JPS6044520A - Manufacture of polyester containing internal particles - Google Patents

Abstract

PURPOSE:To obtain a polyester avoiding coarse particle development having such excellent surface characteristics with fine uneveness as to be suitable for magnetic tape base film production, by adding each specific amount of zinc and phosphorus compounds in specified stages, respectively, in the direct polymerization for the polyester. CONSTITUTION:In manufacturing through direct polymerization process a polyester constituted by >=80mol% of ethylene terephthalate as the main recurring unit, a zinc compound is added, during the esterification, in such an amount as to satisfy the equation: 30<=Zn<=500 [Zn is the amount added of the zinc compound on the basis of Zn atom (ppm)] followed by adding a phosphorus compound (e.g., phosphonic acid), at any point until the completion of the initial condensation, in such an amount as to satisfy the equation 0.1<=Zn/P<=10 (Zn/P is number ratio of said atoms) to have internal particles contained in the objective polyester. Said phosphorus compound will be added together with at least one sort of alkali metal compound selected from Li-, Na-, and K-compounds.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing polyester containing internal particles, and in particular, by precipitating fine insoluble particles at a high concentration in the polymer during the polyester production process, it is possible to produce fibers and films as final products. The present invention relates to a method for producing polyester by direct polymerization, which allows fine irregularities to be formed on the surface at high density.

The internal particle-containing polyester obtained by the method of the present invention is
It can satisfy various market demands for custom-made surfaces such as transparency, surface brightness, slipperiness, surface smoothness, and abrasion resistance. Furthermore, since the production of coarse particles is small, when the film is used as a base film for magnetic tapes, there are fewer defects in magnetic recording signals, that is, dropouts, so it is extremely suitable as a raw material for manufacturing base films for magnetic tapes.

Since polyester p 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 poor processability during spinning or film forming. There is a strong desire to establish a polyester 220 manufacturing method that provides the following properties.

Generally, as a method for improving the slipperiness of polyester/I/fibers or films, a method is adopted in which insoluble fine particles are mixed with polyester to form fine irregularities on the surface of the fibers or films.

Specifically, (1) the so-called external particle method in which fine particles inert to polyester such as titanium dioxide, kaolinite, talc, and silica are added when producing polyester, and (2>polyester/l/ There is a so-called internal particle method in which fine particles are formed by reacting either a carbonic acid component, an oligomer, or a P compound with a metal compound during the production reaction.When comparing the external particle method and the internal particle method, the following The internal particle method is considered to be more advantageous for the reasons shown in the following.

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

(2) In the external particle method, it is necessary to use a dispersant in order to prevent knobs, fish eyes, etc. 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.

(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 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, in the internal particle method, fine particles are precipitated using catalyst residues of alkali metals, alkaline earth metals, etc. used as transesterification catalysts, and the amount and particle size of the fine particles precipitated are adjusted by adding a P compound. method is the predominant method.

Examples of metal compounds include Ca compounds and /-! Taha Li
Most of the examples use compounds.

Many attempts have been made to apply this method directly to the polymerization method, but in all of them, the method has been carried out by adding an alkali metal or alkaline earth metal compound 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 TPA or water to the reaction system;
A method has been proposed in which the conditions during and after the addition of the metal compound or P compound are limited to a specific range.

It is true that internal particles can be generated by these methods, but in order to keep the amount of fine particles precipitated and the particle size constant at all times, it is necessary to strictly control the polymerization conditions, and the amount of precipitated particles must also be satisfied. Not up to the level. In particular, when the film is used as a base film for a magnetic tape due to the generation of large amounts of coarse particles, there are many drop-at defects, which are drop-outs of magnetic recording signals, making it difficult to apply the film to this field. In addition, due to the diversification of market demands in recent years, transparency, surface brightness, slipperiness, surface smoothness,
As requirements for various surface properties such as abrasion resistance become stricter, there is a growing demand for films that simultaneously satisfy contradictory properties such as films with excellent surface smoothness and highly slippery properties. Polyester μ to satisfy
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. The present inventors focused on the above-mentioned circumstances, and by precipitating fine insoluble particles in a polymer at a high concentration using a direct polymerization method, it is possible to create fine irregularities at a high concentration on the surface of the final product fiber or film. It satisfies various market demands for surface properties such as transparency, surface smoothness, ease of slippage, surface smoothness, and WFI wear notes, and produces less coarse particles. The present invention was achieved as a result of extensive research aimed at establishing a method for producing polyester that is suitable as a raw material for production.

