JP2010031207A - Copolymerized polyester resin composition and biaxially oriented film made of this - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a novel copolymerized polyester resin composition having the excellent size stability with respect to temperature and humidity, and capable of obtaining a molded product with a preferable light resistance. <P>SOLUTION: The copolymerized polyester resin composition is made of a 2-4C alkylene glycol, and an aromatic dicarboxylic acid component represented by formulae (I): HO(O)C-R<SP>2</SP>-OR<SP>1</SP>O-R<SP>2</SP>-C(O)OH, wherein R<SP>1</SP>is a 2-10C alkylene group and R<SP>2</SP>is a 2,6-naphthalenediyl group, and (II): HO(O)C-R<SP>3</SP>-C(O)OH, wherein R<SP>3</SP>is a phenylene group or a naphthalenediyl group. Based on the resin composition mass, 0.5-10 mass% of a benzotriazole ultraviolet absorber and 0.05-2.0 mass% of a hindered phenol antioxidant, or 0.5-10 mass% of a benzotriazole ultraviolet absorber having a hindered phenol group are included in a copolymerized polyester with the copolymerization rate of the aromatic dicarboxylic acid component represented by formula (I) being 5-80 mol% based on the total acid component. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a novel copolymerized polyester resin composition and a biaxially oriented film using the same, which are capable of obtaining a molded article having excellent mechanical properties and dimensional stability and good light resistance.

  Aromatic polyesters typified by polyethylene terephthalate and polyethylene-2,6-naphthalate have excellent mechanical properties and chemical properties, and thus are widely deployed in molded articles such as fibers, films, and bottles. However, there is a strong demand for higher performance from the market, and improvements are desired.

  Under such circumstances, Patent Documents 1 to 4 use 6,6 ′-(alkylenedioxy) di-2-naphthoic acid as an acid component as a polyester having higher performance than polyethylene-2,6-naphthalate. Polyalkylene-6,6 ′-(alkylenedioxy) di-2-naphthoate has been proposed. And according to these patent documents, it is disclosed that such polyester is very excellent in dimensional stability and can express very high rigidity.

  However, according to the studies by the present inventors, the polyesters described in these publications have a very high melting point and excessively high crystallinity, so when trying to form a film, particularly a film, etc. It has been found that the melt-extrusion process is destabilized and easily broken during stretching.

JP-A-60-135428 JP-A-60-212420 JP 61-145724 A JP-A-6-145323

  The inventors have studied to provide a new polyester that replaces polyethylene terephthalate, polyethylene-2,6-naphthalate and polyethylene-6,6 ′-(ethylenedioxy) di-2-naphthoate, , 6 '-(alkylenedioxy) di-2-naphthoic acid as a copolymerization component, when copolymerized in a predetermined amount, the same Young's modulus has the same coefficient of thermal expansion as polyethylene terephthalate and polyethylene-2,6-naphthalate On the other hand, it has been found that a copolyester having a lower coefficient of humidity expansion, that is, excellent dimensional stability against changes in temperature and humidity can be obtained. However, although it is a polyester having such excellent characteristics, when it is used outdoors, the light resistance is still insufficient, and further improvement is required depending on the application.

  The present invention has been made based on the background described above, and its object is to provide a novel copolyester resin composition capable of obtaining a molded article having excellent mechanical properties and dimensional stability and also having good light resistance. There is.

  The present inventor diligently studied to achieve the above object, and if a benzotriazole-based ultraviolet absorber is used in combination with a hindered phenol-based antioxidant, 6,6 ′-(alkylenedioxy) di- The inventors have found that the light resistance of a copolymerized polyester obtained by copolymerizing a predetermined amount of 2-naphthoic acid as a copolymerization component can be improved, and have further studied to arrive at the present invention.

Thus, according to the present invention, it is composed of an aromatic dicarboxylic acid component represented by the following formulas (I) and (II) and a glycol component composed of an alkylene glycol having 2 to 4 carbon atoms. In the copolymerized polyester in which the copolymerization ratio of the aromatic dicarboxylic acid component represented is in the range of 5 to 80 mol% based on the total acid component, 0% of the benzotriazole-based ultraviolet absorber is based on the amount of the resin composition material. A copolymer polyester resin composition containing 5 to 10% by mass and 0.05 to 2.0% by mass of a hindered phenol-based antioxidant is provided.
HO (O) C—R ² —OR ¹ O—R ² —C (O) OH (I)
[In the above formula (I), R ¹ represents an alkylene group having 2 to 10 carbon atoms, and R ² represents a 2,6-naphthalenediyl group. ]
HO (O) C—R ³ —C (O) OH (II)
[In the above formula (II), R ³ represents a phenylene group or a naphthalenediyl group. ]

According to the present invention, the copolymer polyester contains 0.5 to 10.0% by mass of a benzotriazole-based ultraviolet absorber having a hindered phenol group based on the amount of the resin composition material. A polyester resin composition is also provided.
Furthermore, according to this invention, the biaxially oriented film which consists of these copolymerization polyester resin compositions is provided.

