JPS6058432A - Production of polyester containing internal particle - Google Patents

Abstract

PURPOSE:To obtain the titled polymer, capable of giving products having fine unevennesses on the surfaces thereof at a high density, and having high static adhesiveness, by adding specific amounts of a magnesium compound, zinc compound and a phosphorus compound respectively to a specific stage of producing a polyester. CONSTITUTION:(A) A magnesium compound and (B) a zinc compound in amounts satisfying the formula 30<=Mg+Zn<=500 [Mg and Zn are amounts added (ppm) in terms of Mg and Zn atoms of the components (A) and (B) respectively based on the formed polymer] and the formula 0.1<=Mg/Zn<=10 are added to a stage of producing a polyester till the completion of esterification reaction of an acid component consisting essentially of terephthalic acid with a glycol component consisting essentially of ethylene glycol, and (C) a phosphorus compound, preferably phosphonic acid in an amount satisfying the formula 1.2<=(Mg+Zn)/ P<=20 which is an atomic ratio between the components (A)-(C) is added till the completion of the initial condensation reaction to carry out the direct polymerization reaction and give the aimed polymer consisting of ethylene terephthalate units.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing polyester with three internal particles,
In detail, fine insoluble t'12 particles are precipitated in the polymer at a high concentration during the production of polyester, forming fine irregularities at a high density on the surface of the final product fiber or filter. This invention relates to a method for producing a polynis spool with highly improved electrostatic adhesion using a polymerization method.

The internal particle-containing polyester obtained by the method of the present invention is
It can satisfy various market demands for surface properties such as transparency, surface brightness, slipperiness, subsurface d' resistance, and abrasion resistance. Furthermore, since the generation of coarse particles is small, when this film is used as a base film for magnetic tape, there are fewer defects in magnetic recording signals, that is, dropouts, so it is easy to manufacture a base film for magnetic tape.
It is extremely suitable as

, 1! Rico, Stell is mechanical, electrical, and thermal.
Since it is excellent in il etc., it can be used for various 1j such as fibers and filtration.
;”1′:E is often used. Fibers and films obtained from polyester whose main component is polyal 4/lenderephthalate generally have a high IIF coefficient of 16, and have a low coefficient of friction because they have poor passage through the process during spinning or film forming. There is a strong desire to establish the production of polyesters that provide excellent slipperiness and films.

In general, as a method to improve the properties of polynisdel 11 III or filtration,
The method used is to mix fine particles of tMlli or film to form fine irregularities on the surface of tMlli or film. , the so-called external particle method in which inert fine particles are added to polyester such as silica, and (2) the carboxylic acid component during the polytoothglue production reaction.・There is a so-called internal particle method in which fine particles are formed by using the external scoop method.When comparing the external scoop method and the internal particle method, the internal particle method is said to be more convenient for the following reasons.

(1) There is no need for equipment for particle refinement, classification, and dispersion, which is advantageous in terms of efficiency.

(2) In the external particle method, a dispersant (IP
However, in the internal particle method, this is not necessary. Generally, it is not a good idea not to add a dispersant because it impairs the heat resistance and electrical properties of the product.

(3) Since the particles produced by the internal particle method generally have low hardness, products with excellent wear resistance can be obtained.

(4) Particles produced by the internal particle method are compatible with polyester, so even when stretched; 1. Since it does not generate id and has a refractive index close to that of polyester, the product has high transparency.

By the way, as for the internal particle method, fine particles are produced using the catalyst residue of alkaline or alkaline earth metal used as Nisdell exchange catalyst, and regarding the amount and particle size of fine particles precipitated, ■] Addition of compound The mainstream method is to adjust the In most cases, a Ca compound and/or a 1.1 compound is used as the metal compound.

Many attempts have been made to apply this method to the direct combination method, but all of them have been carried out by adding a metal compound to the alkali after the esterification reaction has substantially completed. . However, with this method, it is difficult to precipitate fine internal particles at a high concentration; for example, (1) a method of adding T1) A or water to the reaction system;
(2) Methods have been proposed, such as limiting the conditions during and after the addition of the metal compound and (1) compound to a specific range.

It is true that internal particles can be generated using these methods, and it is necessary to strictly control the polymerization conditions in order to keep the precipitated amount and particle size of fine particles constant at all times. The amount of output has also not reached a satisfactory level.In particular, there are many coarse particles, and when this film is used as a base film for magnetic tape, there are many defects in the lack of magnetic recording signals, that is, tronobu-out defects.
Application to this field has been difficult.

