JPS6270442A - Polyester composition - Google Patents

Abstract

PURPOSE:To provide the titled compsn. which has excellent thermal stability and dispersibility and gives a film having excellent slipperiness and wear resistance, by adding a specified fine particle to a polyester composed of an arom. dicarboxylic acid (ester) and ethylene glycol. CONSTITUTION:Amorphous zeolite is crushed, classified and subjected to a wet heat treatment with water, an alcohol, etc. at 70-200 deg.C under a pressure of 1-50kg/cm<2> for several hr to one week to obtain a fine particle (A) which is amorphous according to X-ray diffractometry, exhibits reduction in weight of 5wt% or below at 200 deg.C and 10wt% or below at 300 deg.C by thermogravimetric analysis after standing for 24hr under 80% humidity conditions, has a particle size of 0.01-5mu and is represented by the formula (wherein M is an alkali or alkaline earth metal; x is 0.001-4, y is 1-23, z is 0.001-10). 0.001-3wt% component A is added to a polyester which is composed of an arom. dicarboxylic ester, ethylene glycol and optionally, a third component and in which at least 80mol% of repeating units is ethylene terephthalate unit.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a polyester composition, which particularly has excellent thermal stability and dispersibility when melted, and has good slipperiness and abrasion resistance when formed into a film. The present invention relates to a polyester composition having excellent properties.

[Prior Art] Polyester films, especially biaxially oriented polyester films represented by polyethylene terephthalate,
Because of its excellent electrical properties, mechanical properties, thermal properties, processability, and chemical resistance, it is used as a base film in a wide range of fields such as magnetic tape, capacitors, packaging materials, photolithography, and electrical insulation materials. is used as.

The properties required of such a polyester film vary depending on its use, but the essential requirements for a film include excellent slipperiness and a small number of coarse protrusions. In particular, slipperiness is important for the ease of winding in the film manufacturing process, the passability of post-processing processes such as magnetic tape, and the runnability of the final product as a magnetic tape and wear resistance with guide pins, etc. This is extremely important as it affects the quality of the product. In order to improve the slipperiness of a film, it is generally done to improve the slipperiness by forming fine irregularities on the surface of the film.

A well-known method for providing fine irregularities on the surface of a film is to precipitate fine particles in the reaction system using the residue of a metal compound used as a catalyst during polyester polymerization. This method does not require special equipment, equipment or complicated operations, and can be carried out relatively easily.
Moreover, since the precipitated particles have an organic component in their structure, they have a relatively good affinity with the polymer, and the particles may fall off during the stretching film forming process or be abraded with the guide bin when used as a magnetic tape. Although it has advantages such as less peeling off, it is easy to generate agglomerated particles, it is difficult to control the particle size of precipitated particles, and furthermore, there are problems such as variations in the amount of precipitated particles between batches and difficulty in increasing the amount. There are many issues that need to be addressed.

On the other hand, there is also a method of adding inert fine particles to polyester during the polyester manufacturing process or extrusion process to form protrusions on the film surface and impart slipperiness (hereinafter referred to as the "added particle method"). Also well known.

In the additive particle method, it is important to prepare fine particles with uniform particle size in advance and reduce coarse particles, and usually operations such as particle dispersion, pulverization, classification, and filtration and equipment for such operations are required.
Once the apparatus and operating method are determined, the reproducibility of particle size and particle amount is good, and the advantage is that the particle amount can be increased or decreased as necessary.

[Problems to be solved by the invention] Although the additive particle method has various advantages as mentioned above,
Conventionally known inert fine particles have had many problems because they all lack affinity with polyester or uniform dispersibility in polyester.

In other words, inert fine particles with poor affinity with polyester,
Since it peels off from the polyester due to stretching tension and friction, the added particles are detached due to wear during the stretching film forming process and the film pressurizing process, and these particles adhere to the surface of the film, such as the surface of magnetic tape. This has caused various troubles in post-processing and reduced product quality.

In addition, if the dispersibility of the inert fine particles in the polyester is poor, the added particles will aggregate in the polymer, resulting in a change in the surface roughness of the film, or in severe cases, during the extrusion process. Filter blockage occurs. Furthermore, coarse protrusions are formed on the surface of the film, resulting in a decrease in output and an increase in dropouts when used as a magnetic tape, and when used in capacitors, various problems such as a decrease in withstand voltage occur. This will bring about

By the way, it is essential that the inert fine particles added do not have a negative effect on the properties of the polyester itself, especially on the thermal stability. Polymers whose thermal stability has deteriorated due to the addition of inert fine particles will have a large decrease in the degree of polymerization during the extrusion process, resulting in various problems such as a decrease in film properties, an increase in the generation of foreign matter in the film, and an increase in decomposed oligomers.

