JPH11181114A - Polyester film for lamination with metallic sheet - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a film excellent in heat resistance, impact resistance, and retorting resistance, which film is made from a copolyester having a specified melting point, has a specified or higher glass transition temperature, has a specified or smaller difference between the highest peak temperature of the loss modulus and the glass transition temperature, and has a specified X-ray diffraction intensity ratio and a specified surface orientation coefficient. SOLUTION: There is provided a biaxially oriented film made from a copolyester having a melting point of 210-245 deg.C, wherein the glass transition temperature Tg is 78 deg.C or above, the difference between the highest peak temperature Te of the loss modulus and the Tg is below 30; the X-ray diffraction intensity ratio: I(1-10)/I(100) is 0.10-0.40, the surface orientation coefficient is 0.100-0.150, and the amount of extractives is 0.5 mg/in<2> or lower as measured by extracting the film with ion-exchanged water at 121 deg.C for 2 hr. The copolyester is obtained by reacting terephthalic acid with ethylene glycol, 2,6- naphthalenedicarboxylic acid or the like. I(1-10) and I(100) denote the X-ray diffraction intensities on the (1-10) plane and the (100) plane parallel with the film surface.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polyester film for laminating and forming a metal plate, and more particularly, it shows excellent formability when laminating to a metal plate and performing can forming such as drawing. The present invention relates to a polyester for metal plate lamination molding capable of producing metal cans, such as beverage cans, food cans, and the like, having excellent properties, retort resistance, flavor preserving properties, impact resistance, and the like.

[0002]

2. Description of the Related Art Metal cans are generally coated to prevent corrosion on the inner and outer surfaces, but recently, for the purpose of simplifying the process, improving hygiene, and preventing pollution, rust prevention is performed without using an organic solvent. Development of a method for obtaining the property has been advanced, and as one of the methods, coating with a thermoplastic resin film has been attempted.

[0003] That is, a method of laminating a thermoplastic resin film on a metal plate of tin, tin-free steel, aluminum or the like, followed by drawing or the like is being studied.

As the thermoplastic resin film, it is gradually becoming clear that a copolymerized polyester film is suitable in terms of moldability, heat resistance, impact resistance, and taste and fragrance retention. However, this polyester film does not necessarily show sufficient flavor retention and aroma when the beverage contains extremely important tastes such as green tea and mineral water which is required to be tasteless and odorless. Is sensed.

On the other hand, Japanese Patent Application Laid-Open No. Hei 6-116376 proposes a polyester film for forming a metal plate having an improved flavor, comprising a copolymerized polyester containing a specific amount of an alkali metal element and a germanium element. ing. However, when this film is used, it shows excellent flavor and fragrance retention in the process where heat is not applied at the stage of filling the contents such as a cold back system, but at the stage of filling the contents such as retort treatment. In the step in which the heat treatment is performed, sufficient flavor and fragrance retention cannot always be obtained.

Further, heat resistance, impact resistance, retort resistance,
It has also been found that when a copolymer component of polyester is selected so that a film having an improved flavor preserving property, in particular, a preserving property after the retort treatment is obtained, a tendency to deteriorate molding processability is recognized. Was.

[0007]

SUMMARY OF THE INVENTION Accordingly, the present invention solves the above-mentioned problems of the prior art, while maintaining the excellent heat resistance, impact resistance, and retort resistance of the copolymerized polyester film. An object of the present invention is to provide a polyester film for laminating and processing a metal plate, which has improved flavor preserving property, particularly, preserving property after retort treatment, and does not cause a decrease in processability.

[0008]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies to solve the above-mentioned problems, and as a result, among copolymerized polyesters, ethylene terephthalate is a main repeating unit and has a specific melting point. Using a polymerized polyester, a specific glass transition temperature, dynamic viscoelasticity, if a film having an X-ray diffraction intensity ratio and plane orientation coefficient,
The present inventors have found that it is possible to improve the flavor preserving property, in particular, the preserving property after retort treatment, without impairing the moldability, and have completed the present invention.

