JP2007063307A - Polyester composition, method for producing the same and polyester sheet - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an inexpensive polyester composition having excellent pinhole resistance, flexibility, impact resistance and transparency and advantageous to diversified small-quantity production and to provide a sheet. <P>SOLUTION: The polyester composition comprises 5-50 wt.% of a dimer acid and 0.1-5 wt.% of at least one kind of compound (compound A) selected from the group consisting of an organic acid, an organic acid metal salt, an oxazoline compound and a glycidyl compound and having <1,000 molecular weight. The polyester composition has -50 to 30°C glass transition point (Tg), 120-240°C crystal melting temperature (Tm) and 10-50°C crystal melting temperature (Tm)-temperature-decreasing crystallization temperature (Tmc). <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a flexible polyester composition, a method for producing the same, and a polyester sheet. In particular, the present invention relates to a polyester composition that can easily form a molded article having excellent pinhole resistance, heat resistance, and impact resistance, a method for producing the same, and a polyester sheet.

  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 copolymerization of terephthalic acid, aliphatic dicarboxylic acid, 1,4-butanediol, and ethylene glycol. Since the polymerization temperature is as high as 290 ° C., ethylene glycol, In some cases, the scattering rate of 1,4-butanediol fluctuates, resulting in failure to obtain the desired composition. In addition, a method of kneading two kinds of polymers with a twin screw extruder is also exemplified, but since the extrusion temperature is as high as 260 ° C., it is easy to color, and particularly when oxazoline is used as a compatibilizing agent, ester amide There is a possibility of coloring by bonding. 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 mixture of a copolymerized polyester containing dimer acid and butanediol, and polyethylene terephthalate, but there is no particular rule on the dispersion state of the polymer and the method of dispersing the polymer. Therefore, there is a high possibility that a plurality of crystal melting peaks by DSC are detected.

Patent Document 3 also describes a mixture of an amorphous polyester, a crystalline polyester, and a crystal nucleating agent. However, as in Patent Document 2, there is no particular rule regarding the dispersion state of the polymer and the method of dispersing the polymer. Since it is a polymer blend, there is a high possibility that multiple crystal melting peaks by DSC are detected.
JP 2004-359945 A Japanese Patent No. 3618641 JP 2003-3055 A

  An object of the present invention is to eliminate these disadvantages of the prior art and to provide an inexpensive polyester composition excellent in pinhole resistance, flexibility and impact resistance, a production method thereof, and a polyester sheet.

  In order to achieve the above object, the present invention has a dimer acid content of 5 to 50% by weight and at least one molecular weight selected from the group consisting of an organic acid, an organic acid metal salt, an oxazoline compound and a glycidyl compound, and less than 1,000. Contains 0.1 to 5% by weight of compound (Compound A), has a glass transition point (Tg) of −50 to 30 ° C., a crystal melting temperature (Tm) of 120 to 240 ° C., a crystal melting temperature (Tm) and a temperature-falling crystal. It is achieved by a polyester composition having a conversion temperature (Tmc) of 10 to 50 ° C.

  According to the present invention, because it is excellent in pinhole resistance, flexibility, impact resistance, and inexpensive, it can be used for packaging materials, building materials such as wallpaper, steel sheet laminating applications, process film applications such as protective films and carrier tapes, It is possible to provide a method for producing a polyester composition that is suitable for apparel applications such as emblems, sealing materials and the like, and particularly suitable for producing a small variety of products.

  The polyester composition of the present invention comprises 5 to 50% by weight of dimer acid, at least one compound selected from the group consisting of an organic acid, an organic acid metal salt, an oxazoline compound, and a glycidyl compound (compound (compound) A) is contained in an amount of 0.1 to 5% by weight, the glass transition point (Tg) is −50 to 30 ° C., the crystal melting temperature (Tm) is 120 to 240 ° C., the crystal melting temperature (Tm) -the temperature lowering crystallization temperature ( Tmc) is 10 to 50 ° C.

  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. When dimer acid is obtained using such a production method, an excessively reacted trimer or unreacted unsaturated aliphatic carboxylic acid may be generated as an impurity. These impurities are usually desirably not contained in the polyester composition, but may be inevitably contained as described above depending on the method for producing dimer acid. In this case, as the content of these impurities, when the total amount of the unsaturated aliphatic carboxylic acid, dimer and trimer is 100% by weight, the unsaturated aliphatic carboxylic acid is less than 1% by weight and the trimer. It is preferably less than 25% by weight as a body, and more preferably less than 10% by weight as a trimer. When the unsaturated aliphatic carboxylic acid is contained in an amount of 1% by weight or more, there is a possibility that the mechanical properties of the molded product are lowered, or the physical properties are changed or whitened due to bleed-out after molding. Further, when the content of the trimer is 25% by weight or more, the color tone of the molded product may be lowered.