That is, the first aspect of the present invention is that when producing a polyester whose main repeating unit is ethylene terephthalate by a direct polymerization method, (1) the following CI) is added at any stage until the esterification reaction is substantially completed. An internal particle characterized by adding a Zn compound in an amount satisfying the formula (2) and adding a P compound in an amount satisfying the following formula (II) at any stage until the initial condensation reaction is completed. This is a method for producing polyester containing polyester.

30≦Zn≦500 ・・・・・・・・・・・・・・・
・・・・・・・・・CI) 0.1≦Zn/P≦10 Kawaaki・・・・・・・・・・・・・・・・・・(n) [In the formula, b Zn is Zn Compound Zn w for polyester
, the amount added as a child (1) pm), Zn/P indicates the atomic ratio. ] The second invention of the present invention provides at least one compound selected from Li+Na and a compound satisfying the following formula (I[) at any stage until the initial condensation reaction is completed in the first invention. This is a method for producing a polyester containing internal particles, which is characterized by adding an alkali metal compound and an amount of P compound satisfying the following formula (IV).

3≦M≦400 ・・・・・・・・・・・・・・・・・・
・・・・・・CI[)0.1≦(Z n + 1 /
2 M) / P≦10 ・・−・・−(IV) [
In the formula, the addition of the MI/i alkali metal compound to the polyester as a metal atom it (ppm), (z
n+1/2M)/P indicates the respective atomic ratio. ]The third invention of the present invention provides P used in the first and second inventions.
This is a method for producing a polyester containing internal particles, characterized in that esters of phosphonic acid and/-1'-phosphonic acid are used as compounds.

The fourth invention of the present invention provides that the P compound used in the first and second inventions is selected from phosphonic acid and acetate or phosphonic acid ester, phosphorus e, + phosphoric acid and esters thereof. This is a method for producing an internal particle-containing polyester characterized by using a mixture with at least one type of P compound and adding the mixture at an arbitrary ratio that satisfies the following formula (V).

9/1≦A/B≦1/9 Kawaaki... Song...
(V) In the formula C, h represents the number of moles added of AU phospho*y acid and/or phosphonic acid ester μ, B represents the number of moles added of P compound selected from phosphoric acid, phosphorous acid, and their esters.] The polyester of the present invention has a repeating unit of 8゜/L/
% or more consists of ethylene terephthalate,
Another copolymer component is isophthalic acid.

P-β-oxyethoxybenzoic acid, 2,6-naphthalene dicarboxylic acid, 4,4'-dicarboxylic VIL/dife"-/L'l 4+4'-dicarboxylbenzophenone.

Examples include dicarboxylic acid components such as bis(4-carpoxylphenytV)ethane, adipic acid, sepacic acid, and 5-sodium sulfoisophthalic acid.

In addition, as a glycol component, propylene glycol-/I/
, butanedio-/L/, neopentyl glycol.

diethylene glycol, cyclohetera sanji meta tool,
Ethylene oxide adducts of bispheno-/l/A and the like can be arbitrarily selected and used. In addition, small amounts of amide bonds, urethane bonds, ether bonds,
It may also contain a carbonate bond or the like.

The esterification rate F5 may be determined by either a batch method or a continuous method, but a continuous method is preferable because a product of stable quality can be obtained. When carrying out esterification in a continuous manner, it is preferable from the viewpoint of reaction control to carry out the esterification reaction in two to four reactors.

