JPH0258289B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a method for producing polyester containing internal particles, and more specifically, by precipitating fine insoluble particles at a high concentration in the polymer during the polyester production process, fine irregularities are created on the surface of the final product fiber or film. It can be formed with high density and satisfies various market demands for surface properties such as transparency, surface brightness, slipperiness, surface smoothness, and abrasion resistance, and is free from defects such as knobs and fitting eyes. The present invention relates to a method for producing polyester suitable as a raw material for producing non-woven fibers and films. 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, fibers and films obtained from polyester containing polyalkylene terephthalate as a main component generally have a large coefficient of friction and have poor passability during spinning or film forming processes. There is a strong desire to establish a method for producing polyester that provides the following properties. Generally, a method for improving the slipperiness of polyester fibers and films involves mixing insoluble fine particles with polyester to form fine irregularities on the surface of the fibers or films. The so-called external particle method involves adding inert fine particles to polyester such as titanium dioxide, kaolinite, talc, and silica when producing polyester, and the addition of carboxylic acid components, oligomers, or phosphorus compounds during the polyester production reaction. There is a so-called internal particle method in which fine particles are formed by reacting the metal compound with a metal compound. 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. It is economically advantageous because it does not require equipment for particle refinement, classification, and dispersion. In the external particle method, it is necessary to use a dispersant in order to prevent knobs and eyes due to agglomeration of the added fine particles, but in the internal particle method, this is not necessary. 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 products with excellent wear resistance can be obtained. Particles produced by the internal particle 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, in the internal particle method, fine particles are formed using catalyst residues of alkali metals, alkaline earth metals, etc. used as transesterification catalysts, and the amount and particle size of the fine particles formed are adjusted by adding a phosphorus compound. The method of doing so occupies the mainstream. However, this method has the following problems and cannot be said to satisfy market demands. Coarse particles tend to form, often resulting in products with low transparency. Moreover, coarse particles cause product defects such as fiber knobs and film fixation eyes. Scale tends to form inside the polymerization vessel, and this scale sometimes falls off and mixes into the polyester, causing defects such as knobs and fixing eyes. Polymerization conditions must be strictly controlled in order to keep the precipitated amount and particle size of fine particles constant at all times. 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 focused on the above-mentioned circumstances, and 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 and phosphorus By specifying the amount and timing of addition of the compound, fine particles are precipitated in the polymer at a high concentration during the polyester manufacturing process, resulting in excellent transparency and slipperiness, and eliminating product defects such as knobs and fitting eyes. We have established a method for producing polyester with minimal carbon dioxide 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 ease of slipping. For example, in the case of fibers, there is an increasing demand for them not only to have excellent transparency, but also to have glitter, such as silk-like or pearl-like properties. In the case of films, for example, in the field of magnetic tape films, there are applications where a high level of surface smoothness is required, and where smoothness is required even if some surface smoothness is sacrificed. There is a demand for base films with various surface characteristics depending on the required uses. Furthermore, even for the same application, the requirements for surface properties vary widely depending on the user. These surface properties are largely controlled by the particle concentration, particle size, particle size distribution, particle type, etc. of the insoluble particles contained in the polyester. Therefore, 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, etc. of the particles precipitated in the manufacturing process.
For example, the invention method using the new internal particle method, which the present inventors have already applied for, has extremely high transparency and is suitable for the fields of packaging films and optical films. surface smoothness is required. It is suitable as a base film for video tape using vapor deposition method. but,
Although the slip property shows a good value, a high slip property is required. For example, it is not very suitable for producing base films for music tapes. 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 silk-like or pearl-like appearance. On the other hand, fine particles are formed using conventionally known catalyst residues such as alkali metals and alkaline earth metals.
