JPS5857430A - Production of polyester containing internal particle - Google Patents

Abstract

PURPOSE:To deposit finely divided insoluble particles within polymer at high concentrations and thereby to form fine irregularities on the surface of fiber or film, by adding zirconium, alkaline earth metal or phosphorus compounds in a specified manner in the course of the production of a polyester. CONSTITUTION:A polyester is produced from a dicarboxylic acid consisting essentially of terephthalic acid and an alkylene glycol in the presence of a polycondensation catalyst selected from the group consisting of antimony compounds, titanium compounds and germanium compounds. During a period from the start of the reaction to the time when the polycondensation is allowed to proceed to such an extent that the intrinsic viscosity does not exceed 0.3, a zirconium compound, an alkaline earth metal compound and a phosphorus compound are added in amounts satisfying the relationships, wherein[Zr]is an amount (ppm) in terms of Zr atoms based on formed polyester,[M]is an amount (ppm) in terms of alkaline earth metal based on formed polyester, and[Zr+M]/P represents an atomic ratio.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing polyester containing internal particles, and more specifically, the present invention relates to a method for producing polyester containing internal particles. It is possible to form fine irregularities on the surface with high density, and satisfies various market demands for surface properties such as transparency, surface brightness, slipperiness, surface smoothness, and abrasion resistance. The present invention relates to a method for producing polyester that is free from defects such as fluorocarbon fibers and polyesters and is suitable as a raw material for producing fibers, films, and the like.

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, III and films obtained from polyesters containing polyalkylene terephthalate as a main component generally have a large friction coefficient and have poor process passability during spinning or film forming. There is a strong desire to establish a method for producing polyester that can produce Ill, II, and films.

As a method for improving the slipperiness of polyester fibers or films, a method has been adopted in which insoluble fine particles are mixed with polyester to form fine irregularities on the surface of the fibers or films. ■When manufacturing polyester, titanium dioxide, kaolinite, talc, V
The so-called external particle method, in which inert fine particles are added to polyester such as polyester, and the so-called external particle method, in which either a carboxylic acid component, an oligomer, or a phosphorus compound is reacted with a metal compound to form fine particles. There is an internal particle method. When the external particle method and the internal particle method are compared, the internal particle method is said to be more advantageous for the following reasons.

(2) Particle refinement 1. No equipment for classification and dispersion is required, which is economically advantageous.

■In the external particle method, it is necessary to use a dispersant in order to prevent knobs and fish eyes caused by agglomeration of the added fine particles, but in the internal particle method, this is not necessary. In general, it is a good idea not to add a dispersant because it impedes the heat resistance and electrical properties of the product.■ Particles produced by the internal particle method generally have low hardness, so a product with excellent wear resistance can be obtained. .

■The particles produced by the internal particle method are compatible with polyester, so no voids occur even when stretched.

Also, since it has a refractive index close to that of polyester, the product has high transparency.

By the way, the internal particle method is a method in which fine particles are formed using catalyst residues of alkali metals, alkaline earth metals, etc. used as transesterification catalysts, and the amount and diameter of the fine particles formed are adjusted by adding a phosphorus compound. occupies the mainstream. However, this method has the following problems and cannot be said to satisfy market demands.

■ Coarse particles are likely to be formed, which often results in products with low transparency. Moreover, coarse particles cause product defects such as knobs in fibers and fish eyes in films.

■Scale easily forms inside the polymerization can, which falls off during waiting and mixes into the polyester, causing defects such as knobs and fish eyes.

■Polymerization conditions must be strictly controlled in order to keep the amount of fine particles precipitated and particle size constant at all times.

(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 uniformly and at a high concentration.

The present inventors have focused on the above-mentioned circumstances, and have determined that when producing polyester in the presence of at least one polycondensation catalyst selected from the group consisting of antimony compounds, titanium compounds, and germanium compounds, zirconium compounds By specifying the amount and timing of addition of phosphorus compounds, we can precipitate fine particles at a high concentration in the polymer during the polyester manufacturing process, resulting in products with excellent transparency and slipperiness, as well as products such as knobs and fish eyes. We have established a method for producing polyester with fewer defects and have already applied for a patent.

