JP2009235150A - Polyester composition and method for producing it - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a polyester composition and a sheet excellent in pinhole resistance, flexibility, impact resistance, color tones, and polymer cutting properties. <P>SOLUTION: The polyester composition comprises terephthalic acid, isophthalic acid and unhydrogenated dimer acid as acid components and 1,4-butanediol as a glycol component, and based on the total acid components, 40-75 mol% of the terephthalic acid, 15-30 mol% of the isophthalic acid, and 10-30 mol% of the dimer acid are contained. The polyester composition also contains a titanium compound in amount of 100-200 ppm as a titanium atom, a phosphorus compound in amount of 20-150 ppm as a phosphorus atom, and 0.01-0.1 wt.% of a hindered phenolic antioxidant. In the polyester composition, a glass transition point is 0°C or lower, intrinsic viscosity is 0.6-1.2, and temperature-falling crystallization temperature is 100°C or more. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a flexible polyester composition and a production method. In particular, the present invention relates to a polyester composition with improved polymer cutting properties of a polyester capable of easily forming a molded article having excellent heat resistance, easy adhesion and color tone, and a method for producing the same.

  Polyester has excellent physical and chemical properties and is widely used in films, fibers, sheets and the like. In particular, polyester film has excellent properties in heat resistance, solvent resistance, and mechanical properties, so it is used in many applications such as magnetic recording materials, various photographic materials, packaging materials, electrical insulating materials, and general industrial materials. ing.

  However, the flexibility and impact resistance at low and normal temperatures are lacking, and there is a limit to the expansion of applications. In order to improve such a defect, the method of copolymerizing a soft segment with polyester is considered.

  For example, Patent Document 1 describes a polyester composition obtained by copolymerizing terephthalic acid, aliphatic dicarboxylic acid, 1,4-butanediol, and ethylene glycol (paragraph [0080]). Since 4-butanediol is charged at the same time, the scattering rate fluctuates, and the intended composition cannot be obtained, resulting in a defective product. In addition, although a method of kneading two kinds of polymers with a twin screw extruder is also exemplified (paragraph [0084]), since the extrusion temperature is as high as 260 ° C., it is easy to color, and in particular, oxazoline is used as a compatibilizing agent. When used, there is a possibility of coloring due to an ester amide bond. Furthermore, a method of adding a compatibilizing agent to the copolyester before the polycondensation reaction is mentioned, but in the case of oxazoline, it may react during the polycondensation reaction and may lose some activity during kneading. In the case of an organic acid, it may be partially deactivated by the phosphorus compound in the copolyester, which is not efficient.

  Patent Document 2 describes a copolyester containing dimer diol in an amount of 5 to 50 mol% based on the total glycol component (claim 1, paragraph [0005], [0008], [0009]). Compared with a formulation containing a soft component as an acid component, the efficiency of softening is poor, and dimer diol is produced using dimer acid as a raw material, which is disadvantageous in terms of cost.

  Patent Document 3 describes polybutylene terephthalate obtained by copolymerizing 5 to 50 mol% of dimer acid. However, the examples are based on the DMT method using high-purity dimethyl dimer acid, and there is no description of specific examples using relatively low-purity non-hydrogenated dimer acid.

Patent Document 4 describes an adhesive polyester obtained by copolymerizing terephthalic acid, isophthalic acid, dimer acid, and 1,4 butanediol. However, since it is a flexible polyester, cutting with a strand cutter is difficult.
JP 2004-359945 A JP-A-6-128363 JP-A-5-1133 JP 2002-47471 A

  An object of the present invention is to eliminate the disadvantages of the prior art and to improve the polymer cutting properties of a flexible polyester composition excellent in pinhole resistance, flexibility, impact resistance and color tone, and a method for producing the same Is to provide.

  To achieve the above object, the present invention provides a polyester composition comprising terephthalic acid, isophthalic acid and non-hydrogenated dimer acid as an acid component, and 1,4 butanediol as a glycol component. 40 to 75 mol% of terephthalic acid, 15 to 30 mol% of isophthalic acid, 10 to 30 mol% of dimer acid, and 100 ppm to 200 ppm of titanium compound as titanium atom and 20 ppm or more of phosphorus compound as phosphorus atom to the polyester composition 150 ppm or less, hindered phenolic antioxidant 0.01% by weight or more and 0.1% by weight or less, glass transition point 0 ° C. or less, intrinsic viscosity 0.6 to 1.2, temperature drop crystallization temperature 100 ° C. or more This is achieved with certain polyester compositions.