With the method of controlling the amount of particles produced and the particle size by adding a phosphorus compound, it is not possible to precipitate fine particles at a high concentration as can be obtained with the new internal particle method previously filed by the present inventors. , it is unsuitable for producing raw material resin for applications that require high transparency and surface smoothness. As mentioned above, so far, the particle concentration, average particle diameter,
Since no technology has been established to control the particle size distribution over a wide range, market demands are only met by compromising methods. The present inventors focused on the above-mentioned circumstances, and as a result of intensive research to establish a technology that can control the concentration, average particle size, particle size distribution, etc. of precipitated particles over a wide range using the internal particle method, the present invention was developed. I have come to complete it. That is, the present invention provides a process for producing a polyester from 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. From the start of the reaction until the intrinsic viscosity of the reactant reaches 0.2 as the polycondensation reaction progresses, zirconium compounds, alkali metal compounds, alkaline earth metal compounds and phosphorus are added to the polyester produced in an amount that satisfies the following formula. This is a method for producing polyester containing internal particles, which is characterized by adding a compound. 20≦[Zr]≦2000 20≦[M ₁ ]≦300, 20≦[M ₂ ]≦300 0.5≦Zr+1/2M ₁ +M ₂ /P≦3 [In the formula, [Zr] is Zr for the produced polyester
The amounts added in terms of atoms, [M ₁ ] and [M ₂ ] respectively, are the amounts added in terms of atoms of alkali metals and alkaline earth metals to the produced polyester. M ₁ and M ₂ represent alkali metals and alkaline earth metals, respectively; Zr+1/2M ₁ +M ₂ /P indicates the atomic ratio. ] The amount of polyester produced was calculated theoretically assuming a polyester yield of 100%. The most significant feature of the present invention is that in the production process of polyester, the concentration, average particle diameter, and
The objective is to provide a technology that can control particle size distribution, etc. over a wide range. This precipitated particle control is done by adding zirconium compound,
Addition amount, addition amount ratio, addition timing of alkali metal compounds, alkaline earth metal compounds, and phosphorus compounds,
This can be done by changing the order of addition and the type of alkali metal compound, alkaline earth metal compound, or phosphorus compound. The concentration of these precipitated particles,
Changes in average particle size, 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 amount of the zirconium compound, alkali metal compound, and alkaline earth metal compound added, and as the amount added increases, the amount of precipitated particles also increases. (2) The average particle size varies greatly depending on the amount of phosphorus compound and zirconium compound added. When other conditions are fixed, the average particle size decreases as the amount of addition of both phosphorus compounds and zirconium compounds increases; conversely, the average particle size decreases as the amount of alkali metal compounds and alkaline earth metal compounds increases. growing. (3) The particle size distribution varies greatly depending on the amount ratio of the zirconium compound, alkali metal compound, alkaline earth metal compound, and phosphorus compound and the timing of addition of each compound. That is, as the ratio of zirconium atoms increases in the addition ratio of the zirconium compound and the alkali metal compound and alkaline earth metal compound, the precipitated particle size distribution becomes sharper. Conversely, as the proportion of alkali metal compounds and alkaline earth metal compounds added increases, the particle size distribution becomes wider. Furthermore, when the ratio of the addition amount of zirconium compound to alkali metal compound and alkaline earth metal compound is fixed, the particle size distribution changes depending on the addition amount of phosphorus compound, and the particle size distribution sharpens by increasing the addition amount of phosphorus compound. become. Furthermore, when the amounts of zirconium compounds, alkali metal 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, alkali metal compounds, and alkaline earth metal When the compound is added at the beginning of the esterification reaction, the particle size distribution becomes sharper.
On the other hand, if the zirconium compound, alkali metal compound, or alkaline earth metal compound is added after the esterification reaction has progressed to a certain extent, the particle size distribution will become broader. The above is just one way of particle size control; in reality, the behavior of particle precipitation changes in an extremely complex manner depending on the type, amount, ratio, and timing of each additive. Another feature of the present invention is that coarse particles are less likely to be formed and scales are less likely to occur in the polymerization reactor, making it possible to obtain high-quality products with fewer product defects such as fiber knobs and film frame eyes. It is possible to produce resin. Although the reason why the present invention allows for arbitrary control of precipitated particles and makes it difficult for coarse particles and scale to occur in the polymerization reactor is unknown, It is presumed that this is because a complex is formed between the four. The polyester of the present invention has 80 repeating units.