However, in recent years, due to the diversification of market demands, it has become insufficient to simply satisfy transparency and smoothness. For example, in the case of fibers, there is an increasing demand for not only excellent transparency but also glittering calyxes such as silk-like or burl-like. Well, even in the case of film.

For example, just in the field of magnetic tape films,
There are demands for base films with a variety of surface characteristics, such as applications that require a high level of surface smoothness and applications that require a high degree of slipperiness even if the surface smoothness is sacrificed to some extent. Furthermore, - even for the same application, different users have very different requirements for surface properties. These surface properties are largely controlled by the particle concentration of undissolved particles contained in polyester, particle size distribution, particle type, etc., so in order to satisfy the above market demands, polyester It is necessary to establish a technology that can arbitrarily control the particle concentration/particle size/particle size distribution of the particles precipitated in the manufacturing process.

For example, the method of the invention based on the new internal particle determination, which the present inventors have already applied for, has extremely high transparency and is therefore suitable for the fields of packaging films and films for the optical industry. It is suitable as a base film for video tapes using a vapor deposition method that requires a high degree of surface smoothness. but.

For example, it cannot be said that #i is universally used in the production of base films for music tapes, etc. (Although the slip property shows a reasonably good value, a high slip property is required).

Furthermore, when applied as a fiber, it is necessary to use other means such as making the fiber shape irregularly shaped in order to obtain a silk-like or burl-like appearance.

On the other hand, fine particles are formed using conventionally known catalyst residues such as alkali metals and alkaline earth metals.

The method of controlling the amount of particles produced and the particle size by adding a phosphorus compound cannot precipitate fine particles at a high concentration as seen in the new internal particle method previously filed by the present inventors. It is unsuitable for producing raw material resin for applications that require transparency and surface smoothness.

As stated above, so far, only the internal particle method has been used to determine the particle concentration and average particle diameter of particles precipitated.

Since no technology has been established to control the particle size distribution over a wide range, the only way to do so is to use compromise methods to meet market demands.

The inventors of the present invention have focused on the above-mentioned circumstances, and have conducted intensive research to establish a technology that can control the concentration of precipitated particles, average particle size 2 particle size distribution, etc. over a wide range using the internal particle method. He has completed his invention.

That is, the present invention provides at least one compound selected from antimony compounds, titanium compounds, and germanium compounds.
In the production of polyester from a dicarboxylic acid mainly composed of terephthalic acid and alkylene glycol in the presence of a polycondensation catalyst of various types.

A zirconium compound, an alkaline earth metal compound, and a phosphorus compound are added to the produced polyester in an amount that satisfies the following formula between the start of the reaction and the time when the intrinsic viscosity of the reactant reaches 0.2 due to the progress of the polycondensation reaction. This is a method for producing polyester containing internal particles, which is characterized by the following.

20 ppm≦[Zr]≦2000 ppm50 pp
(Invention) ≦ 500 ppm The most significant feature of the present invention is the concentration and average particle diameter of the precipitated particles in regard to the precipitation of insoluble particles in the polymer during the polyester manufacturing process.

It is an object of the present invention to provide a technology that can control particle size distribution over a wide range. These precipitated particles are controlled by the amounts of zirconium compounds, alkaline earth metal compounds, and phosphorus compounds added.

This can be done by changing the addition amount ratio, addition timing, addition order, and type of alkaline earth metal compound or phosphorus compound. Changes in the concentration of the precipitated particles, the average particle size per particle size distribution, etc. are extremely diverse and cannot be easily described, but they can be roughly summarized as follows.

(1) Control of the concentration of precipitated particles largely depends on the amounts of the zirconium compound and alkaline earth metal compound added, and as the amount added increases, the amount of precipitated particles also increases.