  The dimer acid can be produced by various methods. For example, the above-mentioned production method can be used. Specific conditions at that time include, for example, a range of 230 to 250 ° C. as a clay catalyst and a cocatalyst. After reaction for 1 to 3 hours in the presence of lithium salt, an aqueous solution of phosphoric acid is added to make the catalyst a phosphate, the metal phosphate is removed by filtration, and unsaturated aliphatic carboxylic acid is removed by rotating thin film distillation. Can be produced by separating.

  When the color tone (yellow coloring) is not a concern and when elasticity is desired, it is preferable that the content of the trimer as an impurity is large. For example, when the total amount of unsaturated aliphatic carboxylic acid, dimer and trimer is 100% by weight, 1 to 5% by weight of unsaturated aliphatic carboxylic acid and 10 to 25% by weight of trimer are included. This is advantageous in terms of cost because raw materials can be procured at low cost. Examples of the dimer acid containing such impurities include “PRIPOL 1025” manufactured by Unikema Corporation. When many trimers are contained, the molded product may become hard due to crosslinking, but the molded product is obtained by copolymerizing polyethylene glycol and / or polytetramethylene glycol having a number average molecular weight in the range of 200 to 1,000. Can be suppressed.

  Moreover, in the use which dislikes yellow coloring, and the use from which a softness | flexibility is requested | required, the one where content of unsaturated aliphatic dicarboxylic acid and a trimer is small is preferable. For example, when the total amount of unsaturated aliphatic carboxylic acid, dimer and trimer is 100% by weight, the unsaturated aliphatic dicarboxylic acid is less than 1% by weight and the trimer is less than 5% by weight. Thus, a polyester composition excellent in color tone and flexibility and a molded product thereof can be obtained. Examples of the dimer acid containing such impurities include “PRIPOL 1098” manufactured by Unikema Corporation.

  The above-mentioned dimer acid may be hydrogenated, but since a tin compound, which is a heavy metal, is often used as a catalyst during hydrogenation, hydrogenation should be performed in applications that require food safety such as packaging. It is preferably not (non-hydrogenated).

  The content of the dimer acid is preferably 5 to 50% by weight with respect to the polyester composition, but is preferably 5 to 40% by weight from the viewpoint of heat resistance. If the dimer acid content is less than 5% by weight, sufficient flexibility may not be obtained, and if it exceeds 50% by weight, sufficient mechanical strength may not be obtained and process passability may be reduced. There is sex.

  The glass transition point of the polyester composition is preferably −50 to 30 ° C. from the viewpoint of flexibility, and more preferably −50 to 10 ° C. In particular, when it is −30 to 0 ° C., good flexibility is exhibited when used at room temperature. If the glass transition point exceeds 30 ° C., sufficient flexibility may not be obtained. On the other hand, when the temperature is lower than −50 ° C., the self-supporting property of the molded product may be remarkably lowered.

  The crystal melting temperature (Tm) of the polyester composition is preferably 120 to 240 ° C. from the viewpoint of heat resistance and mechanical properties, and more preferably 150 to 190 ° C. If the crystal melting temperature is less than 120 ° C, the heat resistance after molding will be low, which may cause troubles such as sticking to each member. If it exceeds 240 ° C, the color tone may deteriorate during extrusion molding. There is sex.

  The difference (Tm−Tmc) between the crystal melting temperature and the cooling crystallization temperature (Tmc) of the polyester composition is preferably 10 to 50 ° C. from the viewpoint of moldability and blocking resistance, and more preferably 10 to 40 ° C. It is preferable to set it as 10-30 degreeC. If the difference between the crystal melting temperature and the temperature-falling crystallization temperature (Tm-Tmc) exceeds 50 ° C, a film-forming trouble due to adhesion is likely to occur when the sheet is extruded from the T-die to the casting drum, and the sheet is taken up. May block later. As a method of setting the difference between the crystal melting temperature and the temperature-falling crystallization temperature to 50 ° C. or less, for example, there is a method of kneading two or more kinds of polyesters in the presence of Compound A with a vent type twin screw extruder. The mechanism is that two or more polyesters react with compound A in a vented twin-screw extruder and become uniform (when only one crystal melting peak is detected), so fine crystals that DSC cannot detect. Since nuclei remain in an unmelted state as nuclei, it is presumed that crystallization at lowering temperature occurs at a higher temperature than the copolymer product due to the nucleating agent effect.

