JP2002046174A - Heat shrinkable polyester film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a heat-shrinkable polyester film excellent in shrink finish properties in a hot air shrinking process, not markedly lowered in its shrinkabilty at a low temperature even if kept at room temperature for a long period of time and hard to generate deficiency such as shrink irregularity, wrinkles, strain, folding or the like. SOLUTION: In the heat-shrinkable polyester film of which the heat shrinkage factor in the main shrink direction of the film after treatment in hot water at 80 deg.C for 10 see is 40% or more, the tanδ maximum value of dynamic viscoelasticity in the main shrink direction at 40-120 deg.C is 0.5 or more and the crossing point temperature of the tan δ value of the dynamic viscoelasticity, before and after the film is allowed to stand in an atmosphere of 40 deg.C for 160 hr, is 70 deg.C or lower.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a heat-shrinkable polyester film, and more particularly to a heat-shrinkable shrinking step, in which shrinkage spots, wrinkles, distortions, folds, etc., after heat shrinkage of the film are extremely small and stored. The present invention relates to a heat-shrinkable polyester film excellent in low-temperature shrinkability suitable for use in labels and cap seals, which has a very small reduction in shrinkage finish over time due to aging and a small natural shrinkage ratio.

[0002]

2. Description of the Related Art Conventionally, heat shrinkable films have been widely used for shrink wrapping, shrink labels, cap seals, and the like, utilizing the property of shrinking by heating. Above all, a stretched film made of a vinyl chloride resin, a polystyrene resin, a polyester resin, or the like is used as a label for various containers such as a polyethylene terephthalate (PET) container, a polyethylene container, and a glass container.

[0003] However, vinyl chloride resins have problems such as generation of harmful gases such as hydrogen chloride gas when incinerated. When a heat-shrinkable vinyl chloride resin film is used as a shrinkable label for a PET container or the like, it is necessary to separate the label from the container and discard the label when recycling the container. Further, in applications such as a full label in which a shrinkable label requires a high heat shrinkage depending on the shape of the container, there is a problem that the heat shrinkable vinyl chloride resin film cannot be used because the heat shrinkage is low and the shrinkage is insufficient.

[0004] On the other hand, polystyrene-based resin and polyester-based resin films do not generate harmful substances such as hydrogen chloride gas when incinerated, and are expected to be used as shrinkable labels for containers instead of vinyl chloride-based resin films.

However, polystyrene resin films are
Although the finished appearance after shrinkage is good, special ink must be used for printing due to poor solvent resistance. In addition, it requires incineration at a high temperature and generates a large amount of black smoke and an unpleasant odor at the time of incineration. Further, there is a problem that the shrinkable label cannot be used in an application requiring a high heat shrinkage as in the case of the vinyl chloride resin film because the shrinkage is insufficient. As a material capable of solving these problems, a polyester resin film is highly expected, and the amount of use thereof is increasing.

[0006]

However, the above-mentioned conventional heat-shrinkable polyester films have not been sufficiently satisfactory in heat-shrink properties. In particular, in the hot air shrinking step, shrinkage spots and wrinkles, distortion and folding are likely to occur at the time of shrinking, and further, when coated and shrunk in containers such as PET bottles, polyethylene bottles and glass bottles, they are printed on the film before shrinking in advance. There were problems such as distortion of characters and designs after shrinkage and insufficient adhesion of the film to the container. Furthermore, when stored for a long time at room temperature, the tan
A decrease in δ value occurs, and in the shrinking step, there is a problem that defects such as shrinkage spots and wrinkles, distortion and folding are more likely to occur, and in order to improve it, for example, in a polyester component constituting a film When the amount of the component having a low Tg is increased, the tan δ value of the dynamic viscoelasticity at a low temperature becomes too large, and there is a problem that the natural shrinkage becomes large.

