JP2002226685A - Polyester composition and film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polyester composition capable of developing the productivity of the polyester composition, various effects such as improvement of thermal resistance with the improved productivity and a film thereof. SOLUTION: The polyester composition contains a ligand which is capable to coordinate with a metal or metallic ion, and the ligand as a donor is at least one selected from the group consisting of nitrogen atom, sulfur atom and oxygen atom.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polyester composition and a film, and in particular, has excellent heat resistance, coloring properties, and weather resistance, and is used for various purposes such as magnetic material use, packaging material use, optical material use, electric material use and the like. The present invention relates to a polyester composition and a film which can be developed for various uses.

[0002]

2. Description of the Related Art Polyester films, especially polyethylene terephthalate (hereinafter referred to as PET) films have excellent mechanical, thermal and electrical properties, are widely used in industrial applications, and their demand is increasing. However,
With the expansion of applications and demand, the properties and productivity required for polyester are becoming increasingly severe in each application field, and while being produced in a wide variety of applications such as industrial and magnetic materials, There are many issues to be addressed.

[0003] Generally, when a polyester film is formed, the polymer formed by polymerization once is melted again to form a film. However, a residence time is generated during the melt extrusion. Degradation of the polymer occurs during this residence time, which is a problem which leads to increased filtration pressure due to filter clogging and defects in the film product. This may be due to oxidative decomposition or hydrolysis of the polymer, but it is presumed that the metal catalyst present in the system promotes the reaction. In addition, as a method of improving productivity during film formation, it is desirable to apply a film electrostatically and press it against a cast drum. However, in order to apply the static electricity, it is desirable that the polymer contains a certain amount or more of metal. However, when the productivity is improved by adding a metal, there has been a problem that the metal becomes a catalyst and the heat resistance deteriorates.

[0004]

SUMMARY OF THE INVENTION An object of the present invention is to provide a polyester composition and a film exhibiting various effects such as improvement in heat resistance as well as productivity of the polyester composition.

[0005]

According to the present invention, there is provided a polyester composition containing a ligand capable of coordinating with a metal or a metal ion, wherein the ligand comprises nitrogen as a donor atom. It is characterized by a polyester composition containing at least one atom selected from the group consisting of atoms, sulfur atoms and oxygen atoms.

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION The polyester composition used in the present invention contains a ligand capable of coordinating a metal or a metal ion, and the ligand includes a nitrogen atom, a sulfur atom and an oxygen atom as donor atoms. It contains at least one atom selected from the group consisting of atoms.

In the polyester composition, a dialkyl ester is used as an acid component, and a transesterification reaction is performed between the dialkyl ester and a diol component. The product of this reaction is heated under reduced pressure to remove excess diol component. It can be produced by polycondensation. It can also be produced by a direct polymerization method using a dicarboxylic acid as the acid component.

The ligand used in the present invention may be added during the above-mentioned polycondensation step, and the timing of addition is not particularly limited. It is preferably added after the completion of the exchange reaction or after the completion of the polymerization. Particularly, in order to prevent the catalyst activity from being lowered by the ligand, it is preferable to add the compound after the transesterification reaction or the polymerization reaction.

The nitrogen, sulfur and oxygen atoms, which are donor atoms, are not a covalent bond between the negatively charged nitrogen, sulfur and oxygen atoms and the positively charged metal or metal ion, respectively. Rather ion-
It is considered that they are coordinated by electrostatic attraction due to dipole interaction. Therefore, in order to inactivate the metal or metal ion as a catalyst, it is preferable that at least four or more donor atoms coordinate to block the active site of the metal ion. If four or more ligands are not coordinated, the steric hindrance effect of the ligand tends to be insufficient. On the other hand, if the number exceeds 20, the annular structure becomes large and the conformation for taking in metal or metal ion is distorted, making it difficult to capture metal or metal ion. Thus, the preferred number of coordinating donor atoms is in the range of 4-20, more preferably in the range of 6-10.