- On the other hand, polynisdel as a raw material for film is required to have a high degree of electrostatic density. Usually, a polynisdel film is obtained by melt-extruding polyester and then biaxially stretching the polyester. In order to improve the uniformity of the film thickness and the casting speed with this 1 g product, when the sheet-like material melted and extruded from the extrusion die is rapidly cooled on the surface of the rotating cooling tram,
It is necessary to improve the tightness between the sheet material and the drum surface. As a method of increasing the tightness between the sheet-like material and the drum surface, a wire rod electrode is installed between the extrusion die and the rotating cooling drum, and a high voltage is applied to the upper surface of the unsolidified sheet-like material to generate static electricity. It is known that a method in which a sheet is precipitated and rapidly cooled while closely contacting the surface of a cooling body (hereinafter referred to as electrostatic contact casting method) is effective.

Uniformity of film thickness is an extremely important characteristic of film quality, and film productivity is directly dependent on casting speed, so increasing casting speed is extremely important to improve productivity. ,
Great efforts are being made to improve electrostatic density.

It is known that increasing the electric charge on the surface of a sheet-like object is an effective means for improving electrostatic adhesion. In addition, in order to increase the charge on the surface of a sheet material in the electrostatic adhesion/toyast method, it is effective to modify the polyester R used in the production of polyester films to lower its specific resistance. It is known that there is a method to lower the specific resistance of this polyester Ijrt f'+.
It is known to add an alkali gold FA or an alkaline earth metal compound after completion of the esterification or Nisdell exchange reaction. It is true that this method lowers the specific resistance of the polyester raw material and reaches a certain level of static frit density, but in recent years the market has become more demanding in terms of uniformity and properties of the thickness of fill/A. As higher productivity has become desirable in order to reduce costs, polyester raw materials obtained by conventional methods have not been able to fully meet market requirements at high casting speeds. High quality filt! ! '! ! It has become difficult to build.

In particular, in conventional methods, the precipitation of fine particles and the decrease in resistivity often exhibit contradictory behavior, and selecting conditions that increase the precipitation of particles worsens the decrease in resistivity. It was difficult to deposit at a high concentration and to achieve a high degree of electrostatic adhesion (.I''j).

The inventors have taken into consideration the circumstances described in 1.ir+'I L
By precipitating fine insoluble particles in a polymer at a high Q degree using the ll'l contact method, fine irregularities are formed at high density on the surface of the final product, barrel fiber or film, and furthermore, electrostatic adhesion is improved. The present invention was developed as a result of extensive research aimed at establishing a highly improved method for producing polyester.

That is, the first invention of the present invention provides that when producing a polyester whose main repeating unit is ethylene terephthalate by a direct polymerization method, (1) the following ( 1) Formula and formula (■) are simultaneously satisfied; Adding 111 g of the compound of 11 and the Zn compound; ■ Adding an amount of P that satisfies formula (III) at any stage until the initial synthesis reaction is completed. This is a non-method for producing internal particle-containing polyester, which is characterized by adding one or more compounds.

30≦Job÷Zn≦500・・・・・・・・・・・・ (
I) 0.1≦Mg/Zn≦IQ, , , , , , ,
,,, (II) 1.2≦(Mg+Zn)/P≦20
=-=-(Ill) [wherein, Mg is the amount of Mg compound added to the polyester as Mg atoms (PP11)
, Zn is the addition fil: (ppm) of the Zn compound as Zn atoms to polynisdel, Mg/Zn and (Mg+Zn)/l' indicate the respective atomic ratios. ] The second invention of the present invention provides the following formula (IV) at any stage until the initial synthesis reaction is completed in the first invention:
When adding at least one alkali metal compound selected from 1.1, Na and compound in an amount that simultaneously satisfies formula (V) and (O) P compound that satisfies formula (Vl) below. This is a method for producing polyester containing internal lattice, which is characterized by the following.

3≦M≦400・・・・・・・・・・・・・・・・・・
...(IV)0.1≦Mg/(Zn+M)≦10-・
-(V)1.2≦(f+Zn+1/2M)IP≦20
-(Vl) [wherein M is an alkali metal compound poly;
1. Addition of metal 1 [i as a child ii ((
ppm), Mg/(Zn+M) and (Mg+Zn
+I/2M) C) indicates each B/child ratio. ] The third invention of the present invention provides that (1) the compound used in the first and second inventions is phosponic acid and/or; This is a method for producing Borie and Stelq containing internal particles, which is characterized by using an ester of phosphoric acid.

The fourth origin IJII of the present invention is the first and second origin +j
As the P compound used in 1, a mixture of phosphoric acid and/or phosphonic acid ester and at least one P compound selected from phosphoric acid, phosphoric acid, and esters thereof is used. This is a method for producing a polyester containing internal particles, which is characterized in that the polyester is added in an arbitrary ratio that satisfies the following formula (■).

