Heat-shrinkable polyester film roll and process for producing the same

ES 2 298 362 T3

DESCRIPTION

A roll of heat shrinkable polyester film and a process for producing the same.

Field of the invention

The present invention relates to a film roll of a heat shrinkable polyester film. The present invention relates to a roll of heat shrinkable polyester film having a uniform composition substantially along the entire length or to a roll thereof that is further uniform in heat shrink properties substantially throughout the entire length of the film. the movie. The heat shrinkable polyester film in this roll is characterized in that there is a lower incidence of defective products in product production processes, such as labels, bags or others, and a clearly lower incidence of defects such as insufficient shrinkage, shrinkage shading. , whitening, wrinkling, deformation, uneven shrinkage in the direction orthogonal to the maximum shrinkage direction, etc. in the process of heat shrinkage.

Background technique

A heat shrinkable polyester film is known from JP-A-4117432.

Heretofore, heat shrinkable polyester films (occasionally hereinafter referred to as the film only) have been widely used as products of (cumulative) shrink packaging, shrink labels, seals, etc., for a variety of of containers such as polyethylene terephthalate (PET) containers, polyethylene containers, glass containers, using the heat shrinkage property thereof.

For the production of labels or the like, the following procedures are commonly employed. In fact, a raw polymer in a molten state is continuously extruded into an unstretched film. Subsequently, the unstretched film is stretched and rolled to give a roll of heat shrinkable polyester film. The film on the roll is then unwound and cut into a film of a desired width, which is then rewound on another roll. Subsequently, various characters and figures such as the name of the product and the like are printed on the resulting film. After printing, the film is folded and bonded along both edges by, for example, solvent adhesion, to give a tubular film (in the tube-forming process). Between. Therefore, there are cases in which the sequence of printing and cutting processes is opposite. The tubular film thus obtained can be cut into tubular labels of a desired length, which are subsequently made into bags by joining along one edge of the openings thereof.

Subsequently, the containers covered with the above labels or bags are passed, for example, on a conveyor belt, through a shrink tunnel such as the steam tunnel into which hot steam is blown for heat shrinkage and the tunnel of hot air in which hot air is blown to give the final products (labeled containers) that have the labels or the bags firmly attached to them.

When the variation in the percentage of heat shrinkage of labels, bags, or others is large, occasionally defective labels and bags are produced that do not show an adequate percentage of heat shrinkage in the heat shrinkage process, as that the tunnel is controlled under the same heating conditions during production. As a result, a large variation in heat shrinkage properties leads to worse looking products caused by insufficient shrinkage, shrinkage shading, wrinkling, warping of printed patterns, uneven shrinkage in the direction orthogonal to the maximum shrinkage direction. , etc., which cannot be put on the market.

Typically, labels or bags for a specific product are produced from a single roll of film and therefore a large variation in the heat shrink properties of a film on a roll of film leads to a higher defect fraction in the process of heat shrinkage. Furthermore, when solvent adhesion is employed in the above tube forming process, a large variation in solvent tack in the film supply direction (longitudinal direction) of the film on a roll of film often leads to defects in the appearance of a tubular film produced from the roll of film such as loss of flatness and waviness of the solvent adhesion part of the film due to swelling of the film by penetration of the solvent. When the variation in the adhesiveness of the solvent adhesion of the tubular film is large, the parts joined by the solvent adhesion on labels, bags or the like produced therefrom occasionally separate during the rolling and shrinkage of the film. same around containers in the process of rolling and shrinking or during storage of the final products after shrinkage. In addition, since the tubular film is exposed to high pressure in the tube roll of the previous tubular film, the parts of the tubular film in which there are defects in appearance, such as waviness described above often cause problems of a high incidence of blockage during storage on the roll.

The large variation in adhesiveness of solvent adhesion also leads to problems because, when the tubular film is cut into labels, the cut parts (apertures) are heat fused and as a consequence, the resulting labels cannot be wrapped around containers and because the tubular film becomes difficult to cut, causing defects in the cutting process.

ES 2 298 362 T3

The object of the present invention is to provide a heat shrinkable polyester film roll and a process for producing the same that can solve the various problems in the production processes described above, and therefore decrease the incidence of product defects during label production processes, heat shrinkable bags or the like from a roll of long film and the wrapping and shrinking thereof around containers to produce labeled container products.

Description of the invention

The present invention relates to a film roll of a heat shrinkable polyester film with a length of 500 m or more, as defined in claim 1 and the heat shrinkable polyester film is characterized in that it meets the following requirement (1 ) and the following requirement (2).

(1) When a winding start end of a film that is obtained from a constant region in which the physical properties of the film stabilize in a longitudinal direction is called a first end, and a winding termination end of the film is called referred to as the second end, a first cut-off point of the samples are provided at a position 2 m or less inward from the second end, a final cut-off point of the samples is provided at a position 2 m or less inward from the first end and additionally a plurality of sample cut-points are provided in a range of about 100 m from the first cut-off point; the samples are square samples with a size of 10 cm x 10 cm cut from each of the cut points; and the heat shrinkage percentage of each sample in the maximum shrinkage direction is 20% or more after the respective samples have been immersed in hot water at 85 ° C for 10 seconds, then in water at 25 ° C for 10 seconds and stretch.

(2) When a raw polymer used for the production of the film comprises a main constituent unit and one or more different sub-constituent units thereof and the sub-constituent unit which is present in the greatest amount among all the sub-constituent units, they are denoted primary constituent subunit, the content of the primary sub-constituent unit in each appropriately cut sample from each of the cut-off points described in requirement (1) is more than 7 mole% in 100 mole% of all constituent units and when calculates an average of the content of the primary constituent subunits, the contents of the same of all the samples are in a range of ± 2% in moles with respect to the average content. Furthermore, the main constituent unit of the polyester film is an ethylene terephthalate unit and the primary sub-unit is a unit composed of neopentyl glycol and terephthalic acid and a unit composed of 1,4-cyclohexane dimethanol and terephthalic acid or a unit composed of 1 , 4-butanediol and terephthalic acid or a unit composed of ethylene glycol and isophthalic acid;

and the heat shrinkable polyester film further meets the requirement (6) that when averaging the heat shrinkage percentages in the maximum shrinkage direction of the samples defined in the requirement (1), the shrinkage percentages per heat of all samples are within ± 3% of the mean.

The film roll of the heat shrinkable polyester film of the present invention that meets the requirement (1) above and at least one of the requirements (2) to (5) with the requirements (3) to (5) being described below then it has little variation in film composition along the entire length of the constant region of the film and thus can decrease the incidence of defects in label production processes, bags or the like from the roll of film and can also provide significantly uniform heat shrinkage behavior throughout the entire film. A film roll of a heat shrinkable polyester film that meets the requirement (1) and at least one of the requirements (6) to (8) clearly has little variation in the heat shrink properties of the film, consequently of the heat shrinkage properties of each resulting label, bag or similar, thus allowing to drastically reduce defects in products.

Preferred embodiment of the invention

The present inventors have examined the production processes for labels, bags or the like from the heat shrinkable polyester film described above and the various defects generated in the heat shrink process and have found that these defects do not arise of films prepared from homopolymers, but from films made from polymers that have not only a main constituent unit but one or more sub-constituent units obtained by copolymerization or blending of polymers. Specifically, it was considered that said polymer generated a large variation in the polymer composition in a long film, leading to a variation in the heat shrinkage properties of the resulting products. The present inventors have discovered that the heat shrinkable polyester film roll of the present invention had little variation in composition and heat shrinkage pattern and did not generate the defects described above. Hereinafter, the present invention will be described in detail.

The present invention relates to a roll of heat shrinkable polyester film. The heat shrinkable polyester film roll of the present invention provides heat shrinkable products having excellent heat shrinkage property over a wide range of temperatures, from low to high, having a

ES 2 298 362 T3 excellent appearance with less shading from shrinkage, wrinkling and warping and having excellent gloss and transparency.

The heat shrinkable polyester film in the heat shrinkable polyester film roll of the present invention must satisfy the following requirement (1).

(1) When a start end of a winding of a film than the other party assuming a position 10 m from the start of winding is the first end of the film.

The number of the above constant regions (constant operating regions) is usually 1 per roll of film (along the entire length of the roll of film). But, there are cases where such constant regions are present at multiple sites and in such case, sampling is done only in these constant regions. The above constant region can be evaluated, for example, by measuring the percentage of heat shrinkage in the maximum shrinkage direction of the film according to the method to be described below. Specifically, a region in which a difference in the percentage of heat shrinkage is in a range of less than about 20% (a difference between the maximum value and the minimum value in a plurality of samples is less than about 20% ) can be considered the constant region.

The sampling method will be described below. When the start end of winding a film in a constant region on a film roll is called the first end and the ending end of winding thereof the second end, the first cutting point of the samples is provided at a position to 2 m or less inward from the previous second end, the end cut point is provided at a position 2 m or less inward from the former first end and further a plurality of sample cut points at an interval of approximately 100 m from the first cut point and therefore , samples are collected from sample points provided in approximately equal interval over the entire length of the film in the constant region. In this document, the expression "an interval of approximately 100 µm" means that the samples can be cut in an interval of 100 µm ± approximately 1 µm.

The above sampling method will be described in more detail. For example, in a case of a roll having a heat shrinkable film 498 m in length and in the constant region along the entire length, a first sample (i) is cut from a part of the film at 2 m or less than the termination end of the winding (the second end). The area of ​​the sample will be appropriately determined based on the properties to be measured. Subsequently, the second sample (ii) is cut at a position approximately 100 m from the position where the first sample (i) is cut. Similarly, the third sample (iii) is cut at a position at approximately 200 m, the fourth sample (iv) at approximately 300 m, and the fifth sample (v) at approximately 400 m from the position of the first sample. In this document, since the remaining film is shorter than 100 µm, the sixth sample (vi) (end) is cut at a position from the film 2 m or less from the start end of the winding (the first end).

The above requirement (1) of the present invention is that the percentage of heat shrinkage in the maximum shrinkage direction of each sample cut in this way should be 20% or more. A heat shrinkable polyester film having the percentage of heat shrinkage below 20% is not favorable as the percentage of heat shrinkage thereof is not sufficient to firmly bond to a container when the container wrapped with the film is heat shrunk, to avoid the generation of appearance defects. More preferably, the percentage of heat shrinkage is 40% or more and much more preferably 60% or more.

In this document, the percentage of heat shrinkage in the maximum shrinkage direction means a percentage of heat shrinkage in a direction in which the shrinkage of a sample is the greatest and the maximum shrinkage direction is a direction that has the side shorter after shrinkage of the trimmed square specimen. Percent heat shrinkage (%) is a value determined by immersing a 10 cm x 10 cm sample in hot water at 85 ° C ± 0.5 ° C for 10 seconds without load to induce heat shrinkage, Immediate immersion in water at 25 ° C ± 0.5 ° C for 10 seconds, measuring the length of the sample in the direction of maximum shrinkage and calculating according to the following equation (hereinafter, the percent heat shrinkage in the direction of maximum shrinkage measured in this condition will simply be called percent heat shrinkage).

Heat shrinkage percentage (%) = 100 x (Length before shrinkage - Length after shrinkage) / (Length before shrinkage).

The requirement (2) of the present invention is that when a raw polymer used for the production of the film comprises a main constituent unit and one or more different sub-constituent units thereof and the sub-constituent unit which is present in the greatest amount between all subunits is obtained from a constant region in which the physical properties of the film stabilize in a longitudinal direction is called the first end and one end of winding termination thereof is called the second end, a first film specimen cut-off point is provided at a position 2 m or less inward from the second end, a final specimen cut-off point is provided at a position 2 m or less inward from the first ex4

ES 2 298 362 T3 section and a plurality of additional sample cutoffs are provided in a range of about 100m from the first cutoff; the samples are square samples with a size of 10 cm x 10 cm cut from each of the cut points; all samples have a heat shrinkage percentage of 20% or more in a maximum shrinkage direction after the respective samples have been immersed in hot water at 85 ° C for 10 seconds, subsequently in water at 25 ° C for 10 seconds and have been stretched.

The expression, "a constant region in which the physical properties of the film are stabilized", in the above requirement (1) will be described first. "A constant region in which film properties are stabilized" is a region where the film is stably produced in extrusion and stretching processes and therefore has substantially uniformly controlled physical properties. The present invention is based on a technical concept to standardize an amount of the primary sub-constituent unit and other properties to a level higher than the conventional level in a long film produced in a constant state in extrusion and stretching processes. In actual operation, the composition of the film may vary depending on the supply method of the raw materials and the extrusion condition used for the production of the same and the concept of the present invention for uniformity, it is not intended to apply to the films that are produced in an unstable condition of material supply and / or extrusion processes. Therefore, it is assumed as a prerequisite that the film sampling for the evaluation of particular properties to be uniform is carried out only in a region of the film that occurs in a stable state in the extrusion and stretching processes, that is, "a constant region."

Therefore, for example when a first film part about 10 m in length from the start end of winding is not produced in the constant state, sampling is not performed in this part, but in constitutive it is called the primary constituent subunit. , the content of the primary sub-constituent unit in each appropriately trimmed sample from each of the cut-off points described in requirement (1) is 7 mole% or more in 100 mole% of all constituent units and when An average of the content of the primary constituent subunit is calculated, the contents of the same of all the samples are in a range of ± 2% in moles with respect to the average content.

In this document, "constituent unit" refers to a repeating unit formed in a condensation reaction of one mole of a polybasic carboxyl acid component and one mole of a polyhydric alcohol component used as starting materials; the "major constituent unit" to a unit present in an amount of 50 mole% or more in 100 mole% of all constituent units; the "sub-constituent units" to all units other than the "main constituent unit"; and the "primary constituent subunit" to a unit present in the greatest number of the "constituent subunits". respectively.

In requirement (2), the raw polymer to be used for the production of the polyester film contains one or more sub-constituent units, as well as the main constituent unit. The constituent subunits are essential to provide film properties different from those determined by the main constituent unit, especially heat shrinkage and solvent adhesion properties. The film containing the main constituent unit and the sub-constituent units shows excellent heat shrinkage properties over a wide temperature range. The film also has excellent solvent adhesion property.