Any Zn compound used in the present invention can be used as long as it is soluble in one 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 amount of the Zn compound added is 30 to 500 as Zn atoms to the finally obtained polyester, as shown in formula (1).
In ppm, 50 to 400 ppm is particularly preferred. 30
If it is less than ppm, the amount of fine particles precipitated is small, and the slipperiness of the final product cannot be sufficiently improved. On the other hand, 500
If it exceeds ppm, the slipperiness will reach a saturated state, and rather coarse particles will be generated, resulting in decreased transparency and product defects such as knobs and fish eyes, which is not preferable. Further, it is not preferable because the resin color and stability deteriorate. The Z
It is necessary to add the n 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 film for a magnetic tape, there will be many dropouts of magnetic recording signals, which is not preferable. It is particularly preferable to add it when the esterification rate is 20 to 80, since the oligomer's permeability is improved and insoluble foreign substances in the oligomer can be efficiently removed by filtration. ' By adding it before the end of the esterification reaction, the formation of coarse particles can be suppressed and the esterification rate can be reduced to 2.
By adding in the range of 0 to 80%, thioligomer〇p
Although the cause of the improvement in overfilling is unknown, it is thought to be caused by a subtle change in the composition of the reaction product of the Zn compound, P 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, L++N
a and K carboxylates, phosphates, carbonates, hydrides and alkoxides, etc.

Specifically, lithium acetate, sodium acetate, potassium acetate, lithium benzoate, sodium benzoate, potassium benzoate, and potassium dihydrogen phosphate.

Sodium pyrophosphate, potassium pyrophosphate, sodium tripolyphosphate, potassium tripolyphosphate, sodium bicarbonate, potassium bicarbonate, lithium hydride, sodium hydride, potassium hydride.

Lithium methoxide, sodium methoxide.

Examples include potassium methoxide, lithium ethoxide, sodium ethoxide, potassium ethoxide, etc., but use of carboxylic acid salts is particularly preferred. These compounds may be used alone or in combination of two or more. The combined use of a Li compound and a Na compound is particularly useful because fine particles can be precipitated at a high concentration.

The amount of these alkali metal compounds added is determined by the general formula (II
The amount of metal atoms is preferably in the range of 3 to 400 ppm based on the polyester produced as shown in the formula.

If the amount of the alkali metal compound added exceeds 400 pp crystal, it is not preferable because the resin color deteriorates and coarse particles are generated, resulting in decreased transparency and product defects such as knobs and fish eyes.

The addition of these alkali metal compounds to the reaction system can be appropriately selected at any stage until the initial condensation reaction is completed. The point at which the initial condensation reaction is completed is when the intrinsic viscosity reaches approximately 0.2; after this point, the viscosity of the reaction system is too high and the added components become unevenly mixed, resulting in a homogeneous product. I won't be able to do it. Furthermore, depolymerization of oligomers occurs, which is undesirable because it causes a decrease in productivity and an increase in the amount of DEG by-products.

When adding 50 ppm or more of the alkali metal compound, it is particularly preferable to add it when the esterification rate is 20 to 80. The esterification rate of the alkali metal compound is 2.
When added at the time of 0 to 80 inches.

Oligomer 〇 The filterability is improved, insoluble foreign substances in the oligomer can be efficiently removed by filtration, and the generation of coarse particles is reduced.

These alkali metal compounds may be added alone to the reaction system or may be added simultaneously with other additives as long as the above conditions are satisfied.

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 P compound used in the present invention is phosphoric acid.

ifi phosphoric acid, phosphonic acid and derivatives thereof, specific examples include phosphoric acid, phosphoric acid trimethylester lv1 phosphoric acid triethyl ester, phosphoric acid tributyl ester, phosphoric acid triphenyl ester A/, phosphoric acid monomethyl ester, Dimethyl phosphate/I/, motubutyl phosphate, dibutyl phosphate, phosphorous acid, trimethyl phosphite, triethyl ester ls% phosphate tributyl ester, methylphosphonic acid, dimethyl methylphosphonate ester, ethylphosphonic acid cimethi p ester, phenylphosphonic acid dimethyl ester ester/L/, phenylphosphonic acid diphenyl ester, etc. Among these P compounds, it is preferable to use phosphonic acid and/or phosphonic acid ester because the concentration of precipitated particles becomes high.

Furthermore, any ratio that uses 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 and that satisfies formula (V) By adding . This method is particularly useful because it makes it possible to greatly expand the range of control over the particle diameter and particle concentration of precipitated particles.