(2) The average particle diameter varies greatly depending on the amounts of the phosphorus compound and zirconium compound added. When other conditions are fixed, the average particle size becomes smaller as the amount of addition of either the phosphorus compound or the zirconium compound increases, and conversely, the average particle size increases as the amount of the alkaline earth metal compound is increased.

(3) The particle size distribution varies greatly depending on the ratio of the amounts of the zirconium compound, the alkaline earth metal compound, and the phosphorus compound added and the timing of addition of each compound.

That is, as the ratio of zirconium atoms increases in the ratio of addition of the zirconium compound and the alkaline earth metal compound, the precipitated particle size distribution becomes sharper.

Conversely, as the proportion of alkaline earth metal compound added increases, the particle size distribution becomes wider. Furthermore, when the ratio of the amounts of the zirconium compound and the alkaline earth metal compound added is fixed, the particle size distribution changes depending on the amount of the phosphorus compound added, and the particle size distribution becomes sharper as the amount of the phosphorus compound added is increased. Furthermore, when the amounts of zirconium compounds, alkaline earth metal compounds, and phosphorus compounds added are fixed, the particle size distribution changes depending on the time of addition of each additive, and the zirconium compounds and alkaline earth metal compounds are added at the start of the esterification reaction. As a result, the particle size distribution becomes sharp, and when the reverse pressure zirconium compound or the alkaline earth metal compound is added after the esterification reaction has progressed to a certain extent, the particle size distribution becomes broad.

The above is just one way to control particle size! l! In some cases, the rate of particle precipitation changes in an extremely complex manner depending on the type of each additive, amount added, amount ratio added, time of addition, etc.

Another feature of the present invention is that coarse particles are difficult to form;
In addition, since scale is less likely to occur in the polymerization can, it is possible to produce a raw material resin that yields high-quality products with fewer product defects such as fiber knobs and film fittings.

In the present invention, the precipitated particles can be controlled arbitrarily, and coarse particles and scale within the polymerization reactor are prevented from occurring.
Although the reason for this difference is unknown, it is presumed that a complex is formed between the zirconium compound, the alkaline earth metal compound, and the phosphorus compound.

. In the polyester of the present invention, more than 80 moles or more of its repeating units are alkylene terephthalate color, and other copolymer components include isophthalate li1. P-β
-OxV ethoxyV benzoic acid, 2,6-naphthalene dicarboxylic acid, 4,4'-dicarboxyl diphenyl, 4
．． 4'-dicarboxybenzophenone, bis(4-carboxylphenyl)ethane.

Examples include dicarboxylic acid components such as adipic acid, separic acid, 5-sodium sulfoisophthalic acid, and alkyl ester derivatives thereof. As the glycol component, ethylene glycol, propylene glycol, butanediol, neopentyl glycol, diethylene glycol, cyclohexane dimetatool, ethylene oxide adducts to bisphenol, and the like can be arbitrarily selected and used. In addition, it may contain a small amount of amide bond, urethane bond, ether bond, carbonate bond, etc. as a copolymer component, and in short, it must be polyalkylene terephthalate of 80 mol or more and have fiber-forming ability and film-forming ability. All base 1tQ if you like.
1.

The timone compound, titanium compound, and germanium compound serve as a polycondensation catalyst between the acid component and the alkylene glycol, and any compound can be used as long as it is soluble in one reaction system. For example, as antimony compounds, inorganic acid salts such as Vi3 oxidized antimony, antimony potassium tartrate, antimony glycolate, antimony trifluoride, organic acid salts such as antimony acetate, etc.
Examples of titanium compounds include tetraethyltitanate, tetrabutyltitanate, partial hydrolysates of titanium alkoxides, titanium oxalate, titanyl ammonium oxalate, potassium titanyl oxalate, titanium oxyacetylacetonate, titanium fluoride, etc.Germanium compounds include Examples include germanium oxide, germanium acetate, germanium ethoxide, germanium butoxide, and the like.