The primary sub-constituent unit is the most favorable unit among the sub-constituent units for improving the properties of the resulting film and therefore, it is required to be contained in an amount of 7 mole% or more in 100 mole% of all constituent units. Therefore, the content (mole%) of the above primary sub-constituent unit in each sample trimmed by the sampling method described above should be 7 mole% or more. When the content is below 7% by mole, it is not favorable as there are cases where the effect of the primary sub-constituent unit cannot be sufficiently exerted. The lower limit of the content is more preferably 8% by mole and more preferably 10% by mole.

The raw polymer of the film can contain other sub-building blocks as well as the primary sub-building unit. In such case, the lower limit thereof is, but is not limited to, preferably 5 mole% or more in 100 mole% of all the constituent units to express the beneficial effect on the properties. An excessive amount of the sub-constituent units in the raw materials results in a decrease in the main constituent unit of said properties of the film, such as anti-tear property, tensile strength and heat resistance, which leads to deterioration of these. properties. Therefore, the upper limit of the total constituent subunits including the primary constituent subunit is preferably 50% by mole, more preferably 40% by mole, and most preferably 30% by mole.

The main constituent unit is an ethylene terephthalate unit which is composed of ethylene glycol and terephthalic acid, as it is excellent in anti-breaking properties, tensile strength and heat resistance, etc. of the resulting film. The primary constitutive subunit is a unit that is composed of 1,4-cyclohexane dimethanol and terephthalic acid or a unit that is composed of neopentyl glycol or terephthalic acid or a unit that is composed of 1,4-butanediol and terephthalic acid, since each one of them has the required heat shrinkage potential and exerts heat shrinkage at a low temperature. The other sub-constituent units are preferably selected from the units listed above as a primary sub-constituent unit excluding the unit employed as the primary sub-constituent unit. More specific examples of polyester constituent units will be described in more detail below.

ES 2 298 362 T3

In requirement (2), the variation in the content (mole%) of the above primary sub-constituent units, furthermore, should be small. The object of the present invention is to provide a roll of film having uniform film properties throughout the entire length of the constant region. Variation in the content of the primary sub-constituent used for property improvement in the long film leads to variation in solvent adhesion and heat shrink properties thereof and therefore results in frequent incidence of defects in the tube forming processes and in the rolling and shrinkage process. Therefore, when the contents of the primary sub-constituent unit are determined in a plurality of samples cut out with the sampling method described above and an average thereof is calculated, the contents (% by mole) of the sub-constituent unit Primary of all samples must be within ± 2% by mole of the mean content in requirement (2).

The content of the primary constituent subunit can be determined, for example, by NMR or the like. For the measurement of the content of the primary constituent subunit by NMR, only an amount of the sample of about 30 mg / per measurement is required. Typical procedures for NMR measurement are as follows.

(i) A film sample (approximately 30 mg) is dissolved in a mixture of chloroform D (produced by Euriso-top) and trifluoroacetate D1 (produced by Euriso-top) at a ratio of 10:01 (volume ratio) , to give a sample solution.

(ii) The sample solution is analyzed by proton NMR ("GEMINI-200"; produced by Varian) under a temperature condition of 23 ° C and an integration number of 64.

(iii) The composition of the sample is determined from the maximum proton intensity.

When determining the contents of the primary constituent subunit of all the samples, the mean is called A (% in moles) and the content of the sample (i) is called B1 (% in moles), the expression in the requirement (2 ) "In a range of ± 2% in moles with respect to the mean content", means that a value of | A - B1 | [an absolute value of (A - B1)] must be below 2 (% in moles) and with respect to the contents B2 to B6 (% in moles) for samples (ii) to (vi), the values ​​of | A - Bn | they must also be less than 2 (mole%). In other words, requirement (2) is fulfilled when the difference between the maximum value Bmax in Bn and the value A and the difference between the minimum value Bmin in Bn and the value A are both in a range of ± 2% in moles .

Decreasing the variation in the content of the primary sub-constituent unit in a heat shrinkable film of a roll leads to increased stability in solvent adhesion tack and less incidence of problems in the tubing process. It also leads to a lower incidence of problems in the cutting process. Additionally, since it also leads to a decrease in the variation in the heat shrinkage properties of labels, bags and the like, thus reducing the incidence of problems in the winding and shrinkage processes and therefore a marked decrease. of the defective fractions of the final products. The variation in the content of the primary sub-constituent unit is preferably in a range of ± 1.5% by mole with respect to the mean content, more preferably ± 1% by mole.

It is preferable to also have less variation in the content of the other constituent subunits, for the production of long films that have uniformity in physical properties throughout the entire length of the constant region. The third requirement (3) of the present invention defines a requirement for the secondary sub-constituent unit, present in the film in a second higher amount with respect to the primary sub-constituent unit. Specifically, the requirement (3) is when a raw polymer used for the production of the film comprises a main constituent polymer and two or more different sub-constituent units thereof and the sub-constituent which is present in the second largest amount among all the sub-units constitutive is called secondary constitutive subunit, the content of the secondary sub-constituent unit in each appropriately trimmed sample from each of the cut-off points defined in requirement (1) is 5 mole% or more in 100 mole% of all constituent units and when An average of the content of the secondary constituent subunit is calculated, the contents of the same of all the samples are in a range of ± 2% in moles with respect to the average content.

The secondary constituent subunit is required to be present in the film in an amount of 5 mole% or more to exert the effect. The upper limit of the content is not limited, but the content of all the sub-constituent units including the primary sub-constituent unit is preferably set to be less than 50% by mole. As described above, this is due to a decrease in the content of the main constituent unit leading to decreases in physical properties, such as tensile strength.

Measurement of the content of the secondary sub-constituent unit can be performed according to the procedures for the primary sub-constituent unit. The contents of the secondary constitutive subunit are preferably in a range of ± 3% by mol with respect to the average content. More preferably, they are in a range of the mean ± 2% by mole and more preferably the mean ± 1% by mole. By suppressing the variations of the contents of the primary sub-constituent unit and the secondary sub-constituent unit, it becomes possible to provide the film uniformity in the composition of the resulting film in the longitudinal direction of the film. The requirement (4) of the present invention defines a requirement for the variation of the solvent adhesion resistance, one of the physical properties that reflects the uniformity of the film composition in its constant region.

ES 2 298 362 T3

Specifically, the requirement (4) of the present invention is that with respect to a tubular film roll which is obtained by performing the steps of cutting the film in the constant region having stable physical properties along the longitudinal direction of the film in a certain inner part in a transverse direction in film strips, folding the film strip transversely to overlap the corresponding transverse edges of the film strip, bonding the edges by using 1,3-dioxolane as an adhesion solvent to produce a tubular film and winding the resulting tubular film into a flattened state, when a first sample cut point of the tubular film roll is provided at a position 2 m or less inward from a terminating end of the tubular film roll;

an end cut point is provided at a position 2 m or less inward from a start end thereof;

a plurality of additional sample cut-offs are provided in an interval of approximately 100 m from the first cut-off point;

the tubular sample obtained at each cut point is cut open to a film sample with a width of 15 mm;

The film sample is placed in a tensile tester having tool holders arranged at a distance of 50 mm such that the solvent adhesion part of the film sample is located in the center between the tool holders and;

a solvent adhesion strength of the film sample is measured at a temperature condition of 23 ° C and at a tensile test speed of 200 mm / min., the solvent adhesion strength of each film sample is 1 N / 15 mm width or more, and when a mean solvent adhesion strength is calculated, the solvent adhesion forces of all film samples are within ± 2 N / 15 mm width relative to average.

In the above requirement (4), the samples for the measurement of the solvent adhesion resistance are prepared according to the following procedures. First, a roll of heat shrinkable film is placed before shrinkage in a controlled environment up to a temperature of 30 ± 1 ° C and a relative humidity of 85 ± 2%. After 250 hours of storage, in a tube forming machine, the film on the above film roll is coated with 1,3-dioxolane in a line with a width of 2 ± 1 mm, slightly inwards from a end of a surface of the same (amount of coating: 3.0 ± 0.3 g / mm²), and immediately the film is folded such that the edges of the film adhere to each other, thereby providing a tubular film. The tubular film is flattened and rewound into a roll. The first cut-off point of the samples is provided at a position 2 m or less inward from the termination end of the winding, the final cut-off point is provided at a position 2 m or less inward from the start end from the winding and additionally provided a plurality of sample cut points at an interval of approximately 100 m from the first cut point. Meanwhile, the percent heat shrinkage of the sample film in the vicinity of each cut point is determined to confirm that the film is in the constant region where the physical properties of the film are stable. The size of the sample for the measurement of solvent adhesion resistance is not particularly limited, but since the longitudinal direction of the tubular film corresponds to the transverse direction of the sample and the width of the sample is 15 mm, it is favorable to cut a sample with a width of 150 mm or more along the longitudinal direction so that about 10 samples can be obtained. Each of the tubular samples thus obtained is then cut in the area except for the solvent adhesion part to give a film-shaped sample with a length of about 100 mm and a width of 15 mm. The film sample is used for the measurement of solvent adhesion strength. It is desirable to prepare approximately 10 samples for each of the cut points.

Solvent adhesion strength can be determined by adjusting the sample such that the solvent adhesion portion of the sample is placed in the center between the tensile tester tool holders (a distance between tool holders of 50 mm) and performing the test. tensile in a temperature condition of 23 ° C, a tensile test speed of 200 mm / min. An average of the solvent adhesion resistance is calculated with respect to each cut-off point (when 10 samples were prepared and their solvent adhesion strengths were measured, an average of 10 samples), consider that the average represents the solvent adhesion strength of each cut point. Additionally, an average of the solvent adhesion strength of all samples is also calculated.

To satisfy requirement (4), the solvent adhesion strengths of all samples must be 1 N / 15 mm wide or more. Insufficient solvent adhesion strength below 1N / 15mm width causes the occurrence of defects such as adhesion part separation after the tubular film has been converted into products such as labels and bags. The lower limit of solvent adhesion strength

ES 2 298 362 T3 is more preferably 1.5 N / 15 mm wide or more. Alternatively, too strong solvent tack occasionally causes defects in appearance, for example loss of flatness and waviness of the solvent adhesion portion of the film due to swelling of the film resulting from solvent penetration and thus the solvent adhesion strength of all samples is favorably 8.0 N / 15 mm width or less, preferably 7.0 N / 15 mm width or less. Meanwhile, the reason for the solvent adhesion strength to be expressed in a unit of "N / 15mm width" is that the width of the test sample is 15mm.

In addition to the above to meet requirement (4), when averaging the solvent adhesion strength of all samples, all solvent adhesion strengths of all samples must be within ± 2 N / 15 mm wide compared to the average. A film that does not meet this requirement has areas where the solvent adhesion strength is insufficient and areas where it is too great. Therefore, said tubular films obtained by solvent adhesion are not favorable since the areas thereof in which the solvent adhesion strength is not sufficient are easily separated, while the areas in which the adhesion strength of The solvent is too large and causes defects in the appearance of the products due to the loss of flatness due to the swelling of the adhesion part. The solvent adhesion strength of each sample is preferably in a range of the mean ± 1.8 N / 15 mm width, more preferably the mean ± 1.6 N / 15 mm width.

The absolute value of the mean of the solvent adhesion strength of each sample is favorably 2.5 N / 15 mm width or more. It is preferably 3N / 15mm wide or more and more preferably 3.5N / 15mm wide or more.

By suppressing the variation of solvent adhesion strength of a long film in the range described above, it becomes possible to decrease the incidence of defects, insufficient in solvent adhesion strength or of worse appearance, in products such as labels. and bags produced from tubular films which, in turn, are produced from the above film by solvent adhesion.

Although 1,3-dioxolane is used as the adhesion solvent to determine the solvent adhesion strength, other solvents can be used for the actual production of the tubular films. More specifically, examples of the solvent include aromatic hydrocarbons such as benzene, toulene, xylene, trimylethylbenzene, etc., halogenated hydrocarbons such as methylene chloride, chloroform, etc .; phenols such as phenol, etc .; furans such as tetrahydrofuran, etc. and mixtures thereof.

Additionally, by suppressing the variations in the content of the primary sub-constituent unit and the secondary sub-constituent unit, it becomes possible to decrease the variation in the glass transition temperature. The requirement (5) of the present invention defines the variation in the glass transition temperature which represents the uniformity in the composition of the film in the constant region. In fact, the requirement (5) of the present invention is that when a glass transition temperature of the appropriately trimmed sample is determined from each of the cut-off points defined in requirement (1) of claim 1 and is calculates an average of the glass transition temperatures, the glass transition temperatures of all samples are within ± 4 ° C of the mean.

A film that has a large variation in glass transition temperatures along the longitudinal direction provides a tubular film that has a large variation in Tg along the longitudinal direction. The large variation in Tg often causes cut defects in the tubular film label cutting process, as parts having a high Tg cannot be cut easily. On the other hand, during a long operation of the slitting machine in the slitting process, the slitting blades in the slitting machine gradually heat up, which causes heat fusion of a part having low Tg in the tubular film. in the cut region and therefore results in aperture defects of the resulting labels. Therefore, requirement (5) defines that the variation in the Tg of the long film must be in a range of ± 4 ° C from the mean.

The method for obtaining samples for Tg measurement in requirement (5) is the same as that described in requirement (1). 10 mg of the sample is sufficient for the Tg measurement. Specifically, a sample cutout (10 ± 1 mg) is heated at 300 ° C for 2 minutes and then immediately quenched in liquid nitrogen. The sample is placed and analyzed in a differential scanning calorimeter (DSC) and the Tg can be determined from a DSC standard obtained in the above equipment by increasing the temperature from -40 ° C to 300 ° C at a rate of 20 ° C / min. The glass transition temperature (Tg) is a temperature at an intersection of the tangent lines of the endothermic onset curve of the DSC pattern before and after the endothermic onset curve.

Since a long film on a roll meeting requirement (5) above has a high level of uniformity in Tg along the longitudinal direction of the film, when the film is cut and folded into a long tubular film, the The resulting tubular film also has a high Tg uniformity along the longitudinal direction. Therefore, when the tubular film is further cut into a plurality of labels, it becomes possible to avoid heat melting in the cutting region having a low Tg and to avoid the incidence of defects in the apertures of the resulting labels. Additionally, this also makes it possible to avoid the incidence of cutting errors in a part having high Tg and increase the overall throughput in the label production process.