More than mol% is composed of alkylene terephthalate, and other copolymerized components include isophthalic acid, P-β-oxyethoxybenzoic acid, 2,6-
Naphthalenedicarboxylic acid, 4,4'-dicarboxyldiphenyl, 4,4'-dicarboxybenzophenone, bis(4-carboxylphenyl)ethane, adipic acid, sebacic acid, 5-sodium sulfoisophthalic acid or their Examples include dicarboxylic acid components such as alkyl ester derivatives. In addition, the glycol components include ethylene glycol,
Propylene glycol, butanediol, neopentyl glycol, diethylene glycol, cyclohexanedimethanol, an ethylene oxide adduct of bisphenol A, and the like can be arbitrarily selected and used. In addition, a small amount of amide bond, urethane bond, ether bond, carbonate bond, etc. may be included as a copolymerization component, in short, 80 mol%
All of the above polyalkylene terephthalates can function as a base resin as long as they have fiber-forming ability and film-forming ability. Next, the antimony compound, titanium compound, and germanium compound act 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 the reaction system. For example, antimony compounds include antimony trioxide, antimony potassium tartrate, antimony glycolate, inorganic acid salts such as antimony trifluoride, and organic acid salts such as antimony acetate, and titanium compounds include tetraethyl titanate, tetrabutyl titanate, and titanium. partial hydrolysates of alkoxides, titanic oxalate, titanyl ammonium oxalate, potassium titanyl oxalate, titanium oxyacetylacetonate, titanic fluoride, etc. Germanium compounds include germanium oxide, germanium acetate, germanium ethoxide, germanium butoxide. etc.
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 amount is
0.0005-0.1 mol%, more preferably 0.002-0.03
mol%, in the case of antimony compounds and germanium compounds, 0.01 to 0.1 mol% in terms of antimony atoms and germanium atoms, more preferably
It ranges from 0.03 to 0.06 mol%. 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 a predetermined molecular weight, which is impractical, while if it is too large, the transparency and heat resistance of the resulting polymer will decrease. Further, the zirconium compound is essential as a particulate forming component, and any zirconium compound can be used as long as it is soluble in the reaction system. Typical examples include zirconium alkoxides such as tetra-n-propiozirconate, tetraisopropiozirconate, tetra-n-butylzirconate, and tetra-n-amylzirconate, zirconyl acetate, zirconyl formate, and tartaric acid. Examples include organic acid zirconyl salts such as zirconyl, zirconyl oxalate, zirconyl stearate, and zirconyl benzoate, and inorganic acid zirconyl salts such as zirconyl chloride, zirconyl bromide, zirconyl carbonate, and zirconyl ammonium carbonate. The amount of these zirconium compounds added must be set in the range of 20 to 2000 ppm in terms of zirconium atoms based on the polyester produced. If it is less than 20 ppm, the particle size control effect will be lost, and the addition of alkali metal compounds and alkaline earth metal compounds If the amount 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 2000 ppm, the slipperiness will reach a saturated state, and rather coarse particles will be formed, which will reduce transparency and worsen the polymer color, which is not preferable. 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 polycondensation reaction progresses and the intrinsic viscosity of the reactant reaches 0.2.After this point, the viscosity of the reaction solution increases. If the temperature is too high, the fine particles produced will not be 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 the molecular weight of the reaction product at this point is extremely small and the viscosity of the reaction solution is low. Compounds can be uniformly dispersed. The preferred timing for adding the zirconium compound varies depending on the surface properties of the final product to be obtained. For example, if it is desired to sharpen the particle size distribution of the precipitated particles, it is preferable to make the particle size distribution broader before esterification, or to add particles after esterification has progressed to a certain extent in order to create a pattern of using particles with different particle sizes. Further, alkali metal compounds and alkaline earth metal compounds are also essential as particle-forming components, and any compounds can be used as long as they are soluble in the reaction system. For example, carboxylates, carbonates, hydrides and alkoxides of alkali metals and alkaline earth metals, specifically lithium acetate, sodium acetate, potassium acetate, rubidium acetate, cerium 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, sodium methoxide, potassium methoxide, sodium ethoxide, potassium ethoxide, magnesium methoxide, magnesium ethoxide, calcium methoxide, calcium ethoxide, and the like. Among these compounds, lithium compounds, sodium compounds, magnesium compounds, and calcium compounds are particularly preferred since they can precipitate a large amount of particles even when added in small amounts. The amount of the alkali metal compound and alkaline earth metal compound added is in the range of 20 to 300 ppm in terms of alkali metal atom or alkaline earth metal atom, respectively, based on the produced polyester,
At less than 20ppm, the particle size control effect disappears,