Each of these polycondensation catalysts may be used alone, or two or more types may be used in an appropriate combination. The amount of these polycondensation catalysts added is not particularly limited, but in the case of titanium compounds, the most common is 0.0005 to 0.1 mol %, more preferably 0.002 mol % in terms of titanium atoms based on the acid component in the raw material. In the case of antimony compounds and germanium compounds, the amount is 0.01 to 0.1 mol, more preferably 0.03 to 0.06 mol, in terms of antimony and germanium atoms. 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.
On the other hand, if it is too large, the transparency and heat resistance of the resulting polymer will decrease.

Further, the zirconium compound is essential for forming fine particles, and any zirconium compound can be used as long as it is soluble in the % anti-F) system. As a typical example.

Tetro n-propio zirconate, Tetro isopropio ν ruconate, Tetro n-butyl zirconate,
Zirconium alkoxides such as tetra-n-amyl zirconate, zirconyl acetate.

Zirconyl formate, zirconyl tartrate, zirconyl oxalate,
Organic zirconyl salts such as zirconyl stearate and zirconyl benzoate, zirconyl chloride, zirconyl bromide,
Examples include inorganic acid zirconyl salts such as zirconyl carbonate and zirconyl ammonium carbonate. What is the amount of these zirconium compounds added?

20~ in terms of zirconium atoms for the produced polyester
Must be set within the range of 2000ppm.

If the amount is less than 20 ppm, the particle size control effect disappears, and if the amount of the alkali metal compound added is small, the amount of fine particles produced is small and the slipperiness of the final product cannot be sufficiently improved.On the other hand, if it exceeds zooopppm, the slipperiness will be reduced. This is not preferable because it reaches a saturated state, and rather coarse particles are formed, which reduces transparency and worsens the polymer color. A particularly preferable 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 esterification reaction and the time when the single polycondensation reaction proceeds and the intrinsic viscosity of the reaction product reaches 0.2. Because the mixture is too small, the fine particles produced become unevenly mixed, making it impossible to obtain a homogeneous product. By the way, the intrinsic viscosity of the reactant is about 0.2
The initial polycondensation is almost complete at the time of reaching , but since the molecular weight of the reaction product at this point is extremely small and the viscosity of the reaction solution is low, the zirconium compound can be uniformly dispersed up to this point.

The preferred timing of addition of the zirconium compound varies depending on the surface properties of the final product to be obtained.

For example, when you want to sharpen the particle size distribution of precipitated particles, Kt
'i Before esterification, it is preferable to add after esterification has progressed to some extent in order to create a pattern that is broad or uses a combination of particles with different particle sizes. Further, alkaline earth metal compounds are also essential as particle forming components, and any compound can be used as long as it is soluble in the reaction system. For example, carboxylates, carbonates, hydrides and alkoxides of alkaline earth metals, such as magnesium acetate, calcium acetate, beryllium acetate, strontium acetate, barium acetate, and magnesium formate.

Examples include calcium formate, magnesium benzoate, calcium benzoate, magnesium hydride, calcium hydride, magnesium methoxide, calcium methoxide, magnesium ethoxide, and calcium ethoxide. Among these compounds, calcium-Vium compounds and magne-Vium compounds are particularly preferable because they can precipitate a large amount of particles with the addition of a small amount. The amount of these alkaline earth metal compounds added must be set within the range of 50 to 500 ppm in terms of alkaline earth metal atoms, and 50 ppmJ[
If the grain size control effect disappears with a drop and the amount of zirconium compound added is small, the amount of particles produced is small and the slipperiness of the final product cannot be sufficiently improved.