ES 2 298 362 T3

The film roll of the present invention is preferably a film roll of a film that meets two or more of the requirements (2) to (5) as well as the requirement (1), more preferably of a film that meets all of the requirements. from (1) to (5).

The long film of the present invention has a low variation in the composition thereof as described above, decreasing the frequency of the incidence of defects in the solvent adhesion process, the cutting process and the heat shrink process. . Furthermore, to obtain a film in which the variation in heat shrinkage properties is more rigorously controlled, the film meets the requirement (6) below and optionally the requirement of (7) or (8).

The requirement (6) is that when the mean heat shrinkage percentage in the maximum shrinkage direction of the samples is calculated as described in requirement (1), the heat shrinkage percentage of each sample is in a range ± 5% from the mean.

The long film of the present invention has the heat shrinkage percentages in the maximum shrinkage direction of 20% or more as described in requirement (1). A film that additionally meets the above requirement (6) that the percentage of heat shrinkage of each sample is in a range of the mean ± 5% is uniform in the percentage of heat shrinkage along the entire length of the film. herself and therefore, leads to a decrease in the incidence of defects in the winding and shrinkage process and to a drastic drop in the defective fraction of the final products due to the small variation in the percentage of heat shrinkage of the respective products such as labels, bags etc. . The variation in the percentage of heat shrinkage is preferably in a range of the mean ± 3% and more preferably the mean ± 2%.

The requirement (7) is that when a heat shrinkage stress value in the maximum shrinkage direction of each of the samples trimmed from the cutoff points described in requirement (1) is determined under a temperature condition of 90 ° C, a hot air flow rate of 5 m / sec., A sample width of 20 mm and a distance between tool holders of 100 mm, the maximum heat shrinkage stress values ​​for all samples are 3.0 MPa or more and when averaging the maximum heat shrinkage stress values, the maximum heat shrinkage stress values ​​for all samples They are in a range of ± 1.0 MPa from the mean.

In this document, the maximum value of heat shrinkage stress is specifically determined as follows.

(1) A sample with a length of 200 mm in the maximum shrinkage direction and a width of 20 mm is prepared.

(2) A hot air oven is heated in a tensile tester mounted with a hot air oven (eg Tensiron manufactured by Toyoseiki) to 90 ° C.

(3) The hot air supply is cut off and the sample is placed in the heating oven. The distances between the corresponding tool holders are 100 mm (constant).

(4) After the door of the heating oven was closed immediately and the supply of hot air was interrupted (90 ° C, at a speed of 5 m / s), the heat shrinkage stress was measured.

(5) The maximum value obtained from the resulting graph of heat shrinkage stress was considered as the maximum heat shrinkage stress value (MPa).

A film with the maximum heat shrinkage stress value less than 3.0 MPa is not favorable as the film often causes appearance defects due to insufficient shrinkage stress and insufficient anti-break property problems due to insufficient strength. mechanics of it. The lower limit of the maximum value of the heat shrinkage stress is more preferably 3.5 MPA and furthermore preferably 4.0 MPa. Furthermore, from maximum heat shrinkage stress values ​​obtained as described above, an average is calculated and the variation of the maximum heat shrinkage stress values ​​is determined. When the variation of the maximum values ​​of heat shrinkage stress is in a range of ± 1.0 MPa to ± 0.5 MPa from the mean, the defective fraction in the winding and shrinkage process can be decreased by adjusting accordingly. appropriate condition. Furthermore, the variation in the maximum heat shrinkage stress values ​​is in a range of the mean ± 0.5 MPa, the above adjustment is not required and products such as labels, bags and the like with shrinkage properties can be produced. excellent heat. The variation in the maximum heat shrinkage stress values ​​is more preferably in a range of ± 0.4 MPa from the mean. Meanwhile, the absolute value of the mean of the maximum heat shrinkage stress values ​​is preferably 4.0 MPa or more. The lower limit of the mean is more preferably 4.5 MPa and further preferably 5.0 MPa.

Requirement (8) is that when each 10 cm x 10 cm square sample trimmed from each of the cutoff points described in requirement (1) is immersed in hot water at 85 ° C for 10 seconds, then in water at 25 ° C for 10 seconds and stretched, the heat shrinkage percentages in the direction orthogonal to the maximum shrinkage direction of all samples are 7% or less and when averaging of the

ES 2 298 362 T3 percentages of heat shrinkage in the orthogonal direction, the percentage of heat shrinkage in each sample in the orthogonal direction falls within a range of ± 2% with respect to the mean.

The requirement (8) is a requirement of a film that does not have any appearance defects, that is, uneven shrinkage in the direction orthogonal to the maximum shrinkage direction. In this document, "uneven shrinkage" means that the length of the label after shrinkage is uneven and leads to an appearance defect. For example, an uneven label rolled and contracted around a PET bottle or the like has a downwardly falling top edge line of the label or an upwardly curving bottom edge line.

The percentage of heat shrinkage in the direction orthogonal to the maximum shrinkage direction (orthogonal heat shrinkage) above 7% often produces appearance defects due to uneven shrinkage. The orthogonal heat shrinkage percentage is more preferably 6% or less and further preferably 5% or less.

Additionally, suppressing the variation of the percentages of heat shrinkage in the orthogonal direction to the maximum shrinkage direction of a heat shrinkable film roll in a range of ± 2% with respect to the mean of the orthogonal heat shrinkage, the variation in heat shrinkage of labels, bags or the like becomes less, thus leading to a decrease in the incidence of appearance defects due to uneven shrinkage in the winding and shrinkage process and to a drastic drop in the defective fraction of the final products. The variation in the orthogonal heat shrinkage percentages is preferably in a range of ± 1.8% with respect to the mean of the heat shrinkage percentages, more preferably from the mean ± 1.5% and much more preferably from the mean ± 1%.

A long film meeting requirement (1) as well as requirement (6) has little variation in heat shrinkage properties thereof; allowing a drastic drop in the incidence of defects due to insufficient shrinkage, shrinkage shading, whitening, wrinkling, warping, uneven shrinkage, etc. A film that meets the requirement (1), the requirement (6) and the requirement (8) is more preferable and a film that meets the requirement (1) and all the requirements of (6) to (8) is even more preferable. .

Since a low variation in the composition of the film is favorable to suppress the variation in the heat shrinkage properties, the film according to the invention further fulfills the requirement (2). A film that meets the requirement (1), two or more of the requirements (2) to (5) and two or more of the requirements (6) to (8) is more preferable and a film that meets all the requirements (1 ) to (8) is more preferable.

The present invention also comprises a process for producing the roll of film, as described in claim 6.

Hereinafter, a favorable process for producing the long film having uniform compositions and uniform heat shrinkage properties along the entire length will be described.

Generally, heat-shrinkable polyester films are produced using the method of combining a main constituent unit with one or more sub-constituent units and thereby modulating their properties, for example by mixing two or more polymers of different types and compositions or copolymerizing a plurality of monomers, for the purpose of obtaining a polymer having balanced heat shrinkage properties and physical properties such as tensile strength. To introduce one or more constituent subunits into the film, a method is often practiced to use a single copolymer prepared by copolymerization and to blend a plurality of homopolymers or copolymers of different types.

In the method using a single polymer, a large variation in film composition is less likely to occur from the resulting long film wound on a roll and therefore it can be easy to produce a roll of film that meets the requirements. (2) to (5) of the present invention, but difficult to produce a roll of film that meets the requirements (6) to (8) since the heat shrink properties often vary according to the stretching condition.

On the other hand, the mixing method is widely used in the industry, as it allows a simple modification of the film properties only by changing the proportion of raw polymer mixture and therefore it is adaptable for the industrial production of a diversity of movies. Since it is known that the variation in the composition of a film on a roll is greatest when mixed polymers are used as raw materials, it is favorable to employ the following procedures to obtain the roll of film that meets the requirements defined herein invention.

(i) Uniformization of the shapes of the pieces

In the blending method, usually a plurality of raw polymer pieces of different compositions are mixed in a hopper and conveyed into an extruder, where the polymer is melt extruded into a film. In a case where three polymeric pieces are used as raw polymers, for example, the pieces are respectively supplied continuously or intermittently, in three separate hoppers. Then the polymeric pieces are transported, by means of a hopper with buffer if necessary, finally to a

ES 2 298 362 T3 hopper immediately above an extruder (hereinafter referred to as the end hopper for convenience), in which the pieces are mixed. The mixed blanks are fed into the extruder quantitatively according to the discharge rate and then processed into a film. The present inventors have discovered the uneven supply of raw pieces, that is, that the composition of the pieces supplied from the final hopper into the extruder varies depending in one case on whether the final hopper contains a large quantity of pieces or a small number of pieces, based on the capacity and the shape of the final hopper. The problem is especially important when the polymeric pieces have different shapes or densities. Consequently, the uneven supply of blanks leads to a large variation in the polymer composition of the resulting long film.

Therefore, by producing a heat shrinkable film roll including a step of mixing a mixture of a main polymer used in greater quantity and one or more polymers of different compositions with respect to the main polymers and extruding the resulting mixture, it is favorable adjusting the shapes of the plurality of polymeric pieces to suppress uneven supply of raw pieces to the final hopper, as a means of reducing the variation in composition of the polymeric constituents of the resulting film and, therefore, producing a film that meets the requirements described above, which has a low variation in the properties thereof.

Polyester film blanks are usually produced in a process in which a polymer in the molten state after polymerization is extruded as strands, which are immediately cooled in water and cut on a strand cutter. Therefore, the polyester pieces are usually cylindrical elements having an elliptical cross section. The present inventors have found that when the major and minor axes (mm) of the elliptical cross section and the lengths of the raw polymeric pieces of the secondary constituents have to be mixed with the polymeric pieces of the main constituent are, respectively, in intervals from the mean ± 20% of the raw pieces of the main constituent, the incidence of uneven supply of raw polymer chunks as described above may decrease. More preferably those values ​​are, respectively, in the ranges of the mean ± 15%.

When there is a large difference in the size of the pieces, the smaller pieces tend to sink as the pieces move down the final hopper, making the proportion of the larger pieces greater when the amount of pieces remaining in the hopper. end decreases, resulting in uneven supply of raw materials. However, by using the pieces that meet the above requirement, the uneven supply of raw materials can be reduced and consequently a long film having a uniform film composition can be obtained.

(ii) Optimization of the hopper shape

Since an extruder is used to produce a film, optimizing the final hopper shape is also a favorable step to obtain a film having a uniform composition. Specifically, when the tilt angle of the funnel-shaped hopper is less than 65 °, only small pieces can be moved downward, resulting in uneven supply of raw materials. Using a hopper that has the tilt angle of more than 65 °, it becomes easy to move larger and smaller pieces similarly down the hopper, keeping the top edge of the contents (pieces) horizontal and decreasing the uneven supply of materials in stupid. The angle of inclination is more preferably 70 ° or more. In this document, the tilt angle of the hopper is an angle between an oblique line of the hopper and a horizontal line. A plurality of hoppers can be installed upstream of the final hopper and in such case, the angles of inclination of all hoppers are favorably greater than 65 ° or more, more preferably 70 ° or more.

(iii) Optimization of the hopper volume

As a means of decreasing uneven supply of raw materials to the hopper, it is also advantageous to optimize the volume of the hopper. The optimum capacity of the hopper is in a range of 15 to 120% by mass of a discharge speed. Due to the fact that when the hopper does not have the capacity of about 15% by mass or more, the stable supply of the raw materials becomes difficult, whereas in a hopper that has too large a capacity, the mixing of pieces into Raw remains in the hopper for a long time, possibly causing uneven supply of the pieces. The volume of the hopper is more preferably in a range of 20 to 100% by mass of the discharge rate of the extruder per hour.

(iv) Reduction of fine dusts

It is also advantageous to reduce the amount of fine powders that are produced by mutual grinding of the pieces or the like to obtain a long film having a uniform composition. Since fine dusts also contribute to the incidence of uneven supply of raw materials, it is favorable to remove fine dusts generated in production processes and reduce the amount of fine dusts in the hopper. The proportion of the fine powders in the raw materials (100%), is favorably controlled at 1% by mass throughout the processes before the blank reaches the extruder, more preferably at 0.5% mass. Specifically, the fine powders can be removed, for example, by sieving the pieces and air transporting the rough pieces through a cyclone air filter after cutting the pieces on the strand cutter.

ES 2 298 362 T3 (v) Uniformization of the film surface temperature in the stretching process

Factors contributing to variation in the heat shrink properties of a long film include variation in operational parameters in the stretching process, as well as variation in the polymer compositions that make up the film described above. Therefore, it is advantageous to control a temperature variation in the stretching process and therefore to decrease as much as possible the surface temperature variation of the film being stretched.

In the case of a monoaxial stretching of a polyester film in the transverse direction on a tensioner, there are the stages: the preheating stage before stretching, the stretching stage, the heat treatment stage after stretching, the relaxation stage and the subsequent stretching stage, and so on. Especially, the thermal control in the preheating stage, the stretching stage and the heat treatment stage after the stretching stage is essential and it is favorable to control the variation of the surface temperatures of the film measured at any point in these previous stages. in a range of ± 1 ° C with respect to medium temperature, to produce the film having uniform heat shrinkage properties. It is more favorable to control the temperature in a range of the mean temperature ± 0.5 ° C.

Variations in temperature in the preheating, stretching and heat treatment stages greatly affect the variation in the percentages of heat shrinkage (in the direction of maximum contraction as well as in the direction orthogonal to it) and the maximum values ​​of the heat shrinkage. heat shrinkage stress of the resulting stretched film. Therefore, the smaller the variation in the surface temperature of the film in these stages, the more uniform the heat shrink properties of the stretched film will be, since the film is stretched and heat treated at the same temperature at along the entire length. Needless to say, minor variations in film surface temperature are also favorable during relaxation and in the subsequent stretching step.

Variation in film surface temperatures can be reduced, for example, by using an inverter-mounted blower that can tightly control the supply of hot air to be used for film heating or by using equipment that can suppress the variation in hot air temperature by using low pressure steam of 500 kPa or less (5 kgf / cm² or less) as a heat source.

The variation in the surface temperature of the film measured at any point is a variation in the surface temperature of the film measured continuously during the production of the film at a point, for example, 2 m from the entrance of the stretching process using for example a non-contact surface thermometer. After the production of 1 roll of film, the average temperatures can be calculated. If the resulting variation in the surface temperature of the film is in a range of ± 1 ° C with respect to the mean temperature, it is considered that the film is stretched in the same condition along the entire length of the film in the constant region and having little variation in heat shrinkage properties.