9/I≦＾/B≦1/9・・・・・・・・・・(■)［
In the formula, A is: I, s; 1, phosphoric acid and/or phos; 1
, B represents the number of moles of phosphoric acid ester added, and B represents the number of moles of P compound selected from phosphoric acid, phosphorous acid, and their esters. ] The polynisdel of the present invention has a repeating unit of /(0 mol%
- consists of 1 dilene terephthalate,
Other copolymerization components include isophthalic acid, P-β-oxyethoxybenzoic acid, 2. G-naphthalene/dicarboxylic acid,
4. /l'l Rajbo: Tosyldiphenyls, 4.4'
-Dicarboxylbe/Zofen/N, bis(4-carboxylphenyl)ethane, adipic acid, sebacic acid, 5
- Dicarboxylic brewing ingredients such as sodium sulfoinphthalate can be mentioned. As the glycol component, propylene glycol, butanediol, neopendel glycol, diethylene glycol, cyclohexanedimethanol, ethylene oxide adducts to bisphenol, and the like can be arbitrarily selected and used. In addition, small amounts of amide bonds, urethane bonds, ether bonds, carbonate bonds, etc. may be included as copolymer components.

The esterification reaction can be carried out using either a four-part method or a continuous method, but the continuous method produces more stable quality products? It is preferable because it gives +1. When carrying out esterification in a continuous manner,
From the viewpoint of reaction control, it is preferable to carry out the esterification reaction in two to four reaction vessels.

As the Mg compound used in the present invention, any compound can be used as long as it is soluble in the reaction system. For example, water such as magnesium hydride, oxides such as magnesium oxide, lower fatty acid salts such as magnesium acetate,
Examples include alkoxides such as magnesium methoxide.

Moreover, any Zn compound can be used as long as it is soluble in the reaction system. Examples include organic acid salts such as zinc acetate and zinc benzoate, halides such as zinc chloride, and acetylacetonate salts of zinc.

The cooling power of these Mg compounds and Zn compounds is:
As shown in formula (I), the total amount of Mg atoms and Zn atoms is 30 to 50 with respect to the finally obtained polynisdel.
0 PPI.

If it is less than 30 ppm, the amount of fine particles produced is small, and the slipperiness of the final product cannot be sufficiently improved. Further, it is not preferable because the improvement in electrostatic adhesion becomes insufficient.

On the other hand, if it exceeds 500 PPM, the slipperiness will reach a saturated state, and rather coarse particles will be produced, resulting in decreased transparency and product defects such as fish eyes, which is not preferable.

In addition, the electrostatic adhesion reaches a saturated state, which is not preferable because registration color and stability decrease.

It is necessary to add this one compound and the Zn compound to the reaction system before the esterification reaction is substantially completed.

The point at which the esterification reaction is substantially completed refers to the point at which the esterification rate reaches 91%. If it is added after the esterification reaction is substantially completed, coarse particles will be produced in large quantities, and when the film is used as a base for a magnetic tape, there will be many dropouts of magnetic signals, which is not preferable. Esterification rate is 20-80%
It is particularly preferable to add the oligomer at this point because the filterability of the oligomer is improved and insoluble foreign substances in the oligomer can be efficiently removed by filtration.

In fact, adding TiW before the end of the esterification reaction suppresses the formation of coarse particles, and adding TiW at an esterification rate of 20 to 80% improves the filterability of the ribomer. F, the first cause is unknown, but M
It is thought that this is caused by a slight change in the composition of the reaction product of the g compound, Zn compound, -I+ compound, alkali metal compound, and oligomer.

Any alkali metal compound used in the present invention can be used as long as it is soluble in the reaction system. For example 1,5N
a and I (carboxylate, phosphate, carbonate, hydride, alkoxide, etc.), specifically lithium acetate, sodium acetate, potassium acetate, lithium benzoate, sodium benzoate, potassium benzoate, phosphoric acid Sodium dihydrogen, potassium dihydrogen phosphate, pyrophosphate
Thorium, potassium pyrophosphate, lithium tripolyphosphate, potassium tripolyphosphate, sodium bicarbonate, m
Potassium carbonate, lithium hydride, sodium hydride, potassium hydride, lithium methoxide, sodium methoxide, potassium 11 methoxide, lithium ethoxide, thorium ethoxide, potassium ethoxide, etc. are listed, but the use of carboxylates is especially preferable. These compounds may be used alone or in combination with
M! The above may be used for α. When a Li compound and a Na compound are used in combination, fine particles can be precipitated at a high concentration, so it is particularly useful. The amount of these alkali metal compounds added is 3 to 400 p as a metal atom to the polyester produced as shown by the general formula (IV).
The pND range is preferred, especially the 30-200 ppm+7) range. The amount of alkali metal compound added is /I 00 Pp
Exceeding this limit is undesirable because the resin color deteriorates and coarse particles are generated, resulting in decreased transparency and product defects such as knobs and fins.