[0007]

Means for Solving the Problems The present inventors have made intensive studies on a polyester-based heat-shrinkable film in view of the state of the prior art, and have reached the present invention. That is, in order to achieve the above object, the heat-shrinkable polyester film of the present invention has a temperature of 10 ° C in hot water at 80 ° C.
When the heat shrinkage in the main shrinkage direction after the second treatment is 40% or more,
The tan δ maximum value of the dynamic viscoelasticity in the main shrinkage direction in the temperature range of not less than 120 ° C. and
The temperature at the intersection of the tan δ values of the dynamic viscoelasticity before and after standing for 160 hours in an atmosphere at 70 ° C. is 70 ° C. or less. Here, the temperature at the intersection of the tan δ values of the dynamic viscoelasticity will be described. By comparing the tan δ values before and after the film was left standing in a 40 ° C. atmosphere for 160 hours,
In the film after standing, a decrease in the tan δ value due to a decrease in the loss elastic modulus occurs in a temperature range from a temperature below the glass transition temperature of the polymer constituting the film as a boundary to at least a temperature around 0 ° C. Defines the boundary temperature as the intersection point of the tan δ values.

[0008] The heat-shrinkable polyester film having the above-mentioned properties is suitably used particularly for full label applications and cap seal applications in which the film label requires a high shrinkage ratio due to the shape of the container, and the deterioration of shrinkage finish over time is deteriorated. Because of the small amount, it is possible to maintain excellent shrink finish even after long-term storage. That is, the quality can be maintained for a long period of time even when stored at a higher temperature, for example, a normal temperature, instead of the general low-temperature storage, and the quality holding period can be further extended. That is, even after long-term storage, it is possible to obtain a beautiful shrink-finished appearance with few shrinkage spots, wrinkles, distortions, and folds.

In a preferred embodiment of the present invention, the initial rupture rate in the direction perpendicular to the main shrinkage direction of the film can be 0%. Here, the initial rupture rate is defined as JIS-C-
The elongation at break was measured in the direction orthogonal to the main shrinkage direction according to 2318 (the number of samples n = 20), and the number (x) of the samples having elongation at break of 5% or less was determined. . Initial breaking rate = (x / n) × 100 (%) (Equation 1)

The heat-shrinkable polyester film having the above-mentioned properties is excellent in tear resistance, so that loss due to cutting of the film at the time of printing or tubing can be reduced. It is also possible.

In a further preferred embodiment of the present invention, the tan δ maximum value of the dynamic viscoelasticity in the main shrinkage direction of the film in the temperature range from 0 ° C. to 40 ° C. is 0.03 or less.

A heat-shrinkable polyester film having the above-mentioned properties is excellent in dimensional stability, and is a disadvantage of the heat-shrinkable film, even if the film is stored in a roll-wound form for a long period of time. Tarumi and tight winding,
The occurrence of uneven thickness or the like can be suppressed. That is, even if the film is stored at a higher temperature, for example, room temperature, rather than a general low-temperature storage, a good rolled state of the film can be maintained for a long period of time, so that the storage period can be further extended.

In a further preferred embodiment of the present invention, dimer acid, dimer diol,
At least one of ε-caprolactone can be contained.

The heat-shrinkable polyester film of the present invention contains the above-mentioned components to further improve the shrink finish in a wide temperature range from a low temperature to a high temperature. Deterioration can be reduced, and tear resistance can be improved.

In the present invention, the term "main shrinkage direction" means that a heat-shrinkable polyester film cut into a square is immersed in hot water at 80 ° C. (error range ± 0.5 ° C.), and subjected to no load. From the change in the length of two adjacent sides of the film before and after heat-shrinking after being processed for 10 seconds, it refers to the direction parallel to the side with the larger heat shrinkage calculated using the following equation 2. Heat shrinkage = {([length before heat shrink]-[length after heat shrink]) / [length before heat shrink]} × 100 (%) (Equation 2)

[0016]

