JPH02132121A - Production of internal granule-containing polyester - Google Patents

Abstract

PURPOSE:To obtain the title polymer excellent in surface characteristics and suitable for fiber, film, etc., by making a polymerization through adding each specified amount of zinc compound, zirconium compound, alkali compound, phosphorus compound, etc., to the polymerization system. CONSTITUTION:A blend of (A) a lower alkyl ester of terephthalic acid and (B) ethylene glycol is incorporated with (C) a zinc compound and/or Mg compound followed by ester interchange reaction and then adding (D) as polycondensation catalyst a compound of either antimony, titanium or germanium to the system. Before the intrinsic viscosity of the reaction product reaches 0.2, (E) 20-2000ppm (based on the final polymer) of zirconium compound, (F) 50-500ppm (based on the final polymer) of an alkali (alkaline earth) metal compound, and (G) such an amount of a phosphorus compound as to satisfy the relationship (Zr, M1 and M2 are numbers of atoms for the components E, F and C, respectively), are added to the system followed by polymerization, thus obtaining the objective polymer.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing polyester containing internal particles, and in particular, a method for producing fibers and films as final products by precipitating fine insoluble particles in a polymer at a high temperature during the polyester production process. It is possible to form fine irregularities with high density on the surface of
1. A method for producing polyester that satisfies various market demands for surface properties such as slipperiness and abrasion resistance, and is free from defects such as knobs and fisheyes and is suitable as a raw material for producing fibers, films, etc. It is something.

Since polyester has excellent mechanical, electrical, and thermal properties, it is widely used as a raw material for various materials such as fibers and films. However, polyalkylene teresotalate 1
Fibers and films obtained from polyester as a component generally have a large coefficient of friction and have poor passability during spinning or film production. There is a strong desire to establish a method for producing polyester that can produce high-quality polyester.

- As a method to improve the slipperiness of polyester fibers or films in the crotch, a method has been adopted in which four insoluble fine particles R are combined with polyester to form fine irregularities on the surface of the fibers or films. Specifically, there are two methods: (1) the so-called external grain method in which inert fine grains such as titanium dioxide, kaolinite, talc, and phosphoric acid are added to polyester during the production of polyester, and (2) during the polyester production reaction. Another method is the so-called internal grain Y method, in which a carboxylic acid component, an oligomer, or a phosphorus compound is reacted with a metal compound to form fine abrasions. -1- When comparing the external particle r method and the internal particle Y method, it is said that the internal particle method is more advantageous for the following reasons.

■The device for finer grain size, classification and dispersion is safe and economically advantageous.

(1) In the external grain method, a dispersant must be used in order to prevent knobs, fins, etc. caused by agglomeration of the added fine particles, but this is not necessary in the inner grain method. Generally, dispersants impede the heat resistance and electrical properties of the product, so it is best not to add them.

■Particles produced by the internal particle method generally have low hardness, so
A product with excellent wear resistance can be obtained.

(2) Particles produced by the internal abrasion method have good compatibility with polyester, so no voids occur even when stretched, and since they have a refractive index close to that of polyester, the product has high transparency.

By the way, as for the internal particle method, fine particles -r are formed using catalyst residues of alkali metals, alkali metals, etc. used as transesterification catalysts, and formation of fine particles κ and particles r
The mainstream method for adjusting the diameter is by adding a phosphorus compound. However, this method has the following problems and cannot be said to satisfy the demands of the market.

■ It is easy to form pores, which often results in products with low transparency. What's more, 11 human grains are one of the causes of product defects such as fiber knobs and film fibers.

■Chiai: [Scale tends to form inside the box, and this sometimes falls off and mixes into the polyester, causing defects in knobs, fins, and locks.

■ In order to keep the precipitation of fine grains7,1 and the grain size constant at all times, it is necessary to strictly control the small-scale conditions.

(2) Generally, under conditions where fine particles are precipitated, the concentration of precipitated particles tends to be low, and it is difficult to precipitate fine particles evenly and at a high concentration.