  According to the present invention, it has excellent pinhole resistance, flexibility, impact resistance, color tone, packaging materials, building material applications such as wallpaper, steel sheet laminating applications, process film applications such as protective films and carrier tapes, patches, etc. It is possible to provide a polyester composition improved in polymer cutting property of a flexible polyester, which is suitable for apparel use, a sealing material, and the like, and particularly suitable for producing a small variety of products, and a method for producing the same.

  The polyester composition of the present invention is a polyester composition containing terephthalic acid, isophthalic acid and non-hydrogenated dimer acid as an acid component, and 1,4 butanediol as a glycol component. 40 to 75 mol%, isophthalic acid 15 to 30 mol%, dimer acid 10 to 30 mol%, and with respect to the polyester composition, the titanium compound has a titanium atom of 100 ppm to 200 ppm, the phosphorus compound has a phosphorus atom of 20 ppm to 150 ppm, It contains 0.01% by weight or more and 0.1% by weight or less of a dartphenol antioxidant, has a glass transition point of 0 ° C. or lower, an intrinsic viscosity of 0.6 to 1.2, and a cooling crystallization temperature of 100 ° C. or higher.

  The polyester of the present invention comprises terephthalic acid, isophthalic acid, 1,4 butanediol, and dimer acid.

  The content of the terephthalic acid component needs to be 40 to 75 mol% with respect to the total acid component. If it is less than 40 mol%, sufficient mechanical strength may not be obtained, and if it exceeds 75 mol%, sufficient flexibility cannot be obtained.

  The content of the isophthalic acid component needs to be 15 to 30 mol% with respect to the total acid component, and is preferably 17 to 25 mol% from the viewpoint of thermal adhesiveness with a different material. When it exceeds 30 mol%, the crystallinity of the polyester composition is remarkably lowered, and handling such as cutting, drying and storage becomes difficult. If it is less than 15 mol%, the adhesion to different materials may be insufficient.

  The dimer acid in the present invention refers to a dimer of an unsaturated aliphatic carboxylic acid having 16 or more carbon atoms. This dimer acid is, for example, an unsaturated carboxylic acid having 16 or more carbon atoms extracted from non-petroleum materials such as soybean oil, rapeseed oil, beef tallow, tall oil, etc. (for example, an unsaturated fat mainly composed of linoleic acid or oleic acid). Can be obtained by dimerization with a clay catalyst. When a dimer acid is obtained using such a production method, an excessively reacted trimer or an unreacted unsaturated aliphatic carboxylic acid is generated as an impurity, and further a dimer having an aromatic ring or an alicyclic ring. Usually, it is a mixture of an acid and a dimer acid having no chain structure. Although it is desirable that the dimer acid having unreacted unsaturated fatty acid, trimer, aromatic ring and alicyclic ring is not contained in the polyester composition, depending on the production method of dimer acid, it is unavoidable as described above. It will be included. In this case, when the total amount of unsaturated aliphatic carboxylic acid, dimer and trimer is 100% by weight, it is less than 1% by weight as unreacted unsaturated aliphatic carboxylic acid, and 3% by weight as trimer. It is preferable that it is less than 2% by weight as a trimer. When 1% by weight or more of an unreacted unsaturated aliphatic carboxylic acid is contained, there is a possibility that the polymerization reactivity is lowered, the mechanical properties of the molded product are lowered, the physical properties are changed by bleed-out after molding, and whitening occurs. Further, when the content of the trimer is 3% by weight or more, foreign matter may be remarkably generated at the time of recycling due to gelation. Furthermore, if a dimer acid having a trimer content of 1 to 2% by polymerization is used, the crystallinity is lowered and thermal bonding becomes easy.

  Dimer acid can be produced by various methods. For example, after reacting in the presence of a clay catalyst and a lithium salt as a promoter in the range of 230 to 250 ° C., an aqueous phosphoric acid solution is added. The catalyst can be produced by converting the phosphate to a phosphate, removing the metal phosphate by filtration, and separating the unsaturated aliphatic carboxylic acid by rotating thin film distillation.