However, in the conventional additive particle method, inert fine particles that have excellent affinity with polyester and uniform dispersibility in polyester and do not adversely affect various properties such as thermal stability of polyester have not been proposed. Therefore, a polyester film having sufficiently satisfactory properties could not be obtained.

[Means for Solving the Problems] The present invention solves the problems in the additive particle method, and provides a polyester that has excellent thermal stability and dispersibility, and has excellent slipperiness and abrasion resistance when made into a film. The composition was made to provide a composition which is substantially non-crystalline in terms of X-ray diffraction and shows no weight loss at 200°C by thermogravimetric analysis after standing for 24 hours in an 80% humidity atmosphere. 5% by weight or less, weight loss at 300℃ is 10%
The following (I
) A polyester composition characterized by containing 0.001 to 3% by weight of fine particles represented by the formula.

XMO fist A, Q, 203・ySiO2・zH20...
...CI) (However, in the above general formula (I), when M is an alkali metal M', MO becomes M'20.) That is, the present inventors Suitable as particles,
As a result of extensive research into inert fine particles that have excellent homogeneity and affinity with polyester and do not adversely affect the properties of polyester, we found that after being left in an atmosphere with 80% humidity for 24 days, When using amorphous zeolite fine particles with a weight loss of 5% or less at 200°C and a weight loss of 10% or less at 300°C by thermogravimetric analysis, the heat at the time of melting of the resulting polyester They have also found that it works well without adversely affecting stability, and have completed the present invention.

Hereinafter, the present invention will be explained in detail.

The polyester referred to in the present invention refers to a polyester obtained using an aromatic dicarboxylic acid such as terephthalic acid or naphthalene-2,6-dicarboxylic acid or an ester thereof and ethylene glycol as the main starting materials. It may contain ingredients. As the third component, isophthalic acid as an aromatic dicarboxylic acid component, or
Examples of the glycol component include one or more of propylene glycol, tetramethylene glycol, diethylene glycol, neopentyl glycol, and polyalkylene glycol. In either case, the polyester of the present invention contains 80 mol% of repeating structural units.
Polyesters in which "-" is an ethylene terephthalate unit are preferred.

In the present invention, the inorganic particles contained in the polyester to improve the surface properties and slip properties of the film are:
Substantially amorphous in terms of X-ray diffraction and humidity 80%
Atmosphere F, 200°C by thermogravimetric analysis after standing for 24 hours
x@MO*A standing 203・ysi02・with a weight loss of 5% or less at 300℃ and a weight loss of 10% or less at
It is an amorphous zeolite compound represented by zH2O (M, x, y, z are as defined above).

Ordinary amorphous zeolites, i.e. those whose weight loss is greater than a series of values, are hygroscopic; It is not easy to remove moisture once absorbed by hot air drying or vacuum drying. Therefore, a very small amount of water remaining in the particles is desorbed from the particles during the melt extrusion process, resulting in hydrolysis of the polyester. However, in the case of amorphous zeolite, which shows a weight loss of 5% or less at 200°C and a weight loss of 10% or less at 300°C as determined by thermogravimetric analysis under the above conditions, the hygroscopicity of the particles is small, so polyester cannot be hydrolyzed. By lowering the degree of polymerization, thermal stability is not lowered.

In the present invention, it is particularly preferable that the weight loss at 200°C is 4% or less and the weight loss at 300°C is 8% or less as determined by thermogravimetric analysis under the above conditions.

Such amorphous zeolite with low hygroscopicity can be prepared by adding water, alcohol, etc. to the amorphous zeolite for a predetermined period of time under high temperature and pressure after amorphous zeolite synthesis by a conventional method, before classification, or after pulverization and classification. It can be easily obtained by performing moist heat treatment.

Amorphous zeolite compounds are produced by aging a composition in which the alumina component, silica component, alkali metal and/or alkaline earth metal component is in the zeolite-forming range, and then reacting the composition before zeolite crystals begin to crystallize. or by neutralizing a normal crystalline zeolite with an acid and eluting and removing the alkali metal and/or alkaline earth metal until the crystal structure is destroyed. Particularly preferred is the latter method, that is, a method in which the crystalline zeolite is subjected to a treatment for elution and removal of alkali metals and alkaline earth metals using an acid.

