JP5519156B2 - Method for producing highly crystalline polyester composition - Google Patents

Description

  The present invention relates to a method for producing a highly crystalline polyester composition. More specifically, the present invention relates to a method for producing a polyester composition that can be expected to exhibit excellent mechanical strength, heat resistance, and dimensional stability by having high crystallinity.

  Polyester, particularly polyethylene terephthalate (hereinafter sometimes referred to as PET), polyethylene naphthalate (hereinafter sometimes referred to as PEN), polytrimethylene terephthalate (hereinafter sometimes referred to as PTT) and polytetra. Methylene terephthalate (hereinafter sometimes referred to as PBT) is widely used for fibers, films or other molded articles because of its excellent mechanical, physical and chemical performance.

  Polyester resin has excellent mechanical properties such as strength, elongation, Young's modulus or elastic recovery rate, physical properties such as heat resistance or dimensional stability, or chemical properties such as chemical resistance or water resistance, and is inexpensive. Therefore, it is well known that it has great industrial value. For example, in the case of PET and PEN, it is often used as a fiber, a resin molded product, a film, etc. In the case of PTT, it is a fiber or the like, and in the case of PBT, it is often used as a resin molded product typified by engineering plastics. Polyester, which is a crystalline polymer, is thought to be responsible for physical properties such as strength and Young's modulus of the crystalline part. If the crystallinity of polyester can be increased, various physical properties can be improved (higher strength, higher Young's Efficiency, toughness, dimensional stability improvement, heat resistance improvement, gas barrier property improvement, fatigue improvement, etc.) are expected to be achieved. In addition, if a highly crystalline polyester is used, when a resin molded product is produced, a merit that a resin molding cycle can be shortened can be expected. Also, in the case of copolymerized polyester, the crystallinity is reduced, so the chips are fused together in the drying process, and there is a case where a cake-like lump of Japanese confectionery is generated, causing a process abnormality, which improves the crystallinity. It is also expected from the point that these problems can be suppressed.

  Now, in the process of producing a polyester product, as a method of improving the moldability, in other words, as a method of using a highly crystalline polyester, a method of combining an antimony compound and various compounds has been proposed (for example, Patent Documents). 1-2.) However, the crystallinity of the polyesters obtained by these conventional methods was insufficient.

  On the other hand, as a method for obtaining a highly crystalline polyester, a method of adding a phosphonic acid compound has been proposed in the past (for example, see Patent Documents 3 to 15). These methods are characterized in that fine particles are formed by reacting a metal compound such as an alkaline earth metal or transition metal hydride, oxide or acetate with a phosphorus compound, and a very high crystalline polyester can be obtained. Had.

  However, there is a big problem that aggregated particles are easily generated during the reaction. That is, precipitation other than the desired metal salt, such as the formation of an ethylene glycol salt of a metal compound by the reaction of a metal compound and ethylene glycol, or the formation reaction of a metal compound of terephthalic acid by the reaction of a metal compound and terephthalic acid. There was a problem of particles being by-produced. These by-products, such as metal salts, can be used to a) increase the pack pressure, b) cause thread breakage, c) cause foreign matter in the base, or D) Causes problems such as deteriorating the appearance of polyester molding.

  In the past studies, (1) addition of alkali metals, (2) optimization of the ratio of phosphonic acid compound and metal species, (3) change of types of phosphonic acid compounds and metal compounds, (4) By optimizing the timing of addition of the phosphonic acid compound and the metal compound, attempts were made to reduce side reactions and precipitation of aggregated particles, and to reduce the aggregation of the target phosphonic acid metal salt. (For example, refer to Patent Documents 1 to 11).

  As described above, studies for improving the crystallinity of conventional polyesters have attracted a great deal of attention from the viewpoint of improving physical properties and improving moldability, and further reduction of defects and improvement of physical properties of the obtained polyester molded products are required. I came.

