JP4894176B2 - Heat-shrinkable polyester film and label using recycled PET bottle materials - Google Patents

Description

  The present invention relates to a heat-shrinkable polyester film useful for recycling PET bottles, corresponding to environmental problems and effective use of resources.

  Polystyrene and polyester films are mainly used as heat-shrinkable films for trunk labels such as PET bottle containers and cap seals such as glass containers. The heat-shrinkable polystyrene film is mainly used as a general-purpose type because it is less expensive than the heat-shrinkable polyester film and can be subjected to shrinkage treatment relatively easily. On the other hand, heat-shrinkable polyester film is used for applications that require high quality mainly because it has superior heat resistance, good film gloss, and high tightening stress after shrinkage compared to polystyrene film. Yes.

  On the other hand, from the viewpoint of environmental problems and effective utilization of resources, there is an active movement to recycle polyester recycled materials such as PET bottles, and one of the heat shrinkable polyester films that can be used. For example, Patent Document 1 describes an invention of a heat-shrinkable film material composed of a resin derived from a polyethylene terephthalate container and an amorphous polyester resin.

However, polyethylene terephthalate recycled materials such as PET bottles are made by mixing various containers and have large variations in physical properties such as monomer composition and crystallinity. Can not get the quality product. In addition, it is expected that the film strength is insufficient due to a decrease in molecular weight in the regeneration process, and a cutting problem occurs during processing such as printing. Moreover, the heat-shrinkable polyester film using a large amount of polyethylene terephthalate raw materials including recycled raw materials also has a problem that it cannot be adhered with tetrahydrofuran, which is a general-purpose solvent.
JP 2004-196918 A

  The present invention is a heat-shrinkable polyester system that can be bonded with tetrahydrofuran without being cut during processing such as printing even when recycled raw materials such as PET bottles are used, and that conforms to the PET bottle recycling recommended mark application conditions. A film is provided.

The heat-shrinkable polyester film of the present invention that has solved the above problems has a B / A / B two-kind three-layer structure, and the polyvalent carboxylic acid component of the polyester raw material composition constituting the A layer is terephthal Acid only, polyhydric alcohol component is ethylene glycol 81.6-84.7 mol%, 1,4-butanediol 9.4-9.6 mol%, neopentyl glycol or 1,4-cyclohexanedimethanol 5 0.7 to 9.0 mol%, the content of PET bottle recycled raw material in layer A is 50 to 70% by weight, and the polyester raw material composition constituting layer B is composed of terephthalic acid alone as the polyvalent carboxylic acid component. The polyhydric alcohol component is ethylene glycol 63.5 to 67.5 mol%, 1,4-butanediol 9.4 to 9.6 mol%, neopentyl glycol or 1,4- The heat in the main contraction direction when cyclohexanedimethanol is 22.9-27.1 mol%, contains 25% by weight or more of PET bottle recycled raw material in the film , and is pulled up by being immersed in warm water at 80 ° C. for 10 seconds. The shrinkage rate is 30% or more, the thermal shrinkage rate in the direction perpendicular to the main shrinkage direction is 10% or less, and the main shrinkage direction after the film is stored for 28 days in an atmosphere at a temperature of 30 ° C. and a relative humidity of 85%. A tensile test is performed in the orthogonal direction, and the ratio of the number of test pieces fractured at an elongation of 5% or less to the total number of test pieces is 25% or less.

  The heat-shrinkable polyester film of the present invention is excellent in mechanical strength, can be bonded with a general-purpose solvent, despite the use of recycled PET bottles, and conforms to the PET bottle recycling recommended mark application conditions. It is also useful in terms of environmental issues and effective use of resources.

  The heat-shrinkable polyester film of the present invention contains 25% by weight or more, preferably 25-45% by weight of a PET bottle recycled raw material in the film, and more preferably, the main constituent constituting the film is ethylene terephthalate. It contains one or more secondary constituents, and contains neopentyl glycol or 1,4-cyclohexanedimethanol as the most frequent secondary constituent. More preferably, it is a heat-shrinkable polyester-based polyester film having a multilayer structure of two or more layers having a layer (A layer) containing 45 to 80% by weight of a recycled plastic bottle raw material and another layer (B layer), Layer B contains ethylene terephthalate as a main constituent and one or more secondary constituents composed of a polyvalent carboxylic acid component and / or a polyhydric alcohol component, and the total amount of polyvalent carboxylic acid components is 100 mol%, When the total amount of the monohydric alcohol component is 100 mol%, the content of the polyvalent carboxylic acid component or polyhydric alcohol component which is the most secondary component in the B layer is 20 mol% or more. The film contains a secondary component that becomes amorphous in the front and back layers, ensuring a practical level of mechanical strength even by using recycled materials with low intrinsic viscosity by increasing the addition rate of polyethylene terephthalate in the base layer. By doing so, the shrinkage rate required as a shrinkage label is secured, and adhesion with tetrahydrofuran, which is a general-purpose solvent, is possible. In the present invention, “solvent bonding is possible” means that the solvent bonding strength is 3 N / 15 mm or more according to the evaluation method of Examples described later.