  Molded articles such as films obtained using the composition of the present invention have a low temperature expansion coefficient (αt) and humidity expansion coefficient (αh), and are also highly elastic, so that they are resistant to environmental changes such as temperature and humidity. Since it has excellent dimensional stability and good light resistance, it can be suitably used, for example, for a film for solar cells.

In the copolyester according to the present invention, the acid component is composed of the above formulas (I) and (II), and the glycol component is composed of alkylene glycol having 2 to 4 carbon atoms.
The acid component represented by the formula (I) is one in which R ¹ is an alkylene group having 2 to 10 carbon atoms, and R ² is a 2,6-naphthalenediyl group. 6,6 ′-(ethylenedioxy) di-2-naphthoic acid component, 6,6 ′-(trimethylenedioxy) di-2-naphthoic acid component and 6,6 ′-(butylenedioxy) di-2 -A naphthoic acid component etc. are mentioned. Among these, from the viewpoint of the effect of the present invention, those having an even number of carbon atoms of R ¹ are preferable, and a 6,6 ′-(ethylenedioxy) di-2-naphthoic acid component is particularly preferable.

  Examples of the acid component represented by the formula (II) include a terephthalic acid component, an isophthalic acid component, a 2,6-naphthalenedicarboxylic acid component, and a 2,7-naphthalenedicarboxylic acid component. Among these, a terephthalic acid component and a 2,6-naphthalenedicarboxylic acid component are preferable from the viewpoint of mechanical properties, and a 2,6-naphthalenedicarboxylic acid component is particularly preferable.

  Examples of the alkylene glycol having 2 to 4 carbon atoms include ethylene glycol, trimethylene glycol, tetramethylene glycol, and 90 mol% or more of the glycol component is preferably an ethylene glycol component from the viewpoint of mechanical properties, In particular, 95 to 100 mol% is preferably ethylene glycol.

  By the way, one of the features of the present invention is that 6,6 ′-(alkylene di) represented by the above formula (I) in a range of 5 to 80 mol% based on the number of moles of all acid components of the copolymer polyester. Oxy) di-2-naphthoic acid component is copolymerized. When the ratio of the 6,6 '-(alkylenedioxy) di-2-naphthoic acid component is less than the lower limit, the effect of reducing the humidity expansion coefficient is difficult to be exhibited. On the other hand, the upper limit is preferably 80 mol% or less, and more preferably less than 50 mol% from the viewpoint of moldability. Surprisingly, the 6,6 '-(alkylenedioxy) di-2-naphthoic acid component reduces the coefficient of humidity expansion very efficiently in a small amount and is less than 50 mol%. In addition, a humidity expansion coefficient equivalent to or lower than that of the film described in the example of Patent Document 3 is achieved, and the effect from the viewpoint of the humidity expansion coefficient is saturated even when added in an amount of 50 mol% or more. It can be said that. From such a viewpoint, the upper limit of the copolymerization amount of the preferred 6,6 ′-(alkylenedioxy) di-2-naphthoic acid component is 45 mol% or less, further 40 mol% or less, and further 35 mol% or less. In particular, it is 30 mol% or less, and the other lower limit is 5 mol% or more, further 7 mol% or more, still more 10 mol% or more, particularly 15 mol% or more.

  By using a copolyester obtained by copolymerizing such a specific amount of 6,6 ′-(alkylenedioxy) di-2-naphthoic acid component, a molded product having a small coefficient of thermal expansion and a coefficient of humidity expansion, such as a film Can be manufactured.

  The copolymer polyester of the present invention comprising the above acid component and glycol component is measured at 35 ° C. using a mixed solvent of P-chlorophenol / 1,1,2,2-tetrachloroethane (weight ratio 40/60). The intrinsic viscosity is preferably in the range of 0.4 to 3 dl / g, more preferably in the range of 0.4 to 1.5 dl / g, and particularly preferably in the range of 0.5 to 1.2 dl / g.

  Furthermore, it is preferable from the point of film forming property that melting | fusing point measured by DSC exists in the range of 200-260 degreeC, the range of 210-255 degreeC, especially the range of 220-253 degreeC. When the melting point exceeds the above upper limit, when molding by melt extrusion, it is necessary to make the temperature higher to increase the fluidity, and it tends to be thermally deteriorated, and on the other hand, if the melting temperature is lowered, the fluidity is inferior, Discharge is likely to be non-uniform. On the other hand, when the value is less than the above lower limit, the film forming property is excellent, but the mechanical properties and the like of the copolyester are easily impaired. Usually, other acid components are copolymerized to lower the melting point and at the same time the mechanical properties and the like are lowered. However, the copolymerized polyester of the present invention is excellent in mechanical properties or the like because the film-forming property is improved. It can be.