  The polyester contained in the polyester composition of the present invention contains at least terephthalic acid and dimer acid as the acid component, and at least selected from the group consisting of ethylene glycol, 1,3-propanediol and 1,4-butanediol as the glycol component. It is preferable from a flexible viewpoint that 2 types are included.

  The polyester composition of the present invention described above includes, for example, a polyester (polyester A) having a crystal melting temperature (Tm) of 210 to 260 ° C. and a glass transition point (Tg) of 30 to 80 ° C., and a crystal melting temperature ( A polyester (polyester B) having a Tm) of 150 to 200 ° C. and a glass transition point (Tg) of 10 ° C. or less is obtained by kneading with a vent type twin screw extruder in the presence of the compound A described above. be able to. The crystal melting temperature of the polyester composition thus obtained can be determined from the peak recognized as one peak on the crystal melting curve.

  The crystal melting temperature of polyester A is preferably 210 to 260 ° C. in terms of moldability and mechanical properties of the polyester composition, and more preferably 210 to 240 ° C. in terms of color tone. When the crystal melting temperature of polyester A is less than 210 ° C., the heat resistance of the polyester composition may be reduced, and when it exceeds 260 ° C., the color tone of the polyester composition may be lowered during vent type biaxial extrusion.

  The glass transition point of polyester A is preferably 30 to 80 ° C. from the viewpoint of mechanical properties of the polyester composition, and more preferably 30 to 70 ° C. from the viewpoint of flexibility. If the glass transition point of polyester A is less than 30 ° C, the self-supporting property may be impaired when the polyester composition is molded, and handling may be difficult, and if it exceeds 80 ° C, flexibility may be insufficient.

  Specific examples of polyester A include, for example, polyethylene terephthalate, polypropylene terephthalate, copolymerized polyethylene terephthalate, and copolymerized polyethylene naphthalate. From the viewpoint of flexibility, transparency, and crystallinity, polyethylene terephthalate and polypropylene terephthalate. A copolymerized polyethylene terephthalate is preferable. The intrinsic viscosity of these polyesters A is preferably 0.5 to 0.7 from the viewpoint of compatibility with polyester B and mechanical properties, and more preferably 0.6 to 0.7. To preferred. If the intrinsic viscosity is less than 0.5, the compatibility will be good, but the molecular weight of the product polyester will decrease, so that sufficient mechanical properties may not be obtained. Further, when the intrinsic viscosity exceeds 0.7, the compatibility with the polyester B is lowered, so that a large amount of the compound A is required or it is necessary to react for a long time in the vent type twin screw extruder. The polyester composition may be thermally deteriorated or the color tone may be lowered by the thermal deterioration of Compound A.

  Among the above polymers listed as polyester A, polyethylene terephthalate has an effect of improving the moldability of the polyester composition, and polytrimethylene terephthalate has an effect of improving flexibility and 1,3-propanediol as a raw material. Can be produced by biotechnology, and there is great expectation as a raw material for removing petroleum.

  Moreover, as a copolymerization polyethylene terephthalate, it is preferable from the point of the color tone of a polyester composition that a crystal melting temperature shall be 210-240 degreeC. Examples of copolymer components include aromatic dicarboxylic acid components such as isophthalic acid component, naphthalene dicarboxylic acid component, and sulfoisophthalic acid component, aliphatic dicarboxylic acid components such as adipic acid component, sebacic acid component, and dodecadioic acid component, hexanediol, and nonane. Although components such as diol, spiroglycol, and cyclohexanedimethanol can be copolymerized, it is preferable to use an isophthalic acid component as a copolymerization component in order to control crystallinity without changing the glass transition point. Moreover, when aiming at a compatibility improvement with the polyester B, it is preferable to use C16 or more unsaturated aliphatic carboxylic acid, its dimer, and a trimer as a copolymerization component.

  The crystal melting temperature of polyester B is preferably 150 to 200 ° C. from the viewpoint of flexibility and heat resistance of the polyester composition, and more preferably 150 to 190 ° C. from the viewpoint of flexibility. When the crystal melting temperature is less than 150 ° C., the heat resistance of the polyester composition may be lowered, and when it exceeds 200 ° C., the heat laminating property to a steel sheet or the like may be lowered.

  The glass transition point of polyester B is preferably −50 to 10 ° C. from the viewpoint of flexibility of the polyester composition. When the glass transition point exceeds 10 ° C., sufficient flexibility may not be obtained. Moreover, when it is less than -50 degreeC, compatibility with the polyester A falls and a uniform composition may not be obtained.