  The heat-shrinkable polyester film of the present invention should have a heat shrinkage rate of 30% or more in the main shrinkage direction in warm water at 80 ° C. The reason why the heat shrinkage rate is less than 30% is that when the container is shrunk as a label, a portion that does not adhere to the container is generated and becomes defective. The thermal shrinkage rate in the main shrinkage direction is more preferably 40% or more, and further preferably 50% or more.

  Further, the thermal shrinkage rate in the direction orthogonal to the main shrinkage direction must be 10% or less. When the shrinkage rate exceeds 10%, the container is greatly displaced in the vertical direction when the container is shrunk to cover the container, which results in poor appearance and unstable label position. The thermal shrinkage rate in the direction orthogonal to the more preferred main shrinkage direction is 8% or less, more preferably 6% or less.

The PET bottle recycled raw material content in the heat-shrinkable polyester film of the present invention is 25% by weight or more, preferably 25 to 45% by weight. Those less than 25% by weight do not conform to the PET bottle recycling recommendation mark approved by the PET Bottle Recycling Promotion Council, and the PET bottle recycling efficiency is low, so improvements are desired from the viewpoint of environmental issues and effective use of resources. is there. On the other hand, if it exceeds 45 mass%, the necessary shrinkage rate is insufficient, which is not preferable.

  The recycled plastic bottle material here means a recycled raw material for a polyethylene terephthalate container such as a plastic bottle. There are a recycled material material and a recycled chemical material, but only one of them or a mixed material may be used.

  In the present invention, a preferred embodiment is a heat-shrinkable polyester-based polyester system having a multilayer structure of two or more layers having a layer (A layer) containing 45% by weight or more of a PET bottle recycling raw material and another layer (B layer). It is a film, The addition rate of the PET bottle reproduction | regeneration raw material to A layer has preferable 45 to 80 weight%. When the addition ratio is 25% by weight or more and less than 45% by weight, the mechanical strength is insufficient, and a problem that the film is cut during processing such as printing is likely to occur. If it is less than 25% by weight, the recycling efficiency of PET bottles is low, and improvements are desired from the viewpoint of environmental problems and effective use of resources. On the other hand, if it exceeds 80% by weight, the necessary shrinkage is insufficient. The addition rate of the PET bottle recycled raw material to the layer A is more preferably 45% by weight or more and 70% by weight or less, and further preferably 50% by weight or more and 65% by weight or less.

  When the present invention is a multi-layer structure, the laminated structure includes an A / B two-kind two-layer structure, a B / A / B two-kind three-layer structure, a two-kind four-layer structure, and a third layer. Any of three or more three-layered structures such as B / C / A / C / B and C / B / A / B / C can be adopted, but the reason for stabilizing the solvent adhesion particularly in tetrahydrofuran To B / A / B are preferable. The third layer C layer may be an intermediate composition of the A layer and the B layer, or a layer containing a colorant and an ultraviolet absorber. Moreover, when using for an outermost layer, it is good also as a layer which does not contain a reproduction raw material from a concern of the contamination containing which is a problem of a reproduction raw material. In addition, when it is set as a multilayer structure, the addition amount with respect to the whole film of a PET bottle reproduction | regeneration raw material can be adjusted with the addition amount and each layer ratio of the PET bottle reproduction | regeneration raw material with respect to each layer. The preferred layer ratio is, for example, in the B / A / B two-kind three-layer configuration, the preferred layer ratio of the A layer and the B layer is 30:70 to 70:30.