JP-A-57-042921 JP 56-096913 A Japanese Patent Publication No. 58-034491 JP-A-62-206018 Japanese Patent Laid-Open No. 60-065027 JP 60-058432 A Japanese Patent Laid-Open No. 60-047022 Japanese Patent Laid-Open No. 60-047021 JP 60-044520 A JP-A-60-042420 JP 60-040126 A Japanese Patent Application Laid-Open No. 60-035022 Japanese Unexamined Patent Publication No. 60-032824 JP 60-031526 A Japanese Patent Laid-Open No. 60-015422

  The object of the present invention is to produce a highly crystalline polyester composition capable of reducing the generation of aggregated particles of by-products derived from the reaction of a metal compound with alkylene glycol, terephthalic acid or naphthalenedicarboxylic acid during the transesterification and polycondensation reactions. Is to provide a method.

［上記一般式（ＩＩＩ）中、Ｒ^４は炭素数６〜１２個のアリール基を示し、Ｍ^Ｚ＋は、Ｍｇ^２＋、Ｍｎ ^２＋ 、Ｃｏ ^２＋ 又はＺｎ ^２＋ の金属イオンを示す。但しＺ＝２のとき、ｎ＝１、ｍ＝１である。］ As a result of intensive studies in view of the above prior art, the present inventors have completed the present invention.
That is, in the present invention, a dicarboxylic acid dialkyl ester represented by the following general formula (I) is reacted with a diol component represented by the following general formula (II) by a transesterification reaction, and then a polyester is produced by a polycondensation reaction. The polyester characterized by adding the phosphonic acid metal salt represented by the general formula (III) so as to be 0.01 to 1.0% by mass with respect to the total weight of the polyester composition at any stage of the step of It is a manufacturing method of a composition, and the said subject can be solved by this method.
^{R 1 OCO-R 2 -COOR 1} (I)
[In the general formula (I), R ¹ represents an alkyl group having 1 to 2 carbon atoms, and R ² represents a p-phenylene group or a 2,6-naphthalene group. ]
^HO-R 3 -OH (II)
[In the general formula (II), R ³ represents a linear alkylene group having 2 to 4 carbon atoms. ]

[In the general formula (III), R ⁴ represents an aryl group having 6 to 12 carbon atoms , and M ^{Z +} represents a metal ion of Mg ²⁺ , Mn ²⁺ , Co ²⁺ or Zn ²⁺ . However, when Z = 2, n = 1 and m = 1. ]

  According to the present invention, it is possible to produce a polyester composition with good crystallinity containing a phosphonic acid metal salt that becomes a crystal nucleus without producing a by-product scale or aggregate particles as in the prior art. In addition, it becomes possible to produce a polyester molded product having excellent moldability (yarn-making property, stretchability, and processability).

The present invention will be described in detail below.
The polyester in the present invention is obtained by subjecting an aromatic dicarboxylic acid dialkyl ester and a diol component to a transesterification reaction, followed by a polycondensation reaction, and mainly repeating ethylene terephthalate units obtained by a polycondensation reaction of terephthalic acid and ethylene glycol. The unit polyester is preferably used. Here, “main” means that 70 mol% or more of all repeating units are ethylene terephthalate units. As a method for producing a polyester portion in the method for producing a polyester composition of the present invention, a conventionally known polyester production method is used. That is, first, a dicarboxylic acid glycol ester and / or a low polymer thereof is produced by a transesterification reaction between a dicarboxylic acid diester component such as dimethyl terephthalate and a glycol component such as ethylene glycol. Then, the reaction product is heated under reduced pressure in the presence of a polycondensation catalyst and subjected to a polycondensation reaction until a predetermined degree of polymerization is obtained, whereby a target polyester is produced.

Specifically, a dicarboxylic acid dialkyl ester represented by the following general formula (I) and a diol component represented by the following general formula (II) are used.
^{R 1 OCO-R 2 -COOR 1} (I)
[In the general formula (I), R ¹ represents an alkyl group having 1 to 2 carbon atoms, and R ² represents a p-phenylene group or a 2,6-naphthalene group. ]
^HO-R 3 -OH (II)
[In the general formula (II), R ³ represents a linear alkylene group having 2 to 4 carbon atoms. ]

  Examples of the dicarboxylic acid dialkyl ester represented by the general formula (I) include dimethyl terephthalate, diethyl terephthalate, dimethyl 2,6-naphthalenedicarboxylate, and diethyl 2,6-naphthalenedicarboxylate. Among these, dimethyl terephthalate and dimethyl 2,6-naphthalenedicarboxylate are preferable. Examples of the diol component represented by the general formula (II) include ethylene glycol, 1,3-propylene glycol (trimethylene glycol, 1,3-propanediol), 1.4-butylene glycol (tetramethylene glycol, 1, 4-butanediol).