  The color tone of the dimer acid is preferably 1.0 or less as measured by a Gardner color difference meter. If the Gardner color difference meter exceeds 1.0, the b value (yellowishness) of the polyester composition increases and the appearance may be impaired. In order to obtain a dimer acid of 1.0 or less with a Gardner color difference meter, it is possible to select raw materials or purify unsaturated fatty acids, but if you want to lower it further, perform the reaction during synthesis slowly. (Reducing the reaction temperature and taking time) or by making the distillation conditions stricter.

  The above-mentioned dimer acid needs not to be hydrogenated (non-hydrogenated) from the viewpoint of food safety such as packaging.

  The content of the dimer acid is required to be 10 to 30 mol% with respect to the polyester composition, but is preferably 10 to 25 mol% from the viewpoint of heat resistance. When the content of dimer acid is less than 10 mol%, there is a possibility that sufficient flexibility may not be obtained, and when it exceeds 30 mol%, sufficient mechanical strength cannot be obtained, and process passability may be reduced. is there.

  The glycol component in the present invention needs to be 1,4 butanediol from the viewpoint of crystallinity.

  In particular, the use of 1,4 butanediol produced by fermentation is preferable from the viewpoint of environmental protection because the plant degree of the polyester composition can be increased to 60% or more together with the dimer acid.

Content of the titanium atom in this invention needs to be 100 ppm or more and 200 ppm or less with respect to a polyester composition. If it is less than 100 ppm, sufficient polymerization reactivity cannot be obtained, and if it exceeds 200 ppm, the heat resistance is lowered and coloring is not preferable. Titanium compounds include titanium chelate compounds and titanium alkoxides. Among these, titanium alkoxides are preferable from the viewpoint of reactivity and color tone, and titanium-n-butoxide is particularly preferable from the viewpoints of reactivity and handling.

  In the present invention, the phosphorus atom content is preferably 20 ppm or more and 150 ppm or less from the viewpoint of color tone, heat resistance, and reactivity. Phosphorus compounds include phosphoric acid, alkali metal dihydrogen phosphate, metal dihydrogen phosphate, phosphorous acid, alkali metal phosphite, trimethyl phosphate, ethyl diethylphosphonoacetate, etc. Of these, phosphoric acid, alkali metal dihydrogen phosphate, and dialkali metal hydrogen phosphate are preferable from the viewpoint of heat resistance, color tone, and hydrolysis resistance. In particular, it is preferable from the point of hydrolysis resistance to use together phosphoric acid and alkali metal dihydrogen phosphate.

  In the present invention, the alkali metal atom content is preferably 150 ppm or more and 1000 ppm or less from the viewpoint of hydrolysis resistance and polymer cutting property, and more preferably 250 ppm or more and less than 800 ppm. If it is less than 150 ppm, sufficient hydrolysis resistance or polymer cutting property may not be obtained, and if it exceeds 1000 ppm, the heat resistance may be lowered and the color tone may be deteriorated. Examples of the alkali metal compound include alkali metal phosphates and crystal nucleating agents such as sodium acetate.

  The content of the hindered phenolic antioxidant of the present invention is required to be 0.01% by weight or more and 0.1% by weight or less from the viewpoint of heat resistance, and more preferably 0.01% by weight or more and 0.001% or less. It is not more than 05% by weight. Examples of the hindered phenol-based antioxidant include “IRGANOX” series manufactured by Ciba Specialty Chemicals, Inc. Among them, “IRGANOX 1010 FP” is preferable.

  The glass transition point of the polyester composition is required to be 0 ° C. or less from the viewpoint of flexibility, and more preferably −40 to 0 ° C. In particular, when it is −30 to 0 ° C., good flexibility is exhibited when used at room temperature, and molding processability is improved. When the glass transition point exceeds 0 ° C., sufficient flexibility cannot be obtained.

  The temperature-falling crystallization temperature of the polyester composition is required to be 100 ° C. or higher from the viewpoint of polymer cutting properties, and more preferably 110 ° C. or higher.