  In the above-mentioned B / A / B two-kind three-layer configuration, the front and back layers (B layer) introduce an amorphous component to ensure the necessary shrinkage as a shrink label and secure adhesion with tetrahydrofuran, a general-purpose solvent. It is preferable that the content of the most frequent secondary component (amorphous component) be 20% or more. The amorphous component here is preferably a neopentyl glycol component and / or 1,4-cyclohexanedimethanol, and specific examples include polyethylene terephthalate and neopentyl glycol and / or 1,4-cyclohexanedimethanol. The copolymer is preferably in the range of 20 to 40 mol%. This is because when the copolymerization ratio is 20 mol% or less, adhesion with tetrahydrofuran is difficult, and the necessary shrinkage cannot be obtained. On the other hand, when the copolymerization ratio exceeds 40 mol%, the degree of polymerization is difficult to increase, and also in the preliminary drying before film formation, the drying temperature cannot be raised due to adhesion between the pellets, resulting in a decrease in production efficiency. is there. The amount of the copolymer added to the B layer is preferably 65% by weight or more. In addition, 35% or less is preferable and, as for the addition amount of the PET bottle reproduction | regeneration raw material to B layer, 20% or less is more preferable.

  In the present invention, the intrinsic viscosity of the film is preferably 0.61 dl / g or more. This is because by setting the intrinsic viscosity of the film to 0.61 dl / g or more, the mechanical strength of the film is improved, and defects such as cutting during printing or solvent bonding can be reduced. In order to make the intrinsic viscosity of the film 0.61 dl / g or more, for example, it can be achieved by using a high molecular weight raw material for the polyester used. In the present invention, the intrinsic viscosity may be different between the base layer and the front and back layers. However, the intrinsic viscosity of the whole film may be 0.61 dl / g or more. In addition, the preferable intrinsic viscosity of a film is 0.63 dl / g or more.

  The heat-shrinkable polyester film of the present invention has an ester unit formed from a polyvalent carboxylic acid component and a polyhydric alcohol component as a main constituent unit. In consideration of the tear resistance, strength, heat resistance, etc. of the film, the ethylene terephthalate unit should be selected so that the ethylene terephthalate unit is 50 mol% or more in 100 mol% of the constituent unit of the heat-shrinkable polyester film. Is the main constituent. Therefore, in 100 mol% of the polyvalent carboxylic acid component, the terephthalic acid component (component comprising terephthalic acid or its ester) is 50 mol% or more, and in 100% mol of the polyhydric alcohol component, the ethylene glycol component is 50 mol% or more. It is preferable to do. As for an ethylene terephthalate unit, 55 mol% or more is more preferable, and 60 mol% or more is further more preferable.

  Examples of the polyhydric alcohol for forming the polyhydric alcohol component in the ester unit include 1,3-propanediol, triethylene glycol, 1 in addition to ethylene glycol and neopentyl glycol and 1,4-cyclohexanedimethanol. , 4-butanediol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, 2-methyl-1,5-pentanediol, 2,2-diethyl-1,3-propanediol, 1, Aliphatic diols such as 9-nonanediol and 1,10-decandiol, trimethylolpropane, glycerin, pentaerythritol, diethylene glycol, dimer diol, polyoxytetramethylene glycol, alkylene oxide adducts of bisphenol compounds or derivatives thereof, etc. Can also be used together A.

  In addition to terephthalic acid and its esters, aromatic dicarboxylic acids, their ester-forming derivatives, aliphatic dicarboxylic acids, etc. can be used as the polyvalent carboxylic acids for forming the polyvalent carboxylic acid component. is there. Examples of the aromatic dicarboxylic acid include isophthalic acid, naphthalene-1,4- or -2,6-dicarboxylic acid, and 5-sodium sulfoisophthalic acid. Moreover, derivatives of these aromatic dicarboxylic acids and terephthalic acids include derivatives such as dialkyl esters and diaryl esters. Examples of the aliphatic dicarboxylic acid include glutaric acid, adipic acid, sebacic acid, azelaic acid, oxalic acid, succinic acid and the like, and an aliphatic dicarboxylic acid usually called dimer acid. Furthermore, an oxycarboxylic acid such as p-oxybenzoic acid, and a polyvalent carboxylic acid such as trimellitic anhydride and pyromellitic anhydride may be used in combination as necessary.

  In addition, although not polyhydric alcohols or polycarboxylic acids, lactones represented by ε-caprolactone may be used in part. Lactones are those that ring-open and become units having ester bonds at both ends, and a unit derived from one lactone can be considered to be a carboxylic acid component and an alcohol component. Therefore, when lactones are used, the amount of 1,4-cyclohexanedimethanol component and the amount of other polyhydric alcohol components is 100 mol% of the amount obtained by adding the unit amount derived from lactones to the amount of polyhydric alcohol components. Calculate as Also, when calculating the amount of each polycarboxylic acid component, the amount obtained by adding the unit amount derived from the lactone to the amount of the polyvalent carboxylic acid component is 100 mol%.