The addition of these P compounds increases the gold m/P atomic ratio from 0.1 to 10 as shown in formulas (■) and (IV).
It is preferable to set it in the range of , preferably 0.5 to 3.0. If it is less than 0.1. This is not preferable because it causes a decrease in polymerization activity and an increase in the amount of DEG by-products. On the other hand, if it exceeds 10, Z
This is not preferable because the precipitation of coarse particles due to n-compounds and alkali metal compounds increases and the transparency of the film decreases. Furthermore, the heat resistance of the polymer and the resin color are also deteriorated, which is not preferable.

The addition of these P compounds to the [6 system] can be appropriately selected at any stage until the initial condensation reaction is completed.

If it is added after the initial condensation reaction has finished, the viscosity of the reaction system will be too high and the added components will not be mixed uniformly, making it impossible to obtain a homogeneous product. Furthermore, depolymerization of oligomers occurs, which is undesirable because it causes a decrease in productivity and an increase in the amount of DEG 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 conditions are satisfied.

What is the temperature of the reaction system when adding the above additives?

Any temperature range from 230 to 290°C may be used, but a range from 240°C to 270°C is particularly preferred. If the temperature is lower than 230°C, solidification of the oligomer will occur, which is not preferable. Conversely, if you add it when the temperature exceeds 290℃. D
This is not preferable because side reactions such as an increase in the amount of EG byproducts and coloring are promoted.

The pressure of the reaction system when adding the above additives is normal pressure to 3k
A range of y/-, particularly a range of normal pressure to 1 ume/- is preferred.

Addition under reduced pressure is not preferred because the additives will escape. On the other hand, if it exceeds 3 kf/ctA, the amount of DEG by-product will increase, which is not preferable.

Each of the additives mentioned above may be added in either solid or liquid form, but from the viewpoint of supply accuracy, it is most preferable to add them as an ethylene glycol solution. When it is added in solid form, it is preferably sealed in a container made of polyester IV and added to the reaction system.

transparency. In order to meet the market's demands for various surface properties such as surface optical properties, slipperiness, surface smoothness, and wear resistance, we need technology that can arbitrarily control the concentration, particle size, and particle size distribution of precipitated particles. need to be granted.

Control of this precipitated particles is done by adding Zn compound,
This can be carried out by changing the amount of the alkali metal compound and the P compound added, the addition ratio, the addition time, the addition order, and the type of the alkali metal compound and the P compound. The concentration of this precipitated particle.

Changes in particle size 1, particle size distribution, etc. are extremely diverse.

Although it cannot be easily described, it can be roughly summarized as follows.

(1) Control of the concentration of precipitated particles /L' largely depends on the amount of the metal compound added, and as the amount added increases, the amount of precipitated particles also increases. When the amount of metal compound added is constant, it can be increased by using phosphonic acid or phosphonic acid ester as the P compound.

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

When the addition ratio is kept constant, this can be done by changing the type of P compound. For example, this can be done by changing the addition ratio of phosphonic acids and phosphoric acid or phosphorous acids, and by reducing the addition ratio of phosphonic acids, the average particle size becomes smaller. Furthermore, Zn
When the addition ratio of the compound and the alkali metal compound is constant and the type of P compound is fixed, it can be controlled by changing the type of the alkali metal compound. N
Since the average particle size is smaller when using a Li compound than when using a compound a, the particle size can be arbitrarily controlled by using two or more types of alkali metals and changing the proportion of each added.

(3) Control of the particle size distribution can be greatly changed by changing the addition ratio of the Zn compound and the alkali metal compound and the timing of addition of these metal compounds and P compound. -For simple systems, the particle size distribution becomes sharp.

The above is just one way to control precipitated particles, and in reality there are various types of bulking agents.

Since the behavior of multiparticle precipitation changes in an extremely complex manner depending on the amount added, the ratio of addition, and the timing of addition, it is possible to sufficiently respond to various market demands.

Another feature of the present invention is that coarse particles are hardly generated;
When the final product film is used as a base film for a magnetic tape, it is suitable as a raw material for producing a film with few dropout defects. This point is as mentioned above.

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

The polycondensation catalyst can be appropriately selected from conventionally known catalysts and used! Of course, lubricants made of inorganic or organic fine particles and other various additives may also be used.

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

All parts in Examples and Examples mean parts by weight unless otherwise specified.

In addition, the measurement method used is shown below.