  In the transesterification reaction, it is preferable to use a predetermined amount as a transesterification catalyst for alkali metal compounds, alkaline earth metal compounds, manganese compounds, zinc compounds, tin compounds and the like. Specific examples include sodium acetate, potassium acetate, manganese acetate, and tin acetate.

  Although it does not specifically limit about the polycondensation catalyst used for the manufacturing method of the polyester composition of this invention, Antimony, titanium, germanium, aluminum, a zirconium, and a tin compound can be used. Examples of such a compound include antimony, titanium, germanium, aluminum, zirconium, tin oxide, acetate, carboxylate, hydride, alcoholate, halide, carbonate, sulfate and the like. Moreover, these compounds may use 2 or more types together.

  In addition, the temperature, pressure, and time in the transesterification reaction and the temperature, pressure, and time in the polycondensation reaction should be the same as those for conventional polyesters (eg, polyethylene terephthalate, polyethylene naphthalate). Can do.

<Types of phosphonic acid metal salt>
The method for producing the highly crystalline polyester composition of the present invention can be achieved by adding a phosphonic acid metal salt represented by the following general formula (III).

［上記一般式（ＩＩＩ）中、Ｒ^４は炭素数１〜１２個のアルキル基、炭素数６〜１２個のアリール基又はベンジル基を示し、Ｍ^Ｚ＋は、Ｍｇ^２＋、又は第３〜４周期第２〜１５族の金属イオンを示す。Ｚは２〜４の整数である。
但しＺ＝２のとき、ｎ＝１、ｍ＝１であり、Ｚ＝３のとき、ｎ＝３、ｍ＝２であり、Ｚ＝４のとき、ｎ＝２、ｍ＝１である。］

[In the general formula (III), R ⁴ represents an alkyl group having 1 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms, or a benzyl group, and M ^{Z +} represents Mg ²⁺ , or the third to fourth periods. Group 2-15 metal ions are shown. Z is an integer of 2-4.
However, when Z = 2, n = 1 and m = 1, when Z = 3, n = 3 and m = 2, and when Z = 4, n = 2 and m = 1. ]

The functional group R ⁴ represents an alkyl group having 1 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms, or a benzyl group. Specifically, a methyl group, an ethyl group, a normal propyl group, an isopropyl group, a normal group Butyl group, isobutyl group, sec-butyl group, tert-butyl group, hexyl group, octyl group, decyl group, dodecyl group, phenyl group, o-methylphenyl group, m-methylphenyl group, p-methylphenyl group, o -Ethylphenyl group, m-ethylphenyl group, p-ethylphenyl group, butylphenyl group, hexylphenyl group, 1-naphthyl group, 2-naphthyl group, 4-phenylphenyl group and benzyl group can be exemplified. Among them, an aryl group is preferably selected, and a phenyl group is more preferable. M ^{Z +} is selected from Mg ²⁺ , or metal ions of the 3rd to 4th group 2 to 15 group. Among them, at least one metal element selected from the group consisting of magnesium, manganese, cobalt, zinc, and titanium, more specifically, Mg ²⁺ , Mn ²⁺ , Co in that the obtained polyester composition exhibits high crystallinity. Preferred examples include ²⁺ , Zn ²⁺ and Ti ⁴⁺ . In the general formula (III), when Z = 2, n = 1 and m = 1, when Z = 3, n = 3 and m = 2, and when Z = 4, n = 2 , M = 1. This is to satisfy the formula 2 × n = Z × m. This is because the charge amount of the cation species and the charge amount of the anion species in the compound represented by the general formula (III) are the same. Note that when Z = 2, m is in the range of 0.9 to 1.1, and when Z = 3, m is in the range of 1.8 to 2.2. M is preferably in the range of 0.9 to 1.1. If m deviates from these ranges, the charge amounts of the anion species and the cation species do not match, the amount of impurities contained in the phosphonic acid metal salt increases, and the effect of improving the crystallinity is lowered, which may be undesirable.