This method uses commonly synthesized A-type, X-type, Y-type, Y-type
The alkali metals and alkaline earths in the zeolite are neutralized with acid under conditions in which the crystalline structure is substantially destroyed but the particle shape is not substantially damaged. Amorphous zeolite is produced by removing metal components. The acid used may be either an inorganic acid or an organic acid, and is not particularly limited, but economically,
Hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, etc. are suitable. These acids are used as dilute aqueous solutions. The amorphous zeolite particles obtained by neutralization with acid are filtered, optionally washed with water, dried, and optionally calcined, and then used as additive particles for polyester compositions.

In the present invention, the average particle diameter of the amorphous zeolite fine particles is 0.01 to 5 IL. If the particle size is less than 0.017, the effect of improving the slipperiness of the film will be insufficient, and if it exceeds 5IL, the surface roughness of the film will become too large or the quality of the film will deteriorate due to the presence of large particles. becomes worse.

In order to obtain a zeolite with a desired particle size, it is preferable to prepare a synthetic zeolite with a small primary particle size in advance by appropriately selecting reaction conditions during hydrothermal synthesis of the raw material zeolite. In addition, - Granulation - Amorphous zeolite with relatively large particles of f diameter, for example, l-1OIi, can be used in ball mills, rod mills, vibrating ball mills, vibrating rod mills, roller mills, impact mills, disc mills, stirring grinding mills, It can also be easily obtained by pulverizing it to an appropriate particle size using a fluid energy mill or the like.

It is preferable to remove coarse particles from the amorphous zeolite fine particles thus obtained by dry classification or wet classification, further filtration, or the like. For classification, it is preferable to employ a semi-free whirlpool type, a forced whirlpool type, a hydrocyclo type, a centrifugal separation method, or the like.

The conditions for moist heat treatment to reduce the hygroscopicity of amorphous zeolite are: temperature 70-200°C, pressure 1-50 kg
/cm', and the treatment time is preferably about several hours to one week. Due to such moist heat treatment, the specific surface area of the particles decreases depending on the degree of treatment, so it is presumed that the hygroscopicity of the particles decreases. When subjected to such heat-and-moisture treatment, the hygroscopicity of general crystalline zeolite is not improved, but in the amorphous zeolite of the present invention, the decrease in hygroscopicity due to such heat-and-moisture treatment is extremely significant.

The characteristics of the amorphous zeolite particles whose hygroscopicity has been improved in this way are extremely stable and remain almost unchanged even after being subjected to treatments such as dispersion in ethylene glycol, polymerization reactions, and extrusion into films.For example, 0 polyester film containing amorphous zeolite particles subjected to moist heat treatment
- Melt by heating in a chlorophenol solvent, then centrifuge to separate the added particles from the polymer, and bake in an electric furnace at 450°C for 3 hours in an air atmosphere to remove residual organic compounds and collect the particles. After that, the weight loss of the recovered particles was measured by thermogravimetric analysis after being left for 24 hours in an 80% humidity atmosphere, and the weight loss of the recovered particles was almost the same as that of the particles before being added to the polyester.

In the present invention, the content of amorphous zeolite particles in the polyester composition is 0.001 to 3% by weight. When the particle content is less than 0.001% by weight, the effect of improving the slipperiness and abrasion resistance of the obtained film is insufficient, and when it is used in excess of 3% by weight, the roughness of the film surface This is undesirable because it may become too large, coarse protrusions may increase, and filters may become clogged during the extrusion film forming process.

In producing the polyester composition of the present invention, the amorphous zeolite particles are preferably added during the polyester synthesis reaction. In particular, it is suitable to add it during the transesterification reaction or esterification reaction, after the end of the transesterification reaction or esterification reaction, or before the start of the polycondensation reaction.

Amorphous zeolite particles are usually added as a slurry with a particle concentration of 5 to 30% by weight in a solvent such as ethylene glycol. If the particle concentration of the slurry is less than 5% by weight, the amount of ethylene glycol used increases and the basic unit of ethylene glycol increases, which is not preferable. Also, the particle concentration is 3
When more than 0% by weight of slurry is added, the dispersibility of the particles often deteriorates.

