JP2010053243A - Polyethylene-2,6-naphthalate resin composition and method for producing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a polyethylene-2,6-naphthalate resin composition that has a smooth surface to stand practical use and high Young's modulus when made into a formed product such as films, fibers, etc. <P>SOLUTION: The polyethylene-2,6-naphthalate resin composition is a resin composition of fullerene hydroxide and a polyethylene-2,6-naphthalate copolymerized with diethylene glycol. The amount of fullerene hydroxide added is 0.01-0.2 wt.% and the amount of diethylene glycol copolymerized is 1.5-5.0 wt.%. The method for producing the resin composition includes adding fullerene hydroxide in the range at an arbitrary stage by the end of an esterification reaction or transesterification reaction when the resin composition is produced by subjecting 2,6-naphthalenedicarboxylic acid or its ester-forming derivative and ethylene glycol to an esterification reaction or transesterification reaction and a condensation polymerization reaction. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a polyethylene-2,6-naphthalate resin composition and a method for producing the same. More specifically, the present invention relates to a polyethylene-2,6-naphthalate resin having improved stretch moldability and capable of obtaining a polyethylene-2,6-naphthalate film or polyethylene-2,6-naphthalate fiber having a high Young's modulus. The present invention relates to a composition and a method for producing the same.

Polyester resins have been used as materials for films and fibers because they have excellent moldability and mechanical properties.
However, demands in recent years have become increasingly severe, and further improvements are desired. Specifically, in a base film of a magnetic recording medium, for example, it is required to make the magnetic recording medium thin by, for example, data storage, and to increase the length of the magnetic recording medium in the same volume. There is a need for further improvement. Similarly, improvement in mechanical properties such as Young's modulus has been demanded for fibers such as tire cords.

  In order to respond to such a request, Japanese Patent Laid-Open No. 2002-225198 (Patent Document 1) proposes to improve the Young's modulus of the resulting polyester film by containing plate-like inert particles. . However, in the method described in Patent Document 1, although the Young's modulus is increased, the surface of the obtained molded product is roughened by the plate-like inert particles. And when the surface becomes rough, the surface of the magnetic recording medium obtained with the base film of the magnetic recording medium becomes rough, the recording density cannot be increased, and as a result, even if the magnetic recording medium can be made thin, the recording capacity does not increase. was there. Therefore, the actual situation is that there has not yet been provided anything that does not impair the surface properties while raising the mechanical properties.

  By the way, in recent years, fullerene, which is a kind of nanomaterial, has attracted attention, and in Japanese Patent Application Laid-Open No. 2004-182768 (Patent Document 2), heat resistance is improved by containing 0.25% by mass or more of fullerene in a thermoplastic resin. It has been proposed that it can be done. Japanese Patent Application Laid-Open No. 2004-75933 (Patent Document 3) proposes that the dispersibility can be further improved by using a fullerene having a hydroxyl group added thereto.

JP 2002-225198 A JP 2004-182768 A JP 2004-75933 A

  An object of the present invention is to provide a modified polyester resin composition having a high Young's modulus and surface flatness simultaneously in a molded product such as a film or fiber, and a method for producing the same, by solving the above-described problems of the prior art. It is to provide.

  As a result of repeated studies to solve the above problems, the present inventors have found that a very small amount of a fullerene hydroxide having a specific amount of 0.2 wt% or less is added to a polyethylene-2,6-naphthalate resin among polyesters. Surprisingly, it was found that when coexisting with diethylene glycol, mechanical properties such as Young's modulus can be improved without impairing the flatness of the surface.

  Thus, according to the present invention, it is a resin composition of polyethylene-2,6-naphthalate copolymerized with fullerene hydroxide and diethylene glycol, and the added amount of fullerene hydroxide is based on the weight of the resin composition. Polyethylene-2 in the range of 0.01 to 0.2% by weight, and the copolymerization amount of diethylene glycol is in the range of 1.5 to 5.0% by weight based on the weight of polyethylene-2,6-naphthalate. , 6-Naphthalate resin composition is provided.