Embodiments of the present invention will be described below. The heat-shrinkable polyester film of the present invention needs to have a heat-shrinkage rate of 40% or more after a 10-second treatment in hot water at 80 ° C. in the main shrinkage direction. Heat shrinkage 40%
If it is less than 1, in a full label application or a cap seal application in which a film label requires a high shrinkage rate depending on the shape of the container, shrinkage is insufficient, resulting in poor shrink finish.
In order to obtain a more stable shrink finish appearance, the heat shrinkage after treatment in hot water at 80 ° C. for 10 seconds in the main shrinkage direction is 50%.
% Or more, and particularly preferably 60% or more. Although there is no particular limitation on the heat shrinkage in the direction perpendicular to the main shrinkage direction, if the heat shrinkage is large, the shrinkage of the label in the warp direction and the distortion of the pattern occur, so that the heat shrinkage in hot water at 80 ° C. It is preferable that the heat shrinkage after the treatment for 10 seconds is 15% or less.

According to the present invention, the film is further coated with 40
The maximum value of the tan δ of the dynamic viscoelasticity in the main shrinkage direction before and after standing for 160 hours in an atmosphere of ° C. may be 0.5 or more. If it is less than 0.5, since the crystallinity of the polyester constituting the heat-shrinkable polyester film becomes too high, a whitening phenomenon due to partial crystallization during heat shrinkage occurs, or when tubing processing, Adhesion between films using an organic solvent such as tetrahydrofuran, which is usually performed, is deteriorated or impossible. In order to obtain more stable shrink finish appearance and adhesion with an organic solvent, the maximum value of tan δ in the main shrink direction is preferably 0.6 or more, more preferably 0.8 or more.

Further, in the present invention, it is necessary that the temperature at the intersection of the tan δ values of the dynamic viscoelasticity in the main shrinkage direction is 70 ° C. or less before and after the film is left standing in a 40 ° C. atmosphere for 160 hours. Intersection temperature of tan δ value is 70 ° C
When the film thickness exceeds the range, when the film is stored at room temperature for a long period of time, the shrinkage finish in the heat shrinking step is significantly reduced. As described above, a decrease in the tan δ value accompanying a decrease in the loss elastic modulus occurs in a temperature range from a temperature lower than the tan δ value intersection point to a temperature of at least about 0 ° C. as described above. The finish is more noticeably reduced. As a result, in the heat-shrinking step, defective films such as shrinkage spots, wrinkles, distortion, and breakage increase in the film stored for a long time, which is a problem in industrial production. From the point of view of stability in industrial production, the film is
The temperature at the intersection of the tan δ values before and after standing for 160 hours in an atmosphere is more preferably 68 ° C. or less.

Further, in the present invention, the initial breaking ratio in the direction perpendicular to the main shrinkage direction of the film is preferably 5% or less, particularly preferably 0%. If the initial breaking ratio exceeds 5%, the tear resistance of the film deteriorates.
In the heat-shrinkable polyester film, molecules are oriented in the main shrinkage direction, so if the tear resistance is poor, it is easy to tear along the orientation direction of the molecules, and the tension in processing steps such as printing and tubing processing There is a problem that the film is broken and the operability of processing is reduced.

Further, in the present invention, it is necessary that the maximum value of tan δ of dynamic viscoelasticity in the main shrinkage direction of the film in the temperature range of 0 ° C. or more and 40 ° C. or less is 0.03 or less. When the tan δ maximum value exceeds 0.03, the dimensional stability at room temperature deteriorates, and when the film is stored in the form of a roll for a long time, defects such as film thickening, tight tightening, and uneven thickness are caused. appear.

The thickness of the heat-shrinkable polyester film of the present invention is not particularly limited. For example, the shrinkable film for labels is preferably 10 to 200 μm, more preferably 20 to 100 μm.