That is, the present invention uses ethylene terephthalate as a main repeating unit and has a melting point of 210 to 245.
A biaxially stretched film made of a copolymerized polyester having a maximum temperature of loss elastic modulus of the film (Te) and a glass transition temperature (Tg) measured by DSC.
Satisfies the following formulas (1) and (2), and X
A polyester film for a metal plate laminating process, having a line diffraction intensity ratio satisfying the following formula (3) and a plane orientation coefficient of 0.100 to 0.150.

[0010]

Tg ≧ 78 (1) Te−Tg ≦ 30 (2) (where Tg is DS after heating and melting at 290 ° C. and quenching)
The glass transition temperature (° C.) and Te in the C measurement are the highest peak temperature (° C.) of the loss modulus of the film. )

[0011]

(Equation 4)

The copolymer component of the copolymer polyester is as follows:
2,6-Naphthalenedicarboxylic acid is preferable, and the amount of extraction when the copolymerized polyester film is extracted with ion-exchanged water at 121 ° C. for 2 hours is preferably 0.5 mg or less per square inch. preferable.

[0013]

BEST MODE FOR CARRYING OUT THE INVENTION In the present invention, among various copolyesters, while retaining excellent heat resistance, impact resistance and retort resistance, the flavor and fragrance preservation property, particularly the preservation after retort treatment, is maintained. Since ethylene terephthalate is used as a main repeating unit because it can improve taste and aroma retention, the melting point is 210
To 245 ° C, preferably 215 to 240 ° C.

The copolymer component of the copolymerized polyester in the present invention may be a dicarboxylic acid component or a diol component.

Examples of the dicarboxylic acid component include aromatic dicarboxylic acids such as isophthalic acid, phthalic acid, and 2,6-naphthalenedicarboxylic acid; aliphatic dicarboxylic acids such as adipic acid, azelaic acid, sebacic acid, and decane dicarboxylic acid; Alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid can be exemplified.
Examples thereof include aliphatic diols such as -butanediol, 1,6-hexanediol and diethylene glycol, alicyclic diols such as 1,4-cyclohexanedimethanol, and aromatic diols such as bisphenol A. These can be used alone or in combination of two or more.

The proportion of the copolymer component depends on the type thereof, and as a result, the melting point of the polymer is in the range of 210 to 245 ° C., preferably 215 to 240 ° C. If the melting point is lower than 210 ° C., the heat resistance will be poor. On the other hand, when the melting point exceeds 245 ° C., the crystallinity of the polymer is too large and the moldability is impaired.

Here, the melting point of the copolyester was measured by using Du Pont Instruments 910.
A method in which a melting peak is determined at a heating rate of 20 ° C./min using DSC. The sample amount is about 20 mg.

Further, the intrinsic viscosity (orthochlorophenol, 35 ° C.) of the copolymerized polyester used in the present invention is preferably 0.52 to 1.50, more preferably 0.57 to 1.00, and particularly preferably. Is 0.60
0.80. If the intrinsic viscosity is less than 0.52, the impact resistance may be insufficient, which is not preferable. On the other hand,
If the intrinsic viscosity exceeds 1.50, the moldability may be impaired.

The copolymerized polyester in the present invention is not limited by its production method. For example, in the case of copolymerized polyethylene terephthalate, terephthalic acid, ethylene glycol and a copolymer component are subjected to an esterification reaction, A method in which the product is subjected to a polycondensation reaction to a desired degree of polymerization to give a copolymerized polyethylene terephthalate, or a terephthalic acid dimethyl ester, ethylene glycol and a copolymer component are subjected to a transesterification reaction, and then the obtained reaction product is subjected to Preferable examples include a method in which a polycondensation reaction is performed to obtain a copolymerized polyethylene terephthalate until a desired degree of polymerization is obtained. Further, the copolymerized polyester obtained by the above method (melt polymerization) can be converted into a polymer having a higher degree of polymerization, if necessary, by a polymerization method in a solid state (solid state polymerization).