[0010] The amount of the ligand added is preferably 0.001 to 1 based on the obtained polyester composition.
0% by weight, more preferably 0.01 to 5% by weight. When the content of the ligand is not 0.001 to 10% by weight, a sufficient catalytic activity suppressing effect may not be obtained. If it exceeds 10% by weight, the amount of the ligand itself due to mechanical decomposition or oxidative decomposition cannot be ignored, and the heat resistance may decrease.

In producing polyester, generally,
In many cases, (1) a transesterification catalyst or a polymerization catalyst, and (2) various metal element-containing compounds for improving SI properties (promoting productivity) are added. In the above (1), iron, antimony,
Titanium, aluminum, germanium, manganese, cobalt, zinc, copper, nickel, cadmium, tin, etc. are included, and the above (2) includes lithium, sodium, potassium, rubidium, cesium, beryllium, magnesium, calcium, strontium, Barium and the like are included. Further, it is necessary to reduce the melting specific resistance in order to promote the productivity. For this purpose, a large amount of a metal such as magnesium is sometimes added. However, the above-mentioned metals and metal ions not only promote a normal reaction (ester exchange reaction or polycondensation reaction) but also promote a reverse reaction (depolymerization reaction such as decomposition reaction). Therefore, in the present invention, it is possible to suppress this reverse reaction by adding a predetermined ligand after the esterification reaction or polymerization is completed.

It is preferable to use an inclusion compound as the ligand to be added. Further, as the ligand used in the present invention, linear polyether, linear polyether amide, cyclic polyether, cyclic polyether polyester, cyclic polyketone, cyclic polyamine, cyclic polyamine polyamide, cyclic polythiaether, aza Preferred are crown ethers, thiacrown ethers, cyclic azathia crown ethers, azathia crown ethers, bicyclic cryptands, tricyclic cryptands, spherical cryptands, linear polyamines, sulfur-based ligands such as phosphorous sulfide, and the like. Cyclodextrin is also a preferred ligand that can be used in the present invention.

Each of these ligands contains a donor atom such as a nitrogen atom, an oxygen atom, or a sulfur atom, and a linear ligand is formed so that the donor atom surrounds a metal or a metal ion. It is conceivable that the arranged and cyclic or bicyclic ligands take in metal ions in the ring, hold the metal or metal ion by electrostatic interaction, and suppress the metal activity.

Among the above-mentioned ligands, cyclic polyethers are preferred because of their simple structure and excellent entropy in coordination to metal ions. As such a ligand, among cyclic polyethers, 18-crown-6, 15-crown-5, 12-crown-4, 30
-Crown-10, dibenzo18-crown-6, dibenzo30-crown-10 and the like are preferable, and in the case of a linear polyether, pentaglyme, hexaglyme, decaneglyme, and in the case of a linear polyamine, a tetraamine,
Hexamethylenetetraamine (hexaamine), pentaamine, phosphorous sulfide as a sulfur compound, [2.2.1] cryptand, [2.2.1] cryptand, [2.2.2] as a bicyclic cryptand
Cryptand, [3.2.2] cryptand, [3.
[3.2] cryptand, [3.3.3] cryptand and the like are preferable. Among them, 18-crown-6 is preferable because it can coordinate 6 to a metal ion without structural distortion, and 30-crown-10 coordinates 10 to a metal or metal ion to almost completely convert the metal or metal ion. Surrounding is desirable because it takes a stable conformation.

In the present invention, when an alkali metal or alkaline earth metal is mainly coordinated, the donor atom of the ligand is preferably an oxygen atom. These are oxygen, nitrogen,
Among the sulfur atoms, the oxygen atom with the highest electronegativity can strongly hold metals with small ionic radii such as alkali metals and alkaline earth metals by ionic bonds (ion-dipole interaction) in addition to covalent bonds. That's why. In addition, it can coordinate to a catalyst composed of a transition metal such as antimony or germanium, and can suppress the reverse reaction due to the steric hindrance effect of the ligand, that is, it can suppress the thermal decomposition, oxidative decomposition, and hydrolysis of the polymer. is there. In addition, when the ionic radius of the coordinating metal is large, such as a metal other than an alkali metal or an alkaline earth metal, a nitrogen atom or a sulfur atom may be preferable because a covalent bond is stronger than an ionic bond. .