  Further, the polyester in the present invention has a glass transition temperature (hereinafter sometimes referred to as Tg) measured by DSC of 90 to 125 ° C, more preferably 95 to 123 ° C, particularly 100 to 120 ° C. It is preferable from the viewpoint of heat resistance and dimensional stability. Such a melting point and glass transition temperature can be adjusted by controlling the type and amount of copolymerization component, dialalkylene glycol as a byproduct.

  By the way, in the copolymerized polyester of the present invention, other copolymer components known per se to the obtained copolymerized polyester are, for example, 10 mol% or less, particularly, based on the total acid component, within a range not impairing the effects of the present invention. The copolymer may further be copolymerized within a range of 5 mol% or less.

  In the present invention, the above-mentioned copolymer polyester contains a benzotriazole ultraviolet absorber as an ultraviolet absorber and a hindered phenol antioxidant as an antioxidant at the same time, or a benzotriazole ultraviolet ray having a hindered phenol group. It is important to contain an absorbent. A benzotriazole UV absorber that does not have a hindered phenol group alone cannot provide sufficient light resistance, but a hindered phenol antioxidant is used in combination, or a benzotriazole system that has a hindered phenol group If an ultraviolet absorber is used, a molded product having good light resistance can be obtained.

  Examples of the benzotriazole-based ultraviolet absorber preferably used include those represented by the following formula (B).

（上記式中のＲ_１、Ｒ_２は炭素数１〜１８の分岐してもよく、末端あるいは鎖中に脂環基または芳香環基を有してもよいアルキル基を表す。）

(R ₁ and R ₂ in the above formula represent an alkyl group which may be branched with 1 to 18 carbon atoms and may have an alicyclic group or an aromatic ring group in the terminal or chain.)

Among these, in the above formula (B), R ₁ and R ₂ are preferably benzotriazole ultraviolet absorber B (Tinuvin234 manufactured by Ciba-Geigy Co.), which is —C (Me) ₂ Ph.

  The hindered phenolic antioxidant used in combination with the benzotriazole ultraviolet absorber is not particularly limited, and conventionally known hindered phenolic antioxidants can be used. For example, pentaerythrityl-tetrakis [3- (3,5-di -t-butyl-4-hydroxyphenyl) propionate], octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate 3,3 ', 3 ", 5,5', 5" -Hexa-tert-butyl-a, a ', a "-(mesitylene-2,4,6-triyl) tri-p-cresol, 1,3,5-tris (3,5-di-tert-butyl- 4-hydroxybenzyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione, ethylenebis (oxyethylene) bis [3- (5-tert-butyl-4-hydroxy- m-tolyl) propionate.

  Next, examples of the benzotriazole-based ultraviolet absorber having a hindered phenol group that is preferably used include those represented by the following formula (A).

（上記式中のＲ_１は炭素数１〜１８の分岐してもよく、末端あるいは鎖中に脂環基または芳香環基を有してもよいアルキル基を表し、Ｒ_２は水素またはメチル基を表し、Ｒ_３は炭素数３〜４の分岐を有するアルキル基を表す。）

(R ₁ in the above formula represents an alkyl group which may be branched from 1 to 18 carbon atoms and may have an alicyclic group or an aromatic ring group in the terminal or chain, and R ₂ represents a hydrogen or methyl group. And R ₃ represents an alkyl group having 3 to 4 carbon atoms.)

In particular, in the above formula (A), R ₁ is a t-C ₈ H ₁₇ group, R ₂ is a methyl group, and R ₃ is a t-C ₄ H ₉ group. What is JAST-500) is preferable.

  The copolymer polyester resin composition of the present invention, based on the amount of the composition material, contains 0.5 to 10.0% by mass, preferably 1.0 to 8.0% by mass of the benzotriazole-based ultraviolet absorber. More preferably, it is contained in the range of 2.0 to 6.0% by mass, and further hindered phenolic antioxidant is 0.05 to 2.0% by mass, preferably 0.1 to 1.5% by mass, More preferably, it is contained in the range of 0.5 to 1.0% by mass, or 0.5 to 10.0% by mass of a benzotriazole-based ultraviolet absorber having a hindered phenol group, more preferably 1. It is necessary to contain in the range of 0-8.0 mass%. When the content of the ultraviolet absorber is less than these lower limits, the light resistance improvement effect is insufficient, while when the upper limit is exceeded, the light resistance improvement effect is not only saturated but also the productivity is reduced. However, the moldability of the resulting composition is also unfavorable. In addition, when the content when the hindered phenolic antioxidant is used in combination is less than the lower limit, the light resistance improvement effect by the benzotriazole ultraviolet absorber having no hindered phenol group becomes insufficient, If the upper limit is exceeded, the light resistance improving effect is not only saturated, but also the productivity is lowered and the moldability of the resulting composition is also lowered.