If necessary, additives such as an antioxidant, a heat stabilizer, a viscosity modifier, a plasticizer, a hue improver, a lubricant, a nucleating agent, and an ultraviolet absorber may be added to the copolymerized polyester. it can.

The catalyst used in the polycondensation reaction includes:
Antimony compounds (Sb compounds), titanium compounds (Ti
Compound), a germanium compound (Ge compound) and the like are preferable. Among them, a titanium compound and a germanium compound are preferable in view of the taste and fragrance retention of the film. As the titanium compound, for example, titanium tetrabutoxide,
Preference is given to titanium acetate. As the germanium compound, (a) amorphous germanium oxide,
(B) fine crystalline germanium oxide, (iii) a solution of germanium oxide dissolved in glycol in the presence of an alkali metal or alkaline earth metal or a compound thereof,
(D) A solution obtained by dissolving germanium oxide in water is preferred. Furthermore, when an antimony compound and a titanium compound are used in combination, along with the improvement of the taste and fragrance retention,
This is preferable because the cost can be reduced.

The copolymerized polyester used in the present invention includes:
It is preferable to add a lubricant for the purpose of improving the winding property of the film. The type of lubricant may be inorganic or organic, but inorganic is preferred. Examples of the inorganic lubricant include silica, alumina, titanium oxide, calcium carbonate, barium sulfate, and the like, and examples of the organic lubricant include silicone resin particles and crosslinked polystyrene particles. In particular, a lubricant which is preferable in terms of pinhole resistance is a monodispersed lubricant having a particle size ratio (major axis / minor axis) of 1.0 to 1.2. Examples of such a lubricant include spherical silica, spherical silicone resin particles, and spherical cross-linked polystyrene.

The particle size and amount of the lubricant may be determined based on the film winding property, pinhole resistance and flavor and fragrance retention. That is, in the case of silica having an average particle size of 1.5 μm, 0.06% by weight or more and 0.25% by weight or less, and an average particle size of 0.
In the case of silica having a thickness of 8 μm, the rollability can be secured without impairing the flavor and fragrance retention by adding the silica in the range of 0.1% by weight or more and 0.45% by weight or less.

The lubricant is not limited to the above-mentioned externally added particles. For example, internal precipitated particles obtained by precipitating part or all of the catalyst used in the production of polyester in the reaction step can be used. It is also possible to use externally added particles and internally precipitated particles in combination.

Since the polyester film of the present invention is used particularly for food cans or beverage cans, it is better that the amount of substances eluted or scattered from the film is smaller, but it is substantially impossible to eliminate such substances at all. Impossible. Therefore, in order to use it for food cans or beverage cans, for example, the extraction amount per square inch of the film when extracted with ion exchanged water at 121 ° C. for 2 hours is 0.5 m.
g or less, more preferably 0.1 mg or less.

In order to reduce the amount of extraction, the glass transition temperature of the polyester film may be increased.
The glass transition temperature of a polyester film is determined by the glass transition temperature and the degree of orientation of the polymer constituting the film, but if the degree of orientation is increased, the moldability deteriorates. Preferably, it is higher.

The polyester film of the present invention is used in a state of being biaxially stretched and heat set. At this time, the highest temperature peak temperature (Te) of the loss modulus of the polyester film
And the glass transition temperature (Tg) in the DSC measurement must satisfy the following expressions (1) and (2).

[0028]

Tg ≧ 78 (1) Te−Tg ≦ 30 (2) (where Tg is DS after heating and melting at 290 ° C. and quenching)
The glass transition temperature (° C.) and Te in the C measurement are the highest peak temperature (° C.) of the loss modulus of the film. )

If the Tg of the film is less than 78 ° C., the heat resistance becomes poor, and the flavor and odor retention after retorting deteriorates. For this reason, it is preferable to use, as the copolymerization component of the copolymerized polyester, at least one component that does not change or increases the glass transition temperature when the proportion of the copolymerization component is increased. As a component that increases the glass transition temperature when the proportion of the copolymer component is increased, 2,6-dicarboxylic acid component is used.
Naphthalenedicarboxylic acid has a diol component of 1,
Preferred is 4-cyclohexanedimethanol.

