JP3271774B2 - Polyester shrink film - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel polyester shrink film, and more particularly to a polyester film having a good finished appearance without distortion or wrinkles of a design due to uneven shrinkage at the time of mounting, and a perforation cutability. The present invention relates to a polyester-based shrink film suitable for use as labels, cap seals, and other packaging materials of, for example, glass bottles and plastic bottles.

[0002]

2. Description of the Related Art In recent years, polyester shrink films have excellent transparency and shrinkage during transportation and storage.
That is, since there is no dimensional shortage or flatness deterioration due to natural shrinkage, labels, cap seals, and other packaging materials for mounting on glass bottles, plastic bottles, and the like by heating and shrinking are attracting attention. .

In order to develop a necessary heat shrinkage, a copolymer component is added to polyethylene terephthalate (Japanese Patent Laid-Open No. 63-156833), or the copolymer is blended with polyethylene terephthalate (Japanese Patent Publication No. 64-10332).

[0004] However, the conventional polyester shrink film composed of a polyester copolymer or a blend thereof with polyethylene terephthalate is compared with those of polyvinyl chloride or polystyrene conventionally used as shrink films. The temperature dependence of the heat shrinkage is large, and the heat shrinkage sharply increases near the glass transition temperature, causing distortion and wrinkles of the design due to uneven shrinkage at the time of mounting, and the finished appearance is impaired In addition to the above, when the polyester is oriented and crystallized, when cutting and opening two perforations usually inserted in a direction perpendicular to the main shrinkage direction for the purpose of cutting and opening later in a cap seal or the like, It is easy to tear in the main contraction direction perpendicular to the cutting direction, and it cannot perform smooth cutting. It is.

[0005]

DISCLOSURE OF THE INVENTION The present invention overcomes the drawbacks of the conventional polyester shrink film, has no distortion or wrinkles in the design due to uneven shrinkage during mounting, and has a good finished appearance. In addition, the present invention has been made to provide a polyester shrink film having excellent perforation cutability.

[0006]

Means for Solving the Problems In order to develop a polyester shrink film having favorable properties, the present inventors have conducted intensive studies on improving the physical properties of the film, and as a result, a mixed diol component having a specific composition has been obtained. And a polyester obtained by polycondensing a dicarboxylic acid component mainly composed of terephthalic acid and a polyester obtained by polycondensing a mixed diol component having another specific composition and a dicarboxylic acid component mainly composed of terephthalic acid. And optionally used, obtained by molding a polyester mixture obtained by mixing a polyester obtained by polycondensing a diol component mainly composed of ethylene glycol and a dicarboxylic acid component mainly composed of terephthalic acid at a specific ratio. A specific heat-shrinkable film made by stretching a film at a specific magnification in at least one direction. The shrink film having found that can achieve the purpose, and completed the present invention based on this finding.

That is, the present invention comprises (A) a dicarboxylic acid component unit composed mainly of terephthalic acid and a mixed diol component unit composed of 80 to 60 mol% of ethylene glycol and 20 to 40 mol% of cyclohexanedimethanol. Composed of 97 to 85 % by weight of a polyester, (B) a dicarboxylic acid component unit mainly composed of terephthalic acid, and a mixed diol component unit composed of 85 to 70 mol% of ethylene glycol and 15 to 30 mol% of diethylene glycol. 3 to 15 % by weight of a polyester mixture, or polyester 92 of the above-mentioned component (A)
To 70 % by weight of the polyester ( 3-1 ) of the component (B).
5 % by weight, (C) a dicarboxylic acid component unit mainly composed of terephthalic acid, and 95 mol% or less of ethylene glycol unit.
A heat-shrinkage at 100 ° C. obtained by stretching a film formed from a polyester mixture of 5 to 15 % by weight of a polyester composed of a diol component unit containing the above and 1.5 to 8 times in at least one direction. Is 50 in one direction
% Or more and 10% or less in a direction perpendicular thereto ,
The heat shrinkage rate is 1 to 20 in the heat shrinkage curve in the main shrinkage direction.
% In a temperature range of 10 ° C. or higher . In the present invention, terephthalic acid is mainly used.
Dicarboxylic acid component unit is terephthalic acid unit 85 mol%
It means a dicarboxylic acid component unit including the above.