  The copolymerized polyester resin composition of the present invention is not limited to the effects of the present invention, and other thermoplastic polymers, plasticizers, lubricants, flame retardants, release agents, pigments, nucleating agents, fillers or glass fibers, Carbon fiber, layered silicate and the like may be blended as necessary, and making such a polyester composition is preferable because it can impart further characteristics to the resulting molded article. Other thermoplastic polymers include polyamide resins, polycarbonates, ABS resins, polymethyl methacrylate, polyamide elastomers, polyester elastomers, polyether imides, liquid crystalline resins, and 6,6 ′-(alkylenedioxy). ) Other polyester resins in which the copolymerization amount of di-2-naphthoic acid deviates.

Below, the manufacturing method which can obtain the copolyester composition of this invention is demonstrated.
First, the copolyester used in the present invention can be produced according to a conventionally known polyester production method. For example, when the alkylene glycol is ethylene glycol, 6,6 ′-(alkylenedioxy) di-2-naphthoic acid or an ester-forming derivative thereof and, for example, 2,6-naphthalenedicarboxylic acid, terephthalic acid or an ester-forming derivative thereof, Then, an esterification reaction or a transesterification reaction with ethylene glycol is performed to produce a polyester precursor. Then, the obtained polyester precursor can be produced by polycondensation in the presence of a polycondensation catalyst and, if necessary, solid phase polymerization. Two kinds of polyesters having different ratios of the above formulas (I) and (II) may be prepared and melt-kneaded so that the ratios of the above formulas (I) and (II) are intended. In this case, one polyester that does not contain the aromatic dicarboxylic acid component of the formula (I) may be used.

  In the step of producing the polyester precursor, it is possible to use ethylene glycol in an amount of 1.1 to 6 times, more preferably 2 to 5 times, particularly 3 to 5 times the number of moles of the total acid component. It is preferable from the point.

  Moreover, as reaction temperature at the time of manufacturing a polyester precursor, it is preferable to carry out above the boiling point of ethylene glycol, and it is preferable to carry out especially in the range of 190-250 degreeC. When the temperature is lower than 190 ° C., the reaction does not proceed sufficiently. When the temperature is higher than 250 ° C., diethylene glycol as a side reaction product is likely to be generated. In addition, the reaction can be performed under normal pressure, but may be performed under pressure to further increase productivity. More specifically, the absolute pressure is 10 kPa to 200 kPa, the reaction temperature is usually 150 ° C. to 250 ° C., preferably 180 ° C. to 230 ° C., and the reaction time is 10 minutes to 10 hours, preferably 30 minutes to 7 hours. Preferably it is done.

  In the step of producing this polyester precursor, a known esterification or transesterification reaction catalyst may be used. For example, an alkali metal compound, an alkaline earth metal compound, a titanium compound, and the like can be given.

  Next, the polycondensation temperature is in the range of a temperature not lower than the melting point of the obtained copolyester and not higher than 230 to 280 ° C., more preferably not lower than 5 ° C. and higher than the melting point by 30 ° C. The polycondensation reaction is usually preferably performed under a reduced pressure of 50 Pa or less. If it is higher than 50 Pa, the time required for the polycondensation reaction becomes long and it becomes difficult to obtain a copolymer polyester having a high degree of polymerization.

  Examples of the polycondensation catalyst include metal compounds containing at least one metal element. In addition, you may use together a polycondensation catalyst as a catalyst of esterification reaction or transesterification. Examples of the metal element include titanium, germanium, antimony, aluminum, nickel, zinc, tin, cobalt, rhodium, iridium, zirconium, hafnium, lithium, calcium, and magnesium. More preferable metals are titanium, germanium, antimony, aluminum, tin, etc. Among them, a titanium compound is preferable because it exhibits high activity in both the esterification reaction, the transesterification reaction, and the polycondensation reaction.

  These catalysts may be used alone or in combination. The amount of the catalyst is preferably 0.001 to 0.5 mol%, more preferably 0.005 to 0.2 mol%, based on the total acid component of the copolyester.

  In the production of the copolymer polyester resin composition of the present invention, the ultraviolet absorber and the antioxidant used in combination as necessary may be added simultaneously or separately to the polycondensation reaction system of the copolymer polyester, Alternatively, melt mixing may be performed after the polycondensation reaction is completed. Alternatively, the copolymerized polyester once chipped may be melt-mixed with the ultraviolet absorber (and the antioxidant if necessary) in a melt extruder, and in this case, the ultraviolet absorber (and A method in which polyester chips (so-called master batch) containing a relatively high concentration of the antioxidant (if necessary) is mixed in the form of chips and then melt mixed is preferable.