The inventors of the present invention have taken note of the above-mentioned concerns and have proposed a method for producing polyester in the presence of a polycondensation catalyst of at least 1 FTi selected from the group consisting of antimony compounds, titanium compounds and germanium compounds. Production of polyester by specifying the addition time and addition time of zirconium and phosphorus compounds. We have established a method for producing polyester that is precipitated at a single concentration, has excellent transparency and ease of manufacture, and has fewer product defects such as knobs and fins, and has already applied for a patent.

However, in recent years, due to the diversification of demand in the industry, it has become insufficient to satisfy the requirements of transparency and slipperiness. In addition, there is an increasing demand for glittering properties such as silk-like or pearl-like effects.Furthermore, even in the case of films, for example, in the field of magnetic tape films, the surface .1i. Base films with a variety of surface characteristics are in demand, including applications that require a high degree of lubricity, and applications where smoothness can be highly improved even at the expense of some surface smoothness. Furthermore, even for the same application, the requirements for surface properties vary greatly depending on each user.These surface properties are determined by the particle concentration, particle size, particle size distribution, and particle size distribution of undissolved particles contained in polyester. In order to satisfy the market demands described in 1-1, it is necessary to control the grain f'.7ffl degree, grain gamma diameter, grain r diameter distribution, etc. It is necessary to establish a technology that can be controlled easily.
There is a disaster. For example, the invented method based on the Shinnairou R method, which the present inventors have already applied for, has extremely high transparency and is therefore suitable for the fields of packaging films and optical films. Therefore, it is suitable as a base film for video tapes using a vapor deposition method that requires a high degree of surface smoothness. However, although the slipperiness shows a fair value, a high degree of slipperiness is required. For example, it is not very suitable for manufacturing base films for music tables.

Furthermore, when applied as fibers, it is necessary to use other means such as making the fiber shape irregularly shaped in order to obtain a silky or pearly look.

Firstly, in the conventionally known method of forming fine particles using catalyst residues such as alkali metals and alkaline earth metals, and controlling the particle size of Lanali's Niushengyari by adding a phosphorus compound, the present inventors et al. Since it is not possible to precipitate fine particles at a high concentration as can be obtained using the new internal ablation method previously applied for, it is difficult to produce raw material resin for applications that require a high degree of transparency and surface smoothness. is inappropriate.

]・． As mentioned above, to date, no technology has been established to recontrol over a wide range the particle size, average grain size, grain size distribution, etc. of particles precipitated by the internal ablation method alone. , they are merely responding to market demands in a compromising manner.

The present inventors have developed the concentration, average particle size, and particle size distribution of precipitated grains using the internal ablation method.
Confirm the technology that allows you to control 7 units in a wide range
1. As a result of intensive research, we have completed the present invention.

That is, the present invention provides a combination of a lower alkyl ester of a dicarboxylic acid containing terephthalic acid as a main component and an alkylene glycol in the presence of at least one polycondensation catalyst selected from antimony compounds, titanium compounds, and germanium compounds. In the method of producing polyester from polyester, the transesterification reaction is carried out in the presence of a curved compound and/or a manganese compound. 0
．． The following (
1) The zirconium compound satisfying formula 1 is added, the polycondensation reaction proceeds immediately after the end of the transesterification reaction, and while the intrinsic viscosity of the reactant does not exceed 0.2, the following
A method for producing an internal ablation-containing polyester, which comprises adding an alkali metal compound and/or alkaline earth metal compound in an amount that satisfies the formula and a phosphorus compound in an amount that satisfies the following formula (C3). be.

20≦[Z,. ]≦2 0 0 0 (1) 5
0≦[M1]≦500 ■0.5≦L upper early a
≦3 (3) The most significant feature of the present invention is that insoluble particles are precipitated in the polymer in about 1 unit of polyester production.
The purpose of the present invention is to provide a technology that can control the concentration, average particle diameter, diameter distribution, etc. of the precipitated particles over a wide range. The precipitated particles can be controlled by changing the addition and crushing of the zirconium compound, alkali metal compound and phosphorus compound to be added, the addition ratio, the addition time, the addition order, and the type of the alkali metal compound and phosphorus compound. The concentration of the precipitated particles, the diameter of the precipitated particles,
Changes in particle size distribution etc. are extremely diverse and cannot be described in detail, but they can be summarized as follows.