In addition, as a polycondensation reaction catalyst for polyester synthesis, S
Commonly used catalysts such as b, Ge, Ti, Sn, and Si compounds are used.

In addition to amorphous zeolite particles, the polyester composition of the present invention may also contain fine particles of anatase-type titanium dioxide, Wm calcium, calcium phosphate, silica, kaolin, talc, clay, and the like. The amount of these additions is 0.
In addition to such fine particles, fine particles precipitated by a reaction between a catalyst residue and a phosphorus compound in a polyester polycondensation reaction system can also be used in combination. Examples of precipitated fine particles include those consisting of calcium, lithium and phosphorus compounds, those consisting of calcium and phosphorus compounds, or those consisting of calcium, magnesium and phosphorus compounds, and the content of these particles in polyester is 0.0
It is preferably 5 to 1.0% by weight.

From such a polyester composition of the present invention, a polyester film can be produced by a commonly known method, for example, the method described in Japanese Patent Publication No. 30-5639. In addition, from the polyester composition of the present invention, for example,
Easily produce films that are strengthened in the longitudinal direction, i.e., vertically tensilized films, horizontally tensilized films that are strengthened in the transverse direction, or films that are strengthened in both the longitudinal and lateral directions. can do. Furthermore, the polyester composition of the present invention is also suitably used as a raw material for a film produced using film forming conditions that form recessed protrusions on the film surface.

The preferred surface roughness of the polyester film obtained from the polyester composition of the present invention is the average protrusion height Ra
) is from 0.006 to 0.045, and the preferred film thickness is from 1 to 4 ooIL, particularly from 1 to 200.

[Function] Conventionally, many examples of adding synthetic zeolite to polyester have been reported in the additive particle method. However, all of these use crystalline synthetic zeolite. Polyester to which crystalline zeolite has been added is cooled and chipped after polymerization, but has high hygroscopicity. Therefore, when melting, it must be melted under normal drying conditions, such as 160 to 200°C, dry air or nitrogen atmosphere, and normal pressure. Alternatively, even if the zeolite is dried under vacuum, the moisture contained in the zeolite is not completely removed. For this reason,
Under the melting conditions of the polyester, ie, 280-300°C, the water contained in the zeolite is released again, hydrolyzing the polyester and reducing the degree of polymerization of the polyester. Therefore, polyester raw material resins using crystalline synthetic zeolites, which have been widely used in the past, have poor thermal stability in terms of wood quality.

In contrast, in the present invention, amorphous zeolite is subjected to moist heat treatment to reduce the hygroscopic ability of the particles themselves, and the weight loss as measured by thermogravimetric analysis under specific conditions is prepared to be below a predetermined value. is the added particle. Therefore, the obtained polyester composition has various good properties such that even if it is extruded and melted after drying under normal drying conditions, the degree of polymerization of the polyester does not decrease due to the added particles. It has now become possible to use it as a raw material resin for polyester films.

In addition to such excellent thermal stability, the amorphous zeolite particles according to the present invention have extremely excellent dispersibility in polymers, especially when added during the polyester synthesis reaction. Therefore, adverse effects such as generation of coarse particles due to poor dispersion can be prevented.

Moreover, the film obtained from the polyester composition containing the particles is far superior in terms of the relationship between surface roughness and slipperiness, compared to films made from conventional additive particles. Therefore, it can sufficiently meet the required characteristics of a base film for high-density magnetic recording, which will be increasingly demanded in the future, that is, flatness and easy sliding.

Furthermore, the amorphous zeolite according to the present invention has extremely good affinity with polyester. Therefore, during the film manufacturing process, there is less peeling and falling of fine particles from the polyester due to stretching tension, and therefore, various problems caused by falling particles, such as coating spots and dropouts during the coating process, are significantly reduced. . In addition, the obtained film has extremely excellent wear resistance, and when used as a magnetic tape, it can be used as a guide pin or metal bottle in a running system due to the good affinity between amorphous zeolite and polyester. The amount of white powder generated due to friction is significantly reduced.

As described above, in the present invention, by adding amorphous zeolite that has low hygroscopicity, has excellent uniform dispersibility in polyester, and has excellent affinity with polyester,
It has excellent slipperiness and abrasion resistance when made into a film, and has good thermal stability with little decrease in the degree of polymerization during the extrusion film forming process.
A polyester composition having extremely excellent properties for use in films is provided.

