KR101204136B1 - Method for Preparing Profile Extruded Articles Using Copolyester Resin Composition - 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 in that mono and distearyl phosphoric acid is added to a polyester resin copolymerized with 1,4-cyclohexanedimethanol.

According to the present invention, by adding mono and distearyl phosphoric acid 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 dimensional stability while improving the transparency of the product due to its excellent processability in the manufacture of extrusion products.

Profile, extrusion, 1,4-cyclohexanedimethanol, polyester, ethylene glycol, terephthalic acid, mono and distearyl phosphoric acid

Description

Method for preparing profile extruded articles using copolyester resin composition

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, it improves the workability by improving the flowability of the melt during the production of the profile extrusion molding product, thereby improving the transparency of the product and copolyester resin for profile extrusion molding to obtain a product having excellent dimensional stability It relates to a composition and a molded article using the same.

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 the melt viscosity by adding an additive with trifunctional groups 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 a 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, thereby preventing irregular flow. However, due to the high melting point of the zinc-based lubricant, the dispersion is smoothly processed. It does not lose, there is a problem that the cosmetic part is generated by the lubricant is aggregated like a fish eye during production.

Accordingly, the present invention solves the above-described 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 copolyester resin, 1,4-cyclohexanedimethanol is Mono and distearyl phosphoric acid is added to the copolymerized polyester resin to solve the problem of uneven flow of the molten resin during profile extrusion. 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 and a molded article using the same, which improves the workability and transparency of the product and thereby has excellent dimensional stability.

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 5000 ppm mono and distearyl phosphoric acid 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, mono and distearyl phosphoric acid is added to a polyester resin copolymerized with 1,4-cyclohexanedimethanol, and thus, a constant cross-sectional area, such as a pipe or a tube, is used. Profile extruded product having improved processability, such as flowability, thereby obtaining a product having an irregular shape and transparency on the product surface of the product, and further improving dimensional stability. A polyester resin composition and a molded article using the same are provided.

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 said esterification temperature is 240-260 degreeC, More preferably, it is 245-255 degreeC. In addition, the esterification reaction time usually takes about 100 ~ 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, and if it exceeds 20 mol% there is a problem that the reactivity is inferior.

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, mono and distearyl phosphoric acid is added to impart excellent processability such as flowability during molding of the copolymerized polyester resin as described above.

The glidants used in the present invention include, but are not limited to, organic acids such as mono and distearyl phosphoric acid.

In this case, the amount of the product is preferably 50 to 5000ppm (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, when the amount of mono- and distearyl phosphate added exceeds 5000 ppm, screw rotation is difficult due to excessive loading, and excessive powder chips do not cause heat transfer in the product, which lowers the transparency of the unmelted product. The desired molded article 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 Haze: Measured using Haze-meter from Nippon Denshoku, Japan

◎ Surface defect: When the product is made by using the extruder as shown in Fig. 1, 300mm in the extrusion direction and 15mm in the direction perpendicular to the extrusion, the pattern caused by irregular flow during production That is, the number of lines occurring in the direction perpendicular to the extrusion is quantified.

◎ Fish eye: When the 300mm in the extrusion direction and 15mm in the direction perpendicular to the extrusion is observed based on the product made using the extruder as shown in Fig. 1, the number of fish eyes generated on the surface of the product is quantified.

◎ Melting pressure: measured by Extrusion Blow Molding of Bekum, Germany. After about 20 kg of the type of sample to be measured is put into the molding machine, after 20 minutes of stabilization time, the difference between the setting internal temperature and the actual internal temperature of the molding machine is less than ± 1 ° C. Measure the average value below 4 bar.

◎ Melt Viscosity: Measured by parallel plate type at shear rate (1 / s) = 1 area using Physica Rheometer of Physica, USA

◎ Melt strength: measured using Extrusion Blow Molding from Bekum, Germany. The RPM of the machine is set to 20, the cycle time is 17 seconds, the die diameter is 30 millimeters, the extruder temperature and the die temperature are 195 ~ 220 ℃ and 190 ~ 205 ℃ for each section. Measure the diameter of the 100 mm bottom from

The melt strength (%) is calculated using the following equation:

{(X-D)} over {D} TIMES 100

Where X is the diameter after 10 centimeter extrusion from the die and D is the diameter of the die. Thus, if X is less than D, the percent melt strength is negative; if greater than D, it is positive.