In the ligand of the present invention capable of coordinating with a metal or a metal ion, the metal or the metal ion is preferably such that the metal or the metal ion is lithium, sodium,
Potassium, rubidium, cesium, beryllium, magnesium, calcium, strontium, barium, iron,
Antimony, titanium, aluminum, germanium, manganese, cobalt, zinc, copper, nickel, cadmium,
It is at least one element selected from the group consisting of tin. The ligand of the present invention coordinates with these metals or metal ions as required to exhibit predetermined performance.

When the ligand used in the present invention is added after the end of the transesterification reaction, it is necessary to add a ligand which does not impair the activity of the polycondensation catalyst metal. As the polycondensation catalyst metal, antimony trioxide, antimony pentoxide, antimony acetate, germanium dioxide, germanium tetraethoxide, tetrabutyl titanate and the like having an ionic radius of 0.53 to 1.00 ° are often used. For example, when using germanium dioxide as a polycondensation catalyst, the ionic diameter of germanium ions is 1.74Å,
Further, the actual state of germanium ions in the reaction system is a form in which an oxygen atom or the like is coordinated, and thus the actual ion radius is larger than that. Therefore, by using 12-crown-4 and 15-crown-5 having smaller pore diameters of 1.2% or 1.7% as ligands, transesterification catalysts without inclusion of germanium dioxide as a polymerization catalyst can be obtained. Only can be included, and if necessary,
The transesterification catalyst can be separated and recovered from the polyester composition.

When the ligand used in the present invention is added after completion of the polycondensation, a ligand having a pore diameter close to the ionic radius of the polycondensation catalyst metal or the ionic radius of the transesterification catalyst is used. By using a ligand having a high ion trapping ability empirically, these catalysts can be included, and if necessary, these catalysts can be recovered from the polyester composition. . In addition, in the present invention, it is preferable that when adding a metal to be added in order to increase the electrostatic application force, the metal be included in advance by an inclusion compound and charged in a form retaining only ionicity.

In the present invention, when a ligand containing only oxygen as the donor atom is used, the alkali atom present in the polyester resin is not used because of the high affinity of the oxygen atom for alkali metals and alkaline earth metals. metal,
The ligand amount S [mol / ton-polymer] with respect to the total amount of alkaline earth metals Ma [mol / ton-polymer] is such that when the molar ratio Rma = S / Ma, Rma is 0.001 to 30. Within the range is preferred. More preferably, Rma is from 0.01 to 10, even more preferably from 0.1 to 5.

When a ligand consisting of only nitrogen and sulfur is used as the donor atom, the nitrogen and sulfur atoms have a high affinity for the transition metal and the like. Ligand amount S with respect to total amount Mt [mol / ton-polymer]
[mol / ton-polymer] is Rmt when the molar ratio Rmt = S / Mt.
Is preferably in the range of 0.001 to 30. Rmt is more preferably 0.01 to 10, and even more preferably 0.1 to 5.

Further, when a ligand containing all of nitrogen, sulfur and oxygen as a donor atom is used, the ligand is coordinated with respect to the total amount Ms [mol / ton-polymer] of all metals present in the system. When the molar ratio Rms = S / Ms, the amount S [mol / ton-polymer] is preferably in the range of 0.001 to 30. R
ma is more preferably 0.01 to 10, and even more preferably 0.1 to 5.

In the present invention, the value of the melting specific resistance of the polyester composition is preferably less than 15 × 10 ⁷ Ω · cm,
More preferably, it is less than 10 × 10 ⁷ Ω · cm. If the melt specific resistance value is 15 × 10 ⁷ Ω · cm or more, antistatic applied cast unsuccessful, it easily enters the air between the film and the casting drum during melt extrusion casting, forced to lower the deposition rate It is easy to be in a situation where you can not get it. Here, the melting specific resistance refers to a value calculated by measuring the amount of current flowing when a voltage is applied to the polyester composition in a molten state, and is a numerical value serving as an index of electric conductivity.

