JP2001200072A - Heat-shrinkable polyester film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To prepare a heat-shrinkable polyester film which is almost free from defects, such as uneven shrinkage, wrinkles, distortion, and creases, after its heat shrinkage by hot air at the step of shrinking, can have a beautiful shrunk appearance, and is suitably used in full label applications or cap seal applications where a film label requires a high shrinkage depending on the shape of a container. SOLUTION: The heat shrinkage of this film in the main shrinkage direction after treated for 10 sec in 80 deg.C water is 40% or higher, and there are two endotherm peaks obtained by the irreversible heat flux curve at near the glass transition point of the film.

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 suitable mainly for use in labels and cap seals, and more particularly, to shrinkage spots, wrinkles, distortions, and breaks after heat shrinkage of a film in a shrinking step by hot air. The present invention relates to a shrinkable polyester-based film which is extremely free from intrusion and the like and requires a high shrinkage.

[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 because of 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.

However, the above-mentioned conventional heat-shrinkable polyester films are not sufficiently satisfactory in heat-shrink properties. In particular, shrinkage spots, wrinkles, distortions and folds are likely to occur during shrinkage.
When printing and shrinking on containers such as polyethylene bottles and glass bottles, letters printed on the film before shrinking in advance,
There have been problems such as distortion of the design after shrinkage and insufficient adhesion of the film to the container.

[0007]

SUMMARY OF THE INVENTION The present invention solves the above-mentioned problems of the conventional heat-shrinkable polyester film. In the shrinking step with hot air, the shrinkage spots, wrinkles, distortions, and folds after the heat shrinkage of the film. It is possible to obtain a beautiful shrink-finished appearance with very few occurrences of intrusion and the like. In particular, an object of the present invention is to provide a heat-shrinkable polyester film suitably used for a full label application or a cap seal application in which a film label requires a high shrinkage ratio depending on a container shape.

[0008]

In order to achieve the above object, the heat-shrinkable polyester film of the present invention has a heat shrinkage rate in the main shrinkage direction after a 10-second treatment in hot water of 80 ° C. in the main shrinkage direction. 40% or more, characterized by having two or more endothermic peaks (peaks due to enthalpy relaxation) near the glass transition of the film, which are obtained by an irreversible heat flux curve.

It has excellent shrink finish in a wide temperature range from low temperature to high temperature having the above characteristics, and is particularly suitable for full label applications and cap seal applications where a film label requires a high shrinkage rate depending on the shape of the container. Used, it is possible to obtain a beautiful shrink-finished appearance with extremely few shrinkage spots, wrinkles, distortions and folds.

In this case, the heat-shrinkable polyester film has an endothermic peak temperature near the glass transition of the film of 40 ° C., which is obtained from an irreversible heat flux curve.
It is preferable that the temperature be in the range of not less than 90 ° C. and not more than 90 ° C.

[0011] The glass transition temperature of the film, obtained from a reversible heat flux curve, can be less than 75 ° C.

[0012]

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.

In the present invention, it is necessary that the film has two or more endothermic peaks (peaks due to enthalpy relaxation) near the glass transition obtained from the irreversible heat flux curve in the temperature modulation scanning calorimetry. . If there is only one peak due to relaxation of the enthalpy of the film, for example, in a full label application or a cap seal application, a beautiful shrink finish cannot be stably obtained in a portion requiring a high shrinkage of the packaged object, Defects such as folding and wrinkling occur. In order to obtain a stable shrink finish, it is necessary that the film has two or more peaks due to enthalpy relaxation obtained from the irreversible heat flux curve. The upper limit of the number of peaks is not particularly limited, and it is preferable that the number of peaks is large in order to obtain a more stable shrinkage finish. The number of peaks is preferably 2 or 3 because it is difficult to control the peaks within the range.

Further, in the present invention, the peak temperatures due to enthalpy relaxation near the glass transition of the film obtained from the irreversible heat flux curve in the temperature modulation scanning calorimetry are all within the temperature range from 40 ° C. to 90 ° C. It is necessary. Those having a peak temperature in a temperature range of less than 40 ° C. cause a change in shrinkage characteristics with the passage of time, and in particular, a problem of deterioration in shrink finish due to a decrease in shrinkage in a low temperature range. In the case where the peak temperature is in a temperature range exceeding 90 ° C., the processing temperature in the heat shrinking step has to be increased, and the defect rate in the step is reduced because the appropriate processing temperature condition width is narrowed. In addition, it becomes difficult to process at a high speed, which is a problem in industrial production.