In addition, if the amount of the 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 300 ppm, the particle size control effect and the slipperiness improvement effect will reach a saturated state, and rather coarse particles will be produced, which will reduce transparency and worsen the polymer color, which is not preferable. Although the alkali metal compound and the alkaline earth metal compound may be added in either solid or liquid form, it is most preferable to add them 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 and alkaline earth 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 reactant reaches 0.2. In this case, since the viscosity of the reaction liquid is too high, the 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 when this point is reached, but the molecular weight of the reaction product at this point is extremely small and the viscosity of the reaction solution is low. can be dispersed into The preferred timing of addition of the alkali metal compound and alkaline earth metal compound varies depending on the surface properties of the final product to be obtained. For example, if you want to make the particle size distribution of precipitated particles sharp, it is preferable to add it before esterification, and if you want to make it broader, it is preferable to add it after esterification has progressed to some extent. The alkali metal compound and alkaline earth metal compound may be added alone or in combination of two or more. In particular, it is preferable to use two or more types in combination because the particle size can be controlled over a wide range. Phosphorus compounds have the unique effect of controlling the concentration and size of particles formed by zirconium compounds, alkali metal compounds, and alkaline earth metal compounds. Together with this, it is the most characteristic component of the present invention. Examples of such phosphorus compounds include phosphoric acid, phosphonic acid, and their derivatives. enyl ester, phosphoric acid monomethyl ester, phosphoric acid dimethyl ester, phosphoric acid monoethyl ester, phosphoric acid diethyl ester, phosphoric acid monobutyl ester, phosphoric acid dibutyl ester, methylphosphonic acid, methylphosphonic acid dimethyl ester, ethylphosphonic acid dimethyl ester, phenylphosphonic acid Examples include acid dimethyl ester, benzylphosphonic acid diethyl ester, phenylphosphonic acid diethyl ester, phenylphosphonic acid diphenyl ester, and these may be used alone or in combination of two or more. In particular, the combination of two or more types is preferable in terms of widening the particle size control range. As mentioned above, these phosphorus compounds control the concentration and particle size of insoluble particles formed by zirconium compounds, alkali metal compounds, and alkaline earth metal compounds, so the amount added depends on the amount of zirconium added. It should _be determined based _on the balance between
It was confirmed that the effect of adding the phosphorus compound was effectively exhibited by setting the addition amount within the range of ~3.0. However, if the amount of the phosphorus compound is too small, the insoluble particles formed in the polymer cannot be made sufficiently fine, and the transparency of the final product decreases and knobs, fish eyes, etc. are likely to occur. Moreover, it is not preferable because the stability of the polymer decreases. On the other hand, if it is in excess, the polymerization rate will decrease and this will be industrially disadvantageous. 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, alkali metal compounds, and alkaline earth metal compounds, but it is important to avoid the formation of ether bonds. In order to reduce the amount, it is preferable to add it after the end of the esterification reaction. Further, for the same reason, it is preferable to add it after adding the zirconium compound, the alkali metal compound, and the alkaline earth metal compound. In addition, in the method of the present invention, it is also effective to add basic compounds such as amines and ammonium compounds as a third component during the esterification reaction in order to suppress the formation of ether bonds. All are within the scope of the present technology. Also,
The method of the present invention can obtain similar effects regardless of whether it is applied to a batch 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 zirconium compounds, alkali metal compounds, and alkali as insoluble particle forming components. This method allows the concentration, average particle size, particle size distribution, etc. of precipitated particles to be controlled over a wide range by specifying the addition timing, addition amount, and addition amount ratio of the earth metal compound and the phosphorus compound. In addition, by adopting the method of the present invention, it is possible to impart controlled irregularities to the surface of the final product fiber or film, and it is possible to provide various surfaces such as transparency, surface brightness, slipperiness, surface smoothness, and abrasion resistance. It is possible to obtain a polyester that satisfies the requirements for 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 groups remaining in the reaction product and the saponification value of the reaction product. Intrinsic viscosity [η] is the polymer with phenol (6 parts by weight)
and tetrachloroethane (4 parts by weight) and measured at 30°C. The amount of diethylene glycol in the polymer was determined by decomposing the polymer with methanol and by gas chromatography as mole % relative to ethylene glycol. The precipitated particle diameter 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 R _T of film, center line average roughness
R _A and surface roughness density were measured using a Surfcom 300A surface roughness meter, with a needle diameter of 1μ, a weight of 0.07g, and a measurement standard length.