(1) The concentration of precipitated particles can be controlled by the addition of a zirconium compound and an alkali metal compound and/or an alkali-1 class metal compound [depending largely on i, the addition t
When jy is increased, precipitation also increases.

(21 'tz average particle size changes greatly depending on the addition of phosphorus compounds and zirconium compounds {4. When other conditions are fixed, the average particle size becomes smaller as the amount of addition increases for both phosphorus compounds and zirconium compounds. On the other hand, if the amount of the alkali metal compound and/or alkali class II metal compound added is increased, the average particle size becomes larger.

(3) The grain size distribution varies greatly depending on the addition of the zirconium compound, alkali metal compound and/or alkaline earth metal compound, and phosphorus compound and the timing of addition of each compound. That is, as the ratio of the zirconium raw material r- increases in the addition ratio of the zirconium compound and the alkali metal compound and/or the alkali metal compound, the precipitate grain γ size distribution becomes sharper. Conversely, as the proportion of the alkali metal compound and/or alkali 1° class metal compound added increases, the diameter distribution becomes wider. Also, zirconium compounds and alkali metal compounds and/or alkali IJ. Addition of Jl class metal compounds! When the it ratio is fixed, the particle size distribution changes depending on the addition of the phosphorus compound, and by increasing the addition of the phosphorus compound, the particle size distribution becomes negative.

The following only shows one direction of abrasion diameter control, and in reality, the type of each additive and the addition [1l1
The behavior of ablation precipitation changes extremely complicatedly depending on the addition ratio, addition time, etc.

Another feature of the present invention is that coarse particles are difficult to form and scale is difficult to occur within the Sengofue, resulting in high-quality products with fewer product defects such as fiber knobs and film fish eyes. This means that raw material resin can be produced.

In the polyester of the present invention, more than 80% of the repeating positions are composed of alkylene terephthalate, and other octadlyic components include isophthalic acid, P-β-
Oxyethoxybenzoic acid, 2,6-naphthalene dicarboxylic acid, 4.4'-1 carboxyl diphenyl, 4.4
' -dicarboxybenzophenone, bis(4-carpoxylphenyl)ethane, adipic acid, sebacic acid, 5
- dicarboxylic acid components such as sodium sulfoisophthalic acid or their alkyl ester derivatives.

Further, as the glycol component, ethylene glycol, propylene glycol, butanediol, neobentyl glycol, diethylene glycol, cyclohexanenomethanol, ethylene oxide adduct of bisphenol A, etc. can be arbitrarily selected and used. In addition, the copolymerization components include a small amount of H-, 1. may contain amide bonds, urethane bonds, ether bonds, carbonate bonds, etc.
As long as 80 mol% or more of the resin is polyalkylene terephthalate and has fiber-forming ability and film-forming ability, it can function as a base resin.

Next, antimony compounds, titanium compounds, and germanium compounds serve as polycondensation catalysts for transesterification products of low-handling alkyl esters of dicarboxylic acids and alkylene glycol. compounds can be used. For example, antimony compounds include antimony trioxide, antimony potassium tartrate, antimony glycolate, inorganic acids such as antimony trifluoride, and organic acid salts such as ammonium acetate, and titanium compounds include tetraethyl titanate and tetrabutyl titanate. , partial hydrolysates of titanium alkoxides, titanic oxalate, titanyl ammonium oxalate, potassium titanyl oxalate, titanium oxyacetinoleacetonate, titanium fluoride 9, and germanium compounds such as germanium oxide, germanium acetate, and germanium ethoxylate. Examples include germanium oxide, germanium oxide, and the like. These polycondensation catalysts may be used individually or in a suitable combination of two or more. The amount of these polycondensation catalysts added is not particularly limited, but in the case of titanium compounds, the amount of polycondensation catalyst added is 0.0005 to 0.1 based on the acid component in the raw material.
mol%, more preferably 0.002 to 0.03 mol%,
In the case of antimony compounds and germanium l1 compounds, it is also 0.0 in terms of antimony element r and germanium atom.
1 to 0.1 mol%, more preferably 0.03 to 0.06
The range is mole %. However, if the amount of polycondensation catalyst is too small, the reaction rate will be slow and it will take a long time to obtain the desired molecular weight, which is impractical; if it is too large, the resulting polymer will have poor transparency and heat resistance.