  Specific examples of polyester B include, for example, polyethylene terephthalate copolymer, polytrimethylene terephthalate copolymer, polybutylene terephthalate copolymer, and the like. Examples of copolymer components include aromatic dicarboxylic acid components such as isophthalic acid component, naphthalene dicarboxylic acid component, and sulfoisophthalic acid component, aliphatic dicarboxylic acid components such as sebacic acid component, adipic acid component, and dodecadioic acid component, hexanediol, and nonane. Examples thereof include glycol components such as diol, polyols such as polyethylene glycol and polytetramethylene glycol, and dimer acid. Among them, it is preferable from the viewpoint of flexibility and crystallinity that the polybutylene terephthalate copolymer contains 5 to 60% by weight of dimer acid as a copolymerization component. In particular, the content is preferably 10 to 50% by weight from the viewpoint of improving the flexibility of the polyester composition.

  Further, when the glycol component of polyester B is a 1,4-butanediol residue or a 1,3-propanediol residue, and the acid component is a terephthalic acid residue or a dimer acid residue, flexibility and transparency can be obtained. It is preferable from the viewpoint.

  Moreover, when viscosity increase is severe at the time of the polymerization reaction at the time of manufacturing polyester B, polyols, such as polyethyleneglycol or polytetramethyleneglycol, can be contained as a viscosity reducing agent.

  The number average molecular weight of these polyols is preferably 400 to 1,500, more preferably 600 to 1,000 from the viewpoint of compatibility with the polyester composition. The content of the polyol in the polyester B is preferably 1 to 7% by weight from the viewpoint of flexibility and heat resistance of the polyester composition, and particularly preferably 1 to 5% by weight. In particular, the total content of polyethylene glycol or polytetramethylene glycol of polyester B is preferably 1 to 7% by weight.

  The intrinsic viscosity of the polyester B is preferably 0.7 to 0.9 from the viewpoint of compatibility with the polyester A, and more preferably 0.75 to 0.85. If the intrinsic viscosity is less than 0.7, the mechanical properties of the polyester composition may be lowered. If it exceeds 0.9, the compatibility with the polyester A is lowered, which may cause whitening and embrittlement. There is sex.

  When the above-described polyester A and polyester B are supplied to a vent type twin screw extruder to produce the polyester composition of the present invention, it is necessary to contain compound A (detailed below).

  The compound A in the present invention has a molecular weight of less than 1,000 and is at least one compound selected from the group consisting of organic acids, organic acid metal salts, oxazoline compounds, and glycidyl compounds. In the present invention, the compound A is obtained by compatibilizing polyesters such as polyester A and polyester B (chemical reaction in some cases). For example, each polyester has a single value (chart) for Tg, Tm, and Tmc. In the state where each is recognized as one peak).

  For example, examples of the organic acid include sulfonic acid and carboxylic acid. In the present invention, an organic acid and / or an organic acid metal salt is preferably used, and a sulfonic acid metal salt is particularly preferable.

  Moreover, when using carboxylic acid, it is preferable to use as a metal salt. Examples of the carboxylic acid metal salt include an acetic acid metal salt and a stearic acid metal salt, and the metal species forming the salt is preferably an alkaline earth metal, and in particular, a calcium salt and a magnesium salt are used in combination. Is preferred. If the calcium salt is added in an excessive amount, foreign matters such as calcium terephthalate are likely to be generated, and the magnesium salt is likely to be colored, so it is preferable to use both of them in small amounts.

  Examples of the sulfonic acid include aromatic sulfonic acids such as toluenesulfonic acid, benzenesulfonic acid, and nitrobenzenesulfonic acid, and metal salts thereof, and metal salts are preferable from the viewpoint of handling properties. The metal species of the sulfonic acid metal salt is preferably an alkali metal, and more preferably a potassium salt or a lithium salt from the viewpoint of color tone.

  The method for adding Compound A is not particularly limited, but it may be carried out by any method such as a method using a powder feeder, a method of adding by adhering to the chip surface, a method of adding by dissolving in water or ethylene glycol. it can. Moreover, when the compound A is a liquid, it is preferable to dilute and add with water or ethylene glycol. Some compounds have deliquescence and low heat resistance, but even such compounds can be dissolved or dispersed in water or ethylene glycol to obtain a good polyester composition. Can do. When the liquid is added, a more stable operation is possible by providing an open vent in addition to the vent port for decompressing.