On the other hand, if it exceeds 500 ppm, the particle size control effect and the slipperiness improvement effect have already reached the saturated IIK level, and rather, coarse particles are formed, which lowers the transparency and worsens the polymer color, which is not preferable. Although the alkali metal 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 alkali metal compound should be set between the start of the esterification reaction and the time when the polycondensation reaction progresses and the intrinsic viscosity of the reaction product reaches 0.2 K. Because the viscosity is too high, the particles produced are not mixed uniformly, making it impossible to obtain a homogeneous product. By the way, the initial polycondensation is almost complete when the intrinsic viscosity of the reactant reaches approximately 0.2, but since the molecular weight of the reaction product at this point is extremely small and the viscosity of the reaction liquid is low, up to this point Alkali metal compounds can be uniformly dispersed. The preferred timing of addition of the alkali metal compound varies depending on the surface properties of the final product to be obtained. For example, when it is desired to sharpen the particle distribution of the precipitated particles, it is preferable to add it before esterification, and on the other hand, when broad Kl or ft is desired, it is preferable to add it after esterification has progressed to some extent.

Addition #i of the alkali metal compound may be used alone or in combination of two or more types, and in particular, the combination of two or more types is preferable because the range of particle size control can be widened.

Phosphorus compounds have the unique effect of controlling the concentration and size of particles precipitated by zirconium compounds and alkali metal compounds, and are the most characteristic components of the present invention, along with the zirconium compounds and alkali metal compounds.

Examples of such phosphorus compounds include phosphoric acid, phosphonic acid, and derivatives thereof, and more specifically F
i, phosphoric acid, trimethyl phosphate, triethyl phosphate, tributyl phosphate, triphenyl phosphate, monomethyl phosphate, dimethyl phosphate, monoethyl phosphate, diethyl phosphate, motu phosphate Examples include butyl ester, phosphoric acid dipyl ester, methylphosphonic acid, methylphosphonic acid dimethyl ester, ethylphosphonic acid dimethyl ester, phenylphosphonic acid dimethyl ester, benzylphosphonic acid diethyl ester, phenylphosphonic acid diethyl ester, phenylphosphonic acid diphenyl ester, etc. These may be used alone or in combination of two or more. In particular, it is preferable to use two or more types in combination in order to widen the control range of one particle size.

As mentioned above, these phosphorus compounds control the quality and particle size of insoluble particles formed by zirconium compounds and alkaline earth metal compounds, so the amount of phosphorus added depends on the amount of zirconium added. 5j! It has been confirmed by experiment that Zr
It was aimed that the effect of adding the phosphorus compound can be effectively exhibited by setting the amount of addition in which the atomic ratio of +M/P falls within the range of 0.5 to 3. However, if the amount of the phosphorus compound is too small, the insoluble particles formed in the polymer cannot be made sufficiently fine, leading to a decrease in the permeability of the final product and a tendency to generate knobs, bulges, etc. Moreover, it is not preferable because the stability of the polymer decreases. On the other hand, excessive pricking reduces the polymerization rate and is disadvantageous industrially. Moreover, it is not preferable because it lowers the softening point and stability of the polymer.

The phosphorus compound can be added at any time from the start of the reaction until the intrinsic viscosity of the reactant reaches 0.2, as in the case of zirconium compounds and alkali metal compounds.
It is preferably added after the esterification reaction is completed in order to reduce the formation of ether bonds. Further, for the same reason, it is preferable to add it after adding the zirconium compound or the alkali metal compound.

In addition, in the method of the present invention, it is also effective to add basic compounds such as amines, ammonium compounds, and alkali metal compounds as a third component during the esterification reaction in order to suppress the formation of ether bonds. All changes to this degree are within the scope of the present technology. Furthermore, the method of the present invention can obtain similar effects when applied to either a patch polymerization method or a continuous polymerization method.

The present invention is constructed as described above, and the key point is to selectively use one or more of antimony compounds, titanium compounds, and germanium compounds as polycondensation catalysts, and to use zircomorum compounds and alkaline earth metals as insoluble particle products. By specifying the addition timing, addition amount, and addition amount ratio of the compound and Lillet compound, it is possible to control the concentration of precipitated particles, the average particle size distribution, etc. over a wide range. In addition, by adopting the method of the present invention, controlled irregularities can be imparted to the surface of the final product fiber or film, resulting in various properties such as transparency, surface brightness, slipperiness, surface smoothness, and abrasion resistance. It is possible to obtain an I-lyester that satisfies the requirements for surface properties and is free from defects such as knobs and fish eyes and is suitable as a raw material for producing fibers, films, and the like.