  The temperature-falling crystallization temperature can be controlled by the isophthalic acid content, the dimer acid content, the amount of trimer contained in the dimer acid, and the crystal nucleating agent. In particular, in the polyester composition of the present application, isophthalic acid and dimer acid are copolymerized, and the temperature-lowering crystallization temperature is remarkably lowered. Therefore, application of a crystal nucleating agent is suitable. The crystal nucleating agent in the present invention is preferably 0.01% by weight or more and 1.0% by weight or less, more preferably 0.03% by weight or more and 0.5% by weight or less from the viewpoint of polymer cutting property. Is preferred. Examples of the crystal nucleating agent include silica, talc, sodium formate, sodium acetate, sodium lactate, sodium oxalate, sodium succinate, NA-11 (manufactured by Asahi Denka), etc., but internal precipitation like sodium acetate Type nucleating agents are the most effective and preferred. Also, inorganic particles such as silica and talc have a small crystal nucleating agent effect, and it is difficult to make the temperature-falling crystallization temperature 100 ° C. or more when used alone, so that an internal precipitation type crystal nucleating agent such as sodium acetate is used. It is preferable to use together. Since a crystal nucleating agent such as NA-11 has poor wettability, it aggregates when added to the polymerization reaction system and cannot exhibit its original effect. Therefore, it is effective when the composition of the present invention is to be obtained by reactive extrusion using a twin-screw extruder, or when it is desired to further promote crystallization of the sheet.

  If the crystal nucleating agent is less than 0.01% by weight, it is difficult to set the temperature-falling crystallization temperature to 100 ° C. or higher.

  If the crystal nucleating agent exceeds 1.0% by weight, the viscosity may increase and the degree of polymerization of the polymer may not increase. A compound having a larger effect as a crystal nucleating agent has a stronger tendency to increase the viscosity.

  As a method for adding the crystal nucleating agent, it is preferable to add it to the polymerization reaction system since the purpose is to improve the polymer cutting property. The addition is preferably performed after the transesterification or esterification reaction is substantially completed and before the start of the polymerization reaction from the viewpoint of suppressing side reactions.

  As a method for adjusting the crystal nucleating agent, in the case of inorganic particles, it is preferable from the viewpoint of dispersibility and crystallinity to add a slurry using a bead mill or a homogenizer. In the case of an internally precipitated crystal nucleating agent such as sodium acetate, it is preferable to add it by dissolving it in a glycol component.

  The intrinsic viscosity of the polyester composition needs to be 0.6 to 1.2. In order to improve the compatibility with other polyesters, the content is preferably 0.7 to 0.9. Moreover, when co-extruding with other polyester and making it a laminated sheet, it is preferable to set it as 0.8-1.2 from the point of lamination nonuniformity suppression and stable film forming property. When the intrinsic viscosity is less than 0.6, sufficient mechanical strength, flexibility and heat resistance cannot be obtained, and when it exceeds 1.2, the polymerization time is too long and the polymer is colored, which is not preferable.

As a manufacturing method of the polyester composition of the present invention, it is preferable to manufacture by a direct weight method from the viewpoint of productivity. Specifically, terephthalic acid, isophthalic acid, and 1,4 butanediol are charged, and an esterification reaction is performed at 140 to 230 ° C. in the presence of a titanium compound and an antioxidant, followed by a titanium compound, a phosphorus compound, and a crystal nucleating agent. Then, an antioxidant is added, and a polycondensation reaction can be performed by a conventional method.
At this time, it is preferable from the viewpoint of color tone and heat resistance that the dimer acid should be added during the latter half of the esterification reaction to the beginning of the polymerization. In particular, in the latter half of the esterification reaction, it is preferable from the viewpoint of productivity that dimer acid is gradually added while controlling the reaction system at 200 ° C. to 220 ° C., and in particular, control at 200 to 210 ° C. is preferable from the viewpoint of color tone. preferable. The method for adding dimer acid is preferably from the viewpoint of handling properties by heating to lower the viscosity, and the temperature is preferably from 50 ° C to 70 ° C from the viewpoint of handling properties. In addition, dimer acid may be added alone, but from the viewpoint of reactivity, it is preferable to add it mixed with 1,4 butanediol from the viewpoint of reactivity. In this case, the mixing ratio of the dimer acid and the glycol component is preferably 0.8 to 1.2 mol with respect to 1 mol of the dimer acid from the viewpoint of reactivity and productivity. Such dimer acid may be added in small batches, or may be continuously supplied by a pump or the like.