In the present invention, it is preferable that the melting specific resistance does not increase due to the presence of the ligand. When the melting specific resistance increases, the electrostatic applicability during film formation deteriorates, and the productivity of the film tends to decrease. Here, the melting specific resistance of the polyester composition containing the ligand is R, and the melting specific resistance of the polyester composition not containing the ligand is R.
When 0, it is preferable that R / R0 ≦ 1.3. More preferably, R / R0 ≦ 1.1, and even more preferably, R / R0 ≦ 1.0.

In the present invention, the polyester composition preferably contains ethylene terephthalate or ethylene-2,6-naphthalate as a main component in view of heat resistance and mechanical properties. Further properties such as heat resistance, high rigidity and antistatic properties can be imparted by copolymerizing the ester-forming derivative and a diol.

The dicarboxylic acid component that can be copolymerized includes:
For example, isophthalic acid, phthalic acid, 1,4-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, 2,6
-Naphthalenedicarboxylic acid, 4,4'-diphenyldicarboxylic acid, 4,4'-diphenyletherdicarboxylic acid, 4,4'-diphenylsulfonedicarboxylic acid, and ester-forming derivatives thereof.

Other examples of the alicyclic dicarboxylic acid component which can be copolymerized include 1,4-cyclohexanedicarboxylic acid. In addition, aliphatic dicarboxylic acids such as sebacic acid and dimer acid, and other dicarboxylic acids can be used as the copolymerization component.

As the diol component, ethylene glycol, 1,2-propanediol, neopentyl glycol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexane Diol, 1,2-cyclohexanedimethanol, 1,
Aliphatic, alicyclic, aromatic, such as 3-cyclohexane dimethanol, 1,4-cyclohexane dimethanol, diethylene glycol, triethylene glycol, polyalkylene glycol, 2,2-bis (4'-β-hydroxyethoxyphenyl) propane; Group diols and the like. Only one of these components may be used.
More than one species may be used in combination.

Various catalysts can be used for the esterification and transesterification reactions. For example,
Acetates such as calcium acetate, magnesium acetate, and lithium acetate, and titanium compounds such as titanium tetraethyleneglycoxide can be used.

As the polymerization catalyst, for example, antimony trioxide, antimony pentoxide, germanium dioxide, germanium tetrabutoxide, germanium tetraethoxide, titanium tetraethyleneglycoxide, tetrabutyl titanate and the like can be used.

In the present invention, a stabilizer may be added in the polycondensation step to prevent side reactions such as thermal decomposition of the polyester. Examples of the stabilizer include tetrakis methylene-3- (dodecylthio) propionate methane and tetrakis methylene- (3,5-t-butyl-4).
-Hydroxyhydrocinnamate) @methane, tridecyl phosphate, tris (2,4-dibutylphenyl) phosphite, tetrakis @ methylene-3-
(3 ′, 5′-di-t-butyl-4′-hydroxyphenyl) propionate｝ methane and the like, and these can be used alone or in combination of two or more. The amount of the stabilizer to be added is preferably 0.03 to 2% by weight, more preferably 0.05 to 1.9% by weight, based on the obtained polyester composition. If the amount of the stabilizer is less than 0.03% by weight, the effect of improving the oxidation stability is small, and if it exceeds 2% by weight, the polycondensation reaction may be inhibited.

In the present invention, when a small amount of a basic compound is added in the esterification step, a polyester composition having less side reaction products can be obtained. Examples of such a basic compound include tertiary amines such as triethylamine, tributylamine and benzylmethylamine, and quaternary amines such as tetraethylammonium hydroxide, tetrabutylammonium hydroxide and trimethylbenzylammonium hydroxide.