The addition of these alkali metal compounds to the reaction system can be appropriately selected at any stage until the initial synthesis reaction is completed. The point at which the initial integrated reaction is completed is the point at which the viscosity reaches approximately 0.2. After this point, the viscosity of the reaction system is too high and the a-mixture of the added components becomes uneven, resulting in a homogeneous product. will not be obtained. Furthermore, depolymerization of oligomers occurs, which is undesirable because it causes a decrease in productivity and an increase in the amount of EG by-products. 5. Alkali metal compound. Ωpp
When adding m or more, it is particularly preferable to add when the esterification rate is 20 to 80%. When the alkali metal compound is added when the esterification rate is 20 to 80%,
The filterability of the oligomer is improved, so that insoluble foreign substances in the oligomer can be efficiently removed by filtration, and the generation of coarse particles is reduced.

The addition of these alkali metal compounds to the reaction system is
As long as the above conditions are satisfied, it may be used alone or simultaneously with other additives.

A method in which other additives are added simultaneously is particularly preferred since the number of reaction vessels can be reduced when a continuous method is used. The above metal compound additive n must satisfy formula (II) in the case of the first invention, and must satisfy formula (V) in the case of the second invention. If the addition ratio of 61g compound is less than the above range, the electrostatic 8? This is not preferable because the improvement in neck properties is insufficient.

Conversely, if the addition ratio of Mg compound exceeds the range,
The amount of fine particles produced is small (unfavorable because the slipperiness of the final product cannot be sufficiently improved).

I) Compounds used in the present invention include phosphoric acid, phosphorus/acid, phospho/acid and derivatives thereof,
Specific examples include phosphoric acid, trimedel phosphate, triedyl phosphate, tributyl phosphate,
Triphenyl phosphate, monomethyl phosphate, dimethyl ester phosphate, mozupdelnisder phosphate, υ/acid dibdelnisder, phosphorous acid, 1111. Trimedel phosphate, triedyl sulfite J, sulfur, tributyl phosphite, medylphos, J,
phosphonic acid, medylphosphonic acid dimethyl ester, edyl, 1
．． Shimedyl ester sulfonate, phenylphos; 1,
These include cymedyl phosphoric acid ester, phenylphospho/diethyl phosphoric acid ester, phenylphos, 1, and difuco mono-dyl phosphoric acid ester. Among these 1) compounds, when phosphonic acid and/or nisdel phosphonic acid is used,
This is preferable because the concentration of precipitated particles becomes high. Furthermore, Hoss;
j, a mixture of phosphoric acid and/or Nisdel sponate and at least one compound 1) selected from phosphoric acid, phosphorous acid and their esters, and (■
) It is particularly useful because it is possible to greatly expand the particle size of precipitated particles and the control width of 0 degree particles by adding it in an arbitrary ratio that satisfies the formula. The addition of these P compounds is set in the range of 1.2 to 2o, preferably 1.4 to IO, as the atomic ratio of metal/metal expressed by formulas (■) and (Vl). is preferable. If it is less than 1.2, the specific resistance of the obtained polyester raw material will decrease little, and as a result, the electrostatic adhesion will be insufficient, which is not preferable. On the other hand, if it exceeds 20, it is not preferable because the electrostatic density deteriorates and heat resistance and resistance to resistance deteriorate. The addition of these 1) compounds to the reaction system can be appropriately selected at any stage until the initial synthesis reaction is completed.

If added after the initial synthesis reaction is completed, the viscosity of the reaction system will be too high, resulting in uneven mixing of the added components, making it impossible to obtain a homogeneous product. Furthermore, depolymerization of the oligomer occurs, which is undesirable because it causes a decrease in productivity and an increase in the amount of I)EG by-products. Furthermore, the amount of P compound remaining in the reaction system becomes low, which is not preferable.

These P compounds may be added to the reaction system either singly or simultaneously with other additives as long as the above-mentioned conditions ('I) are satisfied.

”-of the reaction system when adding the additive /! The degree is 230
Any temperature range between 290°C and 290°C is acceptable, but a range of 240°C to 270°C is particularly preferred. 230
If the temperature is below °C, oligomer assimilation occurs, which is not preferable. On the other hand, if it is added at a temperature exceeding 200°C, side reactions such as an increase in the amount of DEC by-product and an increase in color are undesirably promoted.

The pressure of the reaction system when adding the above additives is normal pressure to 3 k
A range of g/cJ is preferred, especially a range of normal pressure to 1 kg/J. It is not preferable to add the additive under reduced pressure because it causes escape of the additive. On the other hand, if it exceeds 3 kg / /
) This is not preferable because the amount of EG by-product increases.