[0008] The base resin used in the shrink film of the present invention includes the above-mentioned polyester of the component (A),
The object of the present invention can be sufficiently achieved even with a mixture of the component (B) and the polyester, but when the film is mounted using an automatic mounting machine, a film having a higher strength is required. Therefore, a mixture of the polyester of the component (A), the polyester of the component (B), and the polyester of the component (C) is more preferable.

The polyester (A) and the polyester (B) are obtained by a polycondensation reaction between a dicarboxylic acid component mainly composed of terephthalic acid and a specific mixed diol component, and the polyester (C) is mainly composed of terephthalic acid. Formed by a polycondensation reaction between a dicarboxylic acid component represented by the formula (I) and a diol component mainly composed of ethylene glycol.

When the proportion of terephthalic acid units contained in the dicarboxylic acid component units in these polyesters decreases, the mechanical strength of the resulting film decreases. Examples of the carboxylic acid component unit other than the terephthalic acid unit which may be present in the dicarboxylic acid component unit include, for example, isophthalic acid, biphenyldicarboxylic acid, 5-tert-butylisophthalic acid, 2,2,6,6-tetramethylbiphenyldicarboxylic acid , 2,6-naphthalenedicarboxylic acid, 1,1,3
Units of aromatic dicarboxylic acids such as -trimethyl-3-phenylindene-4,5-dicarboxylic acid, oxalic acid, succinic acid, adipic acid, azelaic acid, sebacic acid, 1,
Examples include units of aliphatic dicarboxylic acids such as 10-decandioic acid, and units of polycarboxylic acids such as trimellitic acid and 1,2,4,5-benzenetetracarboxylic acid. The proportion of aromatic dicarboxylic acid units other than these terephthalic acid units is preferably 20 mol% or less based on the total of dicarboxylic acid component units, but 10 mol% or less for aliphatic dicarboxylic acid units and 10 mol% for polycarboxylic acid units. Is 2 mol%
It is desirable to do the following. If the proportion of the aliphatic dicarboxylic acid unit exceeds 10 mol%, the glass transition temperature of the obtained polyester is too low, and the natural shrinkage is undesirably increased. On the other hand, when the proportion of the polycarboxylic acid unit exceeds 2 mol%, partial cross-linking of the polyester occurs, which causes a decrease in stretchability, which is not preferable.

On the other hand, the diol component unit in the component (A) polyester has an ethylene glycol unit of 60 to
80 mol%, preferably 65 to 75 mol%, and 40 to 20 mol%, preferably 3 to 40 mol% of cyclohexanedimethanol units.
When the content of the cyclohexanedimethanol unit is more than 40 mol% or less than 20 mol%, the crystallinity becomes large and the desired heat shrinkage cannot be obtained. Moreover, it is also inferior in perforation cutability.

In addition to the two-component unit, other diols and polyol units may be added to the diol component unit in an amount not affecting the physical properties of the polyester, if desired. May be contained at a ratio of 5 mol% or less, preferably 3 mol% or less. When the content of the unit of the other diol or polyol exceeds 5 mol%, the specific amorphousness of the polyester is deteriorated, and the object of the present invention cannot be sufficiently achieved. Examples of such diols include diethylene glycol, propylene glycol, 1,4-butanediol,
Neopentyl glycol, 1,6-hexanediol,
Xylylene glycol and the like, and polyols include glycerin, pentaerythritol, trimethylolpropane and the like.

The diol component unit in the component (B) polyester is composed of 85 to 70 mol% of ethylene glycol units and 15 to 30 mol% of diethylene glycol units. In this case, thermal decomposition is apt to occur, and if it is less than 15 mol%, a shrink film having an excellent finished appearance, which is one of the objects of the present invention, cannot be obtained.

The diol component unit may contain other diol or polyol units, if desired, in addition to the two-component unit as long as the physical properties of the polyester are not adversely affected. Such diols include, for example, propylene glycol, 1,4-butanediol, neopentyl glycol, 1,6-hexanediol, cyclohexanedimethanol, xylylene glycol, and the like, and polyols include glycerin, pentaerythritol, and triglyceride. Methylol propane and the like can be mentioned.