In order to produce a long film having uniformity in composition, only one of the above procedures (i) to (iv) will be required. It is more favorable to employ two or more of the four procedures and more preferably to employ all of the procedures (i) to (iv). Consequently, it is favorable to extrude a film, reducing fine powders by process (iv), using blanks of sizes defined in procedure (i), mixing each blank in a hopper having an angle of inclination of 65 ° or more as described in procedure (ii) and that has a volume that meets the requirement of procedure (iii), supplying the mixed pieces continuously into the extruder and extruding at a controlled discharge rate. Additionally, the raw pieces can be premixed and supplied, via intermediate (buffered) hoppers, to the final hopper and then supplied to the extruder. A plurality of raw pieces can be mixed in a hopper, quantitatively supplying the raw or premixed pieces thereto, for example by use of a mixer or the like. In the latter case, it is favorable to take into account the size of the raw pieces so that uneven supply of the mixture cannot occur during the discharge.

It is favorable to employ the above procedure (v) as well as the above procedures (i) to (iv) to suppress the variation in the heat shrink properties of the long film.

Specific examples of polyester film production are described below. First, raw pieces processed in a way to meet the description in procedure (i) are dried in a dryer such as a hopper dryer, a vane dryer, etc., or in a vacuum dryer and are extrude into film at 200-300 ° C. Alternatively, the undried polyester raw materials are processed in a slant-type extruder to a film while simultaneously removing the water within. Extrusion can be carried out by any method known in the art, such as the T-die method, a tubular method, and the like. The extruded polymer is cooled (quenched) on a mold roll to give an unstretched film. The "unstretched film", meanwhile, contains the film on which a pull is applied to transport the film.

The unstretched film is then subjected to a stretching treatment. The unstretched film cooled on the previous casting roll can be successively stretched in the next stretching process or it can be rolled once on a roll and then stretched.

ES 2 298 362 T3

Since it is practical from a production efficiency point of view to achieve the object of the present invention that the maximum shrinkage direction is the transverse direction (width) of the film, an example of the method of stretching in which the maximum contraction direction is the transverse direction. But it is also possible to stretch the unstretched film to give a film having the maximum shrinkage direction identical to the machine direction (length) of the film, according to common methods, for example by changing the stretching direction by a 90 ° angle.

Regarding the uniformization of the variation in the thickness of the desired heat shrinkable polyester film, the film is preferably heated in a preheating stage, before the film is stretched in the transverse direction, for example, in a tensioner in the stretching stage and in the preheating stage, the unstretched film is preferably heated under a low supply of hot air, so that the thermal conductance does not exceed 0.0013 cal / cm² x sec. x ° C and the surface temperature of the film reaches a range from Tg + 0 ° C to Tg + 60 ° C.

The film is stretched 2.3 to 7.3 times, preferably 2.5 to 6.0 times in the transverse direction at a temperature in a range from Tg -20 ° C to Tg + 40 ° C. Subsequently, the film is heat treated while it is stretched from 0 to 15% or relaxed from 0 to 15%, at a predetermined temperature in a range of 60 ° C to 110 ° C and is further heat treated if desired at a predetermined temperature in a range of 40 ° C to 100 ° C to give a heat shrinkable polyester film. It is preferable to use equipment that can decrease the variation of the surface temperature of the film in the transverse stretching step as described above.

The film can also be stretched 1.0 to 4.0 times, preferably 1.1 to 2.0 times in the longitudinal direction as well as in the transverse direction by the tensioner. The film can be stretched biaxially, biaxially, sequentially or simultaneously and the film can be further stretched if desired. In sequential stretching, the film can be stretched in any order of direction, from transverse to longitudinal, from longitudinal to transverse, from longitudinal, transverse and longitudinal, and from transverse; longitudinal to transverse and the like. When the film is stretched in the longitudinal direction or stretched biaxially, it is also favorable to decrease the variations in the surface temperature of the film as much as possible in the preheating and stretching stages, similar to the transverse stretching stage.

To suppress internal exothermic heat generation associated with stretching and reduce temperature variation in the transverse direction, the thermal conductance in the stretching process is preferably kept at 0.0009 cal / cm² x sec. x ° C or more, more preferably 0.0013 to 0.0020 cal / cm² x sec. x ° C.

A film produced from polyester resins is used for the roll of film of the present invention, as the film has excellent heat shrinkage of the product over a wide temperature range, from low to high in the heat shrinkage process. heat and provides products that look great with less shading from shrinkage, whitening, wrinkling and deformation after heat shrinkage and having excellent gloss and transparency, especially in a relatively low temperature range.

As polyester resins, art-known (co) polyesters prepared by copolycondensation of 1 or more polybasic carboxylic acid components such as aromatic dicarboxylic acids, aliphatic dicarboxylic acids or ester-forming derivatives thereof and an alcohol component can be used. polyhydric. Examples of aromatic dicarboxylic acid include terephthalic acid, isophthalic acid, naphthalene-1,4 or -2,6-dicarboxylic acid, 5-sodium sulfoisophthalic acid, etc. Examples of aliphatic dicarboxylic acid include dimer acid, glutaric acid, adipic acid, sebacic acid, azelaic acid, oxalic acid, succinic acid, etc. Additionally, hydroxycarboxylic acids, such as p-hydroxybenzoic acids or the like and polyvalent carboxylic acids, such as trimellitic anhydride, pyromellitic anhydride, etc., can also be used if necessary. Terephthalic acid, isophthalic acid, 1,4-naphthalene, or 2-6-dicarboxylic acid are favorable. Furthermore, examples of the ester-forming derivative are derivatives such as dialkyl esters, diarylesters, acid halides, etc.

Examples of the polyhydric alcohol component include alkylene glycols such as ethylene glycol, diethylene glycol, dimer diol, propylene glycol, triethylene glycol, 1-4-butanediol, neopentyl glycol, 1,4-cyclohexane dimethanol, 1-6-hexanediol, 3-methyl-1,5-pentanediol. , 2-methyl-1,5-pentanediol, 2,2-diethyl-1,3-propanediol, 1-9-nonanediol, 1,10-decanediol, etc., bisphenol compounds or alkylene oxide adducts of derivatives thereof, trimethylol propane, glycerin, pentaerythritol, polyhydroxytetramutylene glycols, polyethylene glycol, etc. Additionally, ε-caprolactone can also be used for the preparation of the polyester.

The main constituent unit of polyester is an ethylene terephthalate unit from the point of view of anti-breaking property, tensile strength, heat resistance, etc. of the resulting film.

On the other hand, the sub-constituent unit can be selected from any unit, for example, a unit having propylene glycol as a polyhydric alcohol component, a unit having isophthalic acid as a polybasic carboxylic acid component, etc., except a unit of ethyleneterephthalate. However, a unit selected from a group consisting of 1,4-cyclohexanedimethanol and terephthalic acid, neopethylglycol and terephthalic acid, and 1,4-butanediol and terephthalic acid units is preferable as a sub-constituent unit. The incorporation of the constituent subunits into the polyester provides the resulting film with good solvent adhesion property, good heat shrinkage strength at low to high temperatures, and excellent heat shrinkage appearance.

ES 2 298 362 T3 the final products after shrinkage. 1,4-cyclohexane dimethanol and neopentyl glycol have the ability to provide an amorphous part in the resulting polyester and consequently to increase the heat shrink properties of the products. Therefore, the primary constituent subunit is more preferable a unit composed of 1,4-cyclohexanedimethanol and terephthalic acid or a unit composed of neopentyl glycol and terephthalic acid. Alternatively, these units are combined in an equal amount and the mixture can be used as the primary sub-constituent unit.

On the other hand, a unit composed of 1,4-butanediol and terephthalic acid lowers the glass transition temperature of the film and thus contributes to the demonstration of the heat shrinkage force at a lower temperature, but too much addition of the themselves occasionally lead to a decrease in film strength and others, so that the unit is favorably used as a secondary sub-constituent unit, rather than a primary sub-unit.

The polyester film having the favorable composition described above can be produced by a combination of, for example, (i) polyethylene terephthalate (PET) and polycyclohexylenedimethylterephthalate.

(ii) polyethylene terephthalate (PET) and a homopolymer of neopentyl glycol and terephthalic acid.

(iii) polyethylene terephthalate (PET) and polybutylene terephthalate (a homopolyester of 1,4-butanediol and terephthalic acid), (iv) 4 of the above homopolymers, or (v) PET and a copolyester composed of a mixed diol comprising 1 or more Diols selected from the group of neopentyl glycol, 1,4-cyclohexane dimethanol and 1,4-butanediol, (if necessary, ethylene glycol can also be added), and terephthalic acid. Specifically, the pieces of the homopolyester or the copolyester are first produced separately and mixed according to the examples of the above combination. Meanwhile, a combination of homopolyesters with different compositions or a combination of a homopolyester and a copolyester does not cause problems such as bleaching or the like of the resulting film due to poor compatibility between polymers. This is due to the fact that these polymers are significantly heated in an extruder in the blending and melting process, so that the ester exchange reactions between the crude copolymers convert the polymer blend into a blend of copolyesters that they have similarity in composition before the polymer blend is discharged from the extruder. This has been confirmed by the fact that the resulting film has only one peak indicating Tg in the DSC pattern thereof.

The polyester can be prepared according to any common melt polymerization method, including the so-called direct polymerization method, that is, polycondensation of oligomers obtained by a direct reaction of a basic carboxylic acid component and a polyhydric alcohol component and the called the ester exchange method, that is, ester exchange reaction of a polybasic carboxylic acid dimethyl ester component and a polyhydric alcohol component and subsequently polycondensation, any method including the above can be applied. Polyester can be obtained by other polymerization processes. The degree of polymerization of the polyester is preferably 0.3 to 1.3 dl / g as intrinsic viscosity.

Polymerization catalysts such as antimony oxide, germanium oxide, titanium compounds, etc. can be added to the polyester, and additionally, additives for the prevention of disadvantages including coloring, gelling and the like, for example, Mg salts such as magnesium acetate, magnesium chloride, etc., Ca salts such as calcium acetate, calcium chloride, etc., Mn salts such as manganese acetate, manganese chloride, etc., Zn salts such as zinc chloride, zinc substrate, etc. and Co salts such as cobalt chloride, cobalt acetate, etc., respectively at concentrations of 300 ppm (mass ratio, equal hereinafter) or less as metal ions relative to polyester and phosphoric acid derivatives or phosphoric ester such as phosphoric trimethyl ester, phosphoric triethyl ester, etc. at concentrations of 200 ppm or less as phosphorus (P).

It is not favorable to add metal ions at a concentration higher than 300 ppm as total metal ions excluding polymerization catalysts, or to add phosphorus derivatives at concentrations higher than 200 ppm as the total amount of P, since the resulting polymer stains markedly and lowers the heat resistance and anti-hydrolysis property.

In this document, the mass ratio (W / M) of the total phosphorus (P) and the total metal ions (M) is preferably 0.4 to 1.0, from the standpoint of heat resistance, property anti-hydrolysis or the like of the resulting film. When the mass ratio (W / M) is less than 0.4 or more than 1.0, the resulting film is more dyed or mixed with large particles and therefore it is not favorable.

The metal ions and phosphoric acid or derivatives thereof can be added at any time, but generally the metal ions are preferably added when raw materials of the polyesters are added, that is, before the ester exchange or the reaction of Direct esterification and phosphoric acid derivatives are preferably added before the polycondensation reaction.

ES 2 298 362 T3

Additionally, fine particles of silica, titanium dioxide, kaolin, calcium carbonate and the like can be added and antioxidants, UV absorbers, antistatic agents, coloring agents and antibacterial agents can also be further added if desired.

The film roll of the heat shrinkable polyester film of the present invention having a length of 500 m or more is preferably a roll of the heat shrinkable polyester film with a width of more than 0.2 m wound around a winding core. A roll of the film with a width of less than 0.2 m has a low industrial value and a roll of film of the film with a length below 300 m has basically a low variation in composition and heat shrinkage properties. since the film is short, and the merits of the present invention can be effectively expressed since the film is 500 m or more in length. The heat shrinkable polyester film roll more preferably has a film with a width of more than 0.3 m and further preferably more than 0.4 m.

The upper limit of the width of the film roll is usually, but is not particularly limited to, less than 1.5 m respectively, from the point of view of practical handling. Also, the favorable upper limit of the length of the film roll is 6000 µm in the case of a film having a thickness of 45 µm. Examples are plastic, metal, or paper cores with diameters of 3 inches (7.62 cm), 6 inches (15.24 cm), 8 inches (20.32 cm), and so on.

Furthermore, the film thickness of the heat shrinkable polyester film roll of the present invention is, but is not limited to, preferably 10 to 200 pm, more preferably 20 to 100 pm as a heat shrinkable polyester film for labels.

Examples

Hereinafter, the present invention will be described in detail with reference to Examples, these Examples are not intended to limit the scope of the present invention. The physical properties of the films obtained in the Examples and Comparative Examples were determined according to the following procedures.

(1) Confirmation of steady state and location of sample breakpoints

Five film samples were cut from a film roll of a 1000 µm film prepared in each Example or Comparative Example below at an interval of 20 µm from the second end (winding termination end) thereof and another five samples were trimmed at an interval of 20 m from a position 200 m inward from the first end (winding start end) in the direction towards the first end and these samples were subjected to a measurement (to be discussed later) of the percent heat shrinkage in the direction of maximum shrinkage. The variation in the heat shrinkage percentage thereof was in a range of 20%. Additionally, these films were stably produced in the molding and stretching processes. Thus, it was found that the film on each previous film roll corresponds to the constant region along the entire length of the film.

In all measurements except for solvent adhesion strength, the first cut point of the samples was set at the second end (0 m from the winding termination end) of the respective previous film and the final cut point was set. fixed at the first end (0 m from the end of the start of the winding) and therefore, the samples for measurement were all obtained from 11 cut-off points. In each of the property measurements, 10 samples were obtained from each of the cut-off points and a mean value of the property determined from the 10 samples was considered as the property that the sample represents at the point cutting.