  The content of Compound A in the polyester composition is preferably 0.1 to 5% by weight. When the content of Compound A is less than 0.1% by weight, it means that the amount of Compound A present in the kneading step is small, so that polyester A and polyester B are sufficiently contained in the vent type twin screw extruder. The reaction does not proceed, and a plurality of peaks (for example, two peaks) for reading the crystal melting temperature are detected, which may cause whitening and embrittlement. On the other hand, if it exceeds 5% by weight, the color tone may decrease due to thermal deterioration of the compound A itself.

  The molecular weight of Compound A is preferably less than 1,000. When the molecular weight is 1,000 or more, there is a high possibility that a sufficient compatibility effect during kneading cannot be obtained when the content is 0.1 to 5% by weight. If it is contained in a large amount, the glass transition point, crystallization temperature, crystal melting temperature, and the like are affected, which may affect the quality design of the polyester composition.

  As preferable operating conditions and apparatus specifications of the vent type twin screw extruder, it is sufficient that the ratio L / D of screw length (L) / screw diameter (D) is 40 or more, and further L / D is 60 or more. It is preferable because the residence time can be increased. As a standard of the residence time, it is preferably 6 minutes or more, more preferably 9 minutes or more, and particularly preferably 9 to 15 minutes from the viewpoint of color tone. In addition, by reducing the residence time by increasing the extrusion temperature, increasing the amount of Compound A, and selecting highly compatible polyester A and polyester B, the degradation of the polyester composition due to thermal decomposition is minimized. Can be suppressed. However, when the extrusion temperature is increased, the color tone and mechanical properties decrease due to thermal degradation, and when the amount of Compound A is increased, the color tone decreases due to thermal decomposition of Compound A itself, etc., promoting the thermal decomposition of the polyester composition. It is necessary to set conditions carefully because it will take risks such as.

  In addition, when the residence time is lengthened with an extruder having a small L / D, there are techniques such as reducing the discharge amount and increasing the polymer filling rate. In order to take risks such as deterioration of characteristics, it is preferable to manufacture with an extruder having a large L / D, or to use two extruders having a small L / D and to make the residence time longer by using a tandem system.

  The extrusion temperature is preferably the melting point of the polyester having the highest crystal melting temperature of +15 to 30 ° C. from the viewpoint of reactivity, the temperature is gradually lowered in the region downstream from the melting zone, and the temperature of the discharge part is the product polyester composition The melting point of the product is preferably 15 to 30 ° C. from the viewpoint of the color tone and mechanical properties of the polyester composition.

  In addition, it is preferable from the viewpoint of the color tone and mechanical properties of the polyester composition that two or more vent ports are provided to efficiently remove volatile oligomers, moisture and the like. In the present invention, since polyester A and polyester B are reacted in a twin screw extruder in the presence of compound A, it is preferable to positively remove glycol components, moisture, oligomers and the like by-produced at that time.

  When a single-screw extruder is used instead of a vented twin-screw extruder, kneading is insufficient, so it is difficult to achieve compatibilization and the reaction rate is slow, so two or more crystal melting peaks may be detected. Is expensive.

  Moreover, you may contain polyester other than polyester A and polyester B in the range which does not impair the physical property of a polyester composition.

  The polyester composition of the present invention may be extruded from a normal die and formed into chips. However, from the viewpoint of handling properties, a gear pump and a T-type die are used in a vent type twin-screw extruder, and a direct unstretched sheet and It is preferable to do. 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. film haze)
Judgment was made based on the following criteria from the haze value measured using a fully automatic direct reading haze computer HGM-2DP manufactured by Suga Test Instruments Co., Ltd.

A: Less than 5% B: 5% or more and less than 10% X: 10% or more (D. Color tone (b value))
0.6 g of a sample was dissolved in 30 ml of HFIP at room temperature and measured with NDR-2000 (manufactured by Nippon Denshoku). At this time, a 30 ml cell was used, and the determination was made according to the following criteria.

◎: Less than 5 ○: 5 or more and less than 8 ×: 8 or more (E. 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 (F. Polyester composition analysis)
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 quantification of the dimer acid can be analyzed by high performance liquid chromatography. In this example, the determination was performed under the condition D.

  Other carboxylic acid components were measured by high performance liquid chromatography after adding sodium methylate at a concentration of 1 mol / L and methyl acetate and treating with reflux heating for 2 hours. 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
Other carboxylic acid components were measured by high performance liquid chromatography.