The polyester resin used in the heat-shrinkable polyester film of the present invention comprises, as a dicarboxylic acid component, an aromatic dicarboxylic acid or an ester-forming derivative thereof, or an aliphatic dicarboxylic acid, and a polyhydric alcohol component as main components. Is what you do. As an aromatic dicarboxylic acid,
For example, terephthalic acid, isophthalic acid, naphthalene-1,
4- or -2,6-dicarboxylic acid, 5-sodium sulfoisophthalic acid and the like can be mentioned. In addition, examples of these ester derivatives include derivatives such as dialkyl esters and diaryl esters. Examples of the aliphatic dicarboxylic acid include dimer acid, glutaric acid, adipic acid, sebacic acid, azelaic acid, oxalic acid, and succinic acid. Further, an oxycarboxylic acid such as p-oxybenzoic acid and a polyvalent carboxylic acid such as trimellitic anhydride and pyromellitic anhydride may be used in combination, if necessary.

The polyhydric alcohol component of the polyester resin used in the heat-shrinkable polyester film of the present invention includes ethylene glycol, diethylene glycol, dimer diol, propylene glycol, triethylene glycol, 1,4-butanediol, neopentyl glycol. , 1,3-cyclohexanedimethanol, 1,
4-cyclohexanedimethanol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, 2-methyl-1,5-pentanediol, 2,2-diethyl-
1,3-propanediol, 1,9-nonanediol,
Examples thereof include an alkylene glycol such as 1,10-decanediol, an ethylene oxide adduct of a bisphenol compound or a derivative thereof, trimethylolpropane, glycerin, pentaerythritol, polyoxytetramethylene glycol, and polyethylene glycol.
Also, although not a polyhydric alcohol, epsilon caprolactone may be mentioned.

Among these dicarboxylic acid components and polyhydric alcohol components, a dimer acid component as a dicarboxylic acid component, a dimer-diol component as a polyhydric alcohol component,
Alternatively, a polyester containing at least one of the ε-caprolactone components in place of the polyhydric alcohol is preferable. The inclusion of dimer acid and / or dimer-diol and / or ε-caprolactone as a constituent has an effect of lowering the temperature at the intersection of the tan δ values before and after the aging. In addition, since the temperature at the intersection of the tan δ values before and after aging can be reduced while maintaining the tear resistance of the film, the film properties can be easily controlled, and stable shrink finish can be obtained even after aging. The dimer acid and / or dimer-diol is a mixture containing, as a main component, components having the structures of (1) and (2) represented by the following chemical formula 1, and the preferred composition ratio is (1) :( 2) = 10 : 90 to 90:10. Further, it is preferable that the dimer acid and / or the dimer diol have been washed and purified with water.

[0025]

Embedded image

In the present invention, the heat shrinkage in the main shrinkage direction at 80 ° C. and the tan in the main shrinkage direction from 40 ° C. to 120 ° C.
δ maximum value, intersection temperature of tan δ value in the main shrinkage direction before and after the film was left in a 40 ° C. atmosphere for 160 hours, and initial rupture rate in the direction perpendicular to the main shrinkage direction of the film, and 0 ° C.
The tan δ maximum value of the dynamic viscoelasticity in the temperature range of 40 ° C. or less is determined by using the above-described components of the polyester resin and the like and by combining the film forming conditions.
It is possible to control within the scope of the present invention. The polyesters may be used alone or as a mixture of two or more. When two or more kinds are used in combination, a mixed system of polyethylene terephthalate and a copolymerized polyester may be used, or a combination of copolymerized polyesters may be used. Further, a combination with a homopolyester such as polybutylene terephthalate, polycyclohexylene dimethyl terephthalate, or polyethylene naphthalate may be used. A method of mixing two or more polyesters having different Tg can also be an effective means for achieving the present invention. It is preferable that 10 to 90 mol% of the entire polyester contained in the polyester is an ethylene terephthalate unit. More preferably 15
~ 85 mol%. If the content of the ethylene terephthalate unit is less than 10 mol%, the rupture resistance and solvent resistance of the film will deteriorate, and if it exceeds 90 mol%, the heat shrinkage will decrease, and sufficient shrinkage performance will not be obtained, which is not preferable. The polyester can be produced by melt polymerization by a conventional method, but is not limited thereto, and may be a polyester obtained by another polymerization method. The degree of polymerization of the polyester is 0.1 in terms of intrinsic viscosity.
Those having 3 or more and 1.3 or less are preferable.