The diol component unit in the component (C) polyester is mainly composed of an ethylene glycol unit, that is, 95 ethylene glycol units.
% Diethylene glycol, propylene glycol, 1,4-butanediol, neopentyl glycol, 1,6-hexanediol, cyclohexanedimethanol, xylylene glycol, glycerin, pentaene 5 units such as erythritol and trimethylolpropane
It may be contained at a ratio of at most 3 mol%, preferably at most 3 mol%.

These polyesters used in the present invention are:
The polyester can be produced by a polycondensation reaction between the dicarboxylic acid component and the mixed diol component according to a usual polyester production method. At this time, if necessary, as the dicarboxylic acid component, a reactive functional derivative of dicarboxylic acid, for example, an acid halide or an acid ester can be used, or the reaction is performed in the presence of a reaction solvent, a condensing agent, a catalyst, or the like. You can also. The polymerization degree of the polyester used in the present invention is not particularly limited, but the intrinsic viscosity is 0.50 to 1.20, preferably 0.60 to 0.9.
It is desirably in the range of 0.

In the present invention, 97-85% by weight of the above-mentioned component (A) polyester is used as a base material of the shrink film.
% Of the component (B) and 3 to 15% by weight of the component (B), or 92 to 70% by weight of the component (A) and the component (B).
3 to 15% by weight and 5 to 15% by weight of the component (C) polyester
% Of a three-component polyester mixture. In order to obtain a good finished appearance after mounting, the component (B) component preferably has as high a concentration of diethylene glycol units as possible, and it is preferred that the proportion of diethylene glycol units in the total diol component units of the polyester mixture be 0.5%. ~ 6 mol%, preferably 1-4
It is good to add so that it may be in the range of mol%. If this ratio is less than 0.5 mol%, the finished appearance after mounting is inferior,
If it exceeds 6 mol%, it is difficult to stretch uniformly, and the strength of the film decreases.

[0018] In the two-component polyester mixtures, to finished appearance after shrinkage film attached inferior less than (B) the amount of component polyester 3% by weight, 15
If the content exceeds 10% by weight, it is difficult to uniformly stretch the film, and the strength of the film decreases.

On the other hand, in the three-component polyester mixture, when the amount of the component (B) polyester is less than 3 % by weight, the finished appearance after mounting the shrink film is inferior,
If it exceeds 15 % by weight, it is difficult to stretch uniformly, and the film strength is reduced. If the amount of the component (C) polyester is less than 5 % by weight, the effect of improving the strength of the stiffness is not sufficiently exhibited, and it is substantially the same as the case of the two-component polyester mixture, and exceeds 15 % by weight. In this case, a desired heat shrinkage rate cannot be obtained, and the perforation cutability decreases.
In addition, the diethylene glycol component unit in the polyester mixture can be obtained by incorporating the diethylene glycol component unit into the (A) component polyester or both the (A) component polyester and the (C) component polyester without using the (B) component polyester. Even if the same amount as the invention,
Good finish cannot be obtained after mounting. The reason for this is not obvious, but it is likely that some inhomogeneity in the very fine structure is involved.

The apparent glass transition temperature of these polyester mixtures is not particularly limited.
It is desirably in the range of 0 ° C.

The shrink film of the present invention is prepared by melt-mixing a predetermined ratio of the component (A) and the component (B), or the component (A), the component (B) and the component (C). After the polyester mixture is prepared by the above method, it can be produced by film forming and then stretching at a predetermined stretching ratio. This film molding is performed, for example, by drying the polyester mixture and then melt-extruding the polyester mixture at a temperature in the range of 220 to 300 ° C. to form a film having a thickness of about 100 to 500 μm on a casting drum having a surface temperature of 15 to 70 ° C. Done. The stretching treatment is carried out by subjecting the thus obtained film to a temperature equal to or higher than the glass transition temperature, preferably 1.5 to 8 times at least in one direction, preferably 2 to 30 times higher than the glass transition temperature.
It is performed by stretching 6 times. If necessary after this stretching treatment, a temperature 20 ° C. lower than the stretching temperature to 20 ° C.
Further heat treatment may be performed in a high temperature range. In this way, a shrink film having a heat shrinkage at 100 ° C. of 50% or more in one direction and 10% or less in a direction perpendicular thereto is obtained.
To achieve this, the unstretched film is stretched 1.05 to 2.0 times in the machine direction by a roll-type longitudinal stretching machine, then stretched 3 to 6 times in the transverse direction by a tenter, and then heat-treated and wound. Alternatively, it is advantageous that the film is stretched in the transverse direction by a tenter without longitudinal stretching, and then heat-treated and wound.