(G. Elastic modulus of polyester sheet)
The measurement was performed at 25 ° C. using Tensilon manufactured by Orientec Co., Ltd. After the polyester sheet was kept at the measurement temperature for 30 seconds, 10 points each of the elastic modulus (MPa) in the longitudinal direction and the width direction of the sheet having a width of 10 mm and a sample length of 30 mm were measured at a tensile speed of 300 mm / min. The average value of 8 points excluding the minimum value was obtained.

(Reference example)
Production of polyester A-1 101.0 parts by weight of dimethyl terephthalate, 58.1 parts by weight of ethylene glycol, 0.06 part by weight of magnesium acetate, and 0.03 part by weight of antimony trioxide were charged and the temperature was raised from 150 ° C to 240 ° C. However, the ester exchange reaction was performed according to a conventional method, 0.022 part by weight of trimethyl phosphoric acid was added, and initial polymerization was performed at 240 Torr. Then, it moved to the polycondensation reaction kettle, and polycondensation reaction was performed according to a conventional method. Finally, a polycondensation reaction was performed at 290 ° C. and 1 Torr or less to obtain a polyester.

Manufacture of polyester A-2 Charged 85.9 parts by weight of dimethyl terephthalate, 15.1 parts by weight of dimethyl isophthalate, 58.1 parts by weight of ethylene glycol, 0.06 parts by weight of magnesium acetate, and 0.03 parts by weight of antimony trioxide. While the temperature was increased from 150 ° C. to 240 ° C., a transesterification reaction was carried out according to a conventional method, 0.022 parts by weight of trimethyl phosphoric acid was added, and initial polymerization was performed at 240 Torr. Then, it moved to the polycondensation reaction kettle, and polycondensation reaction was performed according to a conventional method. Finally, a polycondensation reaction was performed at 290 ° C. and 1 Torr or less to obtain a polyester.

Production of polyester A-3 86.9 parts by weight of dimethyl terephthalate, 52.6 parts by weight of ethylene glycol, 0.06 part by weight of manganese acetate and 0.03 part by weight of antimony trioxide were charged and the temperature was raised from 150 ° C to 240 ° C. However, after a transesterification reaction was performed according to a conventional method, 13.3 parts by weight of “PRIPOL 1098” (manufactured by Unikema) and 0.017 parts by weight of phosphoric acid were added, and initial polymerization was performed at 240 Torr. Then, it moved to the polycondensation reaction kettle, and polycondensation reaction was performed according to a conventional method. Finally, a polycondensation reaction was performed at 280 ° C. and 1 Torr or less to obtain a polyester.

Production of polyester B-1 55.9 parts by weight of dimethyl terephthalate, 46.7 parts by weight of 1,4-butanediol, 0.04 parts by weight of tetrabutyl titanate, 0.016 parts by weight of “IRGANOX1010FP” were charged from 150 ° C. Transesterification was carried out according to a conventional method while raising the temperature to 210 ° C., and then 0.042 part by weight of trimethyl phosphoric acid was added. Ten minutes later, 0.055 part by weight of tetrabutyl titanate and 0.022 part by weight of “IRGANOX1010FP” Part, 33.4 parts by weight of "PRIPOL 1098" (manufactured by Unikema) preheated to 50 ° C./9.6 parts by weight of 1,4-butanediol was added. After the can internal temperature returned to 210 ° C., the mixture was stirred for 30 minutes and then transferred to a polycondensation reaction kettle, and 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.

Production of polyester B-2 58.8 parts by weight of dimethyl terephthalate, 41.5 parts by weight of 1,3-propanediol, 0.04 part by weight of tetrabutyl titanate, 0.016 part by weight of “IRGANOX1010FP” were charged from 150 ° C. Transesterification was carried out in accordance with a conventional method while raising the temperature to 240 ° C., and then 0.042 part by weight of trimethyl phosphoric acid was added. After 10 minutes, 0.055 part by weight of tetrabutyl titanate and 0.022 part by weight of “IRGANOX1010FP” 1 part of the mixed slurry of “PRIPOL 1098” (manufactured by Unikema Co., Ltd.) 35.1 parts by weight and 1,3-propanediol 8.4 parts by weight was previously added. After the can internal temperature returned to 240 ° C., the mixture was stirred for 30 minutes and then transferred to a polycondensation reaction kettle, and a polycondensation reaction was performed according to a conventional method. Finally, a polycondensation reaction was performed at 250 ° C. and 1 Torr or less to obtain a polyester.