For the purpose of improving the heat resistance such as the degree of coloring and the degree of gelation, the polyester may contain, in addition to a polymerization catalyst such as antimony oxide, germanium oxide, or a titanium compound, an Mg salt such as magnesium acetate or magnesium chloride; , Ca salts such as calcium chloride, manganese acetate, Mn salts such as manganese chloride, zinc chloride, Zn salts such as zinc acetate,
Co salt such as cobalt chloride and cobalt acetate is not more than 300 ppm as a metal ion with respect to the resulting polyester, and phosphoric acid or a phosphate derivative such as trimethyl phosphate or triethyl phosphate is phosphorous (P)
It is also possible to add 200 ppm or less in conversion.

The total amount of metal ions other than the polymerization catalyst is 300 ppm based on the produced polyester, and the P amount is 200 ppm.
If it exceeds ppm, not only the coloring of the polymer becomes remarkable, but also the heat resistance and hydrolysis resistance of the polymer are remarkably reduced.

At this time, in terms of heat resistance, hydrolysis resistance and the like, the molar atomic ratio (P / M) between the total P amount (P) and the total metal ion amount (M) is 0.4 to 1. It is preferably 0. If the molar atomic ratio (P / M) is less than 0.4 or more than 1.0, the composition of the present invention is not preferable because coloring and generation of coarse particles become remarkable.

The method for producing the polyester is not particularly limited, but a so-called direct polymerization method in which an oligomer obtained by directly reacting a dicarboxylic acid and a glycol is polycondensed,
A so-called transesterification method in which a dimethyl ester of a dicarboxylic acid and a glycol are subjected to transesterification and then polycondensation, and the like, may be used, and an arbitrary production method can be applied.

The timing of adding the metal ions and phosphoric acid and derivatives thereof is not particularly limited, but generally, the metal ions are charged at the time of charging the raw materials, that is, before transesterification or esterification, and the phosphoric acids are charged before the polycondensation reaction. Is preferably added.

If necessary, fine particles such as silica, titanium dioxide, kaolin, and calcium carbonate may be added. Further, an antioxidant, an ultraviolet absorber, an antistatic agent, a coloring agent, an antibacterial agent and the like may be added. It can also be added. The intrinsic viscosity for forming a film is not particularly limited, but is usually 0.40 to 1.30 dl / g.

The polyester raw material used in the present invention is dried using a drier such as a hopper drier or a paddle drier, or a vacuum drier, and extruded into a film at a temperature of 200 to 300 ° C. Alternatively, the undried polyester raw material is similarly extruded into a film while removing moisture in a vented extruder. When extruding, T-die method
Any existing method such as the tubular method may be adopted. After extrusion, it is quenched to obtain an unstretched film. The stretching process is performed on the unstretched film. However, in order to achieve the object of the present invention, the transverse direction is practical as the main shrinking direction, and hence the film forming method in the case where the main shrinking direction is the transverse direction is described below. Although an example is shown, when the main shrinkage direction is the vertical direction, the film can be formed according to a normal operation, in addition to changing the stretching direction by 90 degrees in the following method.

Further, if attention is paid to making the thickness distribution of the intended heat-shrinkable polyester film uniform,
When the film is stretched in the transverse direction using a tenter, the heat conduction coefficient is set to 0.00 in a preheating process performed prior to the stretching process.
Tg at a low wind speed of 13 calories / cm ² · sec · ° C or less
Heating is preferably performed until the film temperature reaches + 0 ° C. to Tg + 60 ° C. Tg-20 ° C for transverse stretching
The film is stretched 2.3 to 7.3 times, preferably 2.5 to 6.0 times at a temperature of up to Tg + 40 ° C. After that, 50 ℃ ～ 11
At a temperature of 0 ° C., a heat treatment is carried out with 0-15% elongation or 0-15% relaxation, and 40 ° C.-10
Further heat treatment is performed at a temperature of 0 ° C. to obtain a heat-shrinkable polyester film.