Each of the additives described in No. 111f may be added in either solid or liquid form, but from the viewpoint of feeding accuracy, it is most preferable to add them as an ethylene glycol solution. When adding in solid form, poly 1. It is preferable to seal it in a container made of C-Stel and add it to the reaction system.

In order to meet the market's demands for various surface properties such as transparency, surface brightness, slipperiness, surface smoothness, and abrasion resistance, the concentration, particle size, and particle size distribution of precipitated particles can be adjusted arbitrarily. ) It is necessary to provide technology that allows RJ-R.

In conventionally known methods, for example, particle size is generally controlled by changing the amount of P compound added. If other conditions are the same, the precipitated particle size becomes finer by increasing the amount of P compound added.

It is true that this method is effective as a method of controlling the precipitated particle size, but 1) If the amount of compound added is increased, the electrostatic adhesion will decrease, so it is necessary to maintain the electrostatic adhesion and the precipitated particle size. This is not an appropriate method to control.

Regarding the production of insoluble particles in a polymer while maintaining electrostatic adhesion,
One of the major features of the method of the present invention is that it provides a method in which the particle concentration, particle diameter, and t◇ particle size distribution of precipitated particles can be arbitrarily controlled over a wide range.

Control of this precipitated particle is done by adding Mg compound,
This can be carried out by changing the addition h1 of the Zn compound, the alkali metal compound, and (1) the compound, the addition ratio, the addition time, the addition order, and the type of the alkali metal compound or P compound. Changes in the concentration, particle size, particle size distribution, etc. of the precipitated particles are extremely diverse and cannot be described simply, but they can be roughly summarized as follows.

(1) Control of the concentration of precipitated particles largely depends on the amount of metal compound added, and as the amount added increases, the amount of precipitated particles also increases. If the addition it of the metal compound is constant, 1)
Phos as a compound;! , phosphoric acid; 1. It can be increased by using stonic acid esters.

(2) The average particle size can be determined by changing the addition ratio of the Mg compound to the Zn compound and the alkali metal compound, and the higher the addition ratio of the Mg compound and the Zn compound, the smaller the average particle diameter becomes.

Furthermore, when the addition ratio is kept constant, it can be done by changing the type of P compound. For example: 1. This can be done by changing the addition ratio of sulfonic acids and phosphoric acid or phosphorous acids, and by reducing the addition ratio of phosphoric acid/acids, the average particle size can be reduced. Furthermore, Mg compound and 7. If the addition ratio of the n compound and the alkali metal compound is constant, and the type of the compound is fixed, then by changing the type of the alkali metal compound, two compounds can be added. Since the average particle size is smaller when using the 1.1 compound than when using the 1.1 compound, the particle size can be adjusted arbitrarily to I can do it.

(3) Particle size distribution is controlled by Mg compound and Z
It can be greatly changed by changing the addition ratio of the n compound and the alkali metal compound and the addition time of these metal compounds and the P compound. In general, simple systems have sharp particle size distributions.

The following is only one way of controlling precipitated particles; in reality, the behavior of particle precipitation varies extremely complexly depending on the type, amount, ratio, and timing of each additive, so there are many different ways to control precipitated particles. It is possible to fully respond to the demands of the market.

Another feature of the present invention is that a high degree of electrostatic adhesion is maintained even though the particle size is controlled in various ways using the method described above.

Another feature of the present invention is that it is difficult to generate coarse particles and is suitable as a raw material for producing films with fewer dropout defects when the final product film is used as a base film for magnetic tapes. It will be done.

This point can be achieved by adding the Mg compound and Zn compound to the reaction system substantially before the esterification reaction is completed.

The polymer n1 polymerization catalyst can be appropriately selected from conventionally known catalysts, and it goes without saying that a lubricant made of inorganic or organic fine particles and various other additives may also be used.

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

All parts in the examples mean parts by weight unless otherwise specified.

In addition, the measurement method used is shown below.

(11 Esterification rate The amount of carboxyl Ji remaining in the reaction product is determined by the saponification value of the reaction product.

(2) Intrinsic viscosity The polymer is dissolved in a mixed solvent of phenol (6 parts by weight) and tetrac[fluethane (4 parts by weight), and measured at 30°C.

(3) A tungsten wire electrode was provided between the mouthpiece of the electrostatic adhesion extruder and the cooling drum, and casting was performed by applying a voltage of 10 to 15 kV between the fli electrode and the casting drum. The surface of the raw material for decoding is visually observed and evaluated at the casting speed at which pin/ner bubbles begin to occur. The higher the casting speed of the polymer, the better the electrostatic adhesion.

(4) Number of coarse particles in polymer A small amount of polymer is sandwiched between two cover glasses.
After melt-pressing at 0° C. and rapid cooling, it is observed using a phase contrast microscope, and the number of particles of 10 μ or more is counted using an image analyzer.