Preparation of polyester B-3 50.3 parts by weight of dimethyl terephthalate, 42.0 parts by weight of 1,4-butanediol, 0.04 parts by weight of tetrabutyl titanate, 0.016 parts by weight of “IRGANOX1010FP” were charged from 150 ° C. Transesterification was carried out according to a conventional method while raising the temperature to 210 ° C., and then 0.042 part by weight of trimethyl phosphoric acid was added. Ten minutes later, 0.055 part by weight of tetrabutyl titanate and 0.022 part by weight of “IRGANOX1010FP” Part, "PRIPOL 1025" (manufactured by Unikema) heated to 50 ° C in advance 30.1 parts by weight / 1,4-butanediol 8.0 parts by weight mixed slurry, polyethylene glycol (number average molecular weight: 800) 10 parts by weight did. After the can internal temperature returned to 210 ° C., the mixture was stirred for 30 minutes and then transferred to a polycondensation reaction kettle, and 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.

Production of polyester B-4: 45.5 parts by weight of dimethyl terephthalate, 38.0 parts by weight of 1,4-butanediol, 0.04 parts by weight of tetrabutyl titanate, 0.016 parts by weight of “IRGANOX1010FP” were charged from 150 ° C. Transesterification was carried out according to a conventional method while raising the temperature to 210 ° C., and then 0.042 part by weight of trimethyl phosphoric acid was added. Ten minutes later, 0.055 part by weight of tetrabutyl titanate and 0.022 part by weight of “IRGANOX1010FP” 1 part by weight of 44.2 parts by weight / 1,4-butanediol mixed with “PRIPOL 1098” (manufactured by Unikema) heated to 50 ° C. in advance. After the can internal temperature returned to 210 ° C., the mixture was stirred for 30 minutes and then transferred to a polycondensation reaction kettle, and 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.

Production of polyester B-5 A polyester was obtained in the same manner as polyester B-1, except that the polycondensation reaction was carried out for a longer period and the intrinsic viscosity was 0.9.

Polyester B-6
Polyester was obtained in the same manner as polyester B-1, except that ethylene glycol / 1,4-butanediol was used as the glycol component, the addition amount of “PRIPOL 1098” was changed, and the polymerization temperature was changed to 250 ° C. The content of ethylene glycol / 1,4-butanediol in this polyester was ethylene glycol / 1,4-butanediol = 14 mol% / 86 mol% with respect to the total glycol components.

Production of Polyester C 101.0 parts by weight of dimethyl terephthalate, 83.3 parts by weight of 1,4-butanediol, 0.04 parts by weight of tetrabutoxytitanate, 0.016 parts by weight of “IRGANOX1010FP” were charged at 150 to 210 ° C. The mixture was transesterified according to a conventional method while raising the temperature to 0.042 parts by weight of trimethyl phosphoric acid, and after 10 minutes, 0.055 parts by weight of tetrabutyl titanate and 0.022 parts by weight of “IRGANOX1010FP” were added. Initial polymerization was performed at 240 Torr. Then, it moved to the polycondensation reaction kettle, and 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.

Example 1
10 parts by weight of polyester A-1, 90 parts by weight of polyester B-1, and 1.0 part by weight of sodium ptoluenesulfonate as compound A were kneaded using a bent twin screw extruder with L / D = 60. Then, it was extruded from a T-die while quantitatively using a gear pump to obtain an unstretched sheet. The temperature conditions of the vent type twin screw extruder were 260 ° C. for the polymer supply section, 280 ° C. for the melting section, and the temperature was gradually decreased from the latter half of the extruder, and finally the T die was set to 200 ° C.

  At this time, a 16 μm polymer filter was used, and the polymer residence time was 10 minutes.

  The obtained sheet was transparent and the crystal melting peak was as good as 1 peak.

(Example 2)
20 parts by weight of polyester A-2, 80 parts by weight of polyester B-1, and 1.0 part by weight of p-toluenesulfonic acid as compound A, the temperature setting of the vent type twin-screw extruder was set at a polymer supply unit 220 ° C. An unstretched sheet was obtained in the same manner as in Example 1 except that the melting part was 240 ° C and the T die was 190 ° C.

(Example 3)
An unstretched sheet was obtained in the same manner as in Example 1 except that 20 parts by weight of polyester A-1 and 80 parts by weight of polyester B-2 and 1.0 part by weight of sodium ptoluenesulfonate as compound A were used.

Example 4
10 parts by weight of polyester A-1, 90 parts by weight of polyester B-3, an aqueous solution of ptoluenesulfonic acid as compound A and 1.0 part by weight as ptoluenesulfonic acid were supplied from a nozzle, A non-stretched sheet was obtained in the same manner as in Example 1 except that an opening for discharging the water to the outside of the system was provided.