(1) Esterification rate is determined based on the amount of carboxyl groups remaining in the reaction product and 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 tetrachloroethane (4 parts by weight) and measured at 30°C.

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

(4) Film haze Measure with a direct reading haze meter (manufactured by Toyo Seiki Co., Ltd.).

(5) Film maximum surface roughness (RT), centerline average roughness (RA), and surface roughness density using a Surfcom 300A type surface roughness meter, needle diameter 1 μ, weight 0.07 t s measurement reference length 0.8 m, was measured under the condition of a cutoff of 0.081111, and is expressed as an average value of 10 points.

(6) Coefficient of dynamic friction (μd) of film ASTM-D-
1894-63T under the conditions of 23° C., 65% RH, and a tensile speed of 200 m/min.

Example 1 Using a continuous esterification reactor consisting of a two-stage complete mixing tank equipped with a stirring device, a partial condenser, a raw material inlet, and a product outlet, esterification reaction was performed in the first esterification reactor. The molar ratio of EG to TPA is 1.
EG slurry of TPA adjusted to 7 was continuously supplied.

At the same time, an EG bath solution of zinc acetate dihydrate, an EG bath solution of sodium acetate, an EG bath solution of trimethyl phosphate, and an EG bath solution of dimethylphenyl phosphonate are passed through the reaction vessel from a supply port different from the TPA EG swolly supply port. 200 ppm as Zni atoms and 1 as Na atom per polyester unit in the reaction product.
00 ppm.

51 pI) m and 152 p as P atoms, respectively
pm, and the reaction was carried out at normal pressure for an average residence time of 4.5 hours and at a temperature of 255°C. This reaction product is continuously taken out of the system, and 0.7 parts by weight of EG and sb atoms are calculated based on the polyester unit in the reaction product passing through the second esterification reactor.
E of antimony trioxide in an amount such that 50 pI) m
The G bath solutions were continuously supplied from separate supply ports, and the reaction was carried out at normal pressure for an average residence time of 5.0 hours and at a temperature of 260°C. The esterification rate of the reaction product in the first esterification reactor was 68%, and the esterification rate of the reaction product in the second esterification reactor was 98%.

The esterification reaction product was continuously filtered through a stainless metal filter with an opening of 400 mesh, and then subjected to two-stage continuous polycondensation equipped with a stirring device, a partial condenser 5W, a feed inlet, and a product outlet. Polycondensation was performed by continuously supplying the mixture to a reactor to obtain a polyester having an intrinsic viscosity of 0.620.

The quality of this polymer, melt extrusion of the polymer, 90
Table 1 shows the film properties of a 12μ film obtained by stretching 3.5 times in the longitudinal direction at 130°C and 3.5 times in the transverse direction at 130°C, and then heat treating at 220°C.

The polyester obtained by the method of this example has a low number of coarse particles. The film also has excellent slipperiness and high transparency. Furthermore, the film surface is highly smooth and of high quality.

Comparative Example 1゜In the method of Example 1, the addition of zinc acetate dihydrate was stopped, and the amounts of trimethyl phosphate and dimethyl phenyl phosphonate added were changed to PM so that the atomic ratio of metal to P was 0.8. The polymer quality and film customization obtained in the same manner as in Example 1, except reduced to 21 ppm and 63 ppm, respectively, are shown in Table 1.

The method of this comparative example is inferior in that the number of coarse particles is large.

Comparative Example 2 Table 1 shows the quality and film properties of a polymer obtained in the same manner as in Example 1, except that the addition of trimethyl phosphate and dimethylphenylphosphonate was stopped. In the method of this comparative example, the number of coarse particles is significantly large. It is also inferior in terms of the degree of coloration and thermal stability of the polymer.

Comparative Example 3゜In the method of Example 1, the addition of zinc acetate dihydrate was
Table 1 shows the quality and film properties of the polymer obtained in the same manner as in Example 1 except for transferring it from the esterification reactor to the second varnish 7-μ reactor.

The method of this comparative example is inferior in that the number of coarse particles is large.

Examples 2 to 5 Table 1 shows the polymer quality and film customization obtained by changing the addition ratio of trimethyl phosphate dodimethyl phenyl phosphonate in the method of Example 1.

In both examples, high quality polymers and films were obtained.