(5) Film haze Measured with a 11'r reading haze meter (manufactured by Toyo Seiki Co., Ltd.).

(6) Using the maximum surface roughness of the film 1lr), the center line average roughness RA) and the surface roughness density Surfcom 300A type surface roughness Hl, the needle diameter is 1μ,
Weight: 0.07 g 1 Measuring standard length: 0.811+++, cuff) Off Measured under conditions of 0.08 open, and displayed as the average value of 10 points.

(7) Coefficient of dynamic friction (μd) of film ASTM-D-
1894-G3Tk: Standard, 23°C, e5%RI
I.

Measured at a tensile speed of 200 m/min.

Example 1 A continuous esterification reaction apparatus consisting of a two-stage complete mixing tank equipped with an agitation device, a partial condenser, a raw material inlet, and a product outlet was used, and the first esterification reaction vessel was The F and G slurry of T I) A, adjusted to a molar ratio of EG to TP^ of 1.7, was continuously supplied to the system in which the esterification reaction product of was present.

At the same time, T I) E G slurry of A was supplied, and from a separate supply port from 1, IE a solution of magnesium acetate tetrahydrate, EG solution of zinc oxate dihydrate, and EG of lithium acetate were added.
solution, trimedel 2'', EG solution of sulfate and EG solution of dimedyl phenyl phosphonate, poly, 1 stell unit unit in the reaction product passing through the reaction vessel! Each Mg atom L ”C100pp11.7
．． nB:! 200 ppm of Na atoms, 200 ppm of Na atoms
Iooppm, I' III 'J'? ! : 43 ppm and 127 ppm, respectively, and the reaction was carried out at normal pressure for an average residence time of 1 if 14.5 hours at a temperature of 255°C. This reaction product was continuously taken out of the system and supplied to the second Nisdellization reaction chamber 11. 0.7 parts by weight of E based on the polynisder unit unino i in the reaction product passing through the second esterification reactor
E G fiG of antimono trioxide in an amount of 250 ppII as G and sb atoms was continuously supplied from a separate supply port, and t+ was maintained at normal pressure for a residence time of 5.
．． The reaction was carried out for 0 hours at a temperature of 260°C. The Nisdell conversion rate of the reaction product in the first esterification reactor is 68%, and the esterification rate of the reaction product in the second Nisdell conversion reactor is 98%.
%Met.

The esterification reaction product is continuously filtered through a steel/less metal filter with an opening of 400 mesh, and then filtered through a two-stage continuous filter equipped with a stirrer, a partial condenser, a stratified charging port, and a product outlet. Polycondensation was carried out by continuously supplying the mixture to a type phase-reacting reactor to obtain a polyester having a hardness of 1° and a viscosity of 1fJlO, [i20].

The quality of this polymer, melt extrusion of the polymer, 9
53.5 times vertically at 0°C, 3x horizontally at 130'C
．． 1 obtained by stretching 5 times and then heat-treating at 220°C
The film properties of the 2μ film are shown in Table 1.

The polyester obtained by the method of this example has a low number of fl [large particles] and excellent electrostatic adhesion.

In addition, the film has a high degree of transparency. Furthermore, the surface of the film is highly smooth and is product T.

Comparative Example 1 In the method of Example 1, the addition of magnesyl acetate and tetrahydrate was stopped, and trimedel was added so that the ratio between metal and P was 1.7; 1. The quality and film properties of the polymers obtained in the same manner as in Example 1 are shown in Table 1, except that the loadings of sulfate and dimylphenyl phosphonate were reduced to 24 ppm and 71 ppm as atoms, respectively. .

Is the polyester obtained by the method of this comparative example electrostatic? ! (The adhesion is extremely poor.

Comparative Example 2 In the method of Example 1, the addition of substituent acetate dihydrate and sodium acetate was stopped, and the atomic ratio of the metal and 1) was 1.
．． The same method as in Example 1 except that the loadings of trimedel phosphate and dimedyl phenyl phosphonate were reduced to 7) IOppm and 5Or' pH, respectively. are shown in Table 1.

The polynisdel obtained by the method of this comparative example has extremely poor slipperiness.

Comparative Example 3 In the method of Example 1, the M diameter ratio of metal and ■) is 1.
The addition L1 of trimethyl phosphate-1 and dimethyl phenyl phosphonate was adjusted to 72% each so that the amount of
The quality and film properties of the polymer obtained in the same manner as in Example 1, except that the concentration was increased to 217 ppm and 217 ppm, are shown in Table 1.

Polynisdel subjected to ftJ by the method of this comparative example has extremely poor electrostatic adhesion.

Comparative Example 4 Table 1 shows the quality and filtration properties of the polymer obtained by the same method as in Example 1, except that the addition of trimedel phosphate and dimethyl phenyl phosphonate was stopped. .