  The polyester composition of the present invention may be formed into a chip with a strand cutter extruded from a normal die, but may be directly used as an unstretched sheet. At this time, the melted polyester composition of the present invention can be extruded onto a casting drum, cooled and solidified, or subjected to stretching or various heat treatments as necessary to form a polyester sheet. The polyester sheet thus obtained is suitable for various packaging materials, building material applications such as wallpaper, steel sheet laminating applications, process film applications such as protective films and carrier tapes, and the like.

  Hereinafter, the present invention will be described in more detail with reference to examples. The characteristics in the examples were measured as follows.

(A. Intrinsic viscosity)
It measured at 25 degreeC using the o-chlorophenol solvent.

(B. Analysis of thermal characteristics)
Using a DSC7 model manufactured by PerkinElmer, glass transition point, crystal melting temperature, and cooling crystallization temperature were analyzed under the following conditions.

Atmosphere: Nitrogen (30 ml / min)
Temperature calibration: high purity indium (Tm = 156.61 ° C.)
Temperature increase rate: 10 ° C / min
Temperature drop rate: 10 ° C / min
Sample amount: 10 mg
Sample container: Standard aluminum container Pre-heat treatment: 5 minutes at 300 ° C
(C. Analysis of dimer acid)
Analysis was performed by high performance liquid chromatography, and the composition ratio was determined from the peak area of each component.

    Although measurement conditions can be implemented by a known method, an example is shown below.

Column: Interstil ODS-3 2.0 mmφ × 250 mm
Mobile phase: H ₃ PO ₄ aqueous solution / methanol = 80 / 20- (20 min)
20 / 80- (40min)
Flow rate: 0.4 mL / min
Column temperature: 45 ° C
Detector: Photodiode array (200 to 400 nm)
Chromatogram uses 21512 (D. Amount of metal atom in polyester composition)
The titanium atom and phosphorus atom were quantified by fluorescent X-ray analysis.

  Alkali metal atoms (Na, K) were quantified by atomic absorption spectrometry.

(E. Composition analysis of polyester)
The polyester was hydrolyzed with alkali, and each component was analyzed by gas chromatography or high performance liquid chromatography, and the composition ratio was determined from the peak area of each component.

  The quantitative determination of dimer acid can be analyzed by high performance liquid chromatography.

  The measurement conditions can be analyzed by a known method. For example, an example is shown below.

Equipment: Shimadzu LC-10A
Column: YMC-Pack ODS-A 150 × 4.6 mm S-5 μm
120A
Column temperature: 40 ° C
Flow rate: 1.2ml / min
Detector: UV 240nm
The quantification of the glycol component can be analyzed by a known method using gas chromatography. For example, an example is shown below.

Apparatus: Shimadzu 9A (manufactured by Shimadzu Corporation)
Column: SUPELCOWAX-10 capillary column 30m
Column temperature: 140 ° C. to 250 ° C. (heating rate 5 ° C./min)
Flow rate: Nitrogen 25ml / min
Detector: FID
(F. Evaluation of thermal adhesiveness)
A laminator was used to measure the temperature at which adhesion with foamed vinyl chloride occurred when treated at a pressure of 1 kg / cm 3 for 2 seconds.

(G. Evaluation of hydrolysis resistance)
The polymer which has been vacuum-dried at 120 ° C. for 8 hours is extruded from a T-die onto a casting drum by a single screw extruder to produce an unstretched sheet having a thickness of 25 μm.

  The obtained unstretched sheet was subjected to wet heat treatment at 80 ° C. and 85% RH, and the time until the elongation retention rate became 50% or less was measured.

    From the measurement results, ranking was performed as follows.

○ ... 100 hours or more △ ... 50 to less than 100 hours × ... less than 50 hours (H. carboxylic acid end group amount)
Measured by the method of Malice. (Reference M. J. Malice, F. Huizinga. Anal. Chim. Acta, 22 363 (1960))
(I. Polymerization reactivity evaluation)
The time until reaching the intrinsic viscosity of 0.85 was evaluated as follows in comparison with the blank (Reference Example 1).