Here, the Tg of the polyester was measured by placing a 20 mg film sample in a pan for DSC measurement,
After heating and melting for 5 minutes on a heating stage, the sample pan was quickly cooled and solidified on an aluminum foil spread on ice,
A method of determining a glass transition point at a heating rate of 20 ° C./min using on Instruments 910 DSC.

Further, when the value of Te-Tg exceeds 30, the molecular orientation and the crystallinity of the film become too high, so that the formability is remarkably reduced. Although the value of Te depends on the copolymerization components and the copolymerization amount, a method of adjusting the film forming conditions, particularly the biaxial stretching ratio or the stretching temperature, is preferably mentioned.

Here, Te is determined at a measurement frequency of 10 Hz and a dynamic displacement of ± 25 × 10 ⁻⁴ cm using a dynamic viscoelasticity measuring device.

Further, the polyester film of the present invention comprises:
The X-ray diffraction intensity ratio needs to satisfy the following expression (3).

[0034]

(Equation 6)

If the X-ray diffraction intensity ratio is less than 0.10, the molding processability becomes insufficient. On the other hand, if the X-ray diffraction intensity ratio exceeds 0.40, the heat resistance becomes poor.
Improper.

Further, the polyester film of the present invention needs to have a plane orientation coefficient of 0.100 to 0.150, preferably 0.110 to 0.140.

If the plane orientation coefficient is less than 0.100, if the drawing ratio at the time of deep drawing is high, problems such as cracks in the film occur, which is not preferable. On the other hand, if the plane orientation coefficient exceeds 0.150, the film breaks during deep drawing, making it impossible to process.

Here, the plane orientation coefficient is defined by the following equation.

[0039]

Equation 7] _{f = [(n x + n} y) / 2] -n z

In the above formula, f: plane orientation coefficient;
_nx , _ny , _nz : The refractive indexes in the horizontal, vertical, and thickness directions of the film, respectively. The refractive index is measured as follows.

A polarizing plate analyzer is attached to the eyepiece side of the Abbe refractometer, and each refractive index is measured with a monochromatic NaD line. The mounting liquid uses retylene iodide, and the measurement temperature is 25 ° C.

In order to adjust the X-ray diffraction intensity ratio and the plane orientation coefficient, for example, the film forming conditions, in particular, the stretching ratio of biaxial stretching, the stretching temperature, and the heat setting temperature may be changed.

In order to obtain a polyester film having the above-mentioned Tg, Te, X-ray diffraction intensity ratio and plane orientation coefficient, for example, a copolyester is melt-extruded and quenched to produce an unstretched film, which is then biaxially stretched. When doing
The longitudinal stretching ratio is 2.5 to 3.8 times (preferably 2.7 to 3.8 times).
3.6 times), the longitudinal stretching temperature is 95 to 150 ° C (preferably 110 to 140 ° C), the transverse stretching ratio is 2.7 to 4.0 times (preferably 2.8 to 3.8 times), and the transverse stretching. 100 temperature
~ 150 ° C (preferably 110 ~ 140 ° C), heat setting temperature 140 ~ 230 ° C (preferably 140 ~ 210 ° C)
What is necessary is just to select the condition which makes each said characteristic value become a predetermined value.

Further, the refractive index in the thickness direction of the polyester film is preferably from 1.500 to 1.545, more preferably from 1.505 to 1.530. If the refractive index is too low, the moldability will be insufficient, while if it is too high, the structure will be close to amorphous, and the heat resistance may decrease. The refractive index in the thickness direction of the film is measured by attaching a polarizing plate analyzer to the eyepiece side of an Abbe refractometer and using a monochromatic NaD line to measure the refractive index in the thickness direction. The mounting solution uses methylene iodide, and the measurement temperature is 25 ° C.