Example 1

Based on 6 moles of terephthalic acid, 294 g of 1,4-cyclohexanedimethanol, 469 g of ethylene glycol, and 2.0 g of trimellitic anhydride were added thereto. Thus, 10 g of polyethylene glycol bisphenol-A having m + n = 2 in Formula 1 was added. The reaction is carried out while gradually raising the temperature to 255 ° C while mixing in a 3L reactor equipped with a stirrer and an 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 is removed, and the pressure is slowly reduced to 0.1mmHg, and reacted under high vacuum until the desired intrinsic viscosity, 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 is pre-mixed with 0.66 g of mono and distearyl phosphate using a mixer (Mixer, Tumbler). The profile product was then manufactured using a general profile extruder as shown in FIG. 1. Table 1 shows the information on the surface defect, fish eye, transparency, melt viscosity, melt strength and melt pressure together with the reaction conditions.

Example 2

A profile product was prepared in the same manner as in Example 1, except that 3.9 g of the mono and distearyl phosphate monomer was added. Table 1 shows the information on the surface defect, fish eye, transparency, melt viscosity, melt strength and melt pressure together with the reaction conditions.

Example 3

Master batch of mono and distearyl phosphate as an additive was prepared using a twin screw extruder without premixing using a kneading machine, except that it was added in a master batch form so as to be 1.0 g of the total polymer amount. Was carried out in the same manner as in Example 1 to produce a profile product. Table 1 shows the information on the surface defect, fish eye, transparency, melt viscosity, melt strength and melt pressure together with the reaction conditions.

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. Table 1 shows the information on the surface defect, fish eye, transparency, melt viscosity, melt strength and melt pressure together with the reaction conditions.

Example 5

Except that the polyethylene glycol bisphenol-A monomer was not added in the reaction step was carried out in the same manner as in Example 1 to produce a profile product. Table 1 shows the information on the surface defect, fish eye, transparency, melt viscosity, melt strength and melt pressure together with the reaction conditions.

Example 6

A profile product was prepared by the same method as Example 1 except that 190 g of polyethylene glycol bisphenol-A monomer was added. Table 1 shows the information on the surface defect, fish eye, transparency, melt viscosity, melt strength and melt pressure together with the reaction conditions.

Comparative Example 1

A profile product was prepared in the same manner as in Example 1 except that no mono or distearyl phosphate compound was added. Table 1 shows the information on the surface defect, fish eye, transparency, melt viscosity, melt strength and melt pressure together with the reaction conditions.

Comparative Example 2

Except for adding polyethylene glycol bisphenol-A and mono or distearyl phosphate compound during the extrusion of the profile in the polymerization step was carried out in the same manner as in Example 1 to produce a profile product. Table 1 shows the information on the surface defect, fish eye, transparency, melt viscosity, melt strength and melt pressure together with the reaction conditions.

Comparative Example 3

A profile product was prepared in the same manner as in Example 1, except that mono- and distearyl phosphoric acid was not added and zinc-based lubricant was added instead. Table 1 shows the information on the surface defect, fish eye, transparency, melt viscosity, melt strength and melt pressure together with the reaction conditions.

Comparative Example 4

Except that the addition of a phosphorus stabilizer was carried out in the same manner as in Comparative Example 3 to produce a profile product. Table 1 shows the information on the surface defect, fish eye, transparency, melt viscosity, melt strength and melt pressure together with the reaction conditions.

Comparative Example 5

Except 31% by weight of isophthalic acid compared to terephthalic acid except that the copolymer was prepared in the same manner as in Comparative Example 3 to produce a profile product. Table 1 shows the information on the surface defect, fish eye, transparency, melt viscosity, melt strength and melt pressure together with the reaction conditions.

Comparative Example 6

Profile product was prepared in the same manner as in Example 1 except that trimellitic acid and polyethyleneglycol bisphenol-A monomer were not added in the polymerization step and no other material was added during profile extrusion using the polymerized raw material. Was produced. In this case, however, the profile product was not produced due to the low melt viscosity and strength. Table 1 shows the information on the surface defect, fish eye, transparency, melt viscosity, melt strength and melt pressure together with the reaction conditions.

Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Comparative Example 6 Isophthalic Acid / Terephthalic Acid 0 0 0 31 mol% 0 0 0 0 0 0 31 mol% 0 Mono & D
Stearyl phosphate
(g) 0.66 3.9 1.0 0.66 0.66 0.66 0 0 0 0 0 0 Input form of mono & distearyl phosphate powder powder Masterbatch powder powder powder - - - - - - tree
Melic acid (g) 1.8 1.8 1.8 1.8 1.8 1.8 1.8 1.8 1.8 1.8 1.8 0 Poly
Ethylene
Glycol
Bisphenol-A (g) 10 10 10 10 0 190 10 0 10 10 10 0 taking over
stabilizator
(g) 0 0 0 0 0 0 0 0 0 0.50 0 0 Zinc-based lubricant
(g) 0 0 0 0 0 0 0 0 0.66 0.66 0.66 0 surface
Bad 5
Below 5
Below 5
Below 5
Below 5
Below 5
Below 50
More than 50
More than 5
Below 5
Below 5
Below Molding
no Fish
children none none none none none none none none 5
More than 5
More than 5
More than - transparency
(%) 90.3 90.6 89.9 90.2 90.0 90.1 86.2 86.8 87.4 85.2 87.2 - transparency
(Haze) 1.4 1.6 1.5 1.4 1.3 1.4 2.5 2.6 2.2 2.1 2.3 - Melting
pressure
(bar) 95 ± 4 93 ± 4 96 ± 4 94 ± 4 105 ± 4 75 ± 4 95 ± 4 105 ± 4 95 ± 4 97 ± 4 96 ± 4 94 ± 4 Melting
Viscosity
(Pa.s)
(275 ℃) 2150 2160 2150 2140 2100 2730 2160 2090 2170 2150 2130 1090 Melting
burglar
(%) 21.0 21.2 21.0 21.3 19.0 22.0 21.0 19.0 20.8 21.0 20.1 10.5

As can be seen from the above examples and comparative examples, according to the present invention, the conventional method by adding a mono and distearyl phosphate-based lubricant to the polyester resin copolymerized with 1,4-cyclohexanedimethanol Compared to the case of using the copolyester according to the present invention, a profiled extruded product having excellent color and dimensional stability and a clean product surface can be obtained.

It will be apparent to those skilled in the art that various changes and modifications can be made therein without departing from the spirit and scope of the invention. Accordingly, it is intended that the present invention cover the modifications and variations of this invention provided they come within the scope of the appended claims and their equivalents.

Claims (6)

(a) a dicarboxylic acid component containing terephthalic acid, (ii) 20 to 80 mole% of 1,4-cyclohexanedimethanol and 20 to 80 mole% of ethylene glycol, wherein the dicarboxylic acid Diol component of 1.2-3.0 in molar ratio with respect to acid, (iii) 0.05-0.5 mol% polyfunctional monomer with respect to the said dicarboxylic acid, and (iv) 0.1-20 mol% with respect to the said dicarboxylic acid Copolymerized polyester resins prepared by esterification and polycondensation of polyethylene glycol bisphenol-A monomers represented by Formula 1; And (b) providing a copolymer polyester resin composition comprising 50 to 5000 ppm of a mono or distearyl phosphate-based lubricant represented by the following Chemical Formula 2, based on the copolymer polyester resin; And Profile extrusion molding the copolymer polyester resin composition; And a melt viscosity of the copolymerized polyester resin composition is in the range of 2140 to 2730 Pa? S. Formula 1

Wherein m + n is an integer from 2 to 12, (2)

Wherein n is an integer of 1 or 2. delete delete The method of claim 1 wherein the dicarboxylic acid component comprises 1 to 40 mole percent isophthalic acid relative to terephthalic acid. The method of claim 1, wherein the multifunctional monomer is trimellitic acid (trimellitic acid), trimellitic anhydride (hemimellitic acid), hemimelic acid anhydride, trimesic acid, tricavalic acid, trimethylolpropane, A method for producing a profiled extruded product, characterized in that one selected from the group consisting of trimethylolethane, glycerin and pentaerythritol. delete

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