  That is, as the phosphonic acid metal salt, a phenylphosphonic acid metal salt can be preferably mentioned, and phenylphosphonic acid magnesium salt, phenylphosphonic acid manganese salt, phenylphosphonic acid cobalt salt, phenylphosphonic acid zinc salt, phenylphosphonic acid titanium salt. More preferred can be mentioned.

<About the amount of phosphonic acid metal salt added>
The phosphonic acid metal salt used for this invention needs to contain 0.01-1.0 mass% with respect to the mass of all the polyester compositions.
When the content of the phosphonic acid metal salt is less than 0.01% by mass, the resulting polyester composition has insufficient crystallinity, and when it exceeds 1.0% by mass, the particles of the phosphonic acid metal salt aggregate. High-order aggregated particles are formed, which is not preferable. The content of the phosphonic acid metal salt is preferably in the range of 0.02 to 0.5 mass%, more preferably in the range of 0.03 to 0.2 mass% with respect to the mass of the total polyester composition.

<Time of adding phosphonic acid metal salt>
Here, the addition time of the phosphonic acid metal salt of the general formula (III) in the production of the polyester is not particularly limited, but it can be added at any stage where the polycondensation reaction ends before the start of the transesterification reaction. Preferably, it is added at the time from the end of the transesterification reaction to the start of the polycondensation reaction.

<Method of adding phosphonic acid metal salt>
The method for adding the phosphonic acid metal salt is not particularly limited, but there are a wet method in which the phosphonic acid metal salt is added in a slurry state, or a dry method in which the phosphonic acid metal salt itself is added without containing a solvent. Can be mentioned. The wet method can be preferably employed because adjustment is easy when the amount of the phosphonic acid metal salt itself is very small.

<About wet method>
As the solvent when the wet method is adopted, it is preferable to use a solvent having a low boiling point that can be easily removed from the polyester composition and insoluble in the metal phosphonate. Examples of such solvents include methanol, ethanol, propanol, isopropanol, ethylene glycol, diethylene glycol, 1,3-propanediol, 1,4-butanediol, alcohols such as benzyl alcohol, and hydrocarbon compounds such as toluene, xylene, and tetrahydrofuran. And amide polar solvents such as dimethylformamide and dimethyl sulfoxide. These solvents can be used as a single solvent, or can be used as a mixed solvent in which a plurality of solvent species are combined.

<Dispersant of phosphonic acid metal salt>
A dispersant can be added to the phosphonic acid metal salt slurry used in the wet method, if necessary. As such a dispersant, a monocarboxylic acid compound represented by the following general formula (IV) can be raised.

［上記一般式（ＩＶ）中、Ｒ^５は炭素数１〜１２個のアルキル基、炭素数６〜１２個のアリール基又はベンジル基を示し、Ｍ^＋は、Ｈ^＋、Ｌｉ^＋、Ｎａ^＋、Ｋ^＋、Ｒｂ^＋、Ｃｓ^＋を示す。］

[In General Formula (IV), R ⁵ represents an alkyl group having 1 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms, or a benzyl group, and M ⁺ represents H ⁺ , Li ⁺ , Na ⁺ , K ^<+> , Rb ^<+> , Cs ^<+> is shown. ]

  Among these, specific examples include acetic acid, lithium acetate, sodium acetate, potassium acetate, rubidium acetate, cesium acetate, propionic acid, lithium propioate, sodium propioate, potassium propioate, rubidium propioate, cesium propioate, benzoic acid. Examples include acid, lithium benzoate, sodium benzoate, potassium benzoate, rubidium benzoate, and cesium benzoate. Among these, acetic acid, lithium acetate, sodium acetate, and potassium acetate are particularly preferable because of their availability as a dispersant and excellent dispersion of the obtained particles. A phosphonic acid metal salt slurry can be produced by a method usually employed using such a compound.

<Method for producing phosphonic acid metal salt>
As the phosphonic acid metal salt to be used, a commercially available phosphonic acid metal salt can be used, but it is preferable to prepare fine phosphonic acid metal salt fine particles from a predetermined metal compound with phosphonic acid. If the phosphonic acid metal salt remains as coarse particles, a problem such as that easily occurs, and even if the particles are too fine, the problems described in the background art may occur.