The polyester film of the present invention preferably has a thickness of 6 to 75 μm. Further, it is preferably from 8 to 75 μm, particularly preferably from 10 to 50 μm. 6 μm thick
If it is less than 75%, breakage or the like tends to occur during processing, while
Those exceeding μm are excessive quality and uneconomical.

As a metal plate to which the polyester film of the present invention is bonded, particularly a metal plate for can making, a plate of tin, tin-free steel, aluminum or the like is suitable.
The bonding of the polyester film to the metal plate can be performed, for example, by the following method. The metal plate is heated to a temperature equal to or higher than the melting point of the film, the film is bonded, and then rapidly cooled, and the surface layer (thin layer) of the film in contact with the metal plate is made amorphous and adhered. An adhesive layer is primer-coated on the film in advance, and this surface is bonded to a metal plate. As the adhesive layer, a known resin adhesive, for example, an epoxy adhesive, an epoxy-ester adhesive, an alkyd adhesive, or the like can be used.

[0047]

The present invention will be further described with reference to the following examples.
The characteristics in the examples were measured by the following methods. (1) Intrinsic viscosity of polyester Measured in orthochlorophenol at 35 ° C.

(2) Melting point of polyester Du Pont Instruments 910 D
A method in which a melting peak is determined at a heating rate of 20 ° C./min using SC. The sample amount is 20 mg.

(3) Glass transition temperature of polyester (T
g) 20 mg of a film sample was placed in a pan for DSC measurement, heated and melted for 5 minutes on a 290 ° C. heating stage, and then rapidly cooled and solidified on an aluminum foil spread on ice, and then Du Pont Instruments 910 was prepared.
A method in which the glass transition point is determined at a heating rate of 20 ° C./min using DSC.

(4) Maximum peak temperature of loss elastic modulus of film (Te) The loss elastic modulus was determined at a measurement frequency of 10 Hz and a dynamic displacement of ± 25 × 10 ⁻⁴ cm using a dynamic viscoelasticity measuring apparatus. The peak temperature at this time is shown.

(5) X-ray diffraction intensity ratio

[0052]

[Outside 1]

[0053] (6) mounting a polarizing plate analyzer to the ocular side of the refractometer of surface orientation coefficient Abbe, monochromatic light NaD lines, each horizontal, vertical, the thickness direction of the refractive _{index, n x, n y, n} z : Measure each, and determine the plane orientation coefficient f by the following formula.

[0054]

Equation 8] _{f = [(n x + n} y) / 2] -n z

(7) Deep drawing processability The film was heated above the melting point of the polyester at a plate pressure of 0.1 mm.
Affixed to both sides of 25mm tin-free steel, water-cooled, cut into a circular shape of 150mm diameter, deep drawn in four stages using a drawing die and punch, and a 55mm diameter sideless seamless container (hereinafter abbreviated as can) )made. The following observations and tests were performed on the cans, and the cans were evaluated according to the following criteria. Deep drawing processability -1 ◎: The film has no abnormality at all, and no whitening or breakage is observed in the processed film. ：: No abnormality in the film, and no whitening or breakage was observed in the processed film. Δ: Whitening is observed at the top of the film can. X: Film breakage is observed in a part of the film. Deep drawing processability-2 ◎: Processed without abnormality, rust prevention test of film surface in can (1% NaCl aqueous solution was put in the can, electrodes were inserted, and a voltage of 6 V was applied with the can body as an anode. The current value at that time is measured, and is less than 0.1 mA in the ERV test. ：: Processed without any abnormality, and 0.1 ~ in ERV test
0.2 mA is shown. ×: There is no abnormality in the film, but in the ERV test, the current value exceeds 0.2 mA, and when the energized portion is observed under magnification, pinhole-shaped cracks starting from the coarse lubricant are found in the film.