  As a preferable component constituting the unit other than the ethylene terephthalate unit, a component capable of reducing the high crystallinity by the ethylene terephthalate unit and ensuring low-temperature heat shrinkability and solvent adhesion is preferable. Examples of such a crystallinity-reducing component include isophthalic acid, naphthalene-1,4- or -2,6-dicarboxylic acid for polyvalent carboxylic acid components, and neopentyl glycol, 1,4-dicarboxylic acid for polyhydric alcohol components. Cyclohexanedimethanol, 1,3-propanediol, and 1,4-butanediol are preferable, and neopentyl glycol and 1,4-cyclohexanedimethanol are particularly preferable. In 100 mol% of the constituent unit of the raw material polyester, the unit containing these crystallinity-reducing components is preferably 10 mol% or more, more preferably 12 mol% or more, and further preferably 15 mol% or more.

  The polyester constituting the heat-shrinkable polyester film can be produced by melt polymerization according to a conventional method, but a so-called direct polymerization method in which an oligomer obtained by directly reacting a dicarboxylic acid and a glycol is polycondensed is used. A so-called transesterification method in which a dimethyl ester and a glycol are subjected to a transesterification reaction and then polycondensed, and any production method can be applied. Moreover, the polyester obtained by another polymerization method may be sufficient. Various conventional catalysts can be used as the polymerization catalyst. For example, titanium-based catalysts (titanium tetrabutoxide, etc.), antimony-based catalysts (antimony trioxide, etc.), germanium-based catalysts (germanium dioxide, etc.), cobalt-based catalysts (cobalt acetate) Etc.).

  In addition, in order to improve the slipperiness of the heat-shrinkable film, for example, an inorganic lubricant such as titanium dioxide, fine particle silica, kaolin, calcium carbonate, or an organic lubricant such as a long-chain fatty acid ester is added or applied. May be. Moreover, you may add or apply | coat additives, such as a stabilizer, a coloring agent, antioxidant, an antistatic agent, and an ultraviolet absorber, as needed.

  Furthermore, in the present invention, a tensile test was performed in the direction orthogonal to the main shrinkage direction after the film was stored for 28 days in an atmosphere of a temperature of 30 ° C. and a relative humidity of 85%, and the number of test pieces fractured at an elongation of 5% or less. The ratio (initial fracture rate) to the total number of test pieces is 25% or less. By setting the initial breaking rate within a predetermined range, good processing suitability can be ensured even after the film has been stored for a long time. In order to control the initial breaking rate within a predetermined range, it is preferable to control the mixing amount of the plastic bottle recycling raw material, the laminated structure, and the intrinsic viscosity of the film, and combine it with a film forming method described later.

  The following method is desirable for producing the heat-shrinkable polyester film of the present invention. First, a chip-like PET bottle recycling raw material and other polyester raw materials are prepared, and these are dried using a dryer such as a hopper dryer or a paddle dryer, or a vacuum dryer. Then, it mixes suitably and it extrudes into a film form at the temperature of 200-300 degreeC from an extruder. Alternatively, the undried chips are similarly extruded into a film while removing moisture in a vented extruder. What is necessary is just to co-extrusion for the method of using the laminated film of a multilayer structure. As the PET bottle recycling raw material, it is preferable to use a chip-like material that has been cleaned and pulverized by a known method.

 When extruding, any existing method such as T-die method or tubular method may be adopted. After extrusion, it is quenched with a casting roll to obtain an unstretched film. The “unstretched film” includes a film on which a tension necessary for feeding the film in the manufacturing process is applied. By placing an electrode between the extruder and the casting roll and applying a voltage between the electrode and the casting roll, it is possible to electrostatically adhere the film to the roll in terms of suppressing film thickness unevenness. To preferred.

  The unstretched film is stretched. The stretching treatment may be performed continuously after cooling with the above-described casting roll or the like, or may be wound once in the form of a roll after cooling and then performed. Since it is practical in terms of production efficiency that the maximum shrinkage direction is the film transverse (width) direction, an example of a stretching method in the case where the maximum shrinkage direction is the transverse direction will be shown below. Even when the maximum shrinkage direction is the longitudinal (longitudinal) direction of the film, the film can be stretched according to a normal operation such as changing the stretching direction by 90 ° in the following method.