  Further, according to the present invention, when producing 2,6-naphthalenedicarboxylic acid or its ester-forming derivative and ethylene glycol by esterification reaction or transesterification reaction and polycondensation reaction, esterification reaction or transesterification reaction Polyethylene-2,6-naphthalate resin composition in which hydroxylated fullerene is added in the range of 0.01 to 0.2% by weight based on the weight of the obtained resin composition at an arbitrary stage until the completion of Is also provided. Furthermore, as a preferred embodiment of the present invention, polyethylene-2,6 in which the fullerene hydroxide is added as an ethylene glycol solution and the concentration of the fullerene hydroxide in the solution to be added is in the range of 0.05 to 0.5% by weight. A method for producing a naphthalate resin composition is also provided.

  Diethylene glycol (hereinafter referred to as DEG) is a by-product generated in the polymerization process of polyester such as polyethylene-2,6-naphthalate resin (hereinafter referred to as PEN). In the case of PEN, it is copolymerized in the molecular chain. Usually, it is present at about 1% by weight. It has been known that the stretchability is improved when the proportion of DEG is increased. However, this is only because the crystallinity is lowered and the elongation is easy, and the mechanical properties such as Young's modulus tend to be lowered. It was.

  On the other hand, in the present invention, in PEN among polyesters, by combining DEG of 1.5 to 5.0% by weight and a trace amount of hydroxylated fullerene of 0.01 to 0.2% by weight, Since not only the stretchability is improved but also the mechanical properties such as Young's modulus are improved, and it is not necessary to contain a large amount of inert particles that impair the surface properties as in Patent Document 1. Further, the surface flatness is not impaired in the obtained molded product.

  Therefore, by using the PEN resin composition of the present invention, it is possible to provide a molded article such as a film or fiber having a high Young's modulus while having excellent surface flatness, and its industrial value is Very expensive.

Hereinafter, the present invention will be described in detail.
The polyethylene-2,6-naphthalate resin composition of the present invention contains fullerene hydroxide in the range of 0.01 to 0.2% by weight based on the weight of the resin composition, and at the same time diethylene glycol is added to polyethylene- Copolymerization is required in the range of 1.5 to 5.0% by weight based on the weight of 2,6-naphthalate.

  If the copolymerization amount of DEG is less than the lower limit, the effect of improving the stretchability cannot be obtained, and even if the fullerene hydroxide is contained, the effect of improving the mechanical properties such as Young's modulus becomes poor. On the other hand, when the copolymerization amount of DEG exceeds the upper limit, these DEG usually exist in a state of being copolymerized in the molecular chain of PEN, so that the crystallinity of PEN is lowered and the stretchability is improved. The effect of improving the mechanical characteristics becomes poor, and further, the film formation itself becomes unstable. The content of diethylene glycol is preferably 1.7 to 4.5% by weight, more preferably 2.0 to 4.0% by weight.

  Further, when the amount of the fullerene hydroxide to be contained, that is, the addition amount is less than the lower limit, even if DEG has high stretchability within the above range, the effect of improving the mechanical properties such as Young's modulus becomes poor. On the other hand, DEG tends to increase due to the presence of fullerene hydroxide. When the content of fullerene hydroxide exceeds the upper limit, it becomes difficult to bring the ratio of DEG within the above range. The effect of improving the mechanical characteristics cannot be obtained. A preferable addition amount of the fullerene hydroxide is 0.03 to 0.15% by weight, and further 0.05 to 0.13% by weight.

  Furthermore, the resin forming the resin composition needs to be PEN. Similar investigations were carried out with polyethylene terephthalate, which is a typical polyester, as with PEN, but no effect similar to PEN was obtained. From this point, it is considered that PEN, hydroxylated fullerene and DEG have some influence on each other.