(2) Contents of the primary constituent subunit (% in moles)

Each sample was dissolved in a mixed solution of chloroform D (produced by Euriso-top) and trifluoroacetic acid D1 (produced by Euriso-top) at a ratio of 10: 1 (volume ratio), and the proton NMR of the resulting sample solution by NMR (GEMINI-200; produced by Varian) under a temperature condition of 23 ° C and an integration number of 64. In the NMR measurement, from the predetermined maximum proton intensities, an amount of neopentyl glycol, 1,4-cyclohexanedimethanol, or 1,4-butanediol in polyhydric alcohol components of 100% by mole or an amount of Isophthalic acid and therefore the content of the primary sub-constituent (mole%) in the total constituent units (100 mole%) was calculated.

In Table 2, theoretically calculated values ​​of the constituent units in each sample were summarized. Additionally, Table 3 shows a mean, the maximum value and the minimum value and their differences with respect to the mean. The mean (A) indicates an average of the content of the primary constituent subunit (% in moles) determined from all the samples, the maximum value (Bmax) indicates the maximum value of the content in the samples of each cut-off point and the minimum value (Bmin) indicates the minimum value of the content in the samples of each cut-off point, respectively.

ES 2 298 362 T3 (3) Secondary constituent subunit content (% by mole)

The content was determined according to the procedure for the primary constituent subunit. The results are shown in Table 4.

(4) Solvent adhesion resistance

A film on a film roll was cut along the entire length to give a film with a width of 273mm, which was rewound on the roll. The resulting roll of film was stored for 250 hours in a controlled environment at a temperature of 30 ± 1 ° C and a relative humidity of 85 ± 2%. Subsequently, the film was printed with three different colored inks, dark green, gold and white, manufactured by Toyo Ink Mfg., And coated with 1,3-dioxolane on a line 2 ± 1 mm wide, slightly inward from an edge of a surface thereof on a tube forming machine, (amount of coating: 3.0 ± 0.3 g / mm²), and immediately the film was folded so that both edges would overlap and adhere to each other, resulting in a tubular film (processing speed: 80mm / min). The tubular film was flattened and rewound into a roll.

The samples were cut from the tubular roll. The first cut-off point of the samples was at the termination end of the coil (0 m from the termination end of the coil). The last cut point of the same was at the start end of the winding (0 m from the start end of the winding) and 11 samples were collected together. The tubular sample thus obtained from each point was further trimmed to open it and to give a film sample having the adhesion part in the center thereof. From this film sample, test pieces (n = 10) with a length of 100 mm and a width of 15 mm were cut out and a test piece of film was placed in a tensile tester, the distance between tool holders being previously adjusted to 50mm, ("STM-T", manufactured by Baldwin), so that the solvent adhesion part was placed in the center between the corresponding tool holders. The tensile test was carried out at a temperature of 23 ° C and a tensile test speed of 200 mm / min, and the peel strength of the adhesion part was determined and was called the solvent adhesion strength. The results are shown in Table 5.

(5) Glass transition temperature

A sample (10 ± 1 mg) was heated at 300 ° C for 2 minutes and immediately quenched in liquid nitrogen. The DSC standard of the sample was obtained in a DSC apparatus from Seiko Instrument Inc (Model: DSC220), raising a temperature from -40 ° C to 300 ° C at a speed of 20 ° C / min., To give the temperature of glass transition (° C) of the same. The glass transition temperature (Tg) was determined from a temperature at an intersection of the tangent lines of the endothermic onset curve of the DSC standard before and after the endothermic onset curve. The results are shown in Table 6.

(6) Percentage of heat shrinkage in direction of maximum shrinkage

A film was cut along the longitudinal direction and the orthogonal direction to give a 10 cm x 10 cm square sample. The sample was immersed in hot water at 85 ° C ± 0.5 ° C for 10 seconds without load inducing heat shrinkage and immediately afterwards it was immersed in water at 25 ° C ± 0.5 ° C for 10 seconds. Subsequently, the lengths of the sample in the longitudinal and orthogonal directions were determined and the heat shrinkage was calculated according to the following equation.

Heat Shrinkage Percentage (%) = 100 x (Length before shrinkage - Length after shrinkage) / (Length before shrinkage).

The maximum shrinkage direction is considered to be a direction in which the heat shrinkage is greatest. The results are shown in Table 7.

(7) Product appearance after heat shrinkage

All tubular samples prepared in (4) but not used for measurement of the above solvent adhesion strength were further cut to give heat shrinkable film labels. The heat shrinkable film labels were wrapped around 0.91 square column PET bottles and the resulting label wrapped PET bottles were moved through a steam tunnel manufactured by Fuji Astec Inc., (Type: SH -1500-L) in a condition of residence time in the tunnel of 10 seconds and temperatures of the first and second zones of 80 ° C and 90 ° C respectively and the appearance of the resulting labels was determined by visual examination. The appearance of the label after heat shrinkage was evaluated according to the following rating scale up to 5, 5: Better finish, 4: Good finish, 3: with some defects (2 or less), 2: with defects ( 3 to 5) and 1: with many defects (6 or more) and the samples with the rating scale of 4 or more were considered satisfactory and those with 3 or less defective. The defective heat shrinkage fraction (%) was calculated according to the following equation. In this document, the defects are, for example, wrinkling, label edge folding, color shading, and little shrinkage. The results are shown in Table 7.

ES 2 298 362 T3

Defective heat shrinkage fraction = 100 x (number of defective samples) / (number of total samples).

(8) Maximum value of heat shrinkage stress

A sample of 200 mm in length in the maximum shrinkage direction and 20 mm in the orthogonal direction was prepared. The sample was placed in an oven previously heated to 90 ° C and previously the supply of hot air was interrupted inside it, from a tensile tester mounted with a hot air oven (Tensiron manufactured by Toyoseiki). The distances between corresponding tool holders were 100 mm (constant). Afterwards, the door of the heating oven was closed immediately and the supply of hot air (90 ° C, at the speed of 5 m / s) was resumed, the heat shrinkage stress was detected and measured. A maximum value obtained from the graph resulting from the heat shrinkage stress was considered the maximum heat shrinkage stress value (MPa). The results were summarized in Table 8.

(9) Percentage of heat shrinkage in the direction orthogonal to the direction of maximum shrinkage

In the measurement of the heat shrinkage percentage in the maximum shrinkage direction described in (6), the heat shrinkage percentage in the direction orthogonal to the maximum shrinkage direction was also determined. The results are shown in Table 9.

Preparative Example 1

Polyester synthesis

In a stainless steel autoclave equipped with a stirrer, a thermometer, and a partial reflux condenser, 100 mole% dimethylterephthalate (DMT) was added as a dicarboxylic acid component and 68 mole% ethylene glycol (EG) and a 32 mol% neopentyl glycol (NPG) as polyhydric alcohol components, in a molar ratio of polyhydric alcohol to methyl ester of 2.2. Additionally, 0.05 mol% (based on the acid component) of zinc acetate and 0.025 mol% (based on the acid component) of antimony trioxides respectively were added as ester exchange catalyst and as a polycondensation catalyst. The ester exchange reaction was carried out by distilling the methanol generated inside. Subsequently, the polycondensation reaction was carried out at 280 ° C under a reduced pressure of 26.7 Pa. The polyester thus obtained was extruded in a molten state by the strand polymerization equipment, which was immediately cooled in water and cut by a strand cutter to give a raw piece A. A slightly smaller piece was also prepared. to be used in a Comparative Example. This piece was designated as "raw piece B." The intrinsic viscosities of piece A and piece B were 0.70 dl / g.

Meanwhile, the intrinsic viscosity was determined by using an Ostwald viscometer at 30 ± 0.1 ° C in which 0.1 g of exactly measured piece was weighed, dissolved in 25 ml of a solvent mixture of phenol: tetrachloroethane (3: 2 mass ratio). The intrinsic viscosity (η) was calculated according to the following equation (Huggins equation).

<img file="ES2298362T3_D0001.tif" />

In this document, n_sp is a specific viscosity; t₀ is a solvent drop time in the Ostwald viscometer; t is the time of the fall of a film solution in the Ostwald viscometer; and C is a concentration of the film solution. In the actual measurement, the intrinsic viscosity was calculated by the following approximate equation, that is, the Huggins equation where k is 0.375.

H = -1) + 3χ1π77_γ}

1,6

In this document, η_τ, is a relative viscosity.

ES 2 298 362 T3

Preparative Example 2

Employing the procedure described in Preparative Example 1, polyester raw pieces C to L were prepared according to the compositions shown in Table 1. Piece F and piece G are prepared from the same polyester, but under different conditions. cutting. Piece G is the smallest piece that will be used in the Comparative Example. In the same Table, CHDM is an abbreviation for 1,4-cyclohexanedimethanol, BD for 1,4-butanediol, and DEG for diethylene glycol. The intrinsic viscosities of the polyesters were, respectively, 0.72 dl / g for Piece C, 1.20 dl / g for Piece D, 1.20 dl / g for Piece E, 0.80 dl / g for bit F and G, 0.72 dl / g for bit H, 1.20 dl / g for bit I, 0.79 dl / g for bit J, 0.75 dl / g for bit K and 0.70 dl / g for piece L.

Example 1. (Reference Example, ie this example and the following examples marked "Reference" are not included in the scope of the appended claims) and Example 6

Each piece prepared in the above Preparative Examples was pre-dried separately. As shown in Table 1, Piece A (60% by mass), Piece D (25% by mass) and Piece E (15% by mass) were supplied separately continuously by quantitative screw feeder. to a hopper immediately above an extruder and mixed inside. The mixture was melt extruded at 280 ° C by a monoaxial extruder and then rapidly cooled to give an unstretched film with a thickness of 180 pm. The compositions (theoretical content) of the constituent units in the raw polyester for preparing the film are summarized in Table 2. In Table 2, TPA is terephthalic acid. The hopper had an internal capacity of 150 kg of raw pieces and the discharge speed of the extruder was 450 kg per hour. Furthermore, the tilt angle of the hopper was 70 °.

The above unstretched film was cut in two halves in the longitudinal direction to give two rolls of unstretched film. Films not stretched over a 1,000 m span or more were continuously preheated at 105 ° C for 10 seconds, stretched 4.0 times in the transverse direction at 78 ° C on a tensioner, and heat treated at 80 ° C for 10 seconds, to give 45 µm thick heat shrinkable polyester films, respectively. In Example 1 (Reference) the variations in the surface temperature of the film during the continuous production of the film, were in the ranges of the average temperature ± 1.0 ° C in the preheating process, the average temperature ± 2 .5 ° C in the stretching process and the mean temperature ± 2.0 ° C in the heat treatment process. In Example 6, the variations in the surface temperature of the film were controlled in the ranges of the mean temperature ± 0.5 ° C in the preheating process, the mean temperature ± 0.4 ° C in the stretching process and the mean temperature ± 0.5 ° C in the heat treatment process. The surface temperatures of the films were determined by a non-contact infrared surface thermometer (the same in the following Examples and Comparative Examples).

The films obtained in this way were cut into films with a width of 0.4 m and a length of 1000 m and were wound around a 3 inch (7.62 cm) roll of paper, respectively, to give rolls of shrinkable film by hot. The physical properties (1) to (4) of the film of the film roll obtained in Example 1 (Reference) are summarized in Tables 3 to 5 and the physical properties (5) to (9) of the films of the rolls of film obtained in Example 1 (Reference) and Example 6 were summarized in Tables 6 to 9.

Example 2 and Example 7

Each piece prepared in the above Preparative Examples was pre-dried separately. As shown in Table 1, piece C (75% by mass), piece D (10% by mass) and piece E (15% by mass) were supplied separately and continuously by screw feeder. quantitative to a hopper immediately above an extruder and mixed inside. The mixture was extruded in a melt at 280 ° C by a monoaxial extruder and then rapidly cooled to give an unstretched film with a thickness of 180 pm. The compositions of the constituent units in the raw polyester are summarized in Table 2. The hopper had an internal capacity of 100 kg of raw pieces and the discharge rate of the extruder was 450 kg per hour. Furthermore, the tilt angle of the hopper was 70 °.

The above unstretched film was cut in two halves along the longitudinal direction to give two rolls of unstretched film. Films not stretched over the 1,000 m or longer stretch were continuously preheated at 100 ° C for 10 seconds, stretched 4.0 times at 80 ° C in the cross direction on a tensioner, and then heat treated at 83 ° C for 10 seconds, to give 45 pm thick heat shrinkable polyester films, respectively. The variations of the surface temperatures in the film during the continuous production of the films were, in Example 2, in the ranges of the average temperature ± 1.0 ° C in the preheating process, the average temperature ± 2.5 ° C in the stretching process and the mean temperature ± 2.0 ° C in the heat treatment process. In Example 7, the variations were in the ranges of the mean temperature ± 0.6 ° C in the preheating process, the mean temperature ± 0.5 ° C in the stretching process and the mean temperature ± 0.8 ° C in the heat treatment process. Each film thus obtained was cut into films with a width of 0.4 m and a length of 1000 m, which were wound around a 3-inch (7.62 cm) paper tube to give heat shrinkable film rolls. . The physical properties (1) to (4) of the film of the

ES 2 298 362 T3 roll of film obtained in Example 2 are summarized in Tables 3 to 5 and the physical properties (5) to (9) of those with respect to the films of Example 2 and Example 7 are summarized in the Tables 6 to 9.

Example 3 (Reference) and Example 8

Each piece prepared in the above Preparative Examples was pre-dried separately. As shown in Table 1, piece F (75% by mass), piece H (10% by mass) and piece I (15% by mass) were supplied separately and continuously by screw feeder. quantitative to a hopper immediately above the extruder and mixed inside. The mixture was extruded in a melt at 280 ° C by a monoaxial extruder and then rapidly cooled to give an unstretched film with a thickness of 180 gm. The constituent compositions in the raw polyesters are summarized in Table 2. The hopper had a capacity of 100 kg of raw pieces and the discharge rate from the extruder was 450 kg per hour. The angle of inclination of the hopper was 70 °.