The polyester composition of the present invention can be formed into a film by, for example, a melt extrusion film forming method. That is, after drying the polyester composition,
A non-stretched film is obtained by feeding the mixture to a single-screw or twin-screw extruder equipped with a T-type die, extruding it on a casting drum at a polyester melting temperature, and applying an electrostatic application cast. Also, to obtain an oriented polyester film,
Further, this is successively biaxially stretched or simultaneously biaxially stretched and heat-treated, whereby an oriented polyester film can be obtained.

At this time, the polyester of the present invention may be formed alone, or a film in which the polyester composition of the present invention is mixed with 1% by weight or more of another polyester composition to change the metal concentration may be used. The method of obtaining is also preferable from the viewpoint of improving the productivity and heat resistance of other varieties.

Further, by forming a layered structure of the layer composed of the polyester composition of the present invention and a layer composed of another polyester composition, a laminated film having the characteristics of each layer can be obtained. The laminated film of the present invention, for example, after drying the polyester composition of the present invention and another polyester composition, according to a conventional method, two or more confluent blocks having a rectangular laminated portion, each layer is intended for So that the thickness ratio and configuration of
It can be manufactured by melt-extruding from a die to form an unstretched sheet, followed by biaxial stretching and heat treatment.

In the case of a biaxially stretched film, the stretching ratio is not particularly limited, but it is usually appropriate that the stretching ratio is 2 to 5 times in each of the vertical and horizontal directions. Or vertical,
After the transverse stretching, the film may be stretched again in any of the longitudinal and transverse directions, or, of course, may be simultaneously biaxially stretched. Also,
When forming an easy-adhesion layer, a particle layer, or the like, the coating component may be applied in-line before stretching or between longitudinal stretching and transverse stretching, or may be offline-coated after stretching.

The polyester composition of the present invention can contain inorganic particles and organic particles as required.
The inorganic particles are not particularly limited, and include compounds such as silica, alumina, calcium carbonate, titanium oxide, calcium phosphate, hydroxyapatite, and aluminum silicate. In addition, examples of the organic particles include crosslinked polymer particles.

The metal or metal ion coordinated by the ligand described in the present invention has a low activity as a catalyst for decomposing the polyester. The heat resistance of the resin is improved.

Further, the polyester composition of the present invention comprises
When forming a film, the castability for electrostatic application hardly decreases. This is because the metal or metal ion coordinated by the ligand described in the present invention has lost its catalytic activity while keeping its electrical properties, or, unlike ionic bonding, differs from the case of electrostatic application. It is considered that the ligand which is not strongly bonded to the metal ion due to the high voltage exhibits electrical characteristics by separating from the metal ion.

The polyester composition and film of the present invention are excellent in heat resistance, coloring property and weather resistance, and are used for magnetic materials.
It is suitable for packaging materials, optical materials, electric materials, and various other uses.

[0040]

The present invention will be described in more detail with reference to the following examples. In addition, each characteristic in an Example was measured by the following method. (1) Measurement of ligand content (% by weight): 100 mg of a composition sample was dissolved in 2 ml of hexafluoroisopropanol as a solvent, allowed to stand overnight, dissolved in CDCl ₃ , and subjected to nuclear magnetic resonance. , 400 MHz, ¹ H-NMR
(JOEL GX-400 pulse FT spectrometer) and 22.5 MHz, ¹³ C-NMR (JOEL FT
-900 type pulse FT spectrometer). (2) Intrinsic viscosity of polymer ([η] (dL / g)): o
-Measured at 25 ° C. using chlorophenol as a solvent. (3) Heat resistance% BB of polymer (melt heat resistance test):
8 g of polymer is placed in a test tube, and 0.1MP in a nitrogen atmosphere.
Heat treatment was performed at 300 ° C. for 10 minutes (t ₀ ), 3 hours (t), and 6 hours (t) under the pressure of “a”. At that time, η was measured and calculated by the following equation.

% BB _t = (1 / [η] _t ^{(1 / 0.75)} −1 / [η] _t0 ^{(1 / 0.75)} ) where [η] _t is a value at the time of heat treatment for 3 hours or 6 hours.
[η] _t0 is a value at the time of heat treatment for 10 minutes.