Further, in the present invention, any zirconium compound can be used as long as it is lacking in fine particle forming components and is soluble in the reaction system. Typical examples include zirconium alkoxides such as tetra-n-propiozirconate, tetra-isopropio-biozirconate, tetra-n-butyl zirconate, and tetraloamyl luconate, norconyl acetate, zirconyl formate, zirconyl tartrate, and oxalic acid. Organic acid zirconyl such as zirconyl, zirconyl stearate, zirconyl benzoate etc.ju 1
Zirconyl chloride Q, zirconyl chloride, 12-zirconyl,
? Examples include inorganic acid nonoleconyl salts such as zirconyl ammonium acid. Addition of these zirconium compounds {i
is 2 in terms of zirconium source Y for the produced polyester.
It must be set in the range of 0 to 2000 ppm; if it is less than 20 ppm, the f-J diameter control effect disappears, and if the addition of the alkali metal compound 1■X is small, the formation of fine particles {i is small, It is not possible to improve the slipperiness of the final product by 70%.

・If it exceeds 20,000 ppm, the slipperiness will reach a saturated state, and rather large grains will be formed, resulting in lower transparency and worsening of the polymer color, which is not preferable.

Particularly preferred addition amount is 50 to 800 ppm.

Although the zirconium compound may be added in either solid or liquid form, it is most preferably added as an alkylene glycol solution in order to uniformly disperse the produced particles. If it is added in solid form, it is preferably sealed in a polyester container and added to the reaction system. The timing of addition of the zirconium compound should be set between the start of the transesterification reaction and the time when the integrated reaction progresses and the intrinsic viscosity of the reactant reaches 0.2. is too high, resulting in uneven mixing of the generated fine particles,
A homogeneous product cannot be obtained. Incidentally, the initial ton condensation is almost completed when the intrinsic viscosity of the reactant reaches about 0.2, but at this point the fraction r·M of the reaction product is extremely small and the viscosity of the reaction liquid is low, so this ++. The zirconium compound can be uniformly dispersed up to the II stage. The preferred timing of addition of the zirconium compound depends on the surface properties of the final product to be obtained. for example,
If you want to make the particle size distribution of the precipitated particles r sharp, you can do it at the start of the transesterification reaction or before that, or if you want to make it broader, or if you want to create a pattern for combining particles with different diameters, you can do it after the transesterification reaction has progressed to some extent. It is preferable to add Furthermore, any alkali metal compound and/or alkali 1-class metal compound can be used as long as it is FiJ-deficient as a grain r-forming component and is soluble in the reaction system. For example, carboxylates, carbonates, hydrides and alkoxides of alkali metals or alkali metals, specifically lithium acetate, sodium acetate, potassium acetate, rubidium acetate, cesium acetate, beryllium acetate, magnesium acetate, calcium acetate, Strontium acetate, barium acetate, lithium formate, sodium formate, potassium formate, magnesium formate, calcium formate, lithium benzoate, sodium benzoate, potassium benzoate, magnesium benzoate, calcium benzoate,
Lithium carbonate, sodium carbonate, potassium carbonate, lithium hydride, sodium hydride, potassium hydride, magnesium hydride, calcium hydride, lithium methoxide, natriuno, methoxide, sodium τ.
Examples include potassium methoxide, potassium ethoxide, magnesium methoxide, magnesium 11 ethoxide, calcium methoxide, carunium ethoxide, and the like. Among these compounds, lithium compounds, sodium compounds, magnenium compounds, and calcium compounds are particularly preferred since they can precipitate a large amount of metal by adding only a small amount. The amount of these alkali metal compounds and/or alkaline earth metal compounds added is 50 to 5 in terms of alkali metal and/or alkaline earth metal atoms to the polyester produced.
Must be set in the range of 0 0 ppm, 50
If the amount is less than pplI, the particle size control effect disappears, and if the amount of added zirconium compound I4 is small, the amount of particles produced is small, and the slipperiness of the final product cannot be increased by 1 minute. On the other hand, if it exceeds 500 ppm, the particle size control effect and the slippery property effect reach a saturated state, and rather, large particles are formed, which reduces transparency and worsens the color of the polymer, which is not preferable. .