The above unstretched film was cut in two halves along the longitudinal direction to give two rolls of unstretched film. Each unstretched film over an extension of 1,000 m or more was continuously preheated at 100 ° C for 10 seconds, stretched 4.0 times at 82 ° C in the cross direction on a tensioner, and then heat treated at 80 ° C for 10 seconds, to give a heat shrinkable polyester film with a thickness of 45 gm, respectively. The variations in the surface temperatures in the film during the continuous production of the films were, in Example 3 (Reference), in the ranges of a mean temperature ± 1.0 ° C in the preheating process, a mean temperature ± 2 , 5 ° C in the stretching process and an average temperature ± 2.0 ° C in the heat treatment process. In Example 8, the variations were in ranges of a mean temperature ± 0.6 ° C in the preheating process, a mean temperature ± 0.5 ° C in the stretching process, and a mean temperature ± 0.5 ° C. in the heat treatment process. Each film thus obtained was cut into films with a width of 0.4 m and a length of 1000 m, which were wound around a 3-inch (7.62 cm) paper tube to give heat shrinkable film rolls. . The physical properties (1) to (4) of the film of the film roll obtained in Example 2 (Reference) are summarized in Tables 3 to 5 and the physical properties (5) to (9) of those with respect to the Films from Example 3 (Reference) and Example 8 are summarized in Tables 6 to 9.

Example 4 and Example 9

Each piece prepared in the above Preparative Examples was pre-dried separately. As shown in Table 1, piece F (54% by mass), piece H (36% by mass) and piece I (10% by mass) were supplied separately and continuously by screw feeder. quantitative to a hopper immediately above the extruder and mixed inside. The mixture was melt extruded at 280 ° C by a monoaxial extruder and then rapidly cooled to give an unstretched film with a thickness of 180 gm. The compositions of the constituent units in the raw polyester are summarized in Table 2. The hopper had an internal capacity of 100 kg of raw pieces and the discharge rate of the extruder was 450 kg per hour. The tilt angle of the hopper was 70 °.

The above unstretched film was cut in two halves along the longitudinal direction to give two rolls of unstretched film. Films not stretched over an extension of 1,000 m or more were continuously preheated at 100 ° C for 10 seconds, stretched 4.0 times at 82 ° C in the transverse direction on a tensioner, and then heat treated at 83 ° C for 10 seconds, to give 45 gm thick heat shrinkable polyester films, respectively. The variations in the surface temperature of the film during the continuous production of the films were, in Example 4, in the ranges of the average temperature ± 1.0 ° C in the preheating process, the average temperature ± 2.5 ° C in the stretching process and the mean temperature ± 2.0 ° C in the heat treatment process. In Example 9, the variations were in the ranges of the mean temperature ± 0.6 ° C in the preheating process, the mean temperature ± 0.5 ° C in the stretching process, and the mean temperature ± 0.5 ° C in the heat treatment process. Each film thus obtained was cut into films with a width of 0.4 m and a length of 1000 m, which were wound around a 3-inch (7.62 cm) paper tube to give heat shrinkable film rolls. . The physical properties (1) to (4) of the film of the film roll obtained in Example 4 are summarized in Tables 3 to 5 and the physical properties (5) to (9) of those with respect to the films of Example 4 and Example 9 are summarized in Tables 6 to 9.

Example 5 (Reference) and Example 10

Each piece prepared in the above Preparative Examples was pre-dried separately. As shown in Table 1, piece J (69% by mass), piece K (6% by mass) and piece L (25% by mass) were supplied separately and continuously by screw feeder. quantitative to a hopper immediately above an extruder and mixed inside. The mixture was melt extruded at 280 ° C by a monoaxial extruder and then rapidly cooled to give an unstretched film with a thickness of 180 gm. The compositions of the constituent units in the raw polyester are summarized in Table 2. The hopper had an internal capacity of 150 kg of the raw piece and the discharge rate of the extruder was 400 kg per hour. Furthermore, the angle of inclination of the hopper was 75 °.

The above film was cooled by contacting it with a casting roll electrostatically and applying voltage between the casting roll and an electrode that was installed between the extruder and the casting roll.

ES 2 298 362 T3

The above unstretched film was cut in two halves along the longitudinal direction to give two rolls of unstretched film. Films not stretched over a 1,000 m or longer stretch were continuously preheated at 98 ° C for 15 seconds, stretched 4.0 times at 80 ° C in the cross direction on a tensioner, and then heat treated for 10 seconds at 80 ° C, to give a heat shrinkable polyester film with a thickness of 45 pm, respectively. The variations in the surface temperature of the film during the continuous production of the films were, in Example 5 (Reference), in the ranges of the mean temperature ± 1.0 ° C in the preheating process, the mean temperature ± 2 .5 ° C in the stretching process and the mean temperature ± 2.5 ° C in the heat treatment process. In Example 10 (Reference), the variations were in ranges of the mean temperature ± 0.5 ° C in the preheating process, the mean temperature ± 0.5 ° C in the stretching process and the mean temperature ± 0, 6 ° C in the heat treatment process. Each film thus obtained was cut into films with a width of 0.5 m and a length of 1000 m which were wound around a 3 inch (7.62 cm) paper tube to give heat shrinkable film rolls. The physical properties (1) to (4) of the film of the film roll obtained in Example 5 (Reference) are summarized in Tables 3 to 5 and the physical properties (5) to (9) of those with respect to the Films from Example 5 (Reference) and Example 10 are summarized in Tables 6 to 9.

Comparative Example 1

Piece B (60% by mass), Piece D (25% by mass) and Piece E (15% by mass) were mixed according to the composition shown in Table 1 and then pre-dried. 4 identically shaped hoppers were arranged in series having an internal capacity of 400 kg of raw pieces and having an angle of inclination of 60 °. According to the procedures described in Example 1, except that the chunk mixture was placed in the most upstream hopper and transferred through the second and third hoppers to the fourth hopper (the final hopper), a roll of heat shrinkable film of a heat shrinkable polyester film with a thickness of 45 pm and a length of 1,000 m. The physical properties of the film of the film roll thus obtained are shown in Tables 3 to 9.

Comparative Example 2

Piece B and Piece D were mixed at a ratio of 60:25 (mass ratio) and then pre-dried. 5 identically shaped hoppers were arranged in series having an internal capacity of 400 kg of raw pieces and having an angle of inclination of 60 °. The chunk mix was placed in the most upstream hopper and successively transferred to the fourth hopper. The above mix and piece E were added separately and continuously to the fifth hopper immediately above the extruder by quantitative feeders at a ratio of 85:15 and the resulting mixture was mixed in the hopper. After this, according to the procedures described in Example 1 (Reference), a heat shrinkable film roll of a heat shrinkable polyester film with a thickness of 45 µm and a length of 1000 µm was obtained. The physical properties of the film of the film roll thus obtained are shown in Tables 3 to 9.

Comparative Example 3

Piece G (75% by mass), Piece H (10% by mass) and Piece I (15% by mass) were mixed according to the composition shown in Table 1 and then pre-dried. 3 identically shaped hoppers were arranged in series having an internal capacity of 400 kg of raw pieces and having an angle of inclination of 60 °. According to the procedures described in Example 1 (Reference), except that the mixture of pieces was placed in the hopper most upstream and transferred through the second hopper to the third hopper (the final hopper), a roll of heat shrinkable film of a heat shrinkable polyester film with a thickness of 45 pm and a length of 1,000 m. The physical properties of the film of the film roll thus obtained are shown in Tables 3 to 9.

Comparative Example 4

Piece G (75% by mass) and Piece H (10% by mass) were mixed according to the composition shown in Table 1 and then pre-dried. 4 identically shaped hoppers having an internal capacity of 400 kg of raw pieces and having an inclination angle of 60 ° were arranged in series and the mixture of pieces was placed in the hopper further upstream. In the fourth and final hoppers, the above mix and piece I were supplied separately through a quantitative feeder at a ratio of 85% by mass to 15% by mass. After this, according to the procedures described in Example 1 (Reference), a heat-shrinkable polyester film with a thickness of 45 µm and a length of 1000 µm was obtained. The physical properties of the film of the film roll thus obtained are shown in Tables 3 to 9.

ES 2 298 362 T3

TABLE 1

<img file="ES2298362T3_D0002.tif" />

<td></td><td>COMP.</td>

<td>C0</td><td>OR</td>

<td>ω</td><td> —1</td>

<td>CO</td><td>CL</td>

<td>AND</td><td></td>

<td>c</td><td>LU</td>

<td>φ</td><td> 3</td>

<td>x0 or</td><td>LLI</td>

<td>Tt</td><td> 1</td><td> 1</td><td> 1</td><td> 1</td><td> &gt;</td><td> 1</td><td> 75</td><td>or</td><td>IT</td><td> 1</td><td> 1</td><td> 1</td>

<td rowspan="2">co</td><td></td><td></td><td></td><td></td><td></td><td></td><td>IT</td><td>or</td><td>IT</td><td></td><td></td><td></td>

<td></td><td></td><td></td><td></td><td></td><td></td><td>h *</td><td></td><td></td><td></td><td></td><td></td>

<td rowspan="2">CN</td><td></td><td>or</td><td></td><td>IT</td><td>IT</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td>

<td></td><td>co</td><td></td><td>CN</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td>

<td> -</td><td> 1</td><td> 09</td><td> 1</td><td> 25</td><td>IT</td><td> 1</td><td> 1</td><td> 1</td><td> 1</td><td> 1</td><td> 1</td><td> 1</td>

<td>♦ or</td><td> 1</td><td> 1</td><td> 1</td><td> 1</td><td></td><td> 1</td><td> 1</td><td> 1</td><td> 1</td><td> 69</td><td>co</td><td> 25</td>

<td>ID</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td>

<td>in</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>co</td><td>or</td><td></td><td></td><td></td>

<td></td><td></td><td></td><td></td><td></td><td></td><td>IT</td><td></td><td>co</td><td></td><td></td><td></td><td></td>

<td> *</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td>

<td> 00</td><td></td><td></td><td></td><td></td><td></td><td>IT</td><td></td><td>or</td><td>IT</td><td></td><td></td><td></td>

<td>co</td><td></td><td></td><td></td><td></td><td></td><td>r *</td><td></td><td></td><td></td><td></td><td></td><td></td>

<td>r-</td><td></td><td></td><td>it</td><td>or</td><td>IT</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td>

<td>CN</td><td></td><td></td><td>r-</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td>

<td> *</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td>

<td>co</td><td>or</td><td></td><td></td><td>IT</td><td>ID</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td>

<td></td><td>co</td><td></td><td></td><td>CN</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td>

<td></td><td>in</td><td>or</td><td>in</td><td></td><td>co</td><td> 00</td><td>in</td><td>in</td><td> 1^</td><td> 00</td><td> 00</td><td> 00</td>

<td></td><td>co</td><td>CN</td><td>co</td><td>co</td><td>co</td><td>co</td><td></td><td>co</td><td>co</td><td>co</td><td>co</td><td>co</td>

<td></td><td></td><td>io</td><td> 00</td><td>co</td><td>in</td><td>I ''</td><td></td><td>co</td><td>co</td><td>co</td><td></td><td> 00</td>

<td></td><td>CN</td><td>CN</td><td>CN</td><td>CN</td><td>CN</td><td>CN</td><td>CN</td><td>CN</td><td>CN</td><td>CN</td><td>CN</td><td>CN</td>

<td></td><td>it</td><td>in</td><td></td><td>I '</td><td>co</td><td>IT</td><td>in</td><td></td><td>r-</td><td> 00</td><td>in</td><td>co</td>

<td></td><td>co</td><td>CN</td><td>co</td><td>CO</td><td>co</td><td>co</td><td>CN</td><td>co</td><td>co</td><td>co</td><td>co</td><td>co</td>

<td>Q</td><td></td><td></td><td></td><td></td><td>or</td><td></td><td></td><td></td><td>or</td><td></td><td></td><td>or</td>

<td rowspan="2">co</td><td> •</td><td>i</td><td> 1</td><td></td><td>CJ</td><td> 1</td><td> •</td><td> 1</td><td>or</td><td> 1</td><td> 1</td><td>or</td>

<td></td><td></td><td></td><td></td><td>^T</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td>

<td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td>

<td>Q</td><td></td><td></td><td>co</td><td></td><td></td><td>CN</td><td>CN</td><td></td><td></td><td>CN</td><td></td><td></td>

<td>X</td><td></td><td></td><td>co</td><td></td><td></td><td>CO</td><td>CO</td><td></td><td></td><td>CO</td><td>¹</td><td>¹</td>

<td>OR</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td>

<td>IPG</td><td rowspan="2"> 32</td><td rowspan="2"> 32</td><td> 1</td><td> 1</td><td> 1</td><td> 1</td><td> 1</td><td> 1</td><td> 1</td><td> 1</td><td> 1</td><td> 1</td>

<td>σ</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td>

<td> 0</td><td>co</td><td> 00</td><td>Μ^-</td><td>or</td><td></td><td> 00</td><td> 00</td><td>or</td><td></td><td> 00</td><td>or</td><td></td>

<td>LLI</td><td>co</td><td>co</td><td>co</td><td></td><td></td><td>co</td><td>co</td><td></td><td></td><td>co</td><td></td><td></td>

<td>H</td><td>or</td><td>or</td><td>or</td><td>or</td><td>or</td><td>or</td><td>or</td><td>CO</td><td>π</td><td>n</td><td>or</td><td>or</td>

<td>Z&gt;</td><td>or</td><td>or</td><td>or</td><td>or</td><td>or</td><td>or</td><td>or</td><td>or</td><td>or</td><td>or</td><td>or</td><td></td>

<td>Q</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td>

<td></td><td> &lt;</td><td>m</td><td>OR</td><td>Q</td><td>LLI</td><td>LL</td><td> 0</td><td>X</td><td></td><td> “3</td><td>you</td><td> —1</td>

<td></td><td>or</td><td>or</td><td>or</td><td>or</td><td>OR</td><td>or</td><td>or</td><td>or</td><td>or</td><td>or</td><td>or</td><td>or</td>

<td></td><td>N</td><td>N</td><td>N</td><td>N</td><td>N</td><td>N</td><td>N</td><td>N</td><td>N</td><td>N</td><td>N</td><td>N</td>

<td></td><td>EC</td><td>co</td><td>EC</td><td>in</td><td>co</td><td>to</td><td>Φ</td><td>CÜ</td><td>CÜ</td><td>tO</td><td>CÜ</td><td>Φ</td>

<td></td><td>Ό</td><td>Ό</td><td> £&gt;</td><td>Ό</td><td>Ό</td><td>Ό</td><td>Ό</td><td>Ό</td><td>OR</td><td>OR</td><td>"OR</td><td>Ό</td>