<Post-processing after production>
Moreover, the manufacturing method of the polyester composition of this invention can melt-knead the polyester obtained after finishing polycondensation reaction as needed, and can add and refine | miniaturize a phosphonic acid metal salt. The method of kneading is not particularly limited, but it is preferable to use a normal uniaxial or biaxial kneader. More preferably, in order to suppress a decrease in the degree of polymerization of the resulting polyester composition, a method of using a vented uniaxial or biaxial kneader can be exemplified.

  The conditions during the kneading are not particularly limited. For example, the melting point is higher than the melting point of the polyester and the residence time is within 1 hour, preferably 1 minute to 30 minutes. Moreover, the supply method of the phosphonic acid metal salt and polyester to a kneading machine is not specifically limited. For example, a method of separately supplying a phosphonic acid metal salt and a polyester to a kneader by a dry method, a method of previously mixing a phosphonic acid metal salt and a polyester in a solid state and then supplying them to a kneader, a phosphonic acid metal salt in a high concentration Examples include a method (so-called master batch method) in which a polyester containing is previously prepared and mixed and supplied in a kneader and a polyester chip.

<Intrinsic viscosity of polyester composition>
The intrinsic viscosity (solvent: orthochlorophenol, measurement temperature: 35 ° C.) of the polyester composition of the present invention is not particularly limited, but is preferably in the range of 0.5 to 1.5 dL / g. When the intrinsic viscosity is less than 0.5 dL / g, the mechanical properties of the polyester fiber obtained by melt spinning become insufficient, and when it exceeds 1.5 dL / g, the melt moldability is lowered, which is not preferable. The intrinsic viscosity of the composition is more preferably in the range of 0.6 to 0.1.3 dL / g.

  When the polyester of the polyester composition obtained by the present invention is made of PET, the temperature falling crystallization peak temperature (Tcd) is preferably 205 ° C. or higher and 220 ° C. or lower. When the temperature is 205 ° C. or lower, the effect of improving the yarn forming property and film forming property is small, and it is difficult to obtain a polyester having a Tcd of 220 ° C. or higher by the manufacturing method of the present invention. Moreover, when polyester of the polyester composition obtained by this invention consists of PET, as temperature rising crystallization peak temperature (Tci), 130 to 150 degreeC is preferable. A polyester composition having a Tci of 130 ° C. or lower is difficult to obtain by the production method of the present invention, and when the Tci is 150 ° C. or higher, the effect of suppressing chip fusion of the obtained polyester composition is small. Absent.

  When the polyester of the polyester composition obtained by the present invention is PEN, the temperature lowering crystallization peak (Tcd) is preferably 200 ° C. or higher and 220 ° C. or lower. Below 200 ° C., the effect of improving the yarn forming property and film forming property is small, and it is difficult to obtain a polyester having a Tcd of 220 ° C. or higher by the production method of the present invention. Moreover, when the polyester of the polyester composition obtained by this invention is PEN, as temperature rising crystallization peak (Tci), 170 degreeC or more and 200 degrees C or less are preferable. A polyester composition having a Tci of 170 ° C. or lower is difficult to obtain by the production method of the present invention, and when the Tci is 200 ° C. or higher, the resulting polyester composition has little effect of suppressing chip fusion, Absent. As described later, the crystallinity can be evaluated by Tcd and Tci.

  The polyester composition of the present invention contains a small amount of additives as necessary, for example, lubricants, radical scavengers, antioxidants, solid phase polymerization accelerators, color adjusters, fluorescent whitening agents, antibacterial agents, ultraviolet absorbers, It may contain a light stabilizer, a heat stabilizer, a light shielding agent, a flame retardant, a matting agent, and the like.

  The present invention will be further described in the following examples, but the scope of the present invention is not limited by these examples. Various characteristics were measured by the following methods.

(A) Intrinsic viscosity:
A dilute solution obtained by dissolving a polyester composition sample in orthochlorophenol at 100 ° C. for 60 minutes was obtained from a value measured at 35 ° C. using an Ubbelohde viscometer.

(A) Diethylene glycol (DEG) content:
A polyester composition sample was decomposed using hydrazine hydrate (hydrated hydrazine), and the content of diethylene glycol in the decomposition product was measured using gas chromatography (HP Hewlett Packard (HP 6850)).

