabilizer to the copolymerized polyester resin, the problem that the color of the profile molded product turned yellow was solved, and the present invention was completed based on this.

Accordingly, an object of the present invention is to provide a co-polyester resin composition for profile extrusion molding having excellent color and dimensional stability by improving processability and transparency of a product and preventing yellowing, and a molded product using the same.

Copolymerized polyester resin composition for profile extrusion molding according to the present invention for achieving the above object is:

(a) (iii) a dicarboxylic acid component containing terephthalic acid, (ii) a diol component containing 20 to 80 mol% of 1,4-cyclohexanedimethanol and 20 to 80 mol% of ethylene glycol, And (iii) a copolymerized polyester resin obtained by esterifying and polycondensing a 0.05 to 0.5 mol% polyfunctional monomer with respect to the dicarboxylic acid;

(b) 50 to 4900 ppm of zinc-based lubricant based on the copolymerized polyester resin; And

(c) 10 to 5000 ppm phosphorus stabilizer based on the copolymerized polyester resin;

And a control unit.

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

As described above, in the present invention, by adding zinc-based lubricant and phosphorus stabilizer to a polyester resin copolymerized with 1,4-cyclohexanedimethanol, it has a constant cross-sectional area such as a pipe or a tube by using the same. Co-polyester resin composition for profile extrusion molding which can improve the irregularity, color and dimensional stability of the surface of the product by improving the flowability and transparency of the product while preventing the yellowing phenomenon in the manufacturing of the profile extrusion molded product. And molded products using the same.

The copolyester resin used in the present invention is prepared through the first step of the esterification reaction and the second step of the polycondensation reaction.

The first step, the esterification reaction may be carried out in a batch or continuous manner, and each raw material may be added separately, but it is most preferable to make a dicarboxylic acid component into a diol component in a slurry form. .

More specifically, first, a polyfunctional monomer is used in a copolyester resin produced by reacting a dicarboxylic acid component containing terephthalic acid with a diol component containing ethylene glycol and 1,4-cyclohexanedimethanol, The reaction is optionally carried out by addition of polyethylene glycol bisphenol-A.

Here, the content of the diol component with respect to the dicarboxylic acid component is added in a molar ratio of 1.2 to 3.0, and it is preferable to perform the esterification under the conditions of 230 to 260 ° C and 1.0 to 3.0 kg / cm 2, but not limited thereto. It doesn't happen. Preferably, the esterification reaction temperature is 240 to 260 ° C, more preferably 245 to 255 ° C. In addition, the esterification reaction time usually takes about 100 to 300 minutes, which can be appropriately adjusted according to the reaction temperature, pressure and the molar ratio of glycol to dicarboxylic acid used.

As the dicarboxylic acid component used in the present invention, in addition to the terephthalic acid, isophthalic acid, 1,4-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, succinic acid, glutaric acid in order to improve physical properties , Adipic acid, sebacic acid, 2,6-naphthalenedicarboxylic acid, and the like, but are not particularly limited thereto.

Preferably, 1 to 40 mol% of isophthalic acid is used as compared to the terephthalic acid.

In addition, as a diol component used by this invention, ethylene glycol and 1, 4- cyclohexane dimethanol are used in the quantity of 20-80 mol%, respectively.

In particular, the 1,4-cyclohexane dimethanol is used to improve the moldability and other physical properties of the homopolymer based only on the terephthalic acid and ethylene glycol, cis-, trans- or a mixture of both isomers, etc. Can be. At this time, the amount used is close to the desired mole percent of the final polymer, preferably 20 to 80 mole percent of the total glycol components in order to prevent moldability defects due to crystallization.

In addition to the above-described diol components, other glycol compounds usable in the present invention include 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 2,2-dimethyl-1,3-propanediol, 1, 6-hexanediol, 1,2-cyclohexanediol, 1,4-cyclohexanediol, 1,2-cyclohexanedimethanol and 1,3-cyclohexanedimethanol.

The polyfunctional monomer used in the present invention is a crosslinking agent component for improving profile extrusion moldability, and includes trimellitic acid, trimellitic hydride, hemimeltic acid, hemimeltic anhydride, trimesic acid and tricarbal Ric acid, trimethylolpropane, trimethylolethane, glycerin, pentaerythritol, and the like, but are not limited thereto.