  The polyethylene-2,6-naphthalate resin composition of the present invention may be composed only of polyethylene-2,6-naphthalate, hydroxylated fullerene and diethylene glycol, but within a range not impairing the effects of the present invention. If present, various known additives may be included. For example, the polyethylene-2,6-naphthalate resin composition of the present invention can contain inert fine particles as a lubricant in order to improve winding properties and transportability when manufacturing fibers and films. . Examples of the inert fine particles include inorganic fine particles (for example, kaolin, plate boehmite, titanium oxide, calcium carbonate, silicon dioxide, etc.) containing the elements of Periodic Tables IIA, IIB, IVA, and IVB, silicone resins And fine particles made of a polymer having high heat resistance such as crosslinked polystyrene. When the inert fine particles are contained in the polyethylene-2,6-naphthalate resin composition, the average particle diameter of the fine particles is preferably 0.05 to 1.0 μm, more preferably 0.1 to 0.8 μm. The content of the inert fine particles is preferably 0.05 to 0.5% by weight, more preferably 0.1 to 0.3% by weight in the polyethylene-2,6-naphthalate resin composition. Further, two or more kinds of inert particles having different kinds, shapes or sizes may be used in combination.

[Polyethylene-2,6-naphthalate]
PEN in the present invention is preferably such that 60 mol% or more of all dicarboxylic acid components are 2,6-naphthalenedicarboxylic acid and 60 mol% or more of all glycol components are ethylene glycol. More preferably, 65 mol% or more of all dicarboxylic acid components are 2,6-naphthalenedicarboxylic acid, and 65 mol% or more of all glycol components are ethylene glycol. Furthermore, it is particularly preferable that 90 mol% or more of all dicarboxylic acid components are 2,6-naphthalenedicarboxylic acid and 90 mol% or more of all glycol components are ethylene glycol.

  When polyethylene-2,6-naphthalate has a copolymer component other than DEG, the copolymer component other than DEG includes, for example, succinic acid, adipic acid, sebacic acid, phthalic acid, isophthalic acid, terephthalic acid as a dicarboxylic acid component. , 5-sodium dicarboxylic acid, and glycol components such as, for example, trimethylene glycol, propylene glycol, alkylene glycol such as 1,4-butanediol, and 1,4-cyclohexanedimethanol. In addition, these copolymerization components may use not only 1 type but 2 or more types together.

  The intrinsic viscosity of PEN in the present invention is preferably 0.4 dl / g to 0.8 dl / g at 35 ° C. in an orthochlorophenol solvent, and more preferably 0.5 dl / g to 0.7 dl / g. is there. When the intrinsic viscosity is less than 0.4 dl / g, the mechanical strength required when the polyethylene-2,6-naphthalate resin composition of the present invention is formed into a fiber or film and then used for each product is insufficient. There is. On the other hand, when the intrinsic viscosity exceeds 0.8 dl / g, productivity at the time of melt kneading in the melt polymerization step and molding into a fiber or film may be impaired.

[Fullerene hydroxide]
The fullerene hydroxide in the present invention is a fullerene having a hydroxyl group introduced therein, and preferably has, for example, a C60 skeleton and / or a C70 skeleton. The fullerene hydroxide of the present invention may be either a hydroxylated fullerene in which a hydroxyl group is introduced into the C60 skeleton or a hydroxylated fullerene in which a hydroxyl group is introduced into the C70 skeleton, or both of them are mixed. The fullerene hydroxide is most preferably a hydroxylated fullerene having a hydroxyl group introduced into the C60 skeleton.

  The number of hydroxyl groups per molecule of the fullerene hydroxide in the present invention is preferably 6-12. When the number of hydroxyl groups is in the range of 6 to 12, when blended in polyethylene-2,6-naphthalate, an effect of improving stretch moldability is easily obtained.

[Method for producing polyethylene-2,6-naphthalate resin composition]
The polyethylene-2,6-naphthalate resin composition of the present invention can be produced by a conventionally known method for producing a polyethylene-2,6-naphthalate resin composition. The content of hydroxylated fullerene and copolymerization of diethylene glycol The production method is not particularly limited as long as the amount satisfies the scope of the present invention.

  However, as a result of intensive studies by the present inventors, 2,6-naphthalenedicarboxylic acid or an ester-forming derivative thereof and ethylene glycol are produced by esterification reaction or transesterification reaction and polycondensation reaction. By adding 0.01 to 0.2% by weight of fullerene hydroxide at any stage until the conversion reaction or transesterification reaction is completed, the content of diethylene glycol can be more easily adjusted within the range of the present invention, In addition, the effect of the fullerene hydroxide can be maximized.