(8) Impact resistance For cans with good deep drawing, pour water thoroughly, cool to 0 ° C., drop 10 pieces for each test from a height of 30 cm onto a PVC tile floor. As a result of the ERV test in the can, the results were as follows: ○: 0.2 mA or less for all 10 samples. C: 0.2 mA or more for 1 to 5 pieces. ×: 0.2 mA or more for 6 or more pieces, or cracks of the film were already observed after dropping.

(9) Heat Embrittlement Resistance The can which had been subjected to good deep drawing was heated at 200 ° C. for 5 minutes and then subjected to the impact resistance evaluation described in (8). Was 0.2 mA or less. C: 0.2 mA or more for 1 to 5 pieces. X: The film was 0.2 mA or more for 6 or more pieces, or cracking of the film was already observed after heating at 200 ° C. for 5 minutes.

(10) Retort Resistance The cans having good deep drawing properties are filled with water and retorted in a steam sterilizer at 120 ° C. for 1 hour.
Stored at 50 ° C. for 30 days. After dropping 10 cans for each test from a height of 50 cm onto a PVC tile floor, an ERV test in the cans was performed. ：: 0.2 mA or less for all 10 samples. C: 0.2 mA or more for 1 to 5 pieces. ×: 0.2 mA or more for 6 or more pieces, or cracks of the film were already observed after dropping.

(11) Flavor Retention and Flavor Retention-1 Cans having good deep drawability are filled with ion-exchanged water and stored at room temperature (20 ° C.) for 30 days. A tasting test is carried out by 30 panelists using the immersion liquid, and compared with ion-exchanged water for comparison, and evaluated according to the following criteria. ：: Three or less out of thirty felt changes in taste and aroma as compared with the comparative solution. ：: Four to six out of thirty people felt a change in taste and aroma as compared with the comparative solution. Δ: 7 to 9 out of 30 persons felt a change in taste and aroma as compared with the comparative solution. ×: Ten or more of the 30 persons felt a change in taste and aroma as compared with the comparative solution.

(12) Flavor preservation and flavor retention-2 For cans having good deep drawing, filled with ion-exchanged water, and subjected to a retort treatment at 120 ° C. for 1 hour in a steam sterilizer. C) Store for 30 days. A tasting test is carried out by 30 panelists using the immersion liquid, and compared with ion-exchanged water for comparison, and evaluated according to the following criteria. ：: Three or less out of thirty felt changes in taste and aroma as compared with the comparative solution. ：: Four to six out of thirty people felt a change in taste and aroma as compared with the comparative solution. Δ: 7 to 9 out of 30 persons felt a change in taste and aroma as compared with the comparative solution. ×: Ten or more of the 30 persons felt a change in taste and aroma as compared with the comparative solution.

[Examples 1 to 5 and Comparative Examples 1 and 2] Table 1
Copolymerized polyethylene terephthalate (intrinsic viscosity 0.64, particle size ratio 1.1, average particle size 0.1).
After drying 5 μm of spherical silica (containing 0.2% by weight), it was melt-extruded and quenched and solidified to obtain an unstretched film.
Next, the unstretched film was longitudinally stretched at the temperature and magnification shown in Table 1, then transversely stretched at the temperature and magnification shown in Table 1, and heat-set at 170 ° C. to obtain a biaxially stretched polyester film.

The thickness of the obtained film was 25 μm. Further, the glass transition temperature (Tg) of the film, the peak temperature of the loss modulus (Te), the X-ray diffraction intensity ratio,
Table 2 shows the plane orientation coefficient, the refractive index in the film thickness direction, and the extraction amount with ion-exchanged water. Table 3 shows the evaluation results.

[0063]

[Table 1]

[0064]

[Table 2]

[0065]

[Table 3]

As is apparent from Table 3, in the case of the present invention in which the melting point of the copolyester is 210 to 245 ° C. (Examples 1 to 5), good results were obtained, but the melting point was 210 ° C. When it was less than (Comparative Example 1), the heat resistance was inferior, the flavor retention and retentivity after retort was poor, and when it exceeded 245 ° C. (Comparative Example 2), the moldability was poor.