Measured under conditions of 0.8mm and cutoff 0.08mm, and displayed as the average value of 10 points. Film haze was measured using a direct reading haze meter (manufactured by Toyo Seiki Co., Ltd.). The coefficient of dynamic friction of the film is ASTM-D-1894-
Measurement was conducted in accordance with 63T at 23°C, 65% RH, and a tensile speed of 200 m/min. Example 1 Esterification reaction of 50 parts of terephthalic acid (parts by weight: same hereinafter), 28 parts of ethylene glycol, and 0.022 parts of antimony trioxide, resulting in an esterification rate of 95%.
The product of terephthalic acid 100% is added to this as a reservoir fraction.
parts, 56 parts of ethylene glycol, antimony trioxide
Add a slurry consisting of 0.044 parts, under nitrogen atmosphere,
The pressure was set at 2.5 Kg/cm ² and the reaction temperature was set at 240°C to obtain a product with an esterification rate of 95%. Then, 240 parts of the esterification reaction product corresponding to 100 parts of terephthalic acid was added.
Transferred to a polycondensation reactor at ℃, added 3.81 parts by volume of a 0.1 mol/concentration zirconyl acetate solution in ethylene glycol (300 ppm added in terms of zirconium atoms based on the polyester produced), and stirred at the same temperature under normal pressure for 7 minutes. Then, 0.76 parts by volume of a solution of sodium acetate in ethylene glycol at a concentration of 100 g/ml (adding 184 ppm in terms of sodium atoms to the produced polyester), calcium acetate at a concentration of 50 g/l, 1.32 parts by volume of an ethylene glycol solution of monohydrate (added to the polyester produced), Add 130 ppm (calculated as atoms) to the polyester, stir for 8 minutes at the same temperature under normal pressure, and then add 1.10 parts by volume of an ethylene glycol solution of trimethyl phosphate at a concentration of 100 g/ml (calculated as phosphorus atoms based on the polyester produced). 217ppm added (Zr
+1/2Na+Ca)/P=1.5 (atomic ratio)],
After stirring at the same temperature and normal pressure for 10 minutes, the pressure of the reaction system was gradually lowered to 0.05 mmHg, and the polycondensation reaction was carried out at the same temperature and pressure for about 80 minutes. [η] of the obtained polyethylene terephthalate was 0.632, and diethylene glycol was 2.1%. This polymer was melt extruded at 290℃, 3.5 times longer in the machine direction at 90℃,
After stretching 3.5 times in the transverse direction at 130°C, heat treatment was performed at 220°C to obtain a film with a thickness of 15 μm. The coefficient of dynamic friction of this film is 0.38, and the film haze is
1.8%, maximum surface roughness R _T is 0.25μ, center line average roughness
R _A was 0.017μ, and the surface roughness density was approximately 110 particles/mm. 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. In addition, coarse particles larger than 5μ were observed under a 200x field of view, but were not present at all. Next, using the polymer obtained by the above method, at 285℃
When high-speed spinning was carried out at a discharge rate of 32 g/min and a speed of 6000 m/min, the yarn could be taken off smoothly without any breakage. The obtained thread had a very elegant pearl-like luster. Comparative Example 1 Example 1 except that sodium acetate was not added
The polycondensation reaction was carried out under the same conditions as . [η] of the obtained polyethylene terephthalate is 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 coefficient of dynamic friction of this film is 0.5%, the film haze is 0.4%, the maximum surface roughness R _T is 0.09 μ, and the center line average roughness R _A is
0.010μ, and the surface roughness density was approximately 110 pores/mm.