  When the heat-shrinkable polyester film is stretched in the transverse direction using a tenter or the like, prior to the stretching step, the film surface temperature is heated to a certain temperature within the range of Tg + 0 ° C. to Tg + 60 ° C., and Tg-20 The film is stretched 2.3 to 7.3 times, preferably 2.5 to 6.0 times at a predetermined temperature in the range of from C to Tg + 40C. Thereafter, heat treatment is performed at a predetermined temperature in the range of 50 ° C. to 110 ° C. while stretching 0 to 15% or relaxing 0 to 15%, and if necessary, at a predetermined temperature in the range of 40 ° C. to 100 ° C. Further heat treatment is performed to obtain a heat-shrinkable polyester film.

  As a stretching method, not only horizontal uniaxial stretching with a tenter, but also stretching in the longitudinal direction by 1.0 to 4.0 times, preferably 1.1 to 2.0 times may be performed. When biaxial stretching is performed in this manner, either continuous biaxial stretching or simultaneous biaxial stretching may be performed, and restretching may be performed as necessary. Further, in the sequential biaxial stretching, any of stretching methods such as vertical and horizontal, horizontal and vertical, vertical and horizontal and horizontal and vertical and horizontal directions may be used.

  Although the thickness of the heat-shrinkable polyester film of the present invention is not particularly limited, for example, as a heat-shrinkable polyester film for labels, the total thickness is 20 μm or more, preferably 25 μm or more, and 300 μm or less, preferably 200 μm or less. It is recommended that

  In order to use the heat-shrinkable polyester film as a heat-shrinkable label, a known tube-shaped forming apparatus is used to apply an adhesive solvent with a predetermined width slightly inside from the edge of one side of the film, and immediately the film Are rolled and bonded with overlapping ends, and processed into a tube. This tube can be cut into a predetermined length to obtain the heat-shrinkable label of the present invention.

  The film can be bonded by a melt bonding method in which a part of the film is melted, but it is preferable to use a solvent from the viewpoint of suppressing fluctuations in the thermal shrinkage characteristics of the label. Examples of solvents that can be used include aromatic hydrocarbons such as benzene, toluene, xylene, and totimethylbenzene; halogenated hydrocarbons such as methylene chloride and chloroform; phenols such as phenol; furans such as tetrahydrofuran; Examples of the organic solvent include oxolanes such as 3-dioxolane; among them, 1,3-dioxolane and tetrahydrofuran are preferable in view of high safety. The heat-shrinkable label can be coated after being attached to a container such as a PET bottle and then heat-shrinkable by a known heat-shrinking means (hot air tunnel, steam tunnel, etc.).

Hereinafter, the present invention will be described in more detail by way of examples. However, the following examples are not intended to limit the present invention, and modifications and implementations within the scope of the present invention are included in the present invention. Moreover, the measuring method of the physical property of the film obtained by the Example and the comparative example is as follows.

(1) Thermal shrinkage rate The film was cut into a 10 cm × 10 cm square, immersed in warm water at 80 ° C. ± 0.5 ° C. for 10 seconds under no load, and then thermally shrunk. It is a value obtained by immersing in 5 ° C. water for 10 seconds and then measuring the lengths of the sample in the vertical and horizontal directions according to the following formula. The direction with the largest shrinkage rate is defined as the maximum shrinkage direction.
Thermal shrinkage rate (%) = (length before shrinkage−length after shrinkage) ÷ (length before shrinkage) × 100

(2) Solvent adhesiveness One side of the film is continuously coated with tetrahydrofuran (THF) at a coating amount of 3 g / m ² and a width of 5 mm, the films are immediately bonded together, and the films are joined into a tube shape. After being left in an environment of a temperature of 25 ° C. and a relative humidity of 65% for 24 hours, the tube is cut to a width of 15 mm in a direction perpendicular to the flow direction during processing, a sample is taken, and the joint portion is JIS K 6854 in the above direction. A T-type peel test is performed according to the above.
The number of test pieces was 20, and the test piece length was 60 mm, the distance between chucks was 20 mm, the test piece width was 15 mm, the temperature was 23 ° C., and the tensile speed was 200 mm / min.
○: 3N / 15mm or more ×: Less than 3N / 15mm