In the case of a film, the measurement was carried out in the same manner as in the case of the polymer except that 8 g of the film was put into a test tube and melted. (4) Melt specific resistance: a copper plate 22 cm ^{2 with two} Teflon (registered trademark) spacers interposed between two copper plates as electrodes;
An electrode having a copper plate spacing of 9 mm is prepared. 290 ° C
And the resistance was calculated from the amount of current when a voltage of 5,000 V was applied between the electrodes. (5) Metal Content (FLX) 8 g of the polymer was melted and molded into a plate, and the intensity of fluorescent X-rays was measured. This value was converted to a metal content using a calibration curve prepared in advance with a sample having a known content. (6) Metal content (atomic absorption method) The alkali metal was measured by the atomic absorption method. 8g polymer
Was atomized by flame-type atomization using a hollow cathode lamp as a light source, and was converted to a metal content by using a calibration curve previously detected and detected by a photometry unit. Example 1 A mixture of 100 parts by weight of dimethyl terephthalate and 60 parts by weight of ethylene glycol was further added with 0.04 parts of magnesium acetate based on the amount of dimethyl terephthalate.
A part by weight was added, and the mixture was heated and heated to distill off methanol to carry out a transesterification reaction. The end of the transesterification reaction was determined by the amount of methanol distilled off. Next, to the transesterification reaction product, after adding 0.020 parts by weight of trimethyl phosphate with respect to the amount of dimethyl terephthalate,
0.02 parts by weight of germanium oxide was added to transfer to the polycondensation reaction layer. Subsequently, the reaction system was gradually depressurized while heating and raising the temperature. Under reduced pressure, the inside was stirred at 290 ° C. to polymerize while distilling off methanol. The inside was purged with nitrogen to return to atmospheric pressure, and 0.06 parts by weight of potassium acetate and 18-crown-6 (10 mol% based on the amount of metal (excluding those contained in the particles)) were converted into an ethylene glycol solution. After sufficiently mixing, the mixture is added, and the reaction system is gradually reduced in pressure. The mixture is repolymerized under reduced pressure at 290 ° C. in the same manner as described above. And a polyester composition (W) having an intrinsic viscosity of 0.60 was obtained. As shown in Table 1, the content of 18-crown-6 in the polyester composition was measured to be 8.3 mol%, and the amount of the ligand relative to the metal (Rm
a) was 0.083. Comparative Example 1 Example 1 except that an equimolar amount of ethylene glycol was added instead of adding 18-crown-6.
In the same manner as described above, a chip of polyethylene terephthalate (PL) with [η] = 0.60 was obtained. Table 1 shows the results. (Reference Example 1) Except for adding 1% by weight of an ethylene glycol slurry containing 5% by weight of silica particles having an average particle diameter of 0.05 μm to dimethyl terephthalate before transferring to the polycondensation reaction layer. In the same manner as in Comparative Example 1, chips of the particle-containing polyester (S) having [η] = 0.61 were obtained. (Example 2) A polyester composition was obtained in the same manner as in Example 1 except that dibenzo 18-crown-6 was used in an equimolar amount instead of 18-crown-6. Table 1 shows the results. Example 3 Example 1 except that an equimolar amount of dibenzo 30-crown-10 was used instead of 18-crown-6.
A polyester composition was obtained in the same manner as described above. Table 1 shows the results. Example 4 A polyester composition was obtained in the same manner as in Example 1, except that pentaglyme was used in an equimolar amount instead of 18-crown-6. Table 1 shows the results. (Example 5) A polyester composition was obtained in the same manner as in Example 1 except that an equimolar amount of hexadecane glyme was used instead of 18-crown-6. Table 1 shows the results. (Comparative Example 2) A polyethylene terephthalate (K) of [η] = 0.60 was prepared in the same manner as in Example 1, except that equimolar amounts of ethylene glycol were added instead of potassium acetate and 18-crown-6. ) Chips were obtained. Table 1 shows the results. (Example 6) 1.7% by weight of 18-crown-6 was added, and the amount added to alkali and alkaline earth metal was changed to Rma =
A polyester composition was obtained in the same manner as in Example 1, except that the composition was 3.0. Table 2 shows the results. (Example 7) In place of 18-crown-6, 0.08% by weight of hexaamine was added to reduce the amount of addition to the transition metal.
A polyester composition was obtained in the same manner as in Example 1 except that Rmt was set to 3.0. Table 2 shows the results. (Example 8) Polyester was prepared in the same manner as in Example 1 except that 0.26% by weight of phosphorous sulfide was added instead of 18-crown-6, and the amount added to the transition metal was Rmt = 3.0. A composition was obtained. Table 2 shows the results