  Next, a method for producing a biaxially oriented film using the copolymerized polyester resin composition of the present invention will be described. First, after drying the chip of the copolyester resin composition, the chip is supplied to an extruder heated to a melting point (Tm: ° C.) to (Tm + 50) ° C., and pressed into a sheet form from a die such as a T die. put out. In addition, the polyester resin composition to be used is not limited to one type, for example, a polymer having a large proportion of the above-described formula (I) and a polymer having a large amount of the above-described formula (II), It may be used by being melt-kneaded with the ultraviolet absorber so that the ratio of (II) is in the target range, and by adopting such a method, the ratio of the aforementioned formulas (I) and (II) can be changed. It can be changed arbitrarily and conveniently. The extruded sheet can be rapidly cooled and solidified with a rotating cooling drum or the like to form an unstretched film, and the unstretched film can be biaxially stretched to obtain a biaxially oriented film.

  In addition, from the viewpoint of facilitating the biaxial stretching, the cooling by the cooling drum is preferably performed very quickly, and is preferably performed at a low temperature of 20 to 60 ° C. By performing at such a low temperature, crystallization in the state of an unstretched film is suppressed, and subsequent stretching can be performed more smoothly.

Biaxial stretching may be sequential biaxial stretching or simultaneous biaxial stretching.
Here, a manufacturing method in which longitudinal stretching, lateral stretching, and heat treatment are performed in this order by sequential biaxial stretching will be described as an example. First, the first longitudinal stretching is performed at a glass transition temperature (Tg: ° C.) to (Tg + 40) ° C. of the copolyester, which is stretched 3 to 8 times, and then at a higher temperature (Tg + 10) than the previous longitudinal stretching in the transverse direction. ) To (Tg + 50) ° C. at a temperature of 3 to 8 times, and further heat treatment is preferably performed at a temperature below the melting point of the polymer and at a temperature of (Tg + 50) to (Tg + 150) ° C. for 1 to 20 seconds. . The heat setting time is preferably 1 to 15 seconds.

  Normally, when the stretching ratio is increased, the film-forming stability is impaired. However, since the copolymerized polyester resin composition of the present invention has high stretchability, there is no such problem, and in particular, the stretching ratio is higher. Therefore, even a thin film having a thickness of 10 μm or less, particularly 8 μm or less can be stably formed. The lower limit of the film thickness is not particularly limited, but is usually about 1 μm, preferably 3 μm.

On the other hand, simultaneous biaxial stretching in which longitudinal stretching and lateral stretching are simultaneously performed can be similarly performed, and the stretching ratio, stretching temperature, and the like described in the sequential biaxial stretching may be referred to.
In addition, a coating layer may be provided on the surface of the biaxially oriented film. In that case, a desired coating solution is applied to one or both sides of the unstretched film or the uniaxially stretched film described above, and then the same method as described above. Biaxial stretching and heat treatment may be performed.

The biaxially oriented film of the present invention obtained as described above preferably has a temperature expansion coefficient (αt) of at least one of the film forming direction (MD direction) and the width direction (TD direction), preferably 14 × 10 ^{−. 6} / ° C. or less, more preferably 10 × 10 ⁻⁶ / ° C. or less, further preferably 7 × 10 ⁻⁶ ° C. or less, and particularly preferably 5 × 10 ⁻⁶ / ° C. or less. It is preferable because it can exhibit excellent dimensional stability against dimensional changes due to.

The lower limit of the temperature expansion coefficient (αt) of at least one of the film forming direction and the width direction of the biaxially oriented film is preferably −15 × 10 ⁻⁶ / ° C., more preferably −10 × 10 ⁻⁶ / ° C., more preferably −7 × 10 ⁻⁶ / ° C.

  According to Patent Document 3, it is expected that the temperature expansion coefficient (αt) of the polyester film obtained by copolymerizing polyalkylene-6,6 ′-(alkylenedioxy) di-2-naphthoate is increased. However, according to the present invention, the temperature expansion coefficient (αt) can be reduced by employing a polyester having a specific copolymerization ratio and stretching.

The biaxially oriented film of the present invention has a humidity expansion coefficient (αh) of at least one of the film forming direction and the width direction of 1 × 10 ^{−6 to} 7 × 10 ⁻⁶ /% RH, and further 1 × 10 ⁻⁶ to It is preferably in the range of 6 × 10 ⁻⁶ /% RH.

  Furthermore, the biaxially oriented film of the present invention preferably has a Young's modulus in the film forming direction of 4.5 GPa or more, more preferably 5 GPa or more from the viewpoint of suppressing elongation during high-temperature processing. The upper limit of the Young's modulus (Y) in the film forming direction of the film is preferably about 12 GPa because it is easy to provide a sufficient Young's modulus in the width direction of the film.

  On the other hand, since the Young's modulus in the width direction of the film is in the range of 6 to 14 GPa, more preferably in the range of 7 to 12 GPa, it is easy to adjust the temperature expansion coefficient and humidity expansion coefficient in the width direction of the film within the above ranges. preferable.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further more concretely, this invention is not limited by these Examples. In the present invention, the characteristics are measured and evaluated by the following methods, and unless otherwise specified, the parts are values based on mass.