  First, the reason why the amount of diethylene glycol can be easily within the scope of the present invention by the above-described production method is that the fullerene hydroxide is somehow added by adding the fullerene hydroxide during the transesterification or esterification reaction. This may be because it acts as a catalyst or because a by-product reaction of diethylene glycol occurs more easily. That is, normally, the DEG is only about 1% by weight, but there is an advantage that 1.5% by weight or more of DEG can be present without adding a separate DEG or the like. Further, by adding the fullerene hydroxide during the transesterification reaction or esterification reaction, there is an advantage that it is easier to disperse more uniformly than the step after the polycondensation reaction or melt-kneading after PEN.

  Moreover, the addition amount of the hydroxylation fullerene in the manufacturing method of this invention is the range of 0.01 to 0.2 weight% on the basis of the weight of the resin composition obtained. When the addition amount of the fullerene hydroxide is less than the lower limit, the effect of adding the fullerene hydroxide is small. On the other hand, when the addition amount exceeds the upper limit, the crystallinity of the polyethylene-2,6-naphthalate resin composition is lost as described above. Or particle agglomeration at the time of addition, resulting in a bad effect such as deterioration of the surface properties of the molded product. A preferable addition amount is in the range of 0.03 to 0.15% by weight, and further 0.05 to 0.13% by weight.

  Furthermore, as the addition form of the fullerene hydroxide in the production method of the present invention, it is preferable to add it as an ethylene glycol solution having a fullerene hydroxide concentration of 0.05 to 0.5% by weight. When the fullerene hydroxide is added in the form of a solution in which ethylene glycol is dissolved in the above ratio, a high degree of dispersibility of the fullerene hydroxide can be achieved, and the effects of the fullerene hydroxide can be more easily expressed.

  Hereinafter, the present invention will be further described based on examples. Various physical property values and characteristics in the present invention are measured and defined as follows. Unless otherwise specified, “parts” and “%” mean “parts by weight” and “% by weight”, respectively.

(1) Formability and mechanical properties The polyethylene-2,6-naphthalate resin composition obtained in the examples was spun from a spinneret having a diameter of 0.5 mm and a number of 120 holes at a melting temperature of 320 ° C. After cooling, the emulsion oil agent mainly composed of oleyl oleate was applied with a roller-type oil agent application device so that the amount of the oil agent adhered to the fiber was 0.5%, and then taken up at a speed of 500 m / min, and the thickness was 1200 dtex. Of undrawn yarn was obtained. The undrawn yarn is set in a drawing machine and drawn by a speed difference between a heating supply roll having a temperature of 140 ° C. and a drawing roll. At that time, the speed of the drawing roll is gradually increased until the yarn breaks. The ratio of drawing roll speed / heated supply roll speed at the time when the yarn breaks is taken as the breaking draw ratio, and this operation is continued 5 times, and the average value of the 5 breaking draw ratios is taken as the maximum draw ratio. And it is judged that it is excellent in a moldability, so that this maximum draw ratio is large.
Next, the undrawn yarn is drawn at a draw ratio of 95% with respect to the maximum draw ratio described above by a speed difference between a heated supply roll having a temperature of 140 ° C. and a draw roll, and heat-treated at 220 ° C. to draw the drawn yarn. Got. And the Young's modulus of this drawn yarn was measured based on JIS L 1013 using a tensile load measuring instrument (Autograph manufactured by Shimadzu Corporation). And it was judged that the higher the Young's modulus, the better the mechanical properties.

(2) Copolymerization amount of diethylene glycol in polyethylene-2,6-naphthalate resin composition The resin was hydrolyzed with hydrazine, and the liberated diethylene glycol was analyzed by gas chromatography (6990 manufactured by Hewlett Packard).