Next, Examples and Comparative Examples of the present invention will be shown.

All parts in the examples mean parts by weight unless otherwise specified. The esterification reaction rate (esterification rate) was determined from the amount of carboxyl V groups remaining in the reaction product and the saponification value of the reaction product. Intrinsic viscosity [η] is the polymer of phenol (6 parts by weight) and detofchloroethane (4 parts by weight).
It was dissolved in a mixed solvent of and measured at 30°C. The amount of diethylene glycol in the polymer can be determined by decomposing the polymer with methanol.

It was determined as moles relative to ethylene glycol by gas chromatography.

The precipitated particle size and particle concentration in the polymer were determined by observing a film formed by the method shown in the example using a reflective dark field microscope.

Maximum surface roughness of film R7) s Center line average roughness R
A) and surface roughness density were measured using a Surfzum 300A surface roughness needle under the conditions of a needle diameter of 1μ, a weight of 0.07 F, a measurement standard length of 0.8 mm, and a cutoff of 0.08 mm.
It is expressed as the average value of points.

Film haze was measured using a Vi direct reading haze meter (manufactured by Toyo Seiki Co., Ltd.).

The film Ill! The friction coefficient is ASTM-D-1894-
Measured according to 63TK at 23°C, 65% RH, and tensile speed of 200 shoulders/min.

Example 1 An esterification reaction of 50 parts of terephthalic acid (parts by weight: the same applies hereinafter), 28 parts of ethylene glycol, and 0.022 parts of antimony trioxide with K was carried out, and the product with an esterification rate of 95% was used as a retained fraction. 100 parts of terephthalic acid, 56 parts of ethylene glycol.

A slurry consisting of 0.044 part of antimony trioxide was added, and the pressure was 2.51 #/d and the reaction humidity was 2.
The temperature was set at 40°C to obtain a product with an esterification rate of 95%. Then, the esterification reaction product corresponding to 100 parts of terephthalic acid was transferred to a polycondensation reactor at 240°C.

3.81 parts by volume of a 0.1 mol/ImFl solution of zirconyl acetate in ethylene glycol (300 ppmi added in terms of zirconium atoms to the produced polyester) was added, stirred at the same temperature under normal pressure for 7 minutes, and then 509/J Add 4.07 parts by volume of an ethylene glycol solution of carpamine acetate monohydrate at a concentration of (400 ppm added in terms of calcium atoms to the polyester produced), and stir for 8 minutes at the same temperature and normal pressure. .

Furthermore, 1.43 parts by volume of an ethylene glycol solution of trimethyl phosphate at a concentration of 100 r/l [274 ppm added Zr+C in terms of phosphorus atoms based on the polyester produced]
a/P=1.5 (atomic ratio)] and stirred at normal pressure and temperature for 10 minutes, then gradually lowered the pressure of the reaction system to 0.
．． 05-HP and the same i! ! The combination reaction was carried out at the same pressure for about 80 minutes. [η] of the obtained polyethylene terephthalate was 0.635, and diethylene glycol was 2.
It was 1%. This polymer was melt extruded at 290°C, 3.5 times larger in the machine direction at 90°C, and 3 times larger in the transverse direction at 130°C.
．． After stretching 5 times.

All were heated at 220° C. to obtain a film with a thickness of 15 μm.

The coefficient of dynamic friction of this film is 0.38. Film haze is 2.0 inches, maximum surface roughness (RT) is 0.29μ, and center line average roughness (RA) is 0.020. Surface roughness density is approximately 1
It was 00 cases/laI. When the particles in this film were observed by reflective dark field microscopy, countless particles of 0.3 to 3.0 microns were observed, and the particle size distribution of these particles was broad. Also.