<td></td><td>Φ</td><td>φ</td><td>Φ</td><td>Φ</td><td>Φ</td><td>Φ</td><td>Φ</td><td>Φ</td><td>Φ</td><td>Φ</td><td>Φ</td><td>Φ</td>

<td></td><td> 0-</td><td>to.</td><td> 0-</td><td>CL</td><td>CL</td><td>CL</td><td> 0-</td><td>CL</td><td> 0.</td><td>CL</td><td>CL</td><td> 0.</td>

ES 2 298 362 T3

TABLE 2

<td rowspan="4">Theoretical content of constitutive unit (% in moles)</td><td>! TPA + BD</td><td> 14,0</td><td> 14,4</td><td> 14,3</td><td> 9,6</td><td> 23,9</td><td> 14,0</td><td> 14,0</td><td> 14,3</td><td> 14,3</td><td rowspan="4">ference</td>

<td>TPA + CHDM</td><td> 1</td><td>I 25.8</td><td> ! 23,1</td><td>I 16.6</td><td> 23,2</td><td> 1</td><td></td><td> 23,1</td><td>¹ 23.1 I</td>

<td>TPA + NPG</td><td> 00</td><td> 1</td><td> 1</td><td> 1</td><td> 1</td><td> 18,1</td><td> 18,1</td><td> 1</td><td></td>

<td>TPA + EG</td><td> 67,9</td><td> 59,8</td><td> 62,6</td><td> 73,8</td><td> 52,9</td><td> 67,9</td><td> 67,9</td><td> 62,6</td><td> 62,6</td>

<td colspan="2"></td><td>EXAMPLE 1*</td><td>EXAMPLE 2</td><td>EXAMPLE 3 *</td><td>EXAMPLE 4</td><td>EXAMPLE 5 *</td><td>AHEM. COMP. 1</td><td>AHEM. COMP. 2</td><td>AHEM. COMP. 3</td><td>AHEM. COMP. 4</td><td>(*) Example of Re:</td>

ES 2 298 362 T3

<img file="ES2298362T3_D0003.tif" />

TABLE 3

<td>ID</td><td>OR</td><td>m</td><td></td><td>CO</td><td>CM</td><td>OR</td><td>CO</td><td>CT&gt;</td>

<td>OR</td><td></td><td>or</td><td>or</td><td>OR</td><td></td><td>CO</td><td>cm</td><td></td>

<td> 00</td><td>CM</td><td>co</td><td></td><td>in</td><td>co</td><td>CM</td><td>in</td><td>CM</td>

<td>OR</td><td></td><td>or</td><td>or</td><td>or</td><td></td><td></td><td>CM</td><td>CM</td>

<td>Tt</td><td>CO</td><td>OO</td><td>co</td><td>co</td><td>or</td><td>or</td><td></td><td>CM</td>

<td>r-</td><td>ID</td><td>τΓ</td><td>r-</td><td>co</td><td></td><td>in</td><td>CM</td><td>CO</td>

<td></td><td>CM</td><td>CM</td><td></td><td>CM</td><td></td><td></td><td>CM</td><td>CM</td>

<td> 00</td><td> 00</td><td>in</td><td></td><td></td><td>co</td><td>co</td><td>in</td><td>CO</td>

<td> 00</td><td>r-</td><td>a</td><td> 00</td><td>cn</td><td>CM</td><td>CM</td><td>co</td><td>r-</td>

<td></td><td>CM</td><td>CM</td><td></td><td>CM</td><td>CM</td><td>CM</td><td>CM</td><td>CM</td>

<td>or</td><td>CO</td><td>co</td><td>or</td><td>CM</td><td>CM</td><td>or</td><td>or</td><td></td>

<td>co</td><td>CO</td><td>in</td><td> 00</td><td>I—</td><td> 00</td><td>co</td><td>in</td><td>m</td>

<td></td><td>CM</td><td>CM</td><td></td><td>CM</td><td></td><td></td><td>CM</td><td>CM</td>

<td></td><td> 00</td><td></td><td>co</td><td>in</td><td></td><td></td><td></td><td></td>

<td> 00</td><td>IT</td><td>co</td><td>co</td><td>co</td><td> 00</td><td> 00</td><td>co</td><td>co</td>

<td></td><td>CM</td><td>CM</td><td></td><td>CM</td><td></td><td></td><td>CM</td><td>CM</td>

<td rowspan="2">0 CL z</td><td></td><td></td><td> 2</td><td></td><td rowspan="2">0 0. z</td><td rowspan="2">0 CL z</td><td></td><td></td>

<td>CHD</td><td>CHD</td><td>CHD</td><td>Q m +</td><td>CHD</td><td>CHD</td>

<td> +</td><td> +</td><td> +</td><td> +</td><td> &lt;</td><td></td><td> +</td><td> +</td><td> +</td>

<td>&lt;Q_</td><td> &lt;</td><td> &lt;</td><td> &lt;</td><td>CL</td><td> &lt; □_</td><td>&lt;Q_</td><td> &lt;</td><td> &lt;</td>

<td> |—</td><td>LL</td><td> 0.</td><td> □_</td><td> 1—</td><td></td><td></td><td>CL</td><td> 0-</td>

<td></td><td>H</td><td>H</td><td> 1-</td><td></td><td></td><td></td><td>H-</td><td>H</td>

<td></td><td></td><td></td><td></td><td></td><td></td><td>CM</td><td>co</td><td></td>

<td> «</td><td>CM</td><td>* co</td><td></td><td>* IT</td><td>CL</td><td>CL</td><td>CL</td><td>I heard</td>

<td>or</td><td>OR</td><td>or</td><td>or</td><td>or</td><td></td><td></td><td></td><td></td>

<td> —1</td><td> —1</td><td> —1</td><td></td><td> —1</td><td>or</td><td>OR</td><td>OR</td><td>or</td>

<td> □_</td><td>Q_ s</td><td> 0.</td><td>Q_ z&gt;</td><td> □.</td><td>or</td><td> 0</td><td>OR</td><td>Q</td>

<td>LLI</td><td>LLI</td><td>LLI</td><td>LLI</td><td>LLI</td><td></td><td></td><td></td><td></td>

<td>Ex</td><td>3 LLI</td><td>Ex</td><td>LLI</td><td>Ex</td><td>JE</td><td>JE</td><td>JE</td><td>JE</td>

<td></td><td></td><td></td><td></td><td></td><td>LLI</td><td>LLI</td><td>LLI</td><td>LLI</td>

ES 2 298 362 T3

<img file="ES2298362T3_D0004.tif" />

TABLE 4

<td></td><td>- Bmin</td><td> 9*0</td><td> 0,8</td><td> 0,6</td><td> 0,5</td><td> 0,7</td><td> 3,2</td><td> 3,0</td><td> 2,0</td><td>r ·.</td>

<td></td><td>or</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td>

<td>ω</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td>

<td>Φ</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td>

<td>or</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td>

<td>AND</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td>

<td>c</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td>

<td>Φ</td><td>OR</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td>

<td></td><td> 1</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td>

<td></td><td>X</td><td>t-</td><td>CD</td><td> 00</td><td>CD</td><td> 00</td><td> 00</td><td></td><td>co</td><td> 1—</td>

<td> &lt;0</td><td>CO</td><td>or</td><td>or</td><td>or</td><td>OR</td><td>CD</td><td>co</td><td>co</td><td>CN</td><td>CN</td>

<td>»Z</td><td>AND</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td>

<td rowspan="2">ecunda</td><td>Q</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td>

<td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td>

<td>ω</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td>

<td>CU</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td>

<td> &gt;</td><td>OR</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td>

<td> 5</td><td>i 1</td><td>CD</td><td> 3,2</td><td> 3,2</td><td rowspan="2"> 9,0</td><td>CO CN</td><td> 0,6</td><td> 0,7</td><td>CN</td><td>^ r cu</td>

<td rowspan="3">Give cons</td><td rowspan="2">sa</td><td rowspan="2"></td><td rowspan="2"></td><td rowspan="2"></td><td rowspan="2">CN</td><td rowspan="2"></td><td rowspan="2"></td><td rowspan="2"></td><td rowspan="2"></td>

<td></td>

<td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td>

<td>c</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td>

<td>Σ5</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td>

<td>x&gt;</td><td>or</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td>

<td>ZD ω</td><td>c X t Cü</td><td></td><td>CD</td><td>co</td><td> 1-</td><td> 00</td><td>co</td><td>T "</td><td></td><td>CN</td>

<td>Φ</td><td>x E</td><td></td><td></td><td></td><td>or</td><td>CO</td><td>K</td><td> 1^-</td><td>co</td><td>CO</td>

<td>TD O</td><td>2 s.</td><td></td><td></td><td></td><td></td><td>CN</td><td></td><td>^T—</td><td>^T'</td><td></td>

<td>TD</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td>

<td>c</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td>

<td>Φ</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td>

<td>c</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td>

<td>or</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td>

<td>OR</td><td rowspan="2">Half (C)</td><td>r ~ -</td><td>or</td><td> 00</td><td>in</td><td>OR_</td><td> 00</td><td></td><td></td><td></td>

<td></td><td>CD</td><td>Tt</td><td>CD</td><td>σΓ</td><td> 23</td><td>co'</td><td>co</td><td></td><td></td>

<td>c</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td>

<td colspan="2">or</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td>

<td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td>

<td colspan="2">(Ü X</td><td>or_</td><td></td><td>co</td><td>co</td><td>CN</td><td>or_</td><td>or</td><td>co_</td><td>co_</td>

<td> +—·</td><td></td><td>'' Φ</td><td></td><td></td><td rowspan="2">CD</td><td>co'</td><td></td><td></td><td></td><td></td>

<td rowspan="2">DC • s</td><td rowspan="2">ω</td><td rowspan="2">T “*</td><td rowspan="2"> 1—</td><td rowspan="2"> 1—</td><td rowspan="2">CN</td><td rowspan="2"></td><td rowspan="2"></td><td rowspan="2"></td><td rowspan="2">T "</td>

<td></td>

<td>co c</td><td>ω</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td>

<td colspan="2">c φ 7 =</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td>

<td rowspan="2"> * 8</td><td>AND</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td>

<td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td>

<td colspan="2">"Oc</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td>

<td colspan="2">«&gt;. Φ</td><td></td><td></td><td></td><td></td><td>Σ</td><td></td><td></td><td></td><td></td>

<td colspan="2"> ? _m xO</td><td>Q</td><td>Q</td><td>Q</td><td>Q</td><td>Q</td><td>Q</td><td>Q</td><td>Q</td><td>Q</td>

<td>-I * -</td><td></td><td>m</td><td>m</td><td>m</td><td>co</td><td>T</td><td>co</td><td>CQ</td><td>CQ</td><td>CQ</td>

<td colspan="2">-S -n</td><td> +</td><td> +</td><td> +</td><td> +</td><td>OR</td><td> +</td><td> +</td><td> +</td><td> +</td>

<td>tn &lt;=</td><td></td><td> &lt;</td><td> &lt;</td><td> &lt;</td><td> &lt;</td><td> +</td><td> &lt;</td><td> &lt;</td><td> &lt;</td><td> &lt;</td>

<td colspan="2" rowspan="2">or Φ</td><td>CL</td><td>CL</td><td>CL</td><td>CL</td><td> &lt;</td><td>CL</td><td> 0.</td><td>Q_</td><td>Q_</td>

<td>Π</td><td> 1-</td><td> 1-</td><td> 1-</td><td>CL</td><td> 1—</td><td> 1-</td><td> 1-</td><td>H</td>

<td colspan="2">ω</td><td></td><td></td><td></td><td></td><td> 1-</td><td></td><td></td><td></td><td></td>

<td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>CN</td><td>co</td><td>tT</td>

<td></td><td></td><td> ♦</td><td>CN</td><td>« CO</td><td></td><td>«In</td><td>CL</td><td>I HEARD</td><td>CL</td><td>CL</td>

<td></td><td></td><td>or</td><td>OR</td><td>or</td><td>or</td><td>or</td><td></td><td></td><td></td><td></td>

<td></td><td></td><td> —1</td><td></td><td> —1</td><td> —1</td><td> —1</td><td>OR</td><td>or</td><td>OR</td><td>or</td>

<td></td><td></td><td>CL</td><td>Q.</td><td>CL</td><td>Q.</td><td>CL S</td><td>or</td><td>OR</td><td>OR</td><td>or</td>

<td></td><td></td><td>LU</td><td>LLI</td><td>LU</td><td>LU</td><td>LU</td><td></td><td></td><td></td><td></td>

<td></td><td></td><td>Ex</td><td>J LU</td><td>Ex</td><td>LU</td><td>Ex</td><td>JE</td><td>JE</td><td>JE</td><td>JE</td>

<td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>LU</td><td>LU</td><td>LU</td><td>LU</td>

ES 2 298 362 T3

TABLE 5

<td></td><td>Ε - Fmin</td><td>or</td><td> 0,4</td><td> 0,5</td><td>COCONUT</td><td> 0,5</td><td>CM</td><td>CUCKOO</td><td>C0cu</td><td> 2,1</td>

<td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td>

<td>Ε</td><td rowspan="2">LU |</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td>

<td>Ε</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td>

<td>m</td><td>X</td><td>ID</td><td></td><td>CD</td><td>CO_</td><td>CD</td><td></td><td> 00-</td><td>OR&gt;</td><td>b »</td>

<td></td><td> ¢0</td><td>or'</td><td>or</td><td>or"</td><td>or'</td><td>or</td><td>CU</td><td>Ί—</td><td></td><td>T—</td>

<td>ζ</td><td>Ε</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td>

<td></td><td>LL</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td>

<td>φ</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td>

<td>C</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td>

<td>φ</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td>

<td> &gt;</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td>

<td>ο</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td>

<td>ω</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td>

<td>ο φ Ό</td><td>Ma ιΐη)</td><td>b-</td><td>cn</td><td>cn</td><td></td><td>OR</td><td>cn</td><td>OR</td><td> 00</td><td> 00</td>

<td rowspan="2">and adhesion</td><td>1 Min (Frr</td><td>co'</td><td>CO</td><td>co'</td><td>co</td><td></td><td></td><td>CU</td><td></td><td></td>

<td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td>

<td>Ό</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td>

<td>φ</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td>

<td>OR</td><td> « 5?</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td>

<td>c φ</td><td>.É cü</td><td>co</td><td>or</td><td>or</td><td>co</td><td> 1-</td><td>Tt</td><td>or</td><td>or</td><td>CD</td>