In this case, the stretching temperature in the roll type longitudinal stretching machine is preferably higher than the transverse stretching temperature in order to keep the heat shrinkage in the longitudinal direction within 10%.

The polyester shrink film of the present invention needs to have a heat shrinkage at 100 ° C. of 50% or more in one direction and 10% or less in a direction perpendicular thereto. If the heat shrinkage at 100 ° C. is less than 50% in the main shrinkage direction, the adherend may be damaged in a portion near the mouth, such as a glass bottle or a plastic bottle, or in a portion requiring high shrinkage, such as the top surface of a cap seal. If the heat shrinkage at 100 ° C. in the direction perpendicular to the main shrinkage exceeds 10%, the pattern will shift or wave after mounting.

Further, the polyester shrink film of the present invention has a temperature region where the heat shrinkage is in the range of 1 to 20% (hereinafter referred to as a low shrinkage temperature region) of 10 ° C. or more in the heat shrinkage curve in the main shrinkage direction. belongs to. In order to develop a good finished appearance without distortion or wrinkles of the design due to uneven shrinkage during mounting, the temperature dependence of the heat shrinkage, especially from the start of shrinkage to the heat shrinkage of 20% In other words, it is necessary that the temperature dependence is small, in other words, the low shrinkage temperature region is wide. Low shrinkage temperature range
If the temperature is lower than 10 ° C., uneven shrinkage is likely to occur, which may cause distortion or wrinkles of the design, which is not preferable.

Although the thickness of the film of the present invention is not particularly limited, it is usually 15 to 150 μm, preferably 20 to 150 μm.
It is selected in the range of -70 µm. The strength of the film varies slightly depending on the thickness of the film, but is generally about 13 as a Young's modulus in a direction perpendicular to the main contraction direction.
0 kg / mm ² or more, when used in an automatic mounting machine 1
Desirably, it is 50 kg / mm ² or more.

The polyester shrink film of the present invention is subjected to surface treatment such as corona discharge treatment and plasma irradiation treatment, and various coatings such as primer treatment and antistatic coating, to thereby provide adhesion of printing ink, metal deposition property, and slip property. , Anti-blocking properties, easy sealing properties, antistatic properties, etc. can also be improved.

[0027]

The polyester shrink film of the present invention has the required heat shrinkability as a shrink film, and has a good finished appearance without distortion or wrinkles of the design due to uneven shrinkage during mounting. In addition, it has the property of excellent perforation cutability, so it is most suitable as a label for glass bottles and plastic bottles and as a shrink film for cap sealing, and is used in a wide range of other packaging materials that can exhibit the effects of such properties. It is a good thing.

[0028]

Next, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.

The heat shrinkage, the low shrinkage temperature region, the Young's modulus, the mounting property, the perforation breakability, and the glass transition temperature in each example were determined according to the following methods.

(A) Heat Shrinkage Rate A shrink film is cut into a 100 mm square sample to prepare a sample. The sample is immersed in a warm water bath adjusted to a predetermined temperature for 30 seconds, and then the vertical or horizontal dimensions are measured. Heat shrinkage

(Equation 1) Was determined in accordance with

(B) Low shrinkage temperature region The heat shrinkage is measured at intervals of 2 ° C. from the shrinkage initiation temperature in the main shrinkage direction to the temperature at which the heat shrinkage exceeds 20%, and the shrinkage curve drawn thereby is 1%. , And T [1] and T [20], respectively, and were determined according to a low shrinkage temperature region (° C.) = T [20] −T [1].