When the particles in this film were observed using reflective field microscopy, numerous particles of 0.3 to 0.6μ were observed.
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 by the above method was subjected to high-speed spinning in the same manner as in Example 1, smooth spinning was possible, but the obtained yarn had a lot of glare, and in terms of gloss, it was different from that of Example 1. The yarn was inferior to that obtained using the method described above. Comparative Example 2 A polycondensation reaction was carried out under the same conditions as in Example 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 coefficient of dynamic friction of this film is 0.55, the film haze is 1.3%, the maximum surface roughness R _T is 0.22μ, the center line average roughness is 0.010μ, and the surface roughness density is approximately 30 pieces/
It was warm in mm. When the particles in this film were observed by reflection dark field microscopy, only a small number of 1 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. Furthermore, 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 smoothness and ease of slipping. Comparative Example 3 When polycondensation was carried out under the same conditions as in Example 1 except that antimony trioxide was not added, the [η] of the obtained polymer was as low as 0.372, making it impossible to form satisfactory films and fibers. It was hot. Example 2 519 parts of terephthalic acid, 431 parts of ethylene glycol
1 part, triethylamine 0.16 parts and antimony trioxide 0.23 parts were charged into a stainless steel autoclave equipped with a stirrer, a distillation column and a pressure regulator, and the autoclave was purged with nitrogen and pressurized to maintain a gauge pressure of 2.5 kg/cm ² .
After the start of the reaction, the esterification reaction was carried out while continuously removing the water produced at ℃ from the top of the distillation column.
After 120 minutes, the pressure is released and the esterification rate is 95%.
The product was obtained. To this esterification product, 5.27 parts by volume of a 0.1 mol/concentration zirconyl acetate solution in ethylene glycol (80 ppm added in terms of zirmanium atoms to the produced polyester) was added, and the mixture was stirred at normal pressure and temperature for 7 minutes. 3.95 parts by volume of an ethylene glycol solution of sodium acetate at a concentration of
6.87 parts by volume (130 ppm added in terms of calcium atoms based on the produced polyester) was added, stirred for 8 minutes at the same temperature under normal pressure, and then 4.57 parts by volume of an ethylene glycol solution of trimethyl phosphate at a concentration of 100 g/[produced polyester] Addition of 168 ppm in terms of phosphorus atoms, (Zr+1/2Na+Ca)/
P = 1.5 (atomic ratio)] and at the same temperature at normal pressure.
Stir for 10 minutes, transfer to a polycondensation reactor at 240 °C,
The pressure of the reaction system was gradually lowered to 0.05 mmHg while the temperature was raised to 275°C over a period of minutes, and the polycondensation reaction was further carried out at the same temperature and pressure for about 80 minutes. The obtained polymer had [η] of 0.637, diethylene glycol content of 2.1%, and was highly transparent. This polymer was made into a 15μ thick film in the same manner as in Example 1. Table 1 shows the physical properties of this film. Example 3 519 parts of terephthalic acid, 431 parts of ethylene glycol
part, triethylamine 0.16 part, antimony trioxide
Example 2: 0.23 parts of zirconyl acetate and 0.12 parts of zirconyl acetate (80 ppm added in terms of zirconium atoms to the produced polyester) were charged into a stainless steel autoclave equipped with a stirrer, a distillation column, and a pressure regulator.
The esterification reaction was carried out in the same manner as above, and a product with an esterification rate of 95% was obtained. To this esterification product, 3.95 parts by volume of an ethylene glycol solution of sodium acetate at a concentration of 100 g/(184 ppm added in terms of sodium atoms to the polyester produced) and 6.87 parts of an ethylene glycol solution of calcium acetate monohydrate at a concentration of 50 g/ (added 130 ppm in terms of calcium atoms to the polyester produced)) and stirred at the same temperature and normal pressure for 8 minutes.