In this case, the amount of the polyfunctional monomer is preferably 0.05 to 0.5 mol% with respect to the dicarboxylic acid, if the amount is less than 0.05 mol% does not reach the melt strength useful for profile extrusion molding In addition, when the content exceeds 0.5 mol%, transparency is lowered due to active crosslinking, and thus a desired molded product cannot be obtained.

On the other hand, polyethylene glycol bisphenol-A that can be additionally used in the present invention is represented by the following general formula (1) as a component for improving the moldability of the copolymer resin:

In this formula, m + n is an integer of 2-12.

At this time, the amount of the polyethylene glycol bisphenol-A is preferably 0.1 to 20 mol% with respect to the dicarboxylic acid, if the amount is less than 0.1 mol% to check the physical properties improvement effect of the addition of polyethylene glycol bisphenol-A Is difficult, there is a problem that the reactivity is lowered when it exceeds 20 mol%.

The esterification reaction does not require a catalyst, but may be optionally added to reduce the reaction time.

After the first step of the esterification reaction as described above is completed, a second step of the polycondensation reaction is carried out, which is usually carried out during the polycondensation reaction on the esterification reaction obtained in the first step prior to starting the polycondensation reaction. As a component used, a polycondensation catalyst, a stabilizer, a coloring agent, etc. can be selectively used as needed.

Polycondensation catalysts usable in the present invention include, but are not limited to, titanium, germanium and antimony compounds.

The titanium-based catalyst is generally used as a polycondensation catalyst of a polyester resin copolymerized with 1,4-cyclohexanedimethanol by 15% or more by weight of terephthalic acid, and even when a small amount is used in comparison with an antimony-based catalyst It is possible and also has the advantage of lower cost than germanium-based catalyst.

Titanium-based catalysts usable in the present invention include tetraethyl titanate, acetyltripropyl titanate, tetrapropyl titanate, tetrabutyl titanate, tetrabutyl titanate, polybutyl titanate, 2-ethylhexyl titanate, octylene Glycol titanate, lactate titanate, triethanolamine titanate, acetylacetonate titanate, ethyl acetoacetic ester titanate, isostearyl titanate, titanium dioxide, titanium dioxide and silicon dioxide co-precipitates, titanium dioxide and zirconium dioxide And coprecipitates.

In this case, since the amount of the polycondensation catalyst affects the color of the final polymer, the amount of polycondensation catalyst may vary depending on the desired color and the stabilizer and colorant used. Preferably, the amount of the polycondensation catalyst is 1 to 100 ppm based on the amount of titanium based on the weight of the final polymer. More preferably, 1-50 ppm is good and 10 ppm or less is preferable based on a silicon element amount. At this time, if the amount of titanium element is less than 1ppm can not reach the desired degree of polymerization, if it exceeds 100ppm the color of the final polymer is yellow and the desired color cannot be obtained.

In addition, stabilizers and coloring agents and the like can be used as other additives.

Stabilizers usable in the present invention typically include phosphoric acid, trimethyl phosphate, triethyl phosphate, triethyl phosphonoacetate, and the like. The amount of the stabilizer is preferably 10 to 100 ppm relative to the weight of the final polymer based on the small amount of the phosphorus. At this time, if the addition amount of the stabilizer is less than 10ppm it is difficult to obtain the desired bright color, if it exceeds 100ppm there is a problem that does not reach the desired high polymerization degree.

In addition, the colorants usable in order to improve the color in the present invention include conventional colorants such as cobalt acetate and cobalt propionate, the addition amount is preferably 0 to 100ppm relative to the weight of the final polymer.

In addition to the colorant, conventionally known organic compounds may be used as the colorant.

On the other hand, the second condensation reaction is carried out after the addition of these components is preferably carried out under reduced pressure conditions of 260 ~ 290 ℃ and 400 ~ 0.1mmHg, but is not limited thereto.

The polycondensation step is carried out for the required time until the desired intrinsic viscosity is reached, the reaction temperature is generally 260 ~ 290 ° C, preferably 260 ~ 280 ° C, more preferably 265 ~ 275 ° C.

In addition, the polycondensation reaction is carried out under a reduced pressure of 400 ~ 0.1mmHg in order to remove the glycol as a by-product to obtain a polyester resin copolymerized with 1,4-cyclohexanedimethanol.