The stretching method is not only uniaxial stretching in a tenter but also 1.0 to 2.3 times or less in a longitudinal direction.
Preferably, stretching of 1.1 to 1.8 times can be performed. However, if the stretching is performed at a ratio of more than 2.3 times, the heat shrinkage after treatment in hot water at 80 ° C. for 10 seconds in the direction orthogonal to the main shrinkage direction increases, and exceeds 15%, which is not preferable in the present invention. The biaxial stretching may be either sequential biaxial stretching or simultaneous biaxial stretching, and may be performed again if necessary. In the sequential biaxial stretching, the order of stretching is as follows:
Any of vertical, horizontal, vertical, horizontal, vertical, horizontal, vertical, and horizontal may be used. Focusing on suppressing internal heat generation of the film due to stretching and reducing film temperature unevenness in the width direction, the heat transfer coefficient of the stretching step is 0.0009 calories / cm ² · sec.
-° C or higher, preferably 0.0013 to 0.0020 calories / cm ² · sec · ° C. As described above, the present invention is achieved by a combination of a polyester composition of a film raw material and a stretching method.

[0036]

Next, the present invention will be described in more detail with reference to examples and comparative examples. However, the present invention is not limited to the following examples, and may be modified without departing from the spirit of the preceding and following embodiments. All this is included in the technical scope of the present invention. Also,
The methods for measuring and evaluating the physical properties of the films obtained in Examples and Comparative Examples are shown below.

(1) Heat Shrinkage The sample film was cut into a square of 10 cm × 10 cm.
After heat-shrinking by treating in hot water at a predetermined temperature of ± 0.5 ° C. for 10 seconds under no load, the length and width of the film were measured, and the heat shrinkage was calculated according to the following two formulas. The direction in which the heat shrinkage was large was defined as the main shrinkage direction. Heat shrinkage = {([length before heat shrink]-[length after heat shrink]) / [length before heat shrink]} × 100 (%) (Equation 2)

(2) Dynamic Viscoelasticity Using a dynamic viscoelasticity measuring device manufactured by IT-Measurement Co., the film was measured under the conditions of a measurement length of 3 cm, a variation of 0.25% and a frequency of 10 Hz. In the temperature range,
The tan δ value was quantified at a pitch of 1 ° C. The temperature at the intersection of the tan δ values is as follows.
% For 2 hours in a thermo-hygrostat controlled at% ± 2% and taken out after aging. The dynamic viscoelasticity before and after was measured by the above method, and both were plotted on the same graph. In a temperature range around 0 ° C., a decrease in the tan δ value with a decrease in the loss elastic modulus occurs. Figure 1 shows tan
The method for obtaining the intersection point temperature of the δ value will be described. The sample size is 4cm in the main shrink direction and 5mm in the perpendicular direction,
The average value of two locations was used.

(3) Initial rupture rate The rupture elongation was measured in the direction perpendicular to the main shrinkage direction according to JIS-C-2318 (number of samples n = 20). The number of samples having a rupture elongation of 5% or less (x) And means a value calculated from the following equation 1. Initial breaking rate = (x / n) × 100 (%) (Equation 1)

(4) Shrink finish Finishing at 150 ° C. (wind speed 10 m /
Seconds) with hot air of 10 seconds and a glass bottle (300m
In l), after attaching a heat-shrinkable film label printed in three colors with grass-colored, gold, and white inks, the label was passed through and the shrinkage finish was visually determined. The rank of shrinkage finish was evaluated on a 5-point scale. 5: Best finish 4: Good finish 3: Slight shrinkage (within 2 places) 2: Shrinkage unevenness (3 to 6 places) 1: Shrinkage There were many spots (6 or more places), and 4 or more were considered acceptable.