Coarse particles of 5μ or more were observed under a 200x field of view, but no coarse particles were observed at all.

Next, high-speed spinning was carried out at 285° C. at a discharge rate of 32 f/min and a speed of 600011 g/min using the above-described polymer, and the yarn could be smoothly taken off without any breakage. The obtained thread had a very elegant burl-like luster.

Comparative Example 1 A polycondensation reaction was carried out under the same conditions as in Example 1 except that calcium acetate was not added. [η] of the obtained polyethylene terephthalate was 0.630. Diethylene glycol was 2.2- and highly transparent. This polymer was made into a 15μ thick film in the same manner as in Example 1. The #friction coefficient of this film is 0.5 inches, the film haze is 0.4%, and the maximum surface roughness (RT) is 0.09μ.
, the center line average roughness (RA) was 0.010μ1, and the surface roughness density was about 110 ke/■. When the particles in this film were observed using reflective dark field microscopy, the particles ranged from 0.3 to 0.
Numerous particles of 6μ were observed, and the particle size distribution of these precipitated particles was extremely sharp. Although this film had excellent transparency and surface smoothness, it was inferior to the film obtained by the method of Example 1 in terms of ease of slipping.

Next, when the polymer obtained above was subjected to high-speed spinning in the same manner as in Example 1, smooth spinning was possible.
Comparative Example 2 A polycondensation reaction was carried out under the same conditions as in Example 1 except that zirconyl acetate was not added. The resulting polymer was made into a 15μ thick film in the same manner as in Example 1. The coefficient of dynamic friction of this film is 0.50. Film haze 1.5%, maximum surface roughness RT) Ho, 26μ,
Center line average roughness ViO, 010μ, surface roughness density approximately 3
There were 0 cases per meal. When the particles in this film were observed by reflection dark field microscopy, only a small number of 0.6 to 2 microns were observed, and the particle density was extremely low compared to the precipitated particles in the film obtained by the method of Example 1. Further, the particle size distribution of the precipitated particles was sharper than that of the precipitated particles in the film obtained by the method of Example 1.

Although this film had good transparency, it was inferior to the film obtained by the method of Example 1 in terms of surface roughness, degree of bending, and slipperiness.

Comparative Example 3 Polycondensation was carried out under the same conditions as in Example 1 except that antimony trioxide was not added. It was impossible.

Example 2 519 parts of terephthalic acid, 431 parts of ethylene glycol,
0.16 parts of triethylamine and 0.16 parts of antimony trioxide.
23 parts were charged into a stainless steel autoclave equipped with a stirrer, a distillation column, and a pressure regulator, and after purging with nitrogen, the pressure was maintained at a gauge pressure of 2.5 kf/-, and the water produced at 240°C was continuously poured from the top of the distillation column. Perform the esterification reaction while removing.

After 120 minutes had passed from the start of the reaction, the pressure was released, and a product with an esterification rate of 95 was obtained. This esterified raw acid KO0
5.27 parts by volume of a solution of zirconyl acetate in ethylene glycol having a concentration of 1 mol/J (adding 80 ppm in terms of zirconium atoms to the produced polyester) was added, and the mixture was stirred at normal pressure and temperature for 7 minutes.

Add 21.14 parts by volume of an ethylene glycol solution of potassium acetate monohydrate at a concentration of 50 f/j (adding 400 ppm in terms of calcium atoms to the produced polyester) and stir at normal pressure and temperature for 8 minutes. Stir.

Next, 6.08 parts by volume of an ethylene glycol solution of trimethyl phosphate at a concentration of 100 f/I [added 224 ppm K in terms of phosphorus atom to the polyester produced, Zr
+Ca/P-1,5 (W ratio)] was stirred at the same temperature under normal pressure for 10 minutes, and transferred to a polycondensation reactor at 240'C.
The pressure of the reaction system was gradually lowered while raising the humidity to 275° C. over 30 minutes to obtain an O,OS mixture H2, and the polycondensation reaction was further carried out at the same time and pressure for about 80 minutes. of the obtained polymer [
η] is 0.637゜diethylene glycol ij 2.1%
It was highly transparent.