Shown in (Example 9) Instead of 18-crown-6 [2.2.
2] 1.12% by weight of cryptand is added to alkali,
Rms = 3. The amount added to alkaline earth metals and transition metals.
A polyester composition was obtained in the same manner as in Example 1 except that the value was set to 0. Table 2 shows the results. (Comparative Example 3) Polyester was prepared in the same manner as in Example 1, except that 0.07% by weight of sodium hydrogen sulfate was added instead of 18-crown-6, and the amount added to the transition metal was changed to Rmt = 3.0. A composition was obtained. Table 2 shows the results. (Example 10) The polyester composition (W) obtained in Example 1 was sufficiently dried, supplied to an extruder, melt-extruded on a casting drum, and fused on a cast drum while applying static electricity. After quenching and solidifying to form a single-layer unstretched film, this was vertically stretched 3.5 times at 90 ° C. and 105 ° C.
Then, the film was stretched 3.5 times at a time to obtain a polyester film having a thickness of 10 μm. The film forming property was good. The film thus obtained had good heat resistance and good productivity. Table 3 shows the results. (Example 11) The polyester composition (W) obtained in Example 1, the polyethylene terephthalate (PL) obtained in Comparative Example 1, and the particle-containing polyester (S) obtained in Reference Example 1 were each sufficiently used. The same method as in Example 10 except that the mixture was dry-blended so that the ligand concentration was the concentration shown in Table 3 (Rma = 0.0021) with respect to the amount of metal (excluding those contained in the particles). Thus, a polyester film was obtained. Table 3 shows the results. (Example 12) The polyester composition (W) obtained in Example 1 and the polyethylene terephthalate (PL) obtained in Comparative Example 1 were sufficiently dried, and the amount of metal (excluding those contained in the particles) Is the ligand concentration shown in Table 3 (Rma
= 0.052), and supplied to the main layer (layer A) extruder. Further, after drying the particle-containing polyester (S) obtained in Reference Example 1, it was dry-blended with polyethylene terephthalate (PL) so that the particle concentration became 0.5% by weight, and a sub-layer (B-layer) extruder was used. Is melt-extruded from a two-layer die onto a casting drum, fused and quenched and solidified on the casting drum while applying an antistatic force, to form an A / B type (thickness ratio: 6/1) double layer. It was a stretched film. Next, the unstretched film was stretched 3.5 times vertically at 90 ° C. and 3.5 times horizontally at 105 ° C. to obtain a laminated polyester film having a thickness of 8 μm (laminated thickness of layer B: 1.33 μm). The film forming property was good. The film thus obtained had good heat resistance and good productivity. Table 3 shows the results. (Example 13) The concentrations of the ligands with respect to the metal amounts (excluding those contained in the particles) of the layer A and the layer B were as shown in Table 3 (layer A: Rma = 0.015, layer B) : R
(ma = 0.000), the polyester composition (W) obtained in Example 1, the polyethylene terephthalate (PL) obtained in Comparative Example 1, and the particle-containing polyester obtained in Reference Example 1. A laminated polyester film was obtained in the same manner as in Example 12, except that (S) was blended and supplied to an extruder. Table 3 shows the results. (Example 14) The concentrations of the ligands with respect to the metal amounts (excluding those contained in the particles) of the layer A and the layer B were as shown in Table 3 (layer A: Rma = 0.053, layer B). : R
ma = 0.032), the polyester composition (W) obtained in Example 1, the polyethylene terephthalate (PL) obtained in Comparative Example 1, and the particle-containing polyester obtained in Reference Example 1. A laminated polyester film was obtained in the same manner as in Example 12, except that (S) was blended and supplied to an extruder. Table 3 shows the results. (Comparative Example 4) A film was formed in the same manner as in Example 12, except that the polyethylene terephthalate (PL) obtained in Comparative Example 1 was supplied instead of the polyester composition (W) obtained in Example 1. The heat resistance was poor, and the productivity also deteriorated. Table 3 shows the results. (Comparative Example 5) A film was formed in the same manner as in Example 10, except that the polyethylene terephthalate (K) obtained in Comparative Example 2 was supplied instead of the polyester composition (W) obtained in Example 1. Although the heat resistance was good, the melting specific resistance was large and the productivity was deteriorated. Table 3 shows the results. Comparative Example 6 A polyethylene terephthalate chip with [η] = 0.60 was prepared in the same manner as in Example 1 except that diethylene glycol was used instead of 18-crown-6. A laminated polyester film was obtained in the same manner as in Example 12, except that polyethylene terephthalate (PL) and the particle-containing polyester (S) obtained in Reference Example 1 were blended and supplied to an extruder. Table 3 shows the results.