(C) Young's modulus A shrink film is cut into a sample having a length of 120 mm and a width of 10 mm in a direction perpendicular to the main shrinkage direction to obtain a sample.
This sample was placed at 23 ° C. and the distance between chucks was 50 m.
The tensile strength is determined by a load cell type tensile tester set at m and a tensile speed of 5 mm, and is calculated from the slope of the initial linear portion of the SS curve at this time according to ASTM-D1894.

(D) Wearability Each of the crosslinked shrink films was formed in a 1.5-liter polyethylene terephthalate bottle filled with hot water of about 60 ° C. in a cylindrical shape with the main shrinkage direction being the circumferential direction. Fit into the shrink tunnel at 150 ° C for 5
After passing through for 2 seconds, it was shrunk and attached, and the degree of deformation of the grid, the presence or absence of wrinkles, etc. were observed and evaluated as follows. ：: No defects in finished appearance, Δ: Some defects in finished appearance, ×: Poor overall appearance. Unable to attach: Under predetermined conditions, it cannot be attached due to insufficient shrinkage.

(E) Wearability and Perforation Cutting Property Each shrink film in which two perforations are inserted into the cap portion of a normal glass bottle at an interval of about 8 mm in a direction perpendicular to the main contraction direction is inserted in the main contraction direction. Were fitted in a cylindrical shape with the circumferential direction, and shrink-fitted by passing through a shrink tunnel at 200 ° C. for 5 seconds, and the finished appearance was visually evaluated. ：: No defects in finished appearance, Δ: Some defects in finished appearance, ×: Poor overall appearance. Unable to attach: Under predetermined conditions, it cannot be attached due to insufficient shrinkage.

After the mounted samples were allowed to stand at room temperature for 24 hours, the perforations were cut, and the cutting properties were evaluated as follows. ：: Can be cut straight, Δ: Can be cut, but tears are present in the direction perpendicular to the cutting direction, ×: Torn in the direction perpendicular to the cutting direction, and cannot be cut.

(F) Glass transition temperature Using a DSC measuring apparatus manufactured by PerkinElmer, the temperature was raised to 300 ° C. at a rate of 20 ° C./min in a nitrogen stream, and then 200 ° C.
/ Min at a rate of 20 min / min.
The temperature was raised to 300 ° C. at a speed of minute, and the glass transition temperature (middle point) at that time was determined.

Example 1 A predetermined amount of a mixture of terephthalic acid, ethylene glycol and cyclohexane dimethanol was charged into a stainless steel autoclave, and a polycondensation reaction was carried out in accordance with a conventional method to make the intrinsic viscosity 0.80. By continuing until the temperature reached, a polyester polymer A-1 having a glass transition temperature of 80 ° C. was produced. It was composed of 100 mol% of terephthalic acid units as dicarboxylic acid component units, 70 mol% of ethylene glycol units and 30 mol% of cyclohexanedimethanol units as diol component units.

Similarly, a polyester polymer B- having a glass transition temperature of 55 ° C. and comprising 100 mol% of terephthalic acid units as dicarboxylic acid component units, 75 mol% of ethylene glycol units and 25 mol% of diethylene glycol units as diol component units. 1 was produced.

The polyester polymer A thus obtained
After mixing and drying 95% by weight of -1 and 5% by weight of the polyester polymer B-1, the mixture was melt-extruded on a casting drum having a surface temperature of 35 ° C. using a T-die at a temperature of 265 ° C. to a thickness of 190 μm. Was formed.
Next, the film was stretched 1.2 times in the machine direction at a temperature of 93 ° C. by a roll type longitudinal stretching machine, and then stretched 4.5 times in a transverse direction at a temperature of 88 ° C. by a tenter. The stretched film is subjected to a 10% heat relaxation treatment at 83 ° C.
A shrink film of 0 μm was obtained. Table 2 shows the physical properties of the shrink film.

Example 2, Comparative Examples 1 and 2 Using the polyesters A-1 and B-1 of Example 1, in the same manner as in Example 1, a film was formed at a mixing ratio shown in Table 1.
Each of the polyester mixture was subjected to a 1.2-fold longitudinal stretching treatment, a 4.5-fold transverse stretching treatment, and a 10% thermal relaxation treatment at a temperature higher by 15 ° C., 10 ° C., and 5 ° C. than the apparent glass transition temperature to obtain a 40 μm thick film. I got a shrink film. Table 2 shows the physical properties of the shrink film.