(3) Surface flatness The polyethylene-2,6-naphthalate resin composition described above was dried at 170 ° C. for 3 hours, then supplied to an extruder hopper, melted at 280 ° C., and surface-exposed using a T-type extrusion die. The film was quenched and solidified on a casting drum maintained at a finish of 0.3 S and a surface temperature of 30 ° C. to obtain an unstretched film made of a polyester resin composition.
This unstretched film is preheated to 75 ° C., further heated by an infrared heater with a surface temperature of 830 ° C. from above 14 mm between low-speed and high-speed rolls, stretched 5.0 times in the longitudinal direction, rapidly cooled, and then Was supplied to a stenter and stretched 4.5 times in the transverse direction at 120 ° C. Further, the film was heat-fixed at 225 ° C. for 3 seconds to obtain a biaxially oriented polyethylene-2,6-naphthalate film having a thickness of 4.5 μm. And according to JIS-B601, the centerline average roughness (Ra) of the obtained film was as follows using a stylus type surface roughness meter (SURFCORDER SE, 30C) of Kosaka Laboratory. Measured with
(A) Stylus tip radius: 2 μm
(B) Measurement pressure: 30 mg
(C) Cut-off: 0.08mm
(D) Measurement length: 8.0 mm
(E) How to summarize data: Repeat measurement 6 times for the same sample, remove one largest value, and determine the centerline average roughness (Ra) as an average value using the remaining 5 data.
It was judged that the smaller the centerline average roughness (Ra) obtained in this way, the better the surface flatness.

(4) Intrinsic viscosity A value measured in orthochlorophenol at 35 ° C. The unit is dl / g.

[Example 1]
(1) Fullerene hydroxide having 12 hydroxyl groups introduced per molecule in C60 skeleton (nanospectra HX10-S manufactured by Frontier Carbon Co.) is used, and 0.4 part of fullerene hydroxide with respect to 99.6 parts of ethylene glycol And stirred at room temperature for 4 hours to prepare a fullerene hydroxide / ethylene glycol solution having a concentration of 0.4 wt%.
(2) A mixture of 100 parts of dimethyl 2,6-naphthalene and 60 parts of ethylene glycol was charged with 0.030 parts of manganese acetate tetrahydrate in a transesterification kettle, and the temperature was gradually raised from 140 ° C to 230 ° C. The transesterification reaction was carried out while distilling the produced methanol out of the system. During this time, using the fullerene hydroxide / ethylene glycol solution prepared in the above (1) at 170 ° C., the addition amount of the fullerene hydroxide was 0.125 wt% relative to the weight of the obtained polyethylene-2,6-naphthalate resin composition. The reaction was continued until the methanol was completely distilled, and 0.020 part of trimethyl phosphate was added as a phosphorus compound to terminate the reaction. Then, after 5 minutes, 0.024 part of the polymerization catalyst antimony trioxide was added and heated to 250 ° C. to distill a part of ethylene glycol, and then the oligomer was transferred to the polycondensation reaction kettle. Thereafter, the reaction is terminated when the desired viscosity is reached at a final internal temperature of 295 ° C. while heating in a high vacuum according to a conventional method, and is continuously extruded in a strand form from the discharge part, and cooled and cut to about 3 mm. Before and after, pellets of polyethylene-2,6-naphthalate resin composition were obtained. The intrinsic viscosity of this polymer was 0.62. Table 1 shows the properties of the obtained polyethylene-2,6-naphthalate resin composition.

[Comparative Example 1]
Except for not adding the fullerene hydroxide, the same operation as in Example 1 was performed to obtain granular pellets of polyethylene-2,6-naphthalate resin composition having an intrinsic viscosity of 0.62. Table 1 shows the properties of the obtained polyethylene-2,6-naphthalate resin composition.

[Comparative Example 2]
The same procedure as in Example 1 was repeated except that the fullerene hydroxide was not added and the diethylene glycol content in the polyethylene-2,6-naphthalate resin composition was 2.87% by weight. 62 granular pellets of polyethylene-2,6-naphthalate resin composition were obtained. Table 1 shows the properties of the obtained polyethylene-2,6-naphthalate resin composition.

[Comparative Example 3]
Except for adding 0.008 parts of potassium acetate as an inhibitor of diethylene glycol by-product reaction, the same operation as in Example 1 was carried out to obtain a pellet of polyethylene-2,6-naphthalate resin composition having an intrinsic viscosity of 0.62. Obtained. Table 1 shows the properties of the obtained polyethylene-2,6-naphthalate resin composition.