A particularly preferable addition h1 varies depending on the type of compound used and the addition ratio with other additives, but is generally 100 to
It is 200 ppm. Alkali-inclusive compounds and/or alkali [. The similar metal compound may be added in either solid or liquid form (6);
For dispersion in ・, it is most preferable to add it as an alkylene glycol solution. 7. In solid form. When adding to the reaction system, it is preferable to enclose it in a polyester container and add it to the reaction system. The timing of addition of the alkali metal compound and/or alkali class II metal compound should be set immediately after the end of the transesterification reaction and while the polycondensation reaction has progressed and the intrinsic viscosity of the reactant does not exceed 0.2. After this point, the viscosity of the reaction solution is too high and the particles produced are not mixed uniformly.
and it becomes impossible to obtain a homogeneous product. Incidentally, the initial tonne condensation is almost completed when the intrinsic viscosity of the reactants reaches approximately 0.2, but the amount of reaction products at this point -J'
Since ijl is extremely small and the viscosity of the reaction solution is low, the alkali metal compound and/or alkaline earth metal compound can be uniformly dispersed up to this stage.

One type of alkali metal compound and/or alkali heptadate compound may be added, or two or more types may be added. {Jl
may be used. In particular, it is preferable to use two or more types in combination because the range of particle size control can be widened.

Phosphorus compounds have the effect of controlling the concentration and size of grains precipitated by zirconium compounds, alkali metal compounds and/or alkali metal compounds. It is the most characteristic component of the present invention together with/or the alkali hepta metal compound.

Examples of such phosphorus compounds include phosphoric acid, sulfonic acid, and derivatives thereof, and more specifically,
Phosphoric acid, trimethyl phosphate, triethyl phosphate, tributyl phosphate, triphenyl phosphate, monomethyl phosphate, dimethyl phosphate, monoethyl phosphate, diethyl phosphate, monobutyl phosphate , phosphoric acid dibutyl ester, methylphosphonic acid, methylphosphonic acid dimethyl ester, ethylphosphonic acid dimethyl ester,
Examples include phenylphosphonic acid dimethyl ester, penzylphosphonic acid diethyl ester, phenylphosphonic acid noethyl ester, phenylphosphonic acid nphenyl ester, etc., and these may be used alone or in combination of two or more. Good too.

Particularly, 2 or more types of A-L are preferred from the viewpoint of widening the control range of particle size.

These phosphorus compounds are used to control the concentration and particle size of insoluble particles formed by zirconium compounds, alkali metal compounds, and/or alkali metal compounds. It should be determined in balance with the addition of {4. It has been found that the effect of adding a phosphorus compound can be effectively exhibited by setting the addition rate such that the original r ratio falls within the range of 0.5 to 3, as confirmed by experiment. However, if the amount of phosphorus compound is too small, the insoluble Rr formed in the polymerer cannot be refined to 1 min, resulting in a decrease in the transparency of the final product and the formation of knobs and fish eyes. It becomes easier. Also, it is not preferred because the stability of the polymer becomes low. If one or the other is in excess, the polymerization rate will decrease,
Industrially disadvantageous. Moreover, it is not preferable because it lowers the softening point and stability of the polymer.

The timing of adding the phosphorus compound is the same as in the case of alkali metal compounds and/or alkali-L metal compounds, in order to reduce the formation of ether bonds, from immediately after the end of the transesterification reaction until the intrinsic viscosity of the reactant reaches 0.2. set between. Further, for the same reason, it is preferable to add it after adding the alkali metal compound and/or the alkali L group metal compound.

The present invention employs a transesterification reaction, and uses an Ilu lead compound and/or a manganese compound as a transesterification catalyst. Specific compounds for each include acetic acid + 111 lead, zinc oxalate, zinc benzoate, and chloride. Zinc, carbonate III! Examples include lead, manganese acetate, manganese oxalate, manganese benzocyanate, and manganese chloride.