[Examples 6 and 7 and Comparative Examples 3 and 4] Table 4
Copolymerized polyethylene terephthalate (intrinsic viscosity: 0.62, particle size ratio: 1.1, average particle size: 0.1)
An unstretched film obtained by melt-extruding 5 μm spherical silica (containing 0.2% by weight) and rapidly cooling and solidifying was stretched and heat-set under the conditions shown in Table 4 to obtain a biaxially stretched polyester film.

The thickness of the obtained film was 25 μm. Further, the glass transition temperature (Tg) of the film, the peak temperature of the loss modulus (Te), the X-ray diffraction intensity ratio,
The surface orientation coefficient, the refractive index in the thickness direction of the film, and the amount of extraction with ion-exchanged water were as shown in Table 5.

The evaluation results are as shown in Table 6. In the case of the present invention having Tg of 78 ° C. or more and Te-Tg of 30 ° C. or less (Examples 6 and 7), good results were obtained. When Tg is less than 78 ° C (Comparative Example 3), heat resistance is inferior, and the flavor and scent retention after retort treatment is poor. When Te-Tg exceeds 30 ° C (Comparative Example 4), moldability is high. Decreased.

[0070]

[Table 4]

[0071]

[Table 5]

[0072]

[Table 6]

[Examples 8 to 11 and Comparative Examples 5 to 8] In Example 2, the stretching and heat setting conditions were changed as shown in Table 7 to obtain the properties shown in Table 8 (particularly, the X-ray diffraction intensity). (A ratio and a plane orientation coefficient were changed) to obtain a biaxially stretched polyester film.

The results are as shown in Table 9. The X-ray diffraction intensity ratio was 0.10 to 0.40, and the plane orientation coefficient was 0.10.
In the case of the present invention which is 0 to 0.150 (Examples 8 to 11)
Showed good results, but the X-ray diffraction intensity ratio was 0.1%.
If it is less than 10 (Comparative Example 5), the deep drawing processability is inferior.
When it exceeds 40 (Comparative Example 6), the heat resistance was inferior, and the flavor and fragrance retention after retort became poor. Also, the plane orientation coefficient is
When it is less than 0.100 (Comparative Example 7), rust prevention is deteriorated due to occurrence of a film crack at the time of deep drawing.
When it exceeds 150 (Comparative Example 8), the deep drawability deteriorated.

[0075]

[Table 7]

[0076]

[Table 8]

[0077]

[Table 9]

[0078]

The polyester film for laminating and processing a metal plate of the present invention is prepared by laminating a metal can with a metal plate after laminating the metal film with a metal plate. While maintaining excellent heat resistance, impact resistance, and retort resistance, the flavor and flavor retention, especially after retort treatment, is improved, and the moldability is not reduced. It is extremely useful as a container film.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁶ Identification code FI B29K 67:00 B29L 7:00

Claims (3)

[Claims] 1. A biaxially stretched film comprising a copolymerized polyester having ethylene terephthalate as a main repeating unit and having a melting point of 210 to 245 ° C., wherein the highest temperature peak temperature (Te) of loss elastic modulus of the film and DSC measurement Has a glass transition temperature (Tg) satisfying the following formulas (1) and (2), an X-ray diffraction intensity ratio satisfying the following formula (3), and a plane orientation coefficient of 0.100 to 0.100.
A polyester film for laminating and processing a metal plate, which is 0.150. Tg ≧ 78 (1) Te−Tg ≦ 30 (2) (where Tg is DS after heating and melting at 290 ° C. and quenching)
The glass transition temperature (° C.) and Te in the C measurement are the highest peak temperature (° C.) of the loss modulus of the film. ) (Equation 2) 2. The copolymer component of the copolymerized polyester,
The polyester film for laminating and processing a metal plate according to claim 1, which is 2,6-naphthalenedicarboxylic acid. 3. The film is treated with ion-exchanged water at 121.degree.
3. The polyester film for laminating and processing a metal plate according to claim 1, wherein the amount of extraction when subjected to the time extraction treatment is 0.5 mg or less per square inch.