(C) Differential scanning calorimeter:
Measurements were made using a TA Instruments Q20 differential scanning calorimeter. The measurement conditions are as follows.
(1) Using a differential scanning calorimeter, the polyester composition sample is heated to 300 ° C. under a nitrogen stream and heated at 20 ° C./min, held for 2 minutes, and then cooled down at 10 ° C./min. The exothermic peak that was measured was observed, and the energy was calculated from the peak area (the temperature at the apex of the exothermic peak was expressed as Tcd).
(2) A polyester composition sample is heated to 300 ° C. under a temperature rising condition of 20 ° C./min, and held and melted at 300 ° C. for 2 minutes, which is obtained by quenching and solidifying in liquid nitrogen. For the composition, a differential scanning calorimeter was used to observe an exothermic peak that appeared under a temperature increase condition of 20 ° C./min under a nitrogen stream, and energy was calculated from the peak area (the temperature at the apex of the exothermic peak). Was written as Tci).
It can be said that the lower the Tci temperature, the higher the crystallinity of the rapidly cooled and solidified polyester composition when the temperature rises, starting from a low temperature and early. Similarly, it can be said that the higher the Tcd temperature is, the higher the crystallinity of the melted polyester composition is when the temperature is lowered, starting from a high temperature and early.

(D) Content measurement of phosphorus and each metal atom:
Measurement was performed using a Rigaku fluorescent X-ray apparatus 3270 type, and quantification was performed. In the case of a polymer, a polyester composition sample was heated and melted to form a circular disk and measured. For the solution, the solution was sealed in a dedicated container and measured.

(E) Determination of aggregated particles:
A thin plate sample was prepared by placing 10.0 mg of a polyester composition chip between two cover glasses and pressing the cover glass on a hot plate heated to 280 ° C. This was observed with an Olympus BX51 in a polarizing lens / dark field, the particles were observed, and (the number of fine particles of 5 μm or more) was counted. A similar count was performed with n = 3, and samples having an average number of fine particles of 5 μm or more exceeding 10 were judged as “×” and those having 10 or less as “◯”.

[Example 1]
(1) Preparation of Manganese Phenylphosphonate (II) Ethylene Glycol Solution At room temperature, 1.58 parts by mass of phenylphosphonic acid (Nissan Chemical) with 100 parts by mass of ethylene glycol (Wako Special Grade), acetic acid as a dispersant (Wako Special Grade) 0.006 parts by mass (corresponding to 1 mol% with respect to phenylphosphonic acid) is supplied to a reactor having a stirrer / refluxer, and manganese (II) acetate tetrahydrate 2.45 parts by mass Part (equal molar amount with respect to phenylphosphonic acid) was added and stirred and dissolved for 60 minutes. The resulting solution was heated, heated to reflux at 80 to 85 ° C. for 30 minutes, and then cooled to obtain an ethylene glycol solution of manganese (II) phenylphosphonate.
The yield of manganese (II) phenylphosphonate was quantified indirectly by a fluorescent X-ray apparatus. To 100 parts by mass of manganese (II) phenylphosphonate ethylene glycol solution, add 400 parts by mass of methanol (Wako Special Grade), stir and centrifuge, extract the organic solvent component of the supernatant of the resulting uniform solution, and extract the organic solvent component The amount of phosphorus / manganese present in the product was measured, and it was confirmed that the yield of manganese (II) phenylphosphonate was 99.5% or more.
(Manganese (II) phenylphosphonate yield) = 100− (Amount of phosphorus component contained in supernatant organic layer) / (Amount of added phenylphosphonic acid) × 100

(2) Preparation of manganese phenylphosphonate manganese (II) slurry The prepared phenylphosphonic acid ethylene glycol solution was brought into a high pressure state of 80 MPa with a continuous atomizer system HJP-25005 type machine manufactured by Sugino Machine. It was discharged from the nozzles facing each other, and the entire amount was crushed by particle collision. This crushing treatment was repeated twice, and then this treatment solution was filtered with a cartridge grade 070 (99.98% filtration accuracy 7 μm equivalent) of Nihon Pall filter profile II, and the final manganese phosphonate. A slurry was obtained.
When the particle size of manganese phenyl phosphonate (II) in the obtained slurry was measured by a particle size distribution analyzer SALD7000 manufactured by Shimadzu Corporation, 99.9% or more of the particles were 0.5 μm or less. .