In addition, in the method of the present invention, in order to suppress the formation of ether bonds, transesterification reaction +1. It is also effective to add amines, ammonium compounds, salts, etc. to 'J as a third component, and all of these changes are within the scope of the technology of the present invention. Furthermore, the method of the present invention can obtain similar effects when applied to either the batch ili method or the continuous market method.

The present invention is constructed as shown in 1- below, and the point is that the transesterification reaction is carried out in the presence of a zinc compound and/or a manganese compound, and one or more of an antimony compound, a titanium compound, and a germanium compound are used as a polycondensation catalyst. -, as well as specifying the time of addition of the metal compound and phosphorus compound, the addition time, and the addition: i1 ratio, This is a method that can control the concentration of precipitated grains, average grain size, grain size distribution, etc. over a wide range. Furthermore, by employing the method of the present invention, it is possible to impart controlled irregularities to the surface of the final product fiber or film, and transparent 4iI
L, Raw materials for manufacturing fibers, films, etc. that have been carefully recognized for various surface properties such as surface brightness, slipperiness, surface/V-slipness, and abrasion resistance, and are free from defects such as knobs and fins. A suitable polyester can be obtained as follows.

Next, we will discuss some examples and comparative examples of wooden inventions.

All parts in the examples are as follows unless otherwise specified.
Taste the ij part. The esterification reaction rate (esterification rate) was determined from the amount of carboxylic acid remaining in the reaction product and the saponification value of the reaction product. The intrinsic viscosity [η] is Dissolve the polymer in a mixed solvent of phenol (6-fold fit AIS) and tetrachloroethane (4-fold {▲1 part),
Measurements were taken at 30°C. The amount of ethylene glycol in the polymer is determined by decomposing the polymer with methanol and measuring it by gas chromatography, f- to determine the mole% of ethylene glycol.
It was measured as

The precipitated grain size and grain r concentration in the polymer are shown in the examples.
The test was carried out by observing a film formed by the method described above using a reflective dark field microscope.

The maximum surface thickness (RT) of the film, the center line average m (R)
A) and surface roughness density are Surfco 1, 300 A
．． Using a mold surface tester, 31 diameter 1μ, depth 1f 0.07g
, measurement reference length 0.8 mm, Kanotooff O. 4111 were determined under the OS-related conditions, and Table IJ<L was obtained using the average value of 10 points.

Film haze is a direct reading haze meter (manufactured by Toyo Seiki Co., Ltd.)
It was measured with

The coefficient of dynamic friction of the film is ASTM-1)-1894-8
According to 3T, 23°C 165%RH, tensile speed 200m
The measurement was performed under the condition of /min.

Example 1 1000 parts of dimethyl terephthalate, 800 parts of ethylene glycol, and 0.14 parts of zinc acetate (48 ppm added in terms of zinc atoms to the produced polyester) were charged into a combined reactor, and the mixture was heated at 195°C for about 4 hours under a nitrogen atmosphere. Transesterification was carried out by heating.

As the transesterification reaction progresses, the reaction temperature changes to -t-5'
+' and finally reached 225°C. At the same temperature, 31.67 volumes of an ethylene glycol solution of antimony trioxide with a concentration of 12 g/Q was added to this transesterification product! -1 part and 2 m3 of 0.1 mole % zirconyl acetate in ethylene glycol 2. 5. Add 5 vol. rjt part (300 ppm added in terms of ruconium based on the polyester produced), heat and stir at the same temperature and normal pressure for 8 minutes, then add 1.
00g/II! Add 8.00 volumes and 11 parts of an ethylene glycol solution of lithium acetate dihydrate at a concentration of
Heat and stir for 7 minutes at the same temperature and normal pressure, and then add 100g/C
10.70 parts by volume of an ethylene glycol solution of trimethyl phosphate with a concentration of 239 ppm added in terms of phosphorus content based on the polyester produced, Zr+%L.
+Zn/P=1.0 (atomic ratio)] and at the same temperature.
After heating and stirring for 10 minutes at regular LF, 2 minutes after 40 minutes.
While heating to 75°C, the 11-force of the reaction system was gradually reduced to 0.05+amHg, and polycondensation was carried out at the same temperature and pressure for about 80 minutes. [η] of the obtained polyethylene terephthalate was 0.828, and diethylene glycol was 2.0%.