(1) Intrinsic viscosity The intrinsic viscosity of the polyester and the composition is an Ostwald viscometer at a constant temperature of 35 ° C. using a mixed solvent of P-chlorophenol / 1,1,2,2-tetrachloroethane (40/60 mass ratio). It measured using.

(2) Hue of resin composition (L * value, a * value, b * value)
The copolymerized polyester resin composition was melted at 295 ° C. under vacuum for 10 minutes, formed into a plate having a thickness of 3.0 ± 1.0 mm on an aluminum plate, and immediately cooled in ice water. Dry crystallization treatment was performed for 2 hours. Thereafter, the plate was placed on a white standard plate for color difference adjustment, and the hunters L *, a *, and b * on the plate surface were measured using a spectroscope manufactured by Macbeth (type ZE-2000). L * indicates lightness, and the larger the value, the higher the lightness, a * indicates that the greater the value, the greater the degree of red coloring, and b * the greater the value, the greater the degree of yellow coloring. Indicates big. Other detailed operations were performed according to JIS Z-8729.

(3) Light Resistance Evaluation of Resin Composition The plate sample prepared as described above was irradiated with ultraviolet rays for 6 hours and 24 hours using a sunshine weather meter (S80) manufactured by Suga Test Instruments Co., Ltd. The hue of the plate before and after the ultraviolet irradiation was measured with a spectroscope (ZE-2000 type) manufactured by Macbeth Co., and light resistance was evaluated from the amount of change in b * value between 6 hours irradiation and 24 hours irradiation.

(4) Young's modulus The film is cut with a sample width of 10 mm and a length of 15 cm so that the MD direction (or TD direction) is the measurement direction, and universal under the conditions of 100 mm between chucks, a tensile speed of 10 mm / min, and a chart speed of 500 mm / min. Pull with a tensile tester (Toyo Baldwin, trade name: Tensilon). The Young's modulus is calculated from the tangent of the rising portion of the obtained load-elongation curve.

(5) Temperature expansion coefficient (αt)
The obtained film was cut into a length of 20 mm and a width of 4 mm so that the MD direction (or TD direction) of the film would be the measurement direction, set in TMA / SS6000 manufactured by Seiko Instruments, and under a nitrogen atmosphere (0% RH). , Pretreatment at 80 ° C. for 30 minutes, and then the temperature was lowered to room temperature. Thereafter, the temperature was raised from 30 ° C. to 80 ° C. at 2 ° C./min, the sample length at each temperature was measured, and the temperature expansion coefficient (αt) was calculated from the following equation. In addition, the measurement direction is the longitudinal direction of the sample cut out, the measurement was performed 5 times, and the average value was used.
αt = {(L ⁶⁰ −L ⁴⁰ )} / (L ⁴⁰ × ΔT)} + 0.5 × 10 ⁻⁶
Here, L ⁴⁰ in the above formula is the sample length (mm) at 40 ° C., L ⁶⁰ is the sample length (mm) at 60 ° C., ΔT is 20 (= 60-40) ° C., 0.5 × 10 ⁻⁶ / ° C. is the temperature expansion coefficient (αt) of quartz glass.

(6) Humidity expansion coefficient (αh)
The obtained film was cut into a length of 15 mm and a width of 5 mm so that the MD direction (or TD direction) of the film would be the measurement direction, set in TMA4000SA made by Bruker AXS, and a humidity of 20% under a nitrogen atmosphere at 30 ° C. The length of each sample at RH and humidity 80% RH was measured, and the humidity expansion coefficient (αh) was calculated by the following equation. In addition, the measurement direction is the longitudinal direction of the cut out sample, the measurement was performed 5 times, and the average value was αh.
αh = (L ⁸⁰ −L ²⁰ ) / (L ²⁰ × ΔH)
Here, L ²⁰ in the above formula is a sample length (mm) when 20% RH, L ⁸⁰ is a sample length (mm) when 80% RH, ΔH: 60 (= 80-20)% RH is there.

[Example 1]
30 kg (74.6 mol) of (6,6 '-(ethylenedioxy) di-2-naphthoic acid), 7.8 kg (32.0 mol) of 2,6-naphthalenedicarboxylic acid dimethyl ester and 25 kg of ethylene glycol Was charged into a pressure vessel equipped with a stirrer, a rectifying column and a cooling tube, and the temperature was raised to 150 ° C. At that time, 2.3 g equivalent of titanium trimellitic acid as titanium element was added, the whole reactor was pressurized to 0.25 MPa with nitrogen, and the pressure vessel internal temperature was raised to 240 ° C. The pressure was always controlled to 0.25 MPa, and the total reflux was reached when the top temperature of the rectifying column reached 200 ° C., and the reaction was continued at a reflux ratio of 1 below 200 ° C. As the reaction progressed, the inside of the container gradually became transparent, and finally the internal temperature was raised to 250 ° C. After confirming that the liquid was transparent, the reaction was completed.