According to the present invention, a zinc-based lubricant is added to impart excellent processability such as flowability during molding of the copolymerized polyester resin as described above.

Zinc-based lubricants used in the present invention include, but are not limited to, zinc organic acids such as zinc stearate, zinc laurate and zinc oleate.

At this time, the amount of the zinc-based lubricant is preferably 50 to 4990ppm (part per millions of resin) relative to the weight of the final polymer. If the amount is less than 50ppm it is not a smooth dispersion due to the small amount, which causes a problem that can not suppress the irregular flow phenomenon that occurs when exiting the extruder die. On the other hand, if the amount of the zinc-based lubricant is more than 4990ppm, screw rotation is difficult due to excessive input, and heat transfer does not occur in the product due to excessive powder chips, which lowers the transparency of the unmolded product and thus the desired molded product. Can not get

On the other hand, in the case of using only the zinc-based lubricant, the flowability is improved, but due to the low thermal stability there is a problem that the color of the product changes during processing. In order to solve this problem, in the present invention, a phosphorus stabilizer is added during processing.

Preferably, as the phosphorus stabilizer, it is preferable to use a phosphorus compound represented by the following Chemical Formula 2:

Wherein R ₁ and R ₂ are the same as or different from each other, hydrogen, an alkyl group having 2 to 18 carbon atoms, or a cycloalkyl group, or an aryl group having 6 to 15 carbon atoms.

More preferably, the phosphorus stabilizer may be distearyl pentaaritriol diphosphite or bis-2,4-dibutyl butylphenyl pentaaritriol diphosphite and the like, but is not particularly limited to the above-mentioned phosphorus compound no.

At this time, the amount of the phosphorus stabilizer is preferably 10 to 5000ppm relative to the total polymer amount. If the amount is less than 10ppm it can not be added in a small amount to meet the required physical properties, whereas if it exceeds 5000ppm it is affected by screw modification due to the addition of excess powder, resulting in a decrease in workability and transparency The desired molded product cannot be obtained.                     

As described above, the copolyester composition for profile extrusion molding has a constant cross-sectional area, such as pipes and tubes, which is improved in irregular shape, color and dimensional stability of the product surface by extrusion molding according to a conventional profile extrusion method. The profile extrusion molded product which has is obtained.

Hereinafter, the present invention will be described in more detail with reference to the following examples and comparative examples, but the scope of the present invention is not limited thereto.

Physical properties shown in the following Examples and Comparative Examples were measured by the following method.

@ Profile extruder: cutter 10, take-off equipment 20, formter 30, forming die 40, extrusion die 50 and extruder 60, as shown in FIG. Using a profile extruder equipped with, the molding machine 30 and the take-out device 20 used for the profile extrusion was used generally used. The L / D ratio of this single screw extruder is 30, and it has a general structure which can extrude polyolefin and polyvinyl chloride.

The temperature of the extruder cylinder was 240 ° C., the die temperature was 220 ° C. and the rpm was 30. The product is in the form of a square tube, the tube thickness is 0.5mm.

◎ Transparency and Color: Measured using Haze-meter of Nippon Denshoku, Japan

Example 1

Based on 6 moles of terephthalic acid, 2.0 g of trimellitic hydride was added to a polyester resin copolymerized with 294 g of 1,4-cyclohexanedimethanol and 469 g of ethylene glycol, and polyethylene glycol bisphenol having m + n = 2 in Formula 1 10 g of -A is reacted while slowly raising the temperature to 255 ° C. while mixing in a 3 L reactor with stirrer and outlet condenser.

At this time, the generated water is discharged out of the system to ester reaction, and when the generation of water, the outflow is finished, the contents are transferred to a polycondensation reactor equipped with a stirrer, a cooling condenser and a vacuum system.

Add 0.5 g of tetrabutyl titanate to the esterification reaction, add 0.4 g of triethylphosphate, add 0.5 g of cobalt acetate, and increase the internal pressure from 240 ° C to 275 ° C. After 40 minutes of low vacuum reaction from atmospheric pressure to 50mmHg, ethylene glycol was removed, and then gradually decompressed to 0.1mmHg until the desired intrinsic viscosity under high vacuum was discharged and cut into chips.