[0043]

[Table 1]

[0044]

[Table 2]

[0045]

[Table 3]

[0046]

Industrial Applicability The polyester composition and film of the present invention are excellent in heat resistance, coloring property, and weather resistance and are suitable for various uses such as magnetic materials, packaging materials, optical materials, electric materials, and the like.

Continued on the front page F term (reference) 4F071 AA43 AA45 AA46 AB06 AC06 AC07 AC12 AC13 AE05 AF45 AF53 AH04 AH12 AH14 AH19 BC01 4J002 CF001 CF061 CF081 DA067 ED016 EE026 EL006 EP006 EU006 EV306 EV316 FD206 FD207 GG02 GP00 G00

Claims (10)

[Claims] 1. A polyester composition containing a ligand capable of coordinating to a metal or a metal ion, wherein said ligand is at least one selected from the group consisting of a nitrogen atom, a sulfur atom and an oxygen atom as a donor atom. Polyester compositions containing seed atoms. 2. The polyester composition according to claim 1, wherein the ligand is an inclusion compound. 3. The method according to claim 1, wherein the metal or metal ion is lithium, sodium, potassium, rubidium, cesium, beryllium, magnesium, calcium, strontium, barium, iron, antimony, titanium, aluminum, germanium, manganese, cobalt, zinc, copper, nickel. 3. The polyester composition according to claim 1, wherein the polyester composition is at least one element selected from the group consisting of cadmium, and tin. 4. The method according to claim 1, wherein the ligand is a linear polyether, a linear polyether amide, a cyclic polyether, a cyclic polyether polyester, a cyclic polyketone, a cyclic polyamine,
At least one compound selected from the group consisting of cyclic polyamine polyamides, cyclic polythiaethers, azacrown ethers, thiacrown ethers, cyclic azathiacrown ethers, azathiacrown ethers, bicyclic cryptands, tricyclic cryptands, and spherical cryptands The polyester composition according to any one of claims 1 to 3. 5. The method according to claim 1, wherein the number of donor atoms contained in the ligand is 4 to 5.
The polyester composition according to any one of claims 1 to 4, which is in a range of 20. 6. The value of the melting specific resistance is 15 × 10 ⁷ Ω · cm.
The polyester composition according to any one of claims 1 to 5, wherein the polyester composition is less than. 7. When the melting specific resistance of a polyester composition containing a ligand is R and the melting specific resistance of a polyester composition not containing the ligand is R0, R / R0 ≦ 1.
The polyester composition according to any one of claims 1 to 6, which is 3. 8. The polyester composition according to claim 1, wherein the polyester contains polyethylene terephthalate or polyethylene-2,6-naphthalate. 9. A film comprising the polyester composition according to claim 1. 10. A laminated film comprising at least one layer of the film according to claim 9.