[Examples 2 and 3 and Comparative Example 4]
The same operation as in Example 1 was repeated except that the amount of the fullerene hydroxide in the composition was changed to the amount shown in Table 1. Table 1 shows the properties of the obtained polyethylene-2,6-naphthalate resin composition.

[Comparative Example 5]
The same operation as in Example 1 was repeated except that 2% by weight of plate-like alumina particles (average particle size 0.6 μm, aspect ratio 10) were contained in place of the fullerene hydroxide. Table 1 shows the properties of the obtained polyethylene-2,6-naphthalate resin composition.

[Comparative Example 6]
(1) Fullerene hydroxide having 12 hydroxyl groups introduced per molecule in C60 skeleton (nanom spectra HX10-S manufactured by Frontier Carbon Co.) was used, and 0.46 of fullerene hydroxide was added to 99.6 parts of ethylene glycol. Part was added and stirred at room temperature for 4 hours to prepare a 0.4 wt% fullerene hydroxide / ethylene glycol solution.
(2) A mixture of 100 parts of dimethyl terephthalate and 70 parts of ethylene glycol is charged with 0.038 parts of manganese acetate tetrahydrate in a transesterification reaction kettle and gradually heated from 140 ° C. to 230 ° C. while being gradually heated. The transesterification was carried out while distilling methanol out of the system. During this time, using the fullerene hydroxide / ethylene glycol solution prepared in (1) above at 170 ° C., the reaction was continued by adding the fullerene hydroxide content in the polyethylene terephthalate resin composition to 0.1 wt%. After completion of the distillation of methanol, 0.017 part of trimethyl phosphate was added as a phosphorus compound to terminate the reaction. Subsequently, 0.030 part of the polymerization catalyst antimony trioxide was added after 5 minutes and heated to 240 ° C. to distill a part of ethylene glycol, and then the oligomer was transferred to the polycondensation reaction kettle. Thereafter, the reaction is terminated when the desired viscosity is reached at a final internal temperature of 290 ° C. while heating in a high vacuum according to a conventional method, and the strand is continuously extruded from the discharge part into a strand shape and cooled to about 3 mm. Granular pellets of the front and rear polyethylene terephthalate resin compositions were obtained. The intrinsic viscosity of this polymer was 0.62. The properties of the obtained polyethylene terephthalate resin composition are shown in Table 1.

[Comparative Example 7]
Except for not adding the fullerene hydroxide, the same operation as in Comparative Example 6 was performed to obtain granular pellets of a polyethylene terephthalate resin composition having an intrinsic viscosity of 0.62. The characteristics of the obtained polyethylene terephthalate resin composition are shown in Table 1.

  According to the present invention, a molded article such as a film or fiber having a high Young's modulus and the like while having excellent surface flatness can be obtained. And can be suitably used as a material for a film for a magnetic recording medium that requires a high Young's modulus, and its industrial value is extremely high.

Claims (3)

  A resin composition of polyethylene-2,6-naphthalate copolymerized with fullerene hydroxide and diethylene glycol, wherein the addition amount of the fullerene hydroxide is 0.01 to 0.2, based on the weight of the resin composition. Polyethylene-2,6, wherein the copolymerization amount of diethylene glycol is in the range of 1.5 to 5.0% by weight based on the weight of polyethylene-2,6-naphthalate -Naphthalate resin composition.   When producing 2,6-naphthalenedicarboxylic acid or its ester-forming derivative and ethylene glycol by esterification reaction or transesterification reaction and polycondensation reaction, any stage until the esterification reaction or transesterification reaction is completed And adding a fullerene hydroxide in the range of 0.01 to 0.2% by weight based on the weight of the resin composition to be obtained, and a method for producing a polyethylene-2,6-naphthalate resin composition .   The polyethylene-2,6-naphthalate resin composition according to claim 2, wherein the fullerene hydroxide is added as an ethylene glycol solution, and the concentration of the fullerene hydroxide in the solution to be added is in the range of 0.05 to 0.5 wt%. Manufacturing method.