Next, 4.57 parts by volume of an ethylene glycol solution of trimethyl phosphate at a concentration of 100 g/ml [added at 168 ppm in terms of phosphorus atoms based on the polyester produced]
Add Zr + 1/2Na + Ca/P = 1.5 (atomic ratio)],
The mixture was stirred at normal pressure and at the same temperature for 10 minutes, and a polycondensation reaction was carried out under the same conditions as in Example 2. The obtained polymer was made into a film with a thickness of 15 μm using the same method as in Example 1. Table 1 shows the physical properties of this film. Examples 4 to 19 and Comparative Examples 4 to 6 In the same manner as in Examples 2 and 3, the zirconium compound was limited to zirconyl acetate, various alkali metal compounds, alkaline earth metal compounds, and phosphorus compounds were used, and these additives were Polycondensation reaction was carried out by changing the amount and timing of addition, and then Example 1
A film with a thickness of 15μ was formed using the same method as above. Table 1 shows the physical properties of the obtained film. The results in Table 1 show that the particle size, particle size distribution, concentration, etc. of the precipitated particles can be arbitrarily controlled over a wide range by changing the type, amount, and timing of each additive. By controlling the particle size of the precipitated particles, the surface characteristics of the film can be varied over a wide range. Example 20 A polycondensation reaction was carried out under the same conditions as in Example 3, except that zirconyl acetate was replaced with 0.24 part of tetra-n-propiozirconate/2n propionate salt (80 ppm added in terms of zirconium atoms to the polyester produced). Then, in the same manner as in Example 1
By forming a film with a thickness of 15 μm, a film of almost the same high quality as in Example 3 was obtained. Example 20 A product with an esterification rate of 95% obtained by esterifying 50 parts of terephthalic acid (parts by weight: same below), 28 parts of ethylene glycol, and 0.038 parts of sodium acetate was used as a retained fraction, and 100 parts of terephthalic acid was added to it.
parts, 56 parts of ethylene glycol, sodium acetate
A slurry consisting of 0.076 parts (184 ppm added in terms of sodium atoms based on the polyester produced) was added, and the pressure was set at 2.5 Kg/cm ² and the reaction temperature was set at 240°C under a nitrogen atmosphere to produce a product with an esterification rate of 95%. I got it. Next, the esterification reaction product equivalent to 100 parts of terephthalic acid was transferred to a polycondensation reactor at 240°C, and 0.1
3.81 parts by volume of an ethylene glycol solution of zirconyl acetate at a molar concentration (300 ppm added in terms of zirconium atoms based on the polyester produced) and 50
1.32 parts by volume of an ethylene glycol solution of calcium acetate monohydrate at a concentration of 100 g/g was added (130 ppm added in terms of atoms to the polyester produced), stirred for 8 minutes at the same temperature under normal pressure, and then added at a concentration of 100 g/ 1.10 parts by volume of an ethylene glycol solution of trimethyl phosphate (added 217 ppm in terms of phosphorus atoms to the polyester produced (Zr+1/2Na+
Ca)/P=1.5 (atomic ratio)], stirred at the same temperature and normal pressure for 10 minutes, and further added 0.06 part by volume of an ethylene glycol solution of titanium tetrabutoxide with a concentration of 0.5 mol/concentration, and stirred at the same temperature under normal pressure. After stirring for 10 minutes at the same temperature, the pressure of the reaction system was gradually lowered to 0.05
mgHg, polycondensation reaction was carried out at the same temperature and pressure for about 80 minutes, and the obtained polyethylene terephthalate had [η] of 0.632 and diethylene glycol of 2.1%.