◎ ・ ・ ・ Delay is less than 15 minutes ○ ・ ・ ・ Delay is from 15 minutes to less than 30 minutes △ ・ ・ ・ Delay is from 30 minutes to less than 45 × ・ ・ ・ Delay is 45 minutes or more (J. Carboxylic acid end group determination)
Measured by the method of Malice. (Reference M. J. Malice, F. Huizinga. Anal. Chim. Acta, 22 363 (1960))
(K. Cutting property of polymer)
The polymer chip was vacuum-dried at 120 ° C. for 6 hours, dissolved at the melting point of the polymer + 30 ° C., then discharged into a 40 ° C., 10 m long water tank, and cut with a strand cutter.

  At this time, whether cutting was possible or not was evaluated based on whether or not the cutter was wound while cutting 50 kg.

Reference example 1
Charge 40.9 parts by weight of terephthalic acid, 12.2 parts by weight of isophthalic acid, 51.8 parts by weight of 1,4-butanediol, 0.03 part by weight of tetrabutyl titanate and 0.011 part by weight of “IRGANOX1010FP” to raise the temperature. Started. When the temperature reached 210 ° C., a mixture (molar ratio 1.0) of 27 parts by weight of dimer acid (PRIPOL 1098: made by Unikema) and 4.3 parts by weight of 1,4 butanediol heated to 60 ° C. It added over 45 minutes with the pump so that it might be set to +/- 5 degreeC. After completion of the dimer acid addition, the temperature was quickly raised to 225 ° C. to complete the esterification reaction. 0.01 parts by weight of phosphoric acid was added, and 10 minutes later, 0.066 parts by weight of tetrabutyl titanate and 0.025 parts by weight of “IRGANOX1010FP” were added and stirred for 10 minutes before moving to a polycondensation reaction kettle. A polycondensation reaction was performed according to a conventional method. Finally, a polycondensation reaction was performed at 240 ° C. and 1 Torr or less to obtain a polyester composition. The polymer at this time was discharged into a 10 m long water tank (water temperature 40 ° C.), stored in a strand state for a whole day and night (room temperature), and after crystallization proceeded, it was chipped again using a strand cutter.

Reference example 2
A polyester composition was obtained in the same manner as in Reference Example 1 except that the copolymerization ratio of terephthalic acid, isophthalic acid, and dimer acid was changed. The obtained polyester composition was designed to minimize the copolymerization amount of isophthalic acid and dimer acid within the scope of the present invention. As shown in Table 1, it is shown that the temperature-falling crystallization temperature cannot be made 100 ° C. or higher without a device such as adding a crystal nucleating agent.

Example 1
Charge 40.9 parts by weight of terephthalic acid, 12.2 parts by weight of isophthalic acid, 51.8 parts by weight of 1,4-butanediol, 0.03 part by weight of tetrabutyl titanate and 0.011 part by weight of “IRGANOX1010FP” to raise the temperature. Started. When the temperature reached 210 ° C., a mixture (molar ratio 1.0) of 27 parts by weight of dimer acid (PRIPOL 1098: made by Unikema) and 4.3 parts by weight of 1,4 butanediol heated to 60 ° C. It added over 45 minutes with the pump so that it might be set to +/- 5 degreeC. After completion of the dimer acid addition, the temperature was quickly raised to 225 ° C. to complete the esterification reaction. 0.01 parts by weight of phosphoric acid, 0.035 parts by weight of sodium dihydrogen phosphate dihydrate and 0.1 parts by weight of sodium acetate were added, and 10 minutes later, 0.066 parts by weight of tetrabutyl titanate, “IRGANOX1010FP” "0.025 part by weight was added and stirred for 10 minutes before moving to a polycondensation reaction kettle and a polycondensation reaction was carried out according to a conventional method. Finally, a polycondensation reaction was performed at 240 ° C. and 1 Torr or less to obtain a polyester composition. When the polymer cutting property of the obtained polyester composition was evaluated, it could be cut without any problem without being wound around the strand cutter.