[Examples] The present invention will be described in more detail below with reference to Examples and Comparative Examples.

The measurement methods and definitions of various physical properties and characteristics in Examples and Comparative Examples are as follows. Furthermore, in the Examples and Comparative Examples, "part" or "%" means "heavy part" or "weight %", respectively.

■ Thermal heavy stitching analysis (TGA analysis) Using a thermal analyzer DT-20B manufactured by Shimadzu Corporation, the change in weight was measured while raising the temperature from room temperature to 400°C at a rate of 5°C/min. The weight loss at 300° C. and 300° C. was measured, and the rate of change was expressed in %.

(2) Leaving in an 80% Humidity Atmosphere A sealed space was created in a saturated aqueous solution containing a solid phase of (NH4)2SO4 at 20°C, and the sample was left in the space for 24 hours.

■ Average particle diameter of zeolite particles The particle size was measured using a photographic method using an electron microscope.

■ Melting thermal stability evaluation of polyester containing zeolite particles 7 g of polymer was placed in a test tube and heated at 160°C and 1 mmHg.
After vacuum drying for 2 hours at
The degree of decrease in the degree of polymerization was evaluated from the rate of decrease (%) in the intrinsic viscosity [η] of the polymer before and after treatment, which was measured by the method described in (1) below.

■ Intrinsic viscosity [η] 1 g of polymer in phenol/tetrachloroethane = 50
Dissolved in 100ml of mixed solvent of 750 (weight ratio),
Measured at 30°C.

(2) Average protrusion height (Ra), maximum protrusion height (Rmax) (for C units) Measured by the method described in JIS BO601-1976. For measurement, surface roughness measuring machine Model 5 manufactured by Koita Institute was used.
Using E-3F, the stylus diameter was 2 pL, the side load was 30 mg, the cutoff value was 0.08 mm, and the measurement length was 25 mm.
Measurement was performed at 12 points, the maximum value and minimum value were each cut, and the average protrusion height was shown as the average value of the 10 points.

■ Coefficient of kinetic friction (gd) with metal A fixed hard chrome-plated metal roll (diameter 6 mm)
) with a wrapping angle of 135° (θ), a load of 53 g (T2) was applied to one end, and l m /
This is run at a speed of min, and the resistance force at the other end (T
+ (g)) was measured, and the coefficient of friction (gd) during running was determined using the following formula.

■ Measurement of surface roughness using multiple interference method After aluminum is deposited on the surface of the film, interference fringes are produced using a measurement wave of -10,544 using multiple interference method, and the number of n-th order interference fringes is determined by taking a photograph of the interference fringes. was counted and converted to 1 mm'. Note that a surface finish microscope manufactured by Nippon Kogaku ■ was used for the measurement, and the mirror reflectance was 65% and the microscope magnification was 200 times.

■ Evaluation of abrasion resistance The film was run over a length of 500°C in the running system shown in Figure 1, and the amount adhered to the 6mmφ 5US420J2 pin with a surface finish of 0.2 shown in 1 due to wear was visually evaluated. The ranking is shown below. Note that the running speed of the film is 1 Om/min, and the tension is approximately 2
00g, and the angle (θ) of the winding with the pin was 135°C.

0: Almost no adhesion.

Δ: Slight adhesion.

×...The amount of adhesion is large.

[Phase] Number of coarse protrusions Aluminum was deposited on the surface of the film and measured using a three-beam interference microscope. The number of n-th order interference fringes at a measurement wavelength of 0.54 g is calculated and shown per 25 crn'.

σb Film-film friction coefficient e(ps, J
L(1) Measured by improving the method of ASTM-D-1894-63.

Example 1 Synthesis of crystalline zeolite particles> Fine particles of synthetic zeolite, generally referred to as type A, were synthesized according to the method described in Japanese Patent Publication No. 32-6713.

Amorphization and moist heat treatment> 1.5 kg of the synthesized A-type zeolite particles (average particle size 0.5 kg) was dispersed in 20 fL of water, and while stirring at room temperature, 40 fL of 0.5N sulfuric acid was added to about 5 kg. I added it over time.

The pH at the end of the addition of sulfuric acid was 6. After stirring as it was for 2 hours, it was filtered, and then about 60 cm of water was poured over the cake, washed with water, and the water slurry was ground in a ball mill, followed by wet heat treatment at 180°C for 3 days with stirring. .

After the treatment, it was dried in a drier to obtain amorphous zeolite particles.