(3) Manufacture of polyester composition chip To a mixture of 100 parts by mass of dimethyl terephthalate and 70 parts by mass of ethylene glycol, 0.063 parts by mass of calcium acetate monohydrate and 0.056 parts by mass of sodium acetate were added to a stirrer, A transesterification reaction was carried out while charging a reactor equipped with a distillation column and a methanol distillation condenser and gradually raising the temperature from 140 ° C. to 240 ° C. while distilling methanol produced as a result of the reaction out of the reactor. . Thereafter, 0.058 parts by mass of trimethyl phosphate was added, and further a manganese phenylphosphonate slurry was added so that the amount of manganese (II) phenylphosphonate reached the amount shown in Table 1, thereby completing the transesterification reaction. Thereafter, 0.04 part by mass of diantimony trioxide was added, transferred to a polycondensation reaction vessel equipped with a stirrer, a nitrogen inlet, a vacuum port and a distillation apparatus, heated to 285 ° C., and a high vacuum of 30 Pa or less. A polycondensation reaction was performed to obtain a polyester composition. Furthermore, it was made into a chip according to a conventional method. The results are shown in Table 1.

[Examples 2-3]
In Example 1, it implemented like Example 1 except having changed into the content shown in Table 1 the kind and quantity of phosphonic acid metal salt, and the solvent kind of slurry. The results are shown in Table 1.

[Example 4]
(1) Preparation of ethylene glycol solution of cobalt (II) phenylphosphonate At room temperature, 1.58 parts by mass of phenylphosphonic acid (Nissan Chemical) and acetic acid as a dispersant for 100 parts by mass of ethylene glycol (Wako Special Grade) (Wako Special Grade) 0.006 parts by mass (corresponding to 1 mol% with respect to phenylphosphonic acid) is supplied to a reactor having a stirrer / refluxer, and cobalt acetate (II) tetrahydrate is 2.49 parts by mass. Part (equal molar amount with respect to phenylphosphonic acid) was added and stirred and dissolved for 60 minutes. The resulting solution was heated, heated to reflux at 80 to 85 ° C. for 30 minutes, and then cooled to obtain an ethylene glycol solution of cobalt (II) phenylphosphonate.
The yield of cobalt (II) phenylphosphonate was quantified indirectly by a fluorescent X-ray apparatus. Add 100 parts by mass of cobalt (II) phenylphosphonate ethylene glycol solution, add 400 parts by mass of methanol (Wako Special Grade), stir and centrifuge, extract the organic solvent component of the supernatant of the resulting homogeneous solution, and extract the organic solvent component The amount of phosphorus and cobalt present in the product was measured, and it was confirmed that the yield of cobalt (II) phenylphosphonate was 99.5% or more.

(2) Purification of Cobalt Phenylphosphonate (II) Fine Particle Powder 400 parts by mass of distilled water is added to 100 parts by mass of an ethylene glycol solution of cobalt (II) phenylphosphonate, and then stirred at 2000 rpm. Process for 20 minutes,
The supernatant component of the resulting homogeneous solution was decanted and removed. Further, 400 parts by mass of distilled water was added and stirred, and then the same centrifugation operation was performed twice to obtain a residue containing phenylphosphonic acid at a high concentration. The residue was cooled with liquid nitrogen and lyophilized in a vacuum of 6.66 kPa (50 mmHg) in a frozen state to obtain a fine powder of cobalt (II) phenylphosphonate.

(3) Manufacture of polyester composition chip In Example 1, in place of the phenylphosphonate manganese slurry, except that cobalt (II) phenylphosphonate fine particle powder was used so as to have the amount shown in Table 1, the same manner A polyester composition chip was polymerized. The results are shown in Table 1.

[Examples 5 to 6]
In Example 1, it implemented like Example 1 except having changed into the content shown in Table 1 the kind of phosphonic acid metal salt and the kind of metal compound. The results are shown in Table 1.