Example 2
A polyester composition was obtained in the same manner as in Example 1 except that 0.5 part by weight of sodium acetate was added as a crystal nucleating agent. Although there was no problem in polymerization reactivity, about 10% thickening was observed with respect to Example 1. When the polymer cutting property of the obtained polyester composition was evaluated, it could be cut without any problem without being wound around the strand cutter.

Example 3
A polyester composition was obtained in the same manner as in Example 1 except that the dimer acid was changed to PRIPOL 1098. There was no problem in polymerization reactivity. When the polymer cutting property of the obtained polyester composition was evaluated, it could be cut without any problem without being wound around the strand cutter.

Example 4
A polyester composition was obtained in the same manner as in Example 1 except that sodium acetate and agglomerated silica having an average particle size of 0.3 μm (ethylene glycol slurry 10 wt%) were used in combination as a crystal nucleating agent. There was no problem in polymerization reactivity. When the polymer cutting property of the obtained polyester composition was evaluated, it could be cut without any problem without being wound around the strand cutter.

Example 5
A polyester composition was obtained in the same manner as in Example 1 except that the addition amounts of terephthalic acid, isophthalic acid, dimer acid, and sodium acetate were changed, and sodium dihydrogen phosphate was changed to disodium hydrogen phosphate. When the polymer cutting property of the obtained polyester composition was evaluated, it could be cut without any problem without being wound around the strand cutter.

Comparative Example 1
A polyester composition was obtained in the same manner as in Example 1 except that the crystal nucleating agent was changed to agglomerated silica having an average particle size of 0.3 μm (ethylene glycol slurry 10 wt%). However, the temperature lowering crystallization temperature did not reach 100 ° C., and the polymer cutting property was frequently wound around the strand cutter, and the cutting property was not possible.

Claims (8)

  A polyester composition containing terephthalic acid, isophthalic acid and non-hydrogenated dimer acid as an acid component, and 1,4 butanediol as a glycol component, wherein 40 to 75 mol% of terephthalic acid and isophthalic acid are based on the total acid component 15 to 30 mol%, dimer acid 10 to 30 mol%, 100 ppm to 200 ppm with titanium compound as titanium atom, 20 ppm to 150 ppm with phosphorus compound as phosphorus atom, hindered phenolic antioxidant with respect to polyester composition A polyester composition containing 0.01% by weight or more and 0.1% by weight or less, having a glass transition point of 0 ° C. or less, an intrinsic viscosity of 0.6 to 1.2, and a temperature-falling crystallization temperature of 100 ° C. or more.   The polyester composition according to claim 1, wherein 1,4-butanediol is synthesized by a fermentation method.   The polyester composition according to claim 1 or 2, comprising an alkali metal atom in a range of 150 ppm to 1000 ppm.   The polyester composition according to any one of claims 1 to 3, wherein the phosphorus compound is phosphoric acid or an alkali metal phosphate.   5. The polyester composition according to claim 1, wherein the polyester composition contains 0.01% by weight or more and 1.0% by weight or less of a crystal nucleating agent.   The polyester composition according to claim 5, wherein at least one of the crystal nucleating agent is sodium acetate.   As an acid component, terephthalic acid is 40 to 75 mol%, isophthalic acid is 15 to 30 mol%, dimer acid is 10 to 30 mol%, 1,4 butanediol is esterified as a glycol component, and then polycondensation comprising a titanium compound. When producing a polyester composition by polycondensation reaction using a catalyst with titanium atoms of 100 ppm or more and 200 ppm or less, dimer acid is added while maintaining the esterification reaction system or polycondensation reaction system at 200 ° C. or more and 220 ° C. or less. In addition, the phosphorus compound is 20 ppm or more and 150 ppm or less as a phosphorus atom, sodium acetate is 0.01 wt% or more and 1.0 wt% or less as a crystal nucleating agent, and a hindered phenolic antioxidant is 0.01 wt% or more and 0.1 By adding less than% by weight before the intrinsic viscosity reaches 0.3, Scan transition 0 ℃ less, intrinsic viscosity 0.6 to 1.2, process for producing a polyester composition, characterized in that to produce a polyester composition is crystallization temperature 100 ° C. or higher.   The method for producing a polyester composition according to claim 7, wherein dimer acid and 1,4 butanediol are mixed and added at 1: 0.8 to 1.2 (molar ratio) at 30 to 70 ° C.