(Synthesis of Polyester) 100 mol% of dimethyl terephthalate (DMT) as a dibasic acid component and ethylene glycol (EG) 73 as a glycol component were placed in a stainless steel autoclave equipped with a stirrer, a thermometer and a partial reflux condenser. With the composition of mol% and neopentyl glycol (NPG) 27 mol%, the glycol was charged so that the molar ratio was 2.2 times the methyl ester,
0.05 mol of zinc acetate (based on the acid component) as a transesterification catalyst, and 0.1 mol of antimony trioxide as a polycondensation catalyst.
025 mol% (relative to the acid component) was added, and transesterification was carried out while distilling off the generated methanol out of the system. Thereafter, a polycondensation reaction was performed at 280 ° C. under a reduced pressure of 0.2 torr to obtain a polyester (A) having an intrinsic viscosity of 0.66 dl / g.

The polyesters shown in Table 1 were obtained in the same manner as described above. In addition, butanediol (BD) and dimerdiol (DIDO) were also used. The intrinsic viscosity of each polyester is (B): 0.69 dl /
g, (C): 1.25 dl / g, (D): 0.60,
(E): 0.63, (G): 0.70, (H): 0.6
It was 5. The reduced viscosity of (F) is (F): 1.3.
It was 0. Reduced viscosity: 25 ml of 0.05 g of polymer
Mixed solution (phenol / tetrachloroethane = 60 /
40) and dissolved at 30 ° C. using an Ostwald viscometer.
Was measured.

[0043]

[Table 1]

(Example 1) 48 wt% of polyester A, 32 wt% of B, and 20 wt% of F shown in Table 1 were mixed in the form of a resin, melt-extruded at 280 ° C., and quenched. An unstretched film was obtained. After pre-heating the unstretched film at 100 ° C. for 10 seconds,
Stretched 1.3 times at 80 ° C., 1.5 times at 80 ° C., and 2.0 times at 75 ° C., and then cooled to 60 ° C., then 3% at 70 ° C.
A heat treatment was performed for 10 seconds while stretching to obtain a heat-shrinkable polyester film having a thickness of 45 μm. Table 2 shows the physical property values of the obtained film.

(Example 2) 95% by weight of polyester G and 5% by weight of B shown in Table 1 were mixed in a resin state, melt-extruded at 280 ° C, and quenched to give a thickness of 180 µm.
Was obtained. 100 ° C.
After preheating for 10 seconds at 1.3 ° C. at 85 ° C.
The film is stretched 1.5 times at 0 ° C., and 2.0 times at 75 ° C., then cooled to 60 ° C., and then heat-treated for 10 seconds while being stretched at 70 ° C. for 3% to obtain a heat-shrinkable polyester film having a thickness of 45 μm. Obtained. Table 2 shows the physical property values of the obtained film.

Example 3 Polyester H shown in Table 1
Was melt-extruded at 280 ° C. and then rapidly cooled to a thickness of 180 μm.
Was obtained. 100 ° C.
After preheating for 10 seconds at 1.3 ° C. at 85 ° C.
The film is stretched 1.5 times at 0 ° C., and 2.0 times at 75 ° C., then cooled to 60 ° C., and then heat-treated for 10 seconds while being stretched at 70 ° C. for 3% to obtain a heat-shrinkable polyester film having a thickness of 45 μm. Obtained. Table 2 shows the physical property values of the obtained film.

(Example 4) Polyester D shown in Table 1 was melt-extruded at 275 ° C and then rapidly cooled to obtain an unstretched film having a thickness of 185 µm. The unstretched film is heated at 105 ° C for 8 hours.
After preheating for 2 seconds, stretched 4.1 times at 78 ° C in the transverse direction, and then heat-treated for 10 seconds while fixing at 65 ° C to a thickness of 45μ.
m of a heat-shrinkable polyester film was obtained. Table 2 shows the physical property values of the obtained film.