  Subsequently, the pressure was returned to normal pressure, 9.0 g of trimethyl phosphate was added, the internal temperature was raised again to 250 ° C., excess ethylene glycol was distilled off, and the reaction liquid was passed through a wire mesh filter with an average opening of 30 μm. Was transferred to a polycondensation vessel.

  Then, gradually increase the temperature inside the reaction vessel, slowly reduce the pressure inside the vessel, and heat the reaction under a high vacuum according to a conventional method. When the final viscosity reaches 290 ° C, the reaction is completed. Then, it was continuously extruded in a strand form from the discharge part, cooled, and then cut to obtain a granular pellet of a copolyester.

  On the other hand, 350 parts of 2,6-naphthalenedicarboxylic acid dimethyl ester and 180 parts of ethylene glycol were charged into a pressure vessel equipped with a stirrer, a rectifying column, and a cooling tube, and the temperature was raised to 150 ° C. At that time, 0.008 part of titanium trimellitic acid as titanium element was added, the whole reactor was pressurized to 0.08 MPa with nitrogen, and the pressure vessel internal temperature was gradually raised to 235 ° C. The pressure was always controlled to 0.08 MPa, and the reaction continued at a reflux ratio of 1 at the top temperature of the rectifying column. After the temperature was raised to 235 ° C., the pressure was returned to normal pressure in 10 minutes, and the reaction product lowered by the release pressure was heated again to 220 ° C., 0.09 part of trimethyl phosphate was added, and the temperature was further raised to partially remove ethylene glycol. The reaction was terminated at 240 ° C. while distilling.

  Subsequently, the reaction solution was transferred to a polycondensation vessel through a 30 μm wire mesh filter. Thereafter, while gradually raising the temperature inside the reaction vessel, the inside of the vessel is slowly depressurized, and the polycondensation reaction is continued until a predetermined stirring power is reached at 290 ° C. and 50 Pa. The intrinsic viscosity is 0.62 dl / g, and the amount of DEG 0.80 wt% of 2,6-polyethylene naphthalate (hereinafter referred to as PEN) was obtained.

  Subsequently, the respective copolyester and PEN chips were blended so that the 6,6 ′-(ethylenedioxy) di-2-naphthoic acid component was 20 mol%, and dried at 160 ° C. for 12 hours. The metered feeder was fed at a speed of 50 kg / h to a twin-screw kneading extruder with a vent of the same direction meshing type having a kneading disc paddle as a screw component.

Next, in the formula (A), R ₁ is a t-C ₈ H ₁₇ group, R ₂ is a methyl group, and R ₃ is a t-C ₄ H ₉ group. JAST-500) was added from the upper charging port of the biaxial kneading extruder using a vibrating quantitative feeder so that the content was 2% by mass shown in Table 1. At this time, the degree of vacuum at the vent port is 300 Pa, the cylinder temperature is 290 ° C., and the residence time in the extruder of the blended chip of copolymer polyester and PEN at the time of addition is 90 seconds (the kneading time after addition of the UV absorber is 70 seconds) It was. And in this biaxial kneading extruder, the ultraviolet absorber and the copolymer polyester resin composition were kneaded, extruded from the polymer discharge port in a molten state, and cut after cooling to obtain granular pellets.

  The copolyester resin composition thus obtained was supplied to an extruder and extruded from a die at 300 ° C. in a molten state onto a cooling drum having a rotating temperature of 50 ° C. to form an unstretched film. Then, between two sets of rollers having different rotational speeds along the film forming direction, the film surface temperature is heated from above by an IR heater so that the film surface temperature becomes 133 ° C., and stretching in the longitudinal direction (film forming direction) is performed. A uniaxially stretched film was obtained at a magnification of 5.8 times. And this uniaxially stretched film is led to a stenter, stretched at 135 ° C in the transverse direction (width direction) at a stretch ratio of 8.5 times, then heat-set at 202 ° C for 10 seconds, and biaxially stretched with a thickness of 5 µm. A film was obtained.

[Comparative Example 1]
Except that the ultraviolet absorber was changed to a benzotriazole ultraviolet absorber B (Tinuvin234 manufactured by Ciba-Geigy) in which R ₁ and R _{2 represented} by the formula (B) are both —C (Me) ₂ Ph The same operation as 1 was repeated. Table 1 shows the properties of the obtained copolyester resin composition and biaxially oriented film.

[Example 2]
As a UV absorber, 2% by mass of the benzotriazole UV absorber B (Tinuvin234 manufactured by Ciba-Geigy) used in Comparative Example 1, and a hindered phenol antioxidant (ADEKA) represented by the following formula (C) 0.5% by mass of AO-50) was added. Otherwise, the same operation as in Example 1 was repeated. Table 1 shows the properties of the obtained copolyester resin composition and biaxially oriented film.