Examples 3 and 4 and Comparative Examples 3 to 6 In the same manner as in Example 1, 95 mol% of terephthalic acid units and 5 mol% of isophthalic acid units as dicarboxylic acid component units, and 1 ethylene glycol unit as diol component units
A polyester polymer C-1 having an intrinsic viscosity of 0.70 and a glass transition temperature of 76 ° C. composed of 00 mol%, 100 mol% of a terephthalic acid unit as a dicarboxylic acid component unit, and 100 mol% of an ethylene glycol unit as a diol component unit. A polyester polymer C-2 having an intrinsic viscosity of 0.70 and a glass transition temperature of 78 ° C. was produced. Also,
In the same manner as in Example 1, a glass transition temperature 6 composed of 100 mol% of terephthalic acid units as dicarboxylic acid component units, 90 mol% of ethylene glycol units and 10 mol% of diethylene glycol units as diol component units.
A polyester polymer D at 8 ° C. was produced.

These polyester polymers and the polyester polymer produced in Example 1 were filmed in the same manner as in Example 1 at the mixing ratios shown in Table 1, and the respective polyester polymers were used in an amount of 15 ° C. from the apparent glass transition temperature.
3. longitudinal stretching at 1.2 ° C, 10 ° C, and 5 ° C higher temperature;
5 times transverse stretching, 10% heat relaxation, thickness 40μ
m shrink film was obtained. Table 2 shows the physical properties of the shrink film.

Example 5 In the same manner as in Example 1, 95 mol% of terephthalic acid units and 5 mol% of adipic acid units were used as dicarboxylic acid component units.
A polyester polymer B-2 having an intrinsic viscosity of 0.80 and a glass transition temperature of 46 ° C composed of 75 mol% of ethylene glycol units and 25 mol% of diethylene glycol units as diol component units was produced.

This polyester polymer and the polyester polymers produced in Examples 1 and 2 were filmed in the mixing ratio shown in Table 1 in the same manner as in Example 1, and the respective polyester mixtures were used to determine the apparent glass transition temperature. Fifteen
3. longitudinal stretching at 1.2 ° C, 10 ° C, and 5 ° C higher temperature;
5 times transverse stretching, 10% heat relaxation, thickness 40μ
m shrink film was obtained. Table 2 shows the physical properties of the shrink film.

[0045]

[Table 1]

Comparative Example 7 In the same manner as in Example 1, an intrinsic viscosity composed of 100 mol% of a terephthalic acid unit as a dicarboxylic acid component unit, 85 mol% of an ethylene glycol unit and 15 mol% of a neopentyl glycol unit as a diol component unit. 0.7
A polyester polymer E having a glass transition temperature of 75 ° C. was produced.

The polyester polymer was formed into a film in the same manner as in Example 1,
1.2 times longitudinal stretching at 4.5 ° C., 4.5 times transverse stretching,
A 10% heat relaxation treatment was performed to obtain a shrink film having a thickness of 40 μm. Table 2 shows the physical properties of the shrink film. Comparative Example 8 In the same manner as in Example 1, an intrinsic viscosity of 100 mol% of a dicarboxylic acid component unit, 72 mol% of an ethylene glycol unit as a diol component unit, 3 mol% of a diethylene glycol unit, and 25 mol% of a cyclohexane dimethanol unit was used. .80 and a glass transition temperature of 76 ° C. to produce a polyester polymer F. This polyester polymer was filmed in the same manner as in Example 1,
At a temperature of 6 ° C. and 81 ° C., a 1.2-fold longitudinal stretching treatment, a 4.5-fold transverse stretching treatment, and a 10% heat relaxation treatment were performed to obtain a shrink film having a thickness of 40 μm. Table 2 shows the physical properties of the shrink film.