The obtained polymer was melt extruded at 290°C and then heated at 90°C.
The film was stretched 3.5 times in the longitudinal direction and 3.5 times in the transverse direction at 130° C., and then heat treated at 220° C. to obtain a film 1 with a thickness of 5 μm. Table 2 shows the physical properties of the obtained film.

Next, using the polymer obtained by the method described in 1-1, heat the polymer at 285°C for 32
When high-speed spinning was carried out at a discharge rate of 6000 m/min, the yarn could be taken off smoothly without any yarn breakage. The obtained thread had an extremely elegant pearl-like luster.

Comparative example 1! [η
] is as low as 0.458, and the film formation and strand formation are poor.
It was iJ Noh.

Comparative Example 2 A condensation reaction was carried out under the same conditions as in Example 1 except that zirconyl acetate was not added. The obtained polymer was made into a 15μ thick film in the same manner as in Example 1. The physical properties of this fill are shown in Table 2. Furthermore, when this polymer was spun at high speed in the same manner as in Example 2, thread breakage occurred at a rate of about 1.11 per 30 minutes, resulting in poor spinning operability. In the same method as in Example 1, the type of transesterification catalyst, additive 1, 11, alkali metal compound, alkali ↑. Types and additions of similar metal compounds and phosphorus compounds 11t
1 By changing the type of zirconium compound, the amount of addition, and the time of addition, condensation was carried out, and the resulting polymer was formed into a film under the same conditions as in Example 1 to obtain a film with a thickness of 15 μm. The polymerization conditions are shown in Table 1, and the physical properties of the obtained film are shown in Table 2.

Tables 1 and 2 show that the particle size, particle size distribution, concentration, etc. of the precipitated particles r can be arbitrarily controlled over a wide range by changing the type of each additive, the amount of addition, and the timing of addition. By controlling the diameter of the precipitated particles r-, the surface properties of the film can be varied over a wide range.

Claims (1)

[Claims] (1) Producing a polyester from a lower alkyl ester of dicarboxylic acid containing terephthalic acid as a main component and alkylene glycol in the presence of at least one polycondensation catalyst selected from antimony compounds, titanium compounds, and germanium compounds. In the method, the transesterification reaction is carried out in the presence of a zinc compound and/or a manganese compound, and (a) the polycondensation reaction proceeds from the start of the transesterification reaction, and the product is produced while the intrinsic viscosity of the reactant does not exceed 0.2. A zirconium compound is added to the polyester in an amount that satisfies the following formula (1), and (b) the polycondensation reaction proceeds immediately after the end of the transesterification reaction, and the intrinsic viscosity of the reaction product becomes 0.
．． Internal particles characterized by adding an alkali metal compound and/or alkaline earth metal compound in an amount that satisfies the following formula (2) and an amount of a phosphorus compound that satisfies the following formula (3) within a period not exceeding 2. Method for producing polyester containing polyester. 20≦[Zr]≦2000(1) 50≦[M_1]≦500(2) 0.5≦(Zr+M_1+M_2)/P≦3(3) [In the formula, [Zr] is the addition in terms of zirconium atom to the polyester produced amount (ppm), [M_1] is the amount (ppm) of the alkali metal compound and/or alkaline earth metal compound added in terms of atoms to the produced polyester, (Zr+M_1+M_2)/P is the atomic ratio, and M_1 is the amount of the alkali metal compound and/or alkaline earth metal compound added in terms of atoms. M_2 is the number of moles of the alkaline earth metal compound in terms of metal relative to the produced polyester, and M_2 is the number of moles of the zinc compound and/or manganese compound used as a transesterification reaction catalyst in terms of metal relative to the produced polyester. However, if M_1 is an alkali metal compound, the value is the number of compounds multiplied by 1/2. ]