The polyester obtained by the method of this comparative example has a significantly large number of 111 particles. In addition, the degree of coloration and thermal stability of the polymer are poor. Furthermore, the electrostatic adhesion is not good.

Comparative Example 5 Obtained in the same manner as in Example 1 except that the addition of magnesium acetate tetrahydrate and zinc acetate dihydrate was transferred from the first Nisderification reactor to the second esterification reactor. Polymer quality and film properties are shown in Table 1.

The polyester obtained by the method of this comparative example is inferior in that it has a large number of coarse particles.

Examples 2 and 3 Table 1 shows the polymer quality and film properties when the addition ratio of trimedel phosphate and dimethyl phenyl phosphate was changed in the method of Example 1. High quality polymers and films have also been obtained. In addition, by changing the addition ratio of the two types of P compounds, it is possible to maintain a high level of electrostatic density and change the surface roughness of the filter without increasing the generation of coarse particles. Addition of methyl phenyl phosphonate? It can be seen that the surface roughness becomes rougher by increasing the I ratio.

Example 4 Table 1 shows the results when the same method as in Example 1 was carried out, but the addition of sodium acetate was stopped and phenylphosphonic acid was used alone as the P compound. It can be seen that high quality polymers and films are obtained.

Examples 5 and 6 Table 1 shows the polymer quality and film properties obtained by changing the amount of sodium acetate and compound I) added in the method of Example 1.

In both examples, high quality polymers and films were obtained. In addition, by changing the amount of sodium acetate added, it is possible to change the surface properties of the film while maintaining a high level of electrostatic density and without increasing the production of large particles. I understand. In other words, the surface roughness becomes rougher by increasing the amount of sodium Daigo added.

Examples 7 and 8 In the method of Example 1, acetic acid
Table 1 shows the polymer quality and film properties when the amount of the compound added was changed.

In all examples, high quality polymer rice films were obtained.Additionally, the addition of zinc acetate-water salt
By changing , a high level of electrostatic adhesion t'1 can be maintained,
Moreover, it can be seen that the surface properties of the film can be changed without increasing the generation of coarse particles. That is, the surface roughness becomes rougher by increasing the amount of zinc acetate dihydrate added.

Example 9 Table 1 shows the results when acetic acid/potassium was used as the aluminum compound in the same method as in Example 1.

Almost the same high quality polymer and film as in Example 1 is obtained.

Example 10 Table 1 shows the results when lithium acetate dihydrate was used as the alkali metal compound and phenylphos;j;/acid was used as the 1) compound in the same method as in Example 1.

In each of the examples, ``high quality polymers and films were used.''I've been beaten 5 times. In addition, by changing the amount of lithium acetate added, high electrostatic adhesion can be maintained.
Moreover, it can be seen that the surface characteristics of the film can be changed without increasing the generation of coarse particles. That is, f′i! increases the amount of acetic acid rhizium added! , the surface roughness is rough.

Examples 12 and 13 Table 1 shows the results when sodium acetate and lithium acetate dihydrate were used as the alkali metal compounds in the same method as in Example 1.

In both examples, high quality polymers and films were obtained. Also addition of sodium acetate and lithium acetate? By changing the l1 coupling, a high degree of static (li
It can be seen that the surface properties of the film can be changed while maintaining adhesion and without increasing the generation of coarse particles.

That is, by increasing the addition ratio of lithium acetate,
The surface roughness of the film can be made finer.

Procedural amendment (voluntary) July 26, 1981 Mr. Manabu Shiga, Commissioner of the Patent Office ■, Incident display Patent application No. 166160/1982 Z Name of invention Method for producing polyester containing internal particles 3. Person who makes corrections Relationship to the incident: Patent applicant 2-2-8 Dojimahama, Kita-ku, Osaka Claims and Detailed Description of the Invention in the Specification 5. Contents of amendment (1) Claim No. 0 will be amended as shown in the attached sheet.

■　Page 15, line 1 of the specification Correct "register color" to "resin color".

(3) Page 27, line 12 r (RA) Correct J to r (RA).

(4) On page 35, lines 6 and 7, replace “oyoba” with “
and” amended.

■ Table 1-1 (b) on page 38 and rRT'' (μ) J, rRA ('μ)'' in Table 1-2 (b) on page 40
are corrected as rRT, (μ)J, and rRA(μ), respectively.

In addition, "Roughness density (pieces/m♂)" is changed to "Roughness density (pieces/m♂)"
m) Correct it as J.

Attached Patent Claims (1) When producing polyester whose main repeating unit is ethylene terephthalate by direct polymerization method, ■
Mg in an amount that simultaneously satisfies the following formula (I) and (n) at any stage until the esterification reaction is substantially completed.
A method for producing an internal particle-containing polyester, characterized by adding a compound and a Zn compound, and (ii) adding an amount of P compound satisfying the following formula (II[) at any stage until the initial condensation reaction is completed. .