(Comparative Example 1) 63% by weight of polyester A, 10% by weight of B, and 27% by weight of C shown in Table 1 were mixed in the form of a resin, melt-extruded at 275 ° C., and quenched. An unstretched film was obtained. After preheating the unstretched film at 110 ° C. for 10 seconds,
Stretched 4.2 times at 10 ° C, and then fixed at 72 ° C for 10 times.
Heat treatment was performed for 2 seconds to obtain a heat-shrinkable polyester film having a thickness of 45 μm. Table 2 shows the physical property values of the obtained film.

Comparative Example 2 55% by weight of polyester A, 20% by weight of B, and 25% by weight of C shown in Table 1 were mixed in the form of a resin, melt-extruded at 275 ° C., quenched, and cooled to a thickness of 190 μm. An unstretched film was obtained. After preheating the unstretched film at 100 ° C. for 8 seconds,
And then heat-treated for 10 seconds while fixing at 72 ° C. to obtain a heat-shrinkable polyester film having a thickness of 45 μm. Table 2 shows the physical property values of the obtained film.

Comparative Example 3 50 wt% of polyester A, 30 wt% of B, and 10 wt% of C shown in Table 1 were mixed in a resin state, melt-extruded at 275 ° C., quenched, and then cooled to a thickness of 175 μm. An unstretched film was obtained. After preheating the unstretched film at 100 ° C. for 8 seconds,
And then heat-treated for 10 seconds while fixing at 83 ° C. to obtain a heat-shrinkable polyester film having a thickness of 45 μm. Table 2 shows the physical property values of the obtained film.

Comparative Example 4 32% by weight of polyester A, 50% by weight of B, 10% by weight of C, and 8% of E shown in Table 1
The mixture was melt-extruded at 280 ° C. and rapidly cooled to obtain an unstretched film having a thickness of 180 μm. The unstretched film was preheated at 110 ° C. for 8 seconds, stretched 4.0 times at 85 ° C. in the transverse direction, and then heat-treated at 75 ° C. for 10 seconds to obtain a heat-shrinkable polyester film having a thickness of 45 μm. Table 2 shows the physical property values of the obtained film.

[0052]

[Table 2]

[0053]

According to the heat-shrinkable polyester film of the present invention, it is possible to obtain a beautiful shrink-finished appearance with extremely few defects such as shrinkage spots, wrinkles, distortion, and folds during shrinkage in the hot air shrinking step. Particularly, since the shrinkage finish with storage is hardly deteriorated with time, the tear resistance is excellent, and the natural shrinkage shrinkage ratio is small, so that it is suitably used for label and cap seal applications.

 ────────────────────────────────────────────────── ─── Continuing on the front page (72) Inventor Nori Tabota 344 Kizu-Maebata, Inuyama-shi, Aichi Toyo Spinning Co., Ltd. Inuyama Plant (72) Inventor Katsuya Ito 2-1-1 Katata, Otsu-shi, Shiga Toyobo 4F210 AA24 AE01 AG01 RA03 RC02 RG02 RG04 RG43

Claims (4)

[Claims] 1. A heat-shrinkable polyester film having a heat-shrinkage rate of 40% or more in a main shrinkage direction after treatment for 10 seconds in hot water at 80 ° C. Tan δ maximum value of dynamic viscoelasticity in the main shrinkage direction in a temperature range of not more than 0.5 ° C.
A heat-shrinkable polyester film, wherein the temperature at the intersection of the tan δ values of the dynamic viscoelasticity before and after standing for 160 hours in an atmosphere is 70 ° C. or less. 2. The heat-shrinkable polyester film according to claim 1, wherein an initial rupture rate in a direction perpendicular to the main shrinkage direction is 5% or less. 3. The heat-shrinkable polyester film according to claim 1, wherein the main shrinkage direction is 0 ° C. or more and 40 ° C.
The maximum value of tan δ of dynamic viscoelasticity in the following temperature range is 0.
A heat-shrinkable polyester film having a ratio of 03 or less. 4. The heat-shrinkable polyester film according to claim 1, wherein at least one of dimer acid, dimer diol, and ε-caprolactone is contained as a constituent monomer component. A heat-shrinkable polyester film.