In addition, by changing the addition ratio of two types of P compounds,
It can be seen that the surface properties of the film can be changed significantly without increasing the formation of coarse particles. That is, by increasing the addition ratio of dimethylphenylphosphonate, the surface roughness becomes rougher.

Example 6 Table 1 shows the results when zinc acetate hydrate and phenylphosphonic acid were used in the same manner as in Example 1.

High quality polymers and films have been obtained. It is also seen that by increasing the amount of sodium acetate added, the surface roughness can be increased without increasing the generation of coarse particles.

Examples 7 to 9 Table 1 shows the results obtained by changing the amounts of sodium acetate and P compound added in the method of Example 1. In both examples, high quality polymers and films were obtained. It can also be seen that by increasing the amount of sodium acetate added, the surface roughness can be increased without increasing the generation of coarse particles.

Examples 10 to 13 Table 1 shows the results when lithium acetate dihydrate was used as the alkali metal compound in the same method as in Example 1.

In both examples, high quality polymers and films were obtained. It is also seen that by changing the amounts of zinc acetate dihydrate and lithium acetate dihydrate, the surface properties of the film can be changed without increasing the formation of coarse particles.

In other words, when the amount of lithium acetate dihydrate added is the same, the smaller the amount of zinc acetate dihydrate added, and when the amount of zinc acetate dihydrate added is the same, the more the amount of lithium acetate dihydrate added is 1 The surface roughness is rough.

Example 14゜Table 1 shows the results when potassium acetate was used as the alkali metal compound in the same method as Example 1.
It can be seen that a high quality polymer and film almost the same as in Example 1 was obtained.

Examples 15 and 16 Table 1 shows the results when sodium acetate and lithium acetate dihydrate were used together as alkali metal compounds in the same method as in Example 1.

In both examples, high quality polymers and films were obtained. It can also be seen that by determining the addition ratio of sodium acetate and lithium acetate dihydrate, the surface characteristics of the film can be changed. That is, by increasing the addition ratio of lithium acetate dihydrate, the surface roughness becomes finer.

Procedural amendment (formality) 1. Display of incidents 1981 Patent Application No. 152259 2. 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 4. Date of amendment order November 8, 1982 (Shipping date: November 29th of the same year) 5. Subject of correction Items 1 to 297 of the specification 6. Contents of amendment Engraving of the statement (no changes to the contents)

Claims (1)

[Claims] (1) When producing polyester P whose main repeating unit is ethylene terephthalate by a direct polymerization method, adding a satisfactory amount of Zn compound;
■ At any stage until the initial condensation reaction is completed, the following (I
F) A method for producing an internal particle-containing polyester, which comprises adding a P compound in an amount that satisfies the formula. 30≦Zn≦500 ・・・・・・・・・・・・・・・
... (I) 0.1≦Z n / P≦10 ...
・・・・・・・・・・・・・・・(II) [In the formula * Z
The amount of Zn atoms added to the polyester of the n u Z n compound (1) pm), Zn/P indicates the atomic ratio. ] (2) Li + Na in an amount that satisfies the following formula (N) and at least one alkali metal compound selected from nitrides at any stage until the initial condensation reaction is completed and the following formula (IV) is satisfied. A method for producing an internal particle synthetic polyester according to claim (1), characterized in that a P compound is added in an amount of . 3≦M≦400 ・・・・・・・・・・・・・・・・・・
・・・・・・・・・・・・(III) 0.1≦(Z n +
1/2 M)/P≦lO・・・・・・(■
) [In the formula, 1M is the addition of the Narkali metal compound to the polyester as a metal atom (ppm), (Z
n+1/2M)/P indicates the respective atomic ratio. 〕(
3) A method for producing an internal particle-containing polyester according to claims (1) and (2), 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 (V ) A method for producing internal particles &W polyester according to claims (1) and (2), characterized in that the polyester is added in an arbitrary proportion that satisfies the following formula. 9/1≦A/B≦1/9 ・・・・・・・・・・・・・・・
・・・・・・・・・(V) [In the formula, A is the number of moles of phosphonic acid and/or phosphonic acid ester added, B is the addition of P compound selected from phosphoric acid, phosphorous acid, and their esters. Shows the number seven. ]