The obtained particles were confirmed to be amorphous by X-ray diffraction. In addition, 80 parts of the obtained particles were added to 2 parts in a humid atmosphere.
After being left for 4 hours, thermogravimetric analysis was performed to evaluate the hygroscopicity, and the weight loss at 200°C was 0.5%, and the weight loss at 300°C was 1.0%, indicating low hygroscopicity. there were.

Production of polyester composition> The obtained particles were centrifugally classified as a 25% slurry of ethylene glycol, and then filtered using a filter.
A 12 parts ethylene glycol slurry of particles with an average particle size of 0.7 pL was obtained.

Separately, 100 parts of dimethyl terephthalate, 60 parts of ethylene glycol, and 0209 parts of magnesium acetate tetrahydrate were taken, heated to temperature, and methanol was distilled off to carry out a transesterification reaction, which took 4 hours from the start of the reaction. ,
The temperature was raised to 230°C to substantially complete the transesterification reaction. Next, after adding 0.04 part of ethyl acid phosphate, the average particle size was 0.7. 2.5 parts of amorphous zeolite slurry was added, and further 0.04 part of antimony trioxide was added to perform polycondensation for 4 hours until the intrinsic viscosity was 0.
．． 66 polyethylene terephthalate resin was obtained.

The thermal stability of the obtained polyester resin when melted at 290° C. was evaluated by the method described in (2) above, and the evaluation results are shown in No. 3 of Table 1.

In addition, when the type of zeolite and the conditions of the moist heat treatment for amorphization were variously changed (No. 2.6.7), or when the moist heat treatment was not performed (N.

The results of thermogravimetric analysis of the particles of 1, 4.5), the evaluation results of the thermal stability during melting of a polyester resin similarly obtained using these particles, and the results of the thermogravimetric analysis of the particles of No. The evaluation results of thermal stability during melting are also listed in Table 1.

As is clear from Table 1, the polyester containing amorphous zeolite with reduced hygroscopicity has a TAG weight loss rate of 5% or less at 200°C and a TAG weight loss rate of 10% or less at 300°C. The resin has excellent thermal stability when melted.

Next, the polyester resin of this example (No. 3 in Table 1)
After drying at 180°C for 6 hours under a nitrogen atmosphere, an amorphous sheet with a thickness of 220g was created using an extruder, and then stretched 3.7 times in the machine direction and 4 times in the transverse direction, and then stretched at 220°C.
Heat setting was performed for 5 seconds to obtain a biaxially stretched polyethylene terephthalate film with a thickness of 15 pL. Table 2 shows the properties of the obtained film.

Example 2 A zeolite called type X was synthesized according to the method described in Japanese Patent Publication No. 32-6712. Disperse 1 kg of this type
．． 14 JJ of 5N hydrochloric acid was added over about 1 hour. After reacting for another 200 hours, it was filtered, washed with water, and made into an approximately 20% water slurry in an autoclave at 200°C for 48 hours.
A moist heat treatment was performed for a period of time. The obtained particles had a TGA weight loss rate of 0.6% and 0 at 200°C and 300°C, respectively.
．． It was 9%. It was also confirmed by X-ray diffraction that it was amorphous. The particles thus obtained were dispersed in ethylene glycol, and after centrifugal classification as a 25% slurry,
It was filtered to obtain a slurry with a concentration of 16%. The particle size of the particles in the slurry was 0.8 g.

The slurry was added to the oligomer after completion of the Ertel exchange reaction in the same manner as in Example 1, and then a polycondensation reaction was performed to obtain a polyester resin containing 0.3% of amorphous zeolite. A two-wheel stretched polyester film was produced from this resin in the same manner as in Example 1.

Table 2 shows the properties of the obtained film.

The thermal stability of the film, that is, the rate of decrease in intrinsic viscosity, was comparable to that of the film without the addition of particles.

Example 3 A zeolite called Y-type was synthesized according to the method described in Japanese Patent Publication No. 36-1639. 1 kg of this Y-type zeolite was dispersed in a 30-gram tree, and 0.5N sulfuric acid was added to the mixture for 5 hours while stirring at 40°C. After addition is complete, add 4 more
After reacting for a period of time, the mixture was filtered and washed with water, and then pulverized in a ball mill in the form of a water slurry. Next, a wet heat treatment was performed in an autoclave at 170°C for 90 hours.