30≦Mg+Zn≦500・・・・・・・・・・・・(
I) 0, 1≦M g / Z n≦10 ・・・・・・
・・・・・・・・・＜Ti)1.2≦(Mg+Zn)/
P≦20・−・・・・−(III) [In the formula, Mg is N1g
Addition of compound as M g atom to polyester ffi (ppr+) N Z n is addition of Zn compound to polyester as Z n atom ffi (p
pm), M g / Z n and CM g + Z I]
) /P indicates each atomic ratio. ] ■ At any stage until the initial condensation reaction is completed, the following (
An amount of Li+ that simultaneously satisfies formula IV) and formula (V)
At least one alkali metal compound selected from Na and compounds and an amount of P satisfying the following formula (Vl)
Claim No. 1 characterized in that a compound is added (
1) A method for producing an internal particle-containing polyester as described in section 1).

3≦M≦400・・・・・・・・・・・・・・・(IV
)0.1≦M g/ (Z n +M)≦10...
・・・・・・・・・・・・・・・・・・(V')" 1.
2≦(M g + Z n + !(M) / P≦2
0・・・・・・・・・・・・(■) [In the formula, M is the addition (ppm) of the alkali metal compound to the polyester as a metal atom, M g /(Zn+M) and CM
g 㼼Z n + '+ M ) / P indicates the respective atomic ratio. (3) A method for producing a polyester containing internal particles according to claims (1) and 0, characterized in that a phosphonic acid and/or a phosphonic acid ester is used as the P compound.

(4) As the P compound, a mixture of phosphonic acid and/or phosphonic acid ester and at least one P compound selected from phosphoric acid, phosphorous acid and their esters is used, and the following formula (■) is used: A method for producing an internal particle-containing polyester according to claims (1) and 0, characterized in that the polyester is added in an arbitrary proportion that satisfies the following.

9/1≦A/B≦1/9 (■) [In the formula, A is the number of moles of phosphonic acid and/or phosphonic acid ester added, B is phosphoric acid, phosphorous acid and the number of moles added of the P compound selected from these esters. ]

Claims (1)

[Claims] (1) When producing a polyester whose main repeating center is ethylene terephthalate by a direct polymerization method,
ffl that simultaneously satisfies the following formulas (1) and (II) at any stage until the Nisderization reaction is substantially completed.
(1) adding a P compound in an amount satisfying the following formula (III) at any stage until the initial synthesis reaction is completed; ,j! How to make Liesple. 30≦61g+Zn≦500・・・・・・・・・(
I) 0.1≦! 1+ @ / Z n≦ 10...
・・・・・・・・・(■■)1.2≦(M g + Zn
) / P≦20 ・-・・-' (Ill) [wherein, lilgL; t Addition amount (ppm) of Mg compound as Mg molecule relative to polynisdel, Zn is Zi+
Compound 1! Z ++ Ii for digital still;
+ attachment as child, foreground (, pr+m). Mg/Zn and (Mg+Zn)/P each indicate the atomic ratio. ] ■) Adding Li in an amount that simultaneously satisfies the following formulas (IV) and (V) at any stage until the initialization integrated reaction is completed.
, Na and at least one alkali metal compound selected from compounds and an amount of P that satisfies the following formula (Vl).
Claim No. 1 characterized in that a compound is added (
1) A method for producing a polyester containing internal particles as described in item 1). 3≦M≦400・・・・・・・・・・・・・・・・・・
... (IV) 0.1≦Mg/(7,n+M)≦10
・・・-・=-(V)1.2≦(11!g+Zn+1
/2M)/I'≦211-(Vl) [where M is the addition of an alkali metal compound as a metal atom to the poly5r stellate (IIPI), 111g/(Zn+M) and (Mg+Zn+1/21i1)/P are respectively 16 of
Indicates the il. ] (3) I) As a compound, phosphonic acid and/or;1. S;1. 1. A method for producing a 1,1-Liesdel containing internal particles as set forth in claims (1) and (2), characterized in that a phosphoric acid ester is used. (4) As the P compound; 1. A mixture of sulfonic acid and/or caustyl phosphonate and at least one 1) compound selected from phosphoric acid, phosphorous acid, and their esters, and A method for producing an internal particle-containing polyester according to claims (1) and 2), characterized in that the polyester is added in an arbitrary proportion that satisfies the following formula (Vi). 9/1≦ 8/B≦ 1/9・・・・・・・・
... (■) In the formula, A is 1, sulfuric acid and /
Or; I indicates the number of moles of Nisder sulfonate added, the number of moles of I) compound added from 13 phosphoric acid, 11F phosphoric acid and their esters. ]