[Examples 3 to 4]
In Example 1, the same operation as in Example 1 was repeated except that the content of the benzotriazole-based ultraviolet absorber A was as shown in Table 1. Table 1 shows the properties of the obtained copolyester resin composition and biaxially oriented film.

[Example 5]
In Example 1, the copolyester and PEN chips were blended so that the 6,6 ′-(ethylenedioxy) di-2-naphthoic acid component was as shown in Table 1, and the longitudinal stretching temperature was 120 ° C. The same operation as in Example 1 was repeated except that the longitudinal draw ratio was 4.5 times, the transverse draw temperature was 120 ° C, the transverse draw ratio was 9 times, and the heat setting temperature was 210 ° C. Table 1 shows the properties of the obtained copolyester resin composition and biaxially oriented film.

[Example 6]
In Example 1, the copolyester and PEN chips were blended so that the 6,6 ′-(ethylenedioxy) di-2-naphthoic acid component was as shown in Table 1, and the longitudinal stretching temperature was 125 ° C. The same operation as in Example 1 was repeated except that the longitudinal draw ratio was 6.2 times, the transverse draw temperature was 135 ° C, the transverse draw ratio was 9.5 times, and the heat setting temperature was 190 ° C. Table 1 shows the properties of the obtained copolyester resin composition and biaxially oriented film.

[Example 7]
In Example 1, the chips of the copolyester and PEN were blended so that the 6,6 ′-(ethylenedioxy) di-2-naphthoic acid component was as shown in Table 1, and the longitudinal stretching temperature was 136 ° C. The same operation as in Example 1 was repeated except that the longitudinal draw ratio was 5.2 times, the transverse draw temperature was 138 ° C., the transverse draw ratio was 8.2 times, and the heat setting temperature was 212 ° C. Table 1 shows the properties of the obtained copolyester resin composition and biaxially oriented film.

[Comparative Example 2]
The same operation as in Example 1 was repeated except that the ultraviolet absorber was not kneaded. Table 1 shows the properties of the obtained copolyester resin composition and biaxially oriented film.

[Comparative Example 3]
The same operation as in Example 1 except that no ultraviolet absorber is kneaded and only 2.0% by mass of a hindered phenol-based antioxidant represented by the above formula (C) (Adeka AO-50) is added. Was repeated. Table 1 shows the properties of the obtained copolyester resin composition and biaxially oriented film.

  In the table, ENA represents 6,6 ′-(ethylenedioxy) di-2-naphthoic acid component, additive A is JAST-500 (manufactured by Johoku Chemical Co., Ltd.), and additive B is Tinuvin234 (Ciba The additive C represents AO-50 (manufactured by ADEKA), and the difference in b * value is the difference in b * value after UV irradiation (24 h) and after UV irradiation (6 h).

  Molded articles such as the biaxially oriented film made of the resin composition of the present invention described above have excellent dimensional stability against temperature and humidity and good light resistance. For example, as a film for solar cells, etc. It can be used suitably.

Claims (4)

An aromatic dicarboxylic acid represented by the following formula (I), which is composed of an aromatic dicarboxylic acid component represented by the following formulas (I) and (II) and a glycol component comprising an alkylene glycol having 2 to 4 carbon atoms. In the copolymerized polyester in which the copolymerization ratio of the acid component is in the range of 5 to 80 mol% based on the total acid component, 0.5 to 10 mass% of the benzotriazole-based ultraviolet absorber is based on the amount of the resin composition material. And a copolyester resin composition containing 0.05 to 2.0% by mass of a hindered phenolic antioxidant.
HO (O) C—R ² —OR ¹ O—R ² —C (O) OH (I)
[In the above formula (I), R ¹ represents an alkylene group having 2 to 10 carbon atoms, and R ² represents a 2,6-naphthalenediyl group. ]
HO (O) C—R ³ —C (O) OH (II)
[In the above formula (II), R ³ represents a phenylene group or a naphthalenediyl group. ]   A copolymerized polyester resin composition containing 0.5 to 10% by mass of a benzotriazole-based ultraviolet absorber having a hindered phenol group in the copolymerized polyester according to claim 1, based on the amount of the resin composition material. The copolymer polyester resin composition according to claim 2, wherein the benzotriazole-based ultraviolet absorber having a hindered phenol group is represented by the following formula (A).

(R ₁ in the above structural formula represents an alkyl group which may be branched from 1 to 18 carbon atoms and may have an alicyclic group or an aromatic ring group in the terminal or chain, and R ₂ represents hydrogen or methyl. And R ₃ represents an alkyl group having 3 to 4 carbon atoms.)   A biaxially oriented film comprising the copolymerized polyester resin composition according to any one of claims 1 to 3.