This polymer was made into a 15μ thick film in the same manner as in Example 1. The physical properties of this film are shown in Table IK.

Example 3 Terephthalic acid 5198. 431 parts of ethylene glycol,
iJ etelamine 0.16 parts, antimony trioxide 0.2
3 parts and 0.12 parts of zirconyl acetate C raw F51 Ho IJ
80 ppm in terms of zirconium atoms for x sprue
IQ addition) was placed in a stainless steel autoclave equipped with a stirrer, a distillation column and a pressure regulator, and esterification reaction No. F5 was carried out in the same manner as in Example 2 to obtain a product with an esterification rate of 95. To this esterification product was added calcium acetate at a concentration of 50 f/# and 1 g of ethylene glycol.
Add 21.14 parts by volume of the solution (400 ppml calculated as calcium atoms based on the produced polyester) and stir for 8 minutes at the same temperature under normal pressure. Then, an ethylene glycol solution of trimethyl phosphate with a concentration of 100 f/j 6.0
8 parts by volume [224 ppm in terms of Rinburuko based on the polyester produced
(atomic ratio)] and stirred at the same temperature and normal pressure for 10 minutes.

Next, a polycondensation reaction was carried out under the same conditions as in Example 2.

The resulting polymer was made into a 15μ thick film using the same method as in Example 1. The physical properties of this film are shown in Table IK.

Examples 4 to 15 and Comparative Examples 4 to 5 A polycondensation reaction was carried out in the same manner as in Examples 2 and 3 by changing the amount and timing of addition of zirconyl acetate and calcium acetate, and the type and amount of phosphorus compound. Example 1
A film with a thickness of 15 μm was formed using the same method as above. Table IK shows the physical properties of the obtained film.

Examples 16 to 23 and Comparative Examples 6 to 7 In the same manner as in Examples 2 and 3, a zirconium compound was replaced with zirconyl acetate, a phosphorus compound was replaced with trimethyl phosphate [limited, and various alkaline earth metal compounds were used,
The polycondensation reaction is carried out by changing the amount and timing of addition of these additives.

Next, a film having a thickness of 15 μm was formed using the same method as in Example 1. Table 2 shows the physical property values of the obtained film.

Based on the results in Tables 1 and 2, the amount of each additive type S was determined.

Addition time f! The particle size of the precipitated particles can be determined by

It can be seen that the particle size distribution, concentration, etc. can be arbitrarily controlled over a wide range. The surface characteristics of the film can be varied over a wide range by changing the particle size of the precipitated particles.

Example 24 Zirconyl acetate was converted into tetra-n-propiozirconate.
0.24 parts of 2n propioalcohol salt (80 ppmiQ added in terms of zirconium atoms to the polyester produced)
A polycondensation reaction was carried out under the same conditions as in Example 3 except that K was changed, and a film with a thickness of 15 μm was formed in the same manner as in Example 1. Obtained.

Claims (1)

[Claims] In the presence of at least one polycondensation catalyst selected from antimony compounds, titanium compounds, and germanium compounds, a dicarboxylic acid containing terephthalic acid as a main component;
When producing polyester from alkylene glycol, a polybond reaction progresses from the start of the reaction and the intrinsic viscosity decreases to 0.
A method for producing a polyester containing internal particles, characterized in that a zirconium compound, an alkaline earth metal compound, and a phosphorus compound satisfying the following general formula are added in amounts not exceeding 2. 20≦[Zr]≦2000 50≦CM)≦500 In the formula, [Zr] is the amount (ppm) added in terms of zirconium atoms to the polyester produced, and [M] is the amount added (in terms of atoms) of alkaline earth metal to the polyester produced. pp
m), Zr+M/P indicates the atomic ratio.