Further, in the present invention, the glass transition temperature of the film obtained from the reversible heat flux curve in the temperature modulation scanning calorimetry needs to be less than 75 ° C. If the glass transition temperature is 75 ° C. or higher, it must be heated to a high temperature in order to obtain the required amount of shrinkage. However, there are restrictions on the heat resistance of the packaged items, and the range of application is naturally narrowed. For example, in the case of a thermoplastic bottle application, the bottle is deformed or deteriorated by heating. The lower limit of the glass transition temperature of the film obtained from the reversible heat flux curve is not particularly limited, but is preferably 50 ° C. or more from the viewpoint of dimensional stability over time of the film.

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.
Epsilon caprolactone, which is not a polyhydric alcohol, can also be used.

In the heat-shrinkable polyester film of the present invention, it is preferable to use one or more of the above-described dicarboxylic acid components and polyhydric alcohol components in combination. The type and content of the components of the monomers used in combination can be appropriately determined in consideration of the desired film properties, economy, etc., but it is composed of a composition containing at least one polyester, and Is preferably an ethylene terephthalate unit. More preferably 15 to 70
Mol%. 10 ethylene terephthalate units
If the amount is less than mol%, the rupture resistance and solvent resistance of the film will deteriorate, and if it exceeds 75% by mol, the heat shrinkage will decrease and sufficient shrinkage performance will not be obtained, which is not preferable.

In order to satisfy the number of endothermic peaks near the glass transition temperature (the number of peaks due to enthalpy relaxation), the range of the endothermic peak temperature, and the glass transition temperature in the heat-shrinkable polyester film of the present invention, the polyester resin described above is required. It is possible to control within the object of the present invention by combining the constituents and the like with the film forming conditions. 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, polyethylene naphthalate, or polybutylene naphthalate may be used.

For the purpose of improving the heat resistance such as the degree of coloring and the degree of gelation, the polyester may further 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 above-mentioned 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) of the total P amount (P) to 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. Generally, the metal ions are charged at the time of charging the raw materials, that is, before ester exchange or esterification, and the phosphoric acid is 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. At this time, the transverse stretching is preferably performed in two or three steps. After a while, 50 ° C ~
At a temperature of 110 ° C., 0-15% elongation or 0-15%
% While relaxing the temperature, if necessary, from 40 ° C
Further heat treatment is performed at a temperature of 100 ° C. to obtain a heat-shrinkable polyester film.

As a stretching method, not only a uniaxial stretching in a transverse direction with 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.

[0030]

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 10 cm × 10 cm square,
After heat-shrinking by treating in hot water at a predetermined temperature of ± 0.5 ° C. under no load for 10 seconds, the length and width dimensions of the film were measured, and the heat shrinkage was determined according to the following equation (1). . The direction in which the heat shrinkage was large was defined as the main shrinkage direction. Heat shrinkage = (length before shrinkage-length after shrinkage) / length before shrinkage x 100 (%) (1)

(2) Number of Endothermic Peaks and Temperature (Number of Peaks and Temperature Due to Enthalpy Relaxation)
Measured in Modulated mode of 920, heating rate 5 ° C / min,
The measurement was performed at a temperature amplitude of ± 1 ° C. and a cycle of 60 seconds. From the obtained irreversible heat flux curve, the number of endothermic peaks and the peak temperature near the glass transition temperature were defined as the number of peaks and the peak temperature due to enthalpy relaxation.

(3) Glass transition temperature From the reversible heat flux curve obtained by the measurement in the above (2),
The glass transition temperature of the sample film was quantified. The glass transition point referred to here is the value of Inflec in the analysis of the step curve.
The tion temperature was calculated.

(4) Shrink finish finish Using a steam tunnel (model: SH-1500-L) manufactured by Fuji Astec Inc., a 334 ml glass bottle (used for a commercially available Asahi Breweries beer water heater manufactured by Asahi Breweries, Ltd.). Returnable bin)
After attaching a heat-shrinkable film label printed in three colors with grass-colored, gold, and white inks manufactured by Toyo Ink Co., Ltd. in advance, the tunnel passage time was 10 seconds, and the zone temperature / 2.
The test was carried out by passing under the condition of zone temperature = 80 ° C./90° C., 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: Some defects (within 2 places) 2: Defects (3 to 6 places) 1: Many defects ( 6 or more) and 4 or more were regarded as acceptable levels (number of samples n = 1)
0). Here, the term "defect" refers to a general term for wrinkles, label end folding, color spots, and insufficient shrinkage.