[Example 7]
In a mixture of 100 parts by mass of dimethyl 2,6-naphthalenedicarboxylate and 50 parts by mass of ethylene glycol, 0.030 parts by mass of manganese acetate tetrahydrate and 0.0056 parts by mass of sodium acetate trihydrate were stirred and rectified. A reactor equipped with a tower and a methanol distillation condenser was charged, and the ester exchange reaction was carried out while gradually raising the temperature from 150 ° C. to 245 ° C. while distilling methanol produced as a result of the reaction out of the reactor. Thereafter, 0.023 parts by mass of trimethyl phosphate was added, and further a manganese phenylphosphonate slurry was added so that the amount of manganese phenylphosphonate was as shown in Table 1, thereby completing the transesterification reaction. Thereafter, 0.024 parts by mass of diantimony trioxide is added to the reaction product, transferred to a polycondensation reaction vessel equipped with a stirrer, a nitrogen inlet, a vacuum port and a distillation apparatus, heated to 305 ° C. and heated to 30 Pa. A polycondensation reaction was carried out under the following high vacuum to obtain a polyester composition. Furthermore, it was made into a chip according to a conventional method. The results are shown in Table 1.

[Examples 8 to 10]
In Example 7, instead of adding the phenylphosphonate manganese slurry so that the amount of manganese phenylphosphonate becomes the addition amount shown in Table 1, phenylphosphonic acid magnesium, cobalt, and zinc become the addition amounts shown in Table 1 A polyester composition chip was produced in the same manner as in Example 7 except that the acid metal salt slurry was added. The results are shown in Table 1.

[Comparative Examples 1, 3, 4]
In Example 1, it implemented like Example 1 except having changed the kind of phosphorus compound, the kind of metal compound, and content of the phenylphosphonic acid metal salt into the content shown in Table 1. The results are shown in Table 1.

[Comparative Example 2]
In Example 1, instead of adding a slurry of manganese (II) phenylphosphonate, an amount of 0.5 wt% shown in Table 1 was added without using phenylphosphonic acid and magnesium acetate as a phenylphosphonic acid metal salt. This was carried out in the same manner as in Example 1 except that the change was made. Therefore, the phenylphosphonic acid metal salt seems to be produced by internal precipitation in the polycondensation reactor. The results are shown in Table 1.

[Comparative Example 5]
In Example 7, it implemented similarly to Example 7 except having changed the metal compound seed | species. The results are shown in Table 1.

  According to the present invention, it is possible to produce a polyester with good crystallinity containing a phosphonic acid metal salt that becomes a crystal nucleus without generating scales and aggregated particles as by-products as in the prior art, It becomes possible to produce a polyester molded product having excellent moldability (thread production, stretchability, and processability).

Claims (4)

After reacting the dicarboxylic acid dialkyl ester represented by the following general formula (I) and the diol component represented by the following general formula (II) by a transesterification reaction, any of the steps for producing a polyester by a polycondensation reaction The production of a polyester composition characterized in that the phosphonic acid metal salt represented by the general formula (III) is added at 0.01 to 1.0 mass% with respect to the total weight of the polyester composition in the step. Method.
^{R 1 OCO-R 2 -COOR 1} (I)
[In the general formula (I), R ¹ represents an alkyl group having 1 to 2 carbon atoms, and R ² represents a p-phenylene group or a 2,6-naphthalene group. ]
^HO-R 3 -OH (II)
[In the general formula (II), R ³ represents a linear alkylene group having 2 to 4 carbon atoms. ]

[In the general formula (III), R ⁴ represents an aryl group having 6 to 12 carbon atoms, and M ^{Z +} represents a metal ion of Mg ²⁺ , Mn ²⁺ , Co ²⁺ or Zn ²⁺ . However, when Z = 2, n = 1 and m = 1. ]   The method for producing a polyester composition according to claim 1, wherein the metal salt of phosphonic acid is a metal salt of phenylphosphonic acid.   The method for producing a polyester composition according to claim 1 or 2, wherein the phosphonic acid metal salt is added in the state of a slurry containing the phosphonic acid metal salt when the phosphonic acid metal salt is added to the step of producing the polyester.   In the method for producing a polyester composition, the polycondensation catalyst used is an antimony compound, a titanium compound, a germanium compound, an aluminum compound, a zirconium compound or a tin compound, and the intrinsic viscosity of the obtained polyester composition is 0.5 to 1. It is 5 dL / g, The manufacturing method of the polyester composition of any one of Claims 1-3 characterized by the above-mentioned.