[0048]

[Table 2]

As is clear from Table 2, the polyester shrink film of the present invention has the heat shrinkability required for a shrink film, and also has a good finished appearance after mounting and good perforation cutability. On the other hand, in the comparative example, when the heat shrinkage at 100 ° C. is less than 50%, the portion requiring high shrinkage is not sufficiently adhered due to insufficient shrinkage,
Even if the heat shrinkage at 100 ° C. is 50% or more, the temperature dependence of the heat shrinkage near the shrinkage starting temperature, that is, the low shrinkage temperature region of less than 8 ° C., is caused by uneven shrinkage at the time of mounting. Distortion and wrinkles occur, resulting in poor finished appearance.
Further, Comparative Examples in which the proportion of the component (A) polyester added is smaller than that of the Examples, are inferior in perforation cutability.

────────────────────────────────────────────────── ─── Continued on the front page (51) Int.Cl. ⁷ Identification code FI B29L 7:00 B29L 7:00 (72) Inventor Kiyoo Koyama United States of America North Carolina 27408 Greensboro Natchez Trace 1715 (72) Inventor Shoichi Saya Tokyo 1-18-1 Kyobashi, Chuo-ku, Tokyo C-I Kasei Co., Ltd. (72) Inventor Kenji Yabe 1-18-1, Kyobashi, Chuo-ku, Tokyo CI Kasei Co., Ltd. (56) References JP-A-57- 159618 (JP, A) JP-A-1-110931 (JP, A) JP-A-4-193526 (JP, A) JP-A-4-356533 (JP, A) JP-A-3-143619 (JP, A) JP-A-3-142224 (JP, A) JP-A-3-86522 (JP, A) JP-A-3-81338 (JP, A) JP-A-62-91555 (JP, A) JP-A-62-92826 ( JP, A) JP-A-62-121732 (JP, A) JP-A-63-122519 (JP, A) JP-A-63-146940 (JP, A) JP-A-63-150331 (JP, A) JP-A-63-202429 (JP, A) JP-A-63-222845 (JP, A) JP-A-63-309424 (JP, A) JP-A-1-258935 (JP, A) JP-A-63-236623 (JP) JP-A-4-135735 (JP, A) JP-A-4-4229 (JP, A) JP-A-61-203161 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB Name) C08J 5/00-5/24 B29C 61/00-61/10 B29C 55/00-55/30 B65D 65/00-65/46 C08L 67/00-67/08 CA (STN) REGISTRY (STN)

Claims (2)

(57) [Claims] 1. A (A) and a dicarboxylic acid component unit composed mainly of terephthalic acid, ethylene glycol 80 to 60 mol% and polyester 97 ~ composed of a mixed diol component units consisting of cyclohexanedimethanol 20-40 mole% 85 % by weight, (B) a dicarboxylic acid component unit mainly composed of terephthalic acid, and ethylene glycol 85 to
70 mol%, and diethylene glycol 15-30 mol%
A film formed from a polyester mixture of 3 to 15 % by weight of a polyester composed of a mixed diol component unit consisting of: and a film stretched 1.5 to 8 times in at least one direction. 50 in one direction
% Or more and 10% or less in a direction perpendicular thereto ,
The heat shrinkage rate is 1 to 20 in the heat shrinkage curve in the main shrinkage direction.
% Polyester resin shrink film characterized by having a temperature range of 10 ° C. or higher . 2. Polyester 92 comprising (A) a dicarboxylic acid component unit composed mainly of terephthalic acid and a mixed diol component unit composed of 80 to 60 mol% of ethylene glycol and 20 to 40 mol% of cyclohexanedimethanol. 70 % by weight, (B) a dicarboxylic acid component unit mainly composed of terephthalic acid, and ethylene glycol 85 to
70 mol%, and diethylene glycol 15-30 mol%
Polyester 3-15% by weight is composed of a mixed diol component units consisting of a dicarboxylic acid component unit consisting mainly of (C) of terephthalic acid, ethylene glycol units 9
A film formed from a polyester mixture of 5 to 15 % by weight of a polyester composed of a diol component unit containing 5 mol% or more is treated in at least one direction by 1.5%.
8-fold is stretched comprising state, and are 100 ° C. thermal shrinkage of not more than 10% in 50% or more and its perpendicular direction in one direction, the heat shrinkage in the main shrinkage direction of the heat shrinkage curve
A polyester-based shrink film characterized in that the temperature range where is within the range of 1 to 20% is 10 ° C. or more .