The resin produced through the reaction process as described above was dried using a dehumidifying dryer for 6 hours at 65 ℃ to prevent the drop of IV. This dried resin was premixed using a kneader (Mixer, Tumbler) with 0.16 g of zinc stearate as zinc-based lubricant and 0.13 g of bis-2,4-dibutylbutylphenyl pentaaritriol diphosphite as a phosphorus compound. Pre-mixing). The profile product was then manufactured using a general profile extruder as shown in FIG. 1.

Example 2

The same procedure as in Example 1 was repeated except that 0.66 g of a phosphorus compound was added to produce a profile product.

Example 3

Master batch production of zinc-based lubricants and phosphorus compounds as additives using twin screw extruder without premixing using a kneader, and then added in master batch form to form 3.90 g and 0.66 g, respectively, based on the total amount of polymer. Except that was carried out in the same manner as in Example 1 to produce a profile product.

Example 4

Except 31% by weight of isophthalic acid compared to terephthalic acid except that the copolymer was prepared in the same manner as in Example 1 to produce a profile product. .

Comparative Example 1

Except not adding a phosphorus compound was carried out in the same manner as in Example 1 to produce a profile product.

Comparative Example 2

A profile product was prepared by the same method as Example 1, except that zinc-based lubricant and phosphorus-based compound were not added.

Comparative Example 3

Except 31% by weight of isophthalic acid compared to terephthalic acid except that a copolymer was prepared in the same manner as in Comparative Example 2 to produce a profile product.

As can be seen from the above examples and comparative examples, according to the present invention, a zinc-based lubricant and a phosphorus-based compound are added to a polyester resin copolymerized with 1,4-cyclohexanedimethanol and used in a conventional method. Compared to the case of using the copolyester according to the present invention can be obtained a profile extrusion molded product having excellent color and dimensional stability.

It is apparent that modifications and improvements are possible by those skilled in the art within the spirit or scope of the present invention. Accordingly, the simple modifications and variations of the present invention are all within the scope of the present invention, and the specific scope of protection of the present invention will be clarified by the appended claims and their equivalents.

Claims (8)

(a) (iii) a dicarboxylic acid component containing terephthalic acid, (ii) a diol component containing 20 to 80 mol% of 1,4-cyclohexanedimethanol and 20 to 80 mol% of ethylene glycol, And (iii) a copolymerized polyester resin obtained by esterifying and polycondensing a 0.05 to 0.5 mol% polyfunctional monomer with respect to the dicarboxylic acid; (b) 50 to 4900 ppm of zinc-based lubricant based on the copolyester resin, wherein the zinc-based lubricant is zinc stearate, zinc laurate or zinc oleate; And (c) 10 to 5000 ppm of a phosphorus stabilizer based on the copolymerized polyester resin, wherein the phosphorus stabilizer is a compound represented by the following formula (2): Copolymer polyester resin composition for profile extrusion molding: Formula 2

Wherein R ₁ and R ₂ are the same as or different from each other, hydrogen, an alkyl group having 2 to 18 carbon atoms, or a cycloalkyl group, or an aryl group having 6 to 15 carbon atoms. According to claim 1, wherein the (a) co-polyester resin profile extrusion molding characterized in that it further comprises 0.1 to 20 mol% of polyethylene glycol bisphenol-A monomer represented by the formula (1) relative to the dicarboxylic acid Copolymerized polyester resin composition for: Formula 1

In this formula, m + n is an integer of 2-12. delete The copolyester resin composition for profile extrusion molding according to claim 1, wherein the phosphorus stabilizer is distearyl pentaaritriol diphosphite or bis-2,4-dibutyl butylphenyl pentaaritriol diphosphite. . delete The copolymer polyester resin composition for profile extrusion molding according to claim 1, wherein the dicarboxylic acid component contains 1 to 40 mol% of isophthalic acid based on terephthalic acid. The method of claim 1, wherein the multifunctional monomer is trimellitic acid (trimellitic acid), trimellitic anhydride (hemimellitic acid), hemimelitic acid, hemimelic anhydride, trimesic acid, tricavalic acid, trimethylolpropane, Copolymer polyester resin composition for profile extrusion molding, characterized in that one selected from the group consisting of trimethylol ethane, glycerin and pentaerythritol. A molded article produced by profile extrusion molding the resin composition according to any one of claims 1, 2, 4, 6 and 7.

Images