<td>ω 'ω</td><td>Max (Frr</td><td></td><td>ID</td><td>ID</td><td></td><td>IT</td><td>CD</td><td>co</td><td>co</td><td>ID</td>

<td>φ</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td>

<td>□ C</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td>

<td></td><td>φ</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td>

<td></td><td>5 IT</td><td></td><td>CD</td><td></td><td>or</td><td>ID_</td><td>CD_</td><td>cu</td><td></td><td>cn</td>

<td></td><td> 2</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>co'</td>

<td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>cu</td><td>co</td><td></td>

<td></td><td></td><td> «</td><td>cu</td><td>* CO</td><td></td><td>* IT</td><td>I heard</td><td>□ L</td><td>CL</td><td>CL</td>

<td></td><td></td><td>or</td><td>OR</td><td>or</td><td>or</td><td>or</td><td></td><td></td><td>S</td><td></td>

<td></td><td></td><td> —1</td><td></td><td> —1</td><td></td><td>—J</td><td>OR</td><td>OR</td><td>OR</td><td>or</td>

<td></td><td></td><td>CL</td><td>Q. 2</td><td> 0-</td><td>Q_</td><td> 0.</td><td>OR</td><td>OR</td><td>OR</td><td>or</td>

<td></td><td></td><td>LU</td><td>LU</td><td>LU</td><td>LU</td><td>LU</td><td> 2</td><td></td><td>ZÉ</td><td>ZÉ</td>

<td></td><td></td><td>"D LU</td><td>LU</td><td>Ex</td><td>LU</td><td>Ex</td><td>JE</td><td>JE</td><td>JE</td><td>JE</td>

<td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>LU</td><td>LU</td><td>LU</td><td>LU</td>

&lt;β Ό c φ k_ Φ * ♦ - φ ι— φ τ&gt;

ο CL Ε φ ΰΤ

ES 2 298 362 T3

TABLE 6

<td></td><td>G - Hmin</td><td> -</td><td> -</td><td> -</td><td> -</td><td> -</td><td>it</td><td> 10</td><td>IT</td><td>IT</td>

<td>OR or</td><td>max -G</td><td></td><td></td><td>CM</td><td></td><td></td><td>ω</td><td>CO</td><td></td><td>CO</td>

<td></td><td>I</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td>

<td>ro</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td>

<td>φ</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td>

<td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td>

<td rowspan="2">sition v</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td>

<td>ro</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td>

<td rowspan="2">c CO k_</td><td rowspan="2">nim min</td><td></td><td></td><td>CO</td><td></td><td>T-</td><td>or</td><td>OR</td><td>CM</td><td>co</td>

<td>CO</td><td> &lt;0</td><td>CO</td><td>co</td><td>co</td><td>CO</td><td>CO</td><td>CO</td><td>co</td>

<td>Φ</td><td> 2 £</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td>

<td>Ό</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td>

<td>ro</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td>

<td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td>

<td>Z5</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td>

<td>ro</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td>

<td>φ</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td>

<td>CL</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td>

<td>AND</td><td>ro</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td>

<td>φ 1-</td><td rowspan="2">ixim max</td><td> &lt;0</td><td>CO</td><td>CT)</td><td>σ&gt;</td><td>CO</td><td>co</td><td> 00</td><td></td><td></td>

<td></td><td>CO</td><td>CO</td><td>CO</td><td>CO</td><td>CO</td><td>co</td><td>CO</td><td>r-</td><td></td>

<td></td><td>i £</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td>

<td></td><td>ro</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td>

<td></td><td rowspan="2"> § 0</td><td>it</td><td> 10</td><td> 1^</td><td> 00</td><td>CM</td><td>IT</td><td>IT</td><td>i ^.</td><td>co</td>

<td></td><td>CO</td><td>CO</td><td>co</td><td>co</td><td>CO</td><td>co</td><td>co</td><td>co</td><td>co</td>

<td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td>

<td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>CM</td><td>co</td><td>Tt</td>

<td></td><td></td><td> *</td><td>CM</td><td>«Co</td><td></td><td>* IT</td><td>I heard</td><td>CL</td><td>CL</td><td>CL</td>

<td></td><td></td><td>or</td><td>OR</td><td>or</td><td>or</td><td>or</td><td></td><td></td><td></td><td></td>

<td></td><td></td><td> —1</td><td> —1</td><td> —1</td><td>-J</td><td> —1</td><td>OR</td><td>OR</td><td>OR</td><td>or</td>

<td></td><td></td><td> 0.</td><td>D_ z&gt;</td><td>CL</td><td>D_</td><td>CL</td><td>OR</td><td>OR</td><td>OR</td><td>or</td>

<td></td><td></td><td>LU</td><td>UJ</td><td>LU</td><td>LU</td><td>LU</td><td> 2</td><td></td><td> 2</td><td>ZÉ</td>

<td></td><td></td><td>Ex</td><td>LU</td><td>Ex</td><td>LU</td><td>Ex</td><td>JE</td><td>JE</td><td>JE</td><td>JE</td>

<td></td><td></td><td></td><td></td><td></td><td></td><td></td><td>LU</td><td>UJ</td><td>LU</td><td>LU</td>

ro Ό c φ&gt; _ φ or k_

Φ Ό

O Q_ E φ llT

ES 2 298 362 T3

TABLE 7

<td colspan="2">Faulty heat shrinkage fraction</td><td> 0,2</td><td>or"</td><td> 0,2</td><td>or</td><td> 0,1</td><td> 9,2</td><td> 6,5</td><td> 00</td><td> 5,9</td><td>or</td><td>or</td><td>or</td><td>or</td><td>or</td><td></td>

<td rowspan="5">Percentage of heat shrinkage in the direction of maximum shrinkage (%)</td><td>1 - Jmin</td><td> 2,9</td><td> 2,6</td><td> 3,2</td><td>3.0 i</td><td>co</td><td> 6,2</td><td>CM IT</td><td>in</td><td> 5,5</td><td> 0,8</td><td> 0,9</td><td>'' T</td><td>ID</td><td> 0,9</td><td></td>

<td>Jmax -1</td><td>CM co</td><td>cm</td><td> 3,0</td><td> 6‘2</td><td>00 cm</td><td> 3,6</td><td> 3,5</td><td> 3,7</td><td> 3,8</td><td>r.</td><td> 8'0</td><td>CM</td><td>CO_</td><td>CM v-</td><td rowspan="5">{'&lt; &lt;k i Ί k (Ί C Ί £ c ü *</td>

<td>Minimum (Jmin)</td><td> 50,8</td><td> 54,5</td><td> 54,4</td><td> 50,8</td><td> 64,6</td><td> 45,0</td><td> 46,3</td><td> 50,9</td><td> 51,3</td><td> 52,7</td><td> 56,1</td><td> 56,1</td><td> 52,5</td><td> 9‘99</td>

<td>Maximum (Jmax)</td><td> 56,9</td><td> 59,8</td><td>or C0</td><td> 56,7</td><td> 70,5</td><td> 54,8</td><td> ' 55,0</td><td> 59,7</td><td> 60,6</td><td> 54,6</td><td> 57,8</td><td> 58,7</td><td> 53,3</td><td> 68,7</td>

<td>Half (1)</td><td> 53,7</td><td> 57,1</td><td> 57,7</td><td>53.8 i</td><td> 67,7</td><td> 51,2</td><td> ' 51,5</td><td> 56,0</td><td> 56,8</td><td> 53,5</td><td> 57,0</td><td> 57,5</td><td> 54,0</td><td> 67,5</td>

<td colspan="2"></td><td>EXAMPLE 1*</td><td>EXAMPLE 2</td><td>EXAMPLE 3 *</td><td>VO —1 Q. 5 LU -3 UJ</td><td>EXAMPLE 5 *</td><td>AHEM. COMP. 1</td><td>AHEM. COMP. 2</td><td>AHEM. COMP. 3</td><td>AHEM. COMP. 4</td><td>EXAMPLE 6</td><td>EXAMPLE 7</td><td>EXAMPLE 8</td><td>EXAMPLE 9</td><td>EXAMPLE 10</td>

ES 2 298 362 T3

TABLE 8

<td></td><td>j K - Lmin</td><td> 0,4</td><td> 0,5</td><td> 0,7</td><td> 0,6</td><td> 0,8</td><td> 1,0</td><td> 1,0</td><td> 0,7</td><td> 0,6</td><td> 0,2</td><td> 0,3</td><td> 0,3</td><td> 0,4</td><td> 0,4</td>

<td>Ίο^-Q_ k— o ra o or CL c Ό</td><td>Lmax - K</td><td> 0,6</td><td> 0,5</td><td> 0,4</td><td> 0,6</td><td> 0,7</td><td>r.</td><td> 0,9</td><td>CD</td><td></td><td> 0,3</td><td> 0,2</td><td> 0,4</td><td> 0,4</td><td> 0,3</td>

<td rowspan="2">OO CÜ k_ * - »coo Φ Ό ω Ό ω φ Φ TD OE X -ra E o ra&gt;</td><td>Minimum (Lmin)</td><td>K</td><td> 7,5</td><td>IT</td><td>l &lt;</td><td> 6,3</td><td> 6,9</td><td>or</td><td>r &lt;</td><td>r &lt;</td><td>r &lt;</td><td>00K</td><td>r &lt;</td><td> 8,0</td><td> 9‘9</td>

<td>Maximum (Lmax)</td><td>co</td><td> 8,5</td><td> 8,6</td><td> 8,9</td><td>8'Z</td><td> 9,0</td><td> 8,9</td><td>co co</td><td>CD</td><td>CN co</td><td> 8,3</td><td> 8,4</td><td> 8,8</td><td>CN K</td>

<td></td><td>Half (K)</td><td>8'Z</td><td>o oo</td><td> ! 8,2</td><td>I 8.3</td><td>r &lt;</td><td>OR)</td><td> 8,0</td><td>8'Z</td><td>or co</td><td>CD</td><td>co</td><td> 0‘8</td><td> 8,4</td><td> 6,9</td>

<td colspan="2"></td><td>EXAMPLE 1*</td><td>EXAMPLE 2</td><td>EXAMPLE 3 *</td><td>EXAMPLE 4</td><td>EXAMPLE 5 *</td><td>AHEM. COMP. 1</td><td>AHEM. COMP. 2</td><td>AHEM. COMP. 3</td><td>AHEM. COMP. 4</td><td>EXAMPLE 6</td><td>EXAMPLE 7</td><td>EXAMPLE 8</td><td>EXAMPLE 9</td><td>EXAMPLE 10</td>

ra Ό c Φ k_ Φ

Φ

Φ TD _O

CL E φ iZT

ES 2 298 362 T3

<img file="ES2298362T3_D0005.tif" />

<td rowspan="5">Percent heat shrinkage in orthogonal direction (%)</td><td>I M - Nmin</td><td></td><td>CN</td><td>l ¹’³</td><td> -</td><td>or_</td><td>CD</td><td>σ&gt; _</td><td> 2,0</td><td>CN</td><td>I 0.5</td><td> 0,3</td><td>Tt θ '</td><td> 9‘0</td><td> 9‘0</td>

<td>Nmax - M</td><td>co</td><td>Yes</td><td>CN</td><td></td><td> 1,4</td><td>ΙΟ CN</td><td>cn CN</td><td> 2,2</td><td>CT&gt; _</td><td> 0,8</td><td> 9‘0</td><td>I 9'0</td><td>¹ 0,7</td><td> | 0,5</td>

<td>Minimum (Nmin)</td><td>C \ T</td><td>ω CN</td><td>CN</td><td>CO</td><td>CN</td><td> 2,0</td><td></td><td>CN</td><td>6'L</td><td> 3,2</td><td> 3,3</td><td> 3,1</td><td> 3,6</td><td>ΙΟ</td>

<td>Maximum (Nmax)</td><td> 5,1</td><td> 5,0</td><td> 4,6</td><td> 5,6</td><td> 3,6</td><td> 6,4</td><td> 5,9</td><td> 5,2</td><td> 5,9</td><td> 4,5</td><td></td><td></td><td> 4,8</td><td> 2,5</td>

<td>Half (M)</td><td> 3,8</td><td> 3,5</td><td> 3,4</td><td>OJ</td><td> 2,2</td><td> ' 3.9</td><td> 3,6</td><td> 3,2</td><td> 4,0</td><td>I 3.7</td><td> 3,6</td><td>3.5 I</td><td></td><td>Or CN</td>

<td colspan="2"></td><td>EXAMPLE 1*</td><td>EXAMPLE 2</td><td>EXAMPLE 3 *</td><td>EXAMPLE 4</td><td>EXAMPLE 5 *</td><td>AHEM. COMP. 1</td><td>AHEM. COMP. 2</td><td>AHEM. COMP. 3</td><td>AHEM. COMP. 4</td><td>EXAMPLE 6</td><td>EXAMPLE 7</td><td>EXAMPLE 8</td><td>EXAMPLE 9</td><td>EXAMPLE 10</td>

ra cd c Φ

L— _φ “φ

L_

Φ n _o

or.

E φ llT

As is evident from the data in Tables 1 to 9, in the Comparative Examples where a relatively smaller piece B or G was used for the Comparative Example and a plurality of hoppers were used in series, uneven supply was observed. of raw pieces, leading to greater variations in film composition and physical properties. As a result, the defective heat shrinkage fraction of the resulting labels was higher. On the other hand, in the Examples where pieces of uniform size were used, there was no uneven supply of the raw pieces and, therefore, there were no significant variations in the composition of the resulting film. Furthermore, in Examples 6 to 10, where the surface temperature of the film was strictly controlled in the stretching process, it was confirmed that the variation in the heat shrinkage properties of the resulting film was also small.

A film roll of a heat shrinkable polyester film of the present invention has little variation in composition and physical properties of the long film rolled along the entire length, leading to

ES 2 298 362 T3 a drastic decrease in the incidence of defects in the solvent adhesion process and in the incidence of defects such as insufficient shrinkage, shrinkage shading, wrinkling, deformation, uneven shrinkage, etc., in the shrinkage process by heat. Additionally, a process for producing a roll of heat shrinkable film of the present invention is very useful in the industrial production of the film, as the process can easily decrease variations in polymer composition and shrinkage properties. long film heat.