It was hot. This polymer was melt extruded at 290℃,
After stretching 3.5 times in the longitudinal direction at 90°C and 3.5 times in the transverse direction at 130°C, it was heat-treated at 220°C to obtain a film with a thickness of 15 μm. The coefficient of kinetic friction of this film is
0.38, film haze is 1.9%, maximum surface roughness R _T
was 0.24 μ, center line average roughness R _A was 0.017 μ, and surface roughness density was approximately 115 ke/mm. When the particles in this film were observed using reflective dark field microscopy, the particles were found to be 0.3
Numerous particles of ~3.0μ were observed, and the particle size distribution of these particles was broad. Also,
Coarse particles larger than 5 μm were observed under a 200x field of view, but were not present at all. Next, using the polymer obtained by the above method, at 285℃
When high-speed spinning was carried out at a discharge rate of 32 g/min and a speed of 6000 m/min, the yarn could be taken off smoothly without any breakage. The obtained thread had a very elegant pearl-like luster. Comparative Example 7 When a polycondensation reaction was carried out under the same conditions as in Example 20 except that sodium acetate and calcium acetate were not added, [η] of the obtained polymer was
The value was as low as 0.430, making it impossible to form a film and produce fibers satisfactorily. Comparative Example 8 Example 20 except that zirconyl acetate was not added
The polycondensation reaction was carried out under the same conditions as . The obtained polymer was made into a 15μ thick film in the same manner as in Example 20. The coefficient of kinetic friction of this film is 0.55
Film haze 1.3%, maximum surface roughness R _T 0.22μ,
Center line average roughness is 0.010μ, surface roughness density is approximately 30
It was hot at ke/mm. When the particles in this film were observed by reflection dark field microscopy, only a small number of 1 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. Although this film had good transparency, it was inferior to the film obtained by the method of Example 1 in terms of surface smoothness and ease of slipping. Comparative Example 9 When polycondensation was carried out under the same conditions as in Example 20 except that titanium tetrabutoxide was not added, the [η] of the obtained polymer was as low as 0.372, indicating that satisfactory film formation and fiberization were not achieved. It was possible. Comparative Examples 10 and 11 By changing the amount of trimethyl phosphate added, (Zr
+1/2Na+Ca)/P atomic ratio of 0.1 and 5
Polycondensation was carried out under the same conditions as in Example 20, except for the following. When the atomic ratio with increased amount of trimethyl phosphate added is 0.1, [η] of the obtained polymer is 0.410.
This was so low that satisfactory film formation and fiberization were impossible. Furthermore, when the atomic ratio was 5 with a reduced amount of trimethyl phosphate added, the polycondensation reaction proceeded without any problem, but the film obtained by the same method as Example 20 had a surface roughness density of about 25 cells/mm. It was inferior in terms of slipperiness. In addition, coarse particles of 5μ or more were present and the quality was low. Example 21 In place of 0.23 part of antimony trioxide, amorphous 2
A polymer obtained by polycondensation in the same manner as in Example 2 except that germanium oxide was added to 0.19 parts was made into a film having a thickness of 15 μm in the same manner as in Example 1. The obtained film had almost the same physical properties as the film of Example 2 and was of high quality. Comparative Example 12 Example except that sodium acetate was not added
The polycondensation reaction was carried out under the same conditions as in 21, and [η] was
A polymer of 0.625 was obtained. This polymer was made into a 15μ thick film using the same method as in Example 1.
The surface roughness density was low and the slipperiness was poor. Comparative Example 13 Example 21 except that zirconyl acetate was not added
A polycondensation reaction was carried out under the same conditions as in Example 1, and the resulting polymer was made into a 15 μm thick film in the same manner as in Example 1. This film had a low surface roughness density and was poor in slipperiness. Comparative Example 14 Polycondensation was carried out under the same conditions as in Example 21 except that germanium dioxide was not added. The [η] of the obtained polymer was as low as 0.372, making it impossible to form a satisfactory film and fiber. Ta.

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Claims (1)

[Claims] 1. Polyester is produced from 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. During production, a zirconium compound, an alkali metal compound, an alkaline earth metal compound, and a phosphorus compound satisfying the following general formula are added from the start of the reaction until the polycondensation reaction progresses and the intrinsic viscosity does not exceed 0.2. A method for producing a polyester containing internal particles. 20≦[Zr]≦2000 20≦[M ₁ ]≦300, 20≦[M ₂ ]≦300 0.5≦Zr+1/2M ₁ +M ₂ /P≦3 [In the formula, [Zr] is the zirconium atom equivalent for the polyester produced. Addition amount (ppm), [M ₁ ],
[M ₂ ] is the amount (ppm) of alkali metal and alkaline earth metal added to the produced polyester in atomic terms, M ₁ and M ₂ are alkali metal and alkaline earth metal, respectively, and Zr + 1/2M ₁ + M ₂ / P indicates the atomic ratio. ]