(Synthesis of Polyester) In a stainless steel autoclave equipped with a stirrer, a thermometer and a partial reflux condenser, 100 mol% of dimethyl terephthalate (DMT) as a dibasic acid component and 72 of ethylene glycol (EG) as a glycol component. With the composition of mol% and neopentyl glycol (NPG) 28 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 0.68 dl / g.

The polyesters shown in Table 1 were obtained in the same manner as described above. Note that 2,6-dimethylnaphthalenedicarboxylic acid (DMN), butanediol (BD), and dimer diol (DIDO) were also used. The intrinsic viscosity of each polyester is (B): 0.70 dl /
g, (C): 1.25 dl / g, and (D): 0.60.

[0037]

[Table 1]

Example 1 77% by weight of polyester A, 13% by weight of B, and 10% by weight of C shown in Table 1 were mixed in a resin state, melt-extruded at 280 ° C., quenched, and cooled to a thickness of 225 μm. An unstretched film was obtained. After preheating the unstretched film at 105 ° C. for 12 seconds,
Stretched 1.4 times at 80 ° C, 1.7 times at 80 ° C, and 2.0 times at 75 ° C, then cooled to 55 ° C, and 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 46 μm. Table 2 shows the physical property values of the obtained film.

Example 2 Polyester A shown in Table 1 was mixed in a resin state at 74 wt%, B at 12 wt%, and C at 14 wt%, melt-extruded at 280 ° C., quenched, and cooled to a thickness of 225 μm. A stretched film was obtained. After pre-heating the unstretched film at 105 ° C. for 12 seconds,
Stretched 1.4 times at 80 ° C., 1.7 times at 75 ° C., and 2.0 times at 75 ° C., then cooled to 55 ° C. and 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 46 μm. Table 2 shows the physical property values of the obtained film.

(Comparative Example 1) 68% by weight of polyester A, 8% by weight of B, and 24% by weight of C were mixed in a resin state as shown in Table 1, melt-extruded at 275 ° C, and quenched to obtain a 175 μm-thick polyester resin. A stretched film was obtained. After pre-heating the unstretched film at 103 ° C. for 15 seconds,
And then heat-treated for 10 seconds while fixing at 73 ° 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 2) Polyester A shown in Table 1 was mixed in a resin state at 52 wt%, B at 25 wt%, and C at 23 wt%, melt-extruded at 275 ° C., quenched, and cooled to 185 μm in thickness. A stretched film was obtained. After preheating the unstretched film at 105 ° C. for 12 seconds, stretch it 4.1 times at 80 ° C. in the transverse direction, and then heat-treat it for 10 seconds while fixing at 70 ° C. 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.

Comparative Example 3 Polyester A shown in Table 1 was 32% by weight, B was 50% by weight, C was 10% by weight, and E was 8% by weight.
The mixture was melt-extruded at 280 ° C. and rapidly cooled to obtain an unstretched film having a thickness of 180 μm. After preheating the unstretched film at 105 ° C. for 12 seconds,
The film was 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.

[0043]

[Table 2]

[0044]

The heat-shrinkable polyester film of the present invention is free from defects such as shrinkage spots, wrinkles, distortion, and folds during shrinkage, and can provide a beautiful shrink-finished appearance. It is suitably used for applications requiring a rate, such as shrink labels, cap seals, shrink wraps, and the like.

[Brief description of the drawings]

FIG. 1 is a measurement example of an endothermic peak calorific value ΔH1.

Continued on the front page (51) Int.Cl. ⁷ Identification code FI Theme coat II (Reference) C08L 67:00 C08L 67:00 (72) Inventor Michishige Morioshi 2-1-1 Katata 2-chome, Otsu-shi, Shiga Toyobo Within the Research Institute, Inc. AE01 AG01 RA03 RC02 RG02 RG04 RG43

Claims (3)

[Claims] 1. The film has a heat shrinkage in the main shrinkage direction of 40% or more after treatment of the film in hot water of 80 ° C. for 10 seconds, and has an endothermic peak near the glass transition of the film obtained from an irreversible heat flux curve of 2%. A heat-shrinkable polyester film characterized by having at least one. 2. The heat-shrinkable polyester film according to claim 1, wherein an endothermic peak temperature near the glass transition of the film obtained from an irreversible heat flux curve is 40 ° C. or higher.
A heat-shrinkable polyester film which is in a temperature range of 0 ° C. or lower. 3. The heat-shrinkable polyester film according to claim 1, wherein the film has a glass transition temperature of less than 75 ° C. obtained from a reversible heat flux curve. Heat-shrinkable polyester film.