(Example 5)
An unstretched sheet was obtained in the same manner as in Example 1 except that 25 parts by weight of polyester A-1 and 75 parts by weight of polyester B-4 and 1.0 part by weight of p-toluenesulfonic acid as compound A were used.

(Example 6)
An unstretched sheet was obtained in the same manner as in Example 1 except that 60 parts by weight of polyester A-1, 30 parts by weight of polyester B-1, and 10 parts by weight of polyester C were used.

(Example 7)
20 parts by weight of polyester A-3, 80 parts by weight of polyester B-1, 0.4 parts by weight of p-toluenesulfonic acid as compound A, and the same procedure as in Example 1 except that the temperature of the twin screw extruder was changed. Thus, an unstretched sheet was obtained.

(Comparative Example 1)
When trying to extrude 80 parts by weight of polyester A-1 and 20 parts by weight of polyester B-3 through a polymer filter with an extrusion temperature of 280 ° C. and 16 μm through a single screw extruder, the filtration pressure increased. It was impossible to extrude.

(Comparative Example 2)
An unstretched sheet was obtained in the same manner as in Example 1 except that Compound A was not added using a bent twin screw extruder of L / D = 30. At this time, the polymer residence time was 3 minutes, and two peaks of crystal melting were also detected.

(Comparative Example 3)
An unstretched sheet was obtained in the same manner as in Example 1 except that 10 parts by weight of polyester A-1 and 90 parts by weight of polyester B-1 were supplied to a single screw extruder and extruded at 280 ° C. The obtained unstretched sheet was turbid, and two peaks of crystal melting were detected.

(Comparative Example 4)
Polyester B-6 was supplied to a single screw extruder and discharged from a T-die to a casting drum. As a result, the polyester B-6 adhered to the casting drum, and a peeling trace from the casting drum remained on the unstretched sheet. Furthermore, when the roll sample after winding was stored for 3 days, it was partially whitened, so it was judged as defective without having to evaluate its physical properties.

Claims (12)

0.1 to 5% of a compound (compound A) having a molecular weight of less than 1,000 selected from the group consisting of 5 to 50% by weight of dimer acid, organic acid, metal salt of organic acid, oxazoline compound and glycidyl compound The glass transition point (Tg) is −50 to 30 ° C., the crystal melting temperature (Tm) is 120 to 240 ° C., the crystal melting temperature (Tm) —the falling crystallization temperature (Tmc) is 10 to 50 ° C. A polyester composition. The polyester composition according to claim 1, comprising terephthalic acid and dimer acid as the acid component, and at least two selected from the group consisting of ethylene glycol, 1,3-propanediol and 1,4-butanediol as the glycol component. object. The polyester composition according to claim 1 or 2, wherein compound A is an organic acid and / or an organic acid metal salt. The polyester composition according to claim 3, wherein Compound A is a sulfonic acid metal salt. The crystal melting temperature (Tm) is 210-260 ° C, the glass transition point (Tg) is 30-80 ° C, the polyester (polyester A), the crystal melting temperature (Tm) is 150-200 ° C, and the glass transition The polyester composition according to any one of claims 1 to 4, wherein a polyester (polyester B) having a point (Tg) of -50 to 10 ° C is kneaded in the presence of compound A by a vent type twin screw extruder. Manufacturing method. The manufacturing method of the polyester composition of Claim 5 whose intrinsic viscosity of the polyester A is 0.5-0.7 and whose intrinsic viscosity of the polyester B is 0.7-0.9. The method for producing a polyester composition according to claim 5 or 6, wherein the polyester B contains 5 to 60% by weight of dimer acid as a copolymerization component. The glycol component of polyester B is a 1,4-butanediol residue or a 1,3-propanediol residue, and the acid component is a terephthalic acid residue or a dimer acid residue. The manufacturing method of the polyester composition of description. The method for producing a polyester composition according to any one of claims 5 to 8, wherein the total content of polyethylene glycol or polytetramethylene glycol of polyester B is 1 to 7% by weight. 10. The polyester A according to claim 5, wherein the polyester A is at least one polyester selected from the group consisting of polyethylene terephthalate, a polyethylene terephthalate copolymer having a crystal melting temperature of 210 ° C. to 240 ° C., and polypropylene terephthalate. Method for producing polyester composition A total content of polyester A and polyester B of 80 to 99% by weight, and a polyester (polyester C) of 1 to 20% by weight having a crystal melting temperature of 240 ° C. or lower, in the presence of compound A, with respect to the total polyester The manufacturing method of the polyester composition in any one of Claims 5-10 knead | mixed with a twin-screw extruder. The polyester sheet containing the polyester composition in any one of Claims 1-4.