The result of thermogravimetric analysis of the obtained particles was 0.3 at 200°C.
%, the weight loss was 0.5% at 300°C. 2 of the particles
After making a 7% ethylene glycol slurry, it was centrifugally classified and further filtered to obtain an average particle size of 0.6LL.
An ethylene glycol slurry having a concentration of 10% particles was obtained.

The obtained slurry was added to a polyester reaction system in the same manner as in Example 1 to obtain a polyester resin containing 0.3% amorphous zeolite and having an intrinsic viscosity of 0.65. A biaxially stretched polyester film was produced from this resin in the same manner as in Example 1.

Table 2 shows the properties of the obtained film.

The obtained polyester film has excellent flatness and slipperiness, and has a small number of coarse protrusions, and has excellent properties for use in magnetic tapes.Moreover, it has excellent thermal stability, and is difficult to polymerize during the extrusion film forming process. There was also little decrease in temperature.

Example 4 Amorphous zeolite obtained from Na-A type was heated at 180°C.
After treatment in an autoclave for 9 hours, centrifugal classification and filtration were performed to obtain particles with average particle sizes of O, S, and t. TG of the particle
Weight loss by A measurement is 3.5% at 200℃, 300℃
It was 7%.

An ethylene glycol slurry of the particles was added to the oligomer after the transesterification reaction in the same manner as in Example 1, and then a polycondensation reaction was performed to obtain 0.3% amorphous zeolite.
% of polyester resin was obtained. From this resin,
A biaxially stretched polyester film was produced in the same manner as in Example 1.

Table 2 shows the properties of the obtained film. This film had excellent properties, with a lower rate of decrease in the degree of polymerization during the extrusion film forming process than in a film without particles added.

Comparative Example I Amorphous zeolite particles synthesized from Na-A type zeolite were used in the same manner as in Example 1, except that the particles with an average particle size of 0.7PL were used at 0.4%. The contained polyester resin was synthesized and formed into a film in the same manner to produce a biaxially stretched polyester film with a thickness of 15 pL.

Table 2 shows the properties of the obtained film. This film showed a very large decrease in the degree of polymerization during the extrusion film forming process.

Comparative Example 2 Crystalline zeolite (type 13x) was pulverized with a sand grinder to obtain particles with an average particle size of 0.9 colors.

Example 1 Polyester resin containing 0.4% of the particles
It was synthesized in the same manner as above, and then formed into a film in the same manner to a thickness of 15. A biaxially stretched film was obtained.

Table 2 shows the properties of the obtained film. This film had a large decrease in the degree of polymerization during the extrusion film forming process and was inferior in thermal stability.

From Table 2, it is clear that the polyester film obtained from the polyester composition of the present invention has excellent thermal stability, and extremely excellent surface flatness and slipperiness.

Special Opening, 'fG2-70442 (10) [Effects of the Invention] As detailed below in 1-1, the polyester composition of the present invention contains amorphous zeolite particles with reduced hygroscopicity, The decrease in the degree of polymerization during the extrusion film forming process is extremely small compared to those containing conventional crystalline zeolite or ordinary amorphous zeolite, and it has excellent thermal stability.

Moreover, since the amorphous zeolite particles according to the present invention have excellent affinity and dispersibility for polyester, the film obtained from the polyester composition of the present invention has less formation of coarse protrusions and is slippery. Excellent performance, suitable for magnetic tapes, floppy disks,
It is extremely useful as a base film in a wide range of fields such as capacitors, photolithography, electrical disconnection, thermal transfer, and packaging.

[Brief explanation of drawings]

FIG. 1 is an explanatory diagram of a film running system used for evaluating the abrasion resistance of films in Examples and Comparative Examples. Figure 1

Claims (1)

[Claims] (1) Substantially amorphous in terms of X-ray diffraction, and determined by thermogravimetric analysis after being left in an 80% humidity atmosphere for 24 hours.
Fine particles expressed by the following formula (I) with a weight loss of 5% by weight or less at 0°C, a weight loss of 10% by weight or less at 300°C, and an average particle size of 0.01 to 5μ are 0.001 ~3% by weight
A polyester composition comprising: xMO・Al_2O_3・ySiO_2・zH_2O・
...(I) In the formula, M represents an alkali metal and/or an alkaline earth metal, x represents a number from 0.001 to 4, y represents a number from 1 to 20, and z represents a number from 0.001 to 10, respectively. show.