(3) Mechanical strength Tensile test (test specimen width: 15 mm, specimen length: 120 mm, distance between chucks: 20 mm) in the direction orthogonal to the maximum shrinkage direction after storage for 28 days in an atmosphere of 30 ° C. × 85% relative humidity The number of test pieces fractured at a tensile rate of 200 m / min, temperature of 23 ° C., number of samples: 20) and elongation of 5% or less was counted and evaluated according to the following criteria. In addition, the ratio (%) with respect to the total number of test pieces of the number of test pieces fractured at an elongation of 5% or less was defined as the initial fracture rate.
○: 0 to 5 (initial breakage rate 0 to 25%)
Δ: 6 to 14 pieces (initial breakage rate 30 to 70%)
×: 15 to 20 (initial breaking rate: 75 to 100%)

(4) Intrinsic Viscosity 0.1 g of a sample (chip or film) is precisely weighed and dissolved in 25 ml of a mixed solvent of phenol / tetrachloroethane = 3/2 (mass ratio) and then 30 ± 0 using an Ostwald viscometer. Measure at 1 ° C. The intrinsic viscosity [η] is obtained by the following formula (Huggins formula).

(Equation 1) η _SP / c = [η] + k [η] ² c
k is a so-called Huggins constant and is a measure of hydrodynamic interaction between solute molecules.
[Η] is a plot of η _SP / c against c from viscosity measurements of several solutions with different concentrations,
The obtained straight line is determined in general from c → 0.
It is the specific viscosity when the η _SP concentration is c.

Experiments 1-3
After drying the raw materials mixed at the raw material mixing ratio shown in Table 2, each is melted at 270 ° C. by a separate single screw extruder, co-extruded from a T-die, cooled with a chill roll, and an unstretched film having a three-layer structure (Thickness: 160 μm) This unstretched film was preheated at 85 ° C. for 10 seconds, stretched 4 times at 80 ° C. in the transverse direction with a tenter, and then heat treated at 78 ° C. for 10 seconds to obtain a thickness of 40 μm. A heat-shrinkable polyester film of (base layer: 20 μm / front and back layers: 10 μm each) was obtained. Table 1 shows the composition and content of the polyester resin used. In Table 1, TPA means terephthalic acid, EG means ethylene glycol, BD means 1,4-butanediol, NPG means neopentyl glycol, and CHDM means 1,4-cyclohexanedimethanol. The heat-shrinkable polyester film formed in Experiments 1 to 3 has sufficient shrinkage and mechanical strength as a heat-shrinkable film as shown in Table 2, and can be bonded with tetrahydrofuran, which is a general-purpose solvent. I understand.

Experiments 4-5
A heat-shrinkable polyester film having a thickness of 40 μm was obtained in the same manner as in Experiments 1 to 3, except that the raw material blending ratio shown in Table 2 was used. As shown in Table 2, those having the same amount of recycled materials added to the base layer and the skin layer (Experiment 4) have low mechanical strength, and those having a high concentration of recycled materials added to the base layer (Experiment 5) have a small shrinkage rate. It can be seen that the film is not sufficiently shrinkable as a shrink film.

  The heat-shrinkable polyester film of the present invention is useful as an environmentally friendly heat-shrinkable label film because it has a quality equivalent to that of a conventional film despite the use of recycled PET bottle materials.

Claims (5)

About the polyester raw material composition which has 2 types 3 layer structure of B / A / B and comprises A layer, a polyhydric carboxylic acid component is only a terephthalic acid and a polyhydric alcohol component is ethylene glycol 81.6-84. 7 mol%, 1,4-butanediol 9.4 to 9.6 mol%, neopentyl glycol or 1,4-cyclohexanedimethanol 5.7 to 9.0 mol% For the polyester raw material composition having a content of 50 to 70% by weight and constituting the B layer, the polyvalent carboxylic acid component is only terephthalic acid, the polyhydric alcohol component is 63.5 to 67.5 mol% of ethylene glycol, 1,4-butane diol 9.4 to 9.6 mol%, a 22.9 to 27.1 mol% neopentyl glycol or 1,4-cyclohexanedimethanol, Fi Containing 25% by weight or more of PET bottle recycled raw material in the container, and having a heat shrinkage rate of 30% or more in the main shrinkage direction when dipped in warm water at 80 ° C. for 10 seconds and perpendicular to the main shrinkage direction The tensile shrinkage test was conducted in the direction perpendicular to the main shrinkage direction after the film was stored for 28 days in an atmosphere at a temperature of 30 ° C. and a relative humidity of 85%, and the elongation was 5% or less. A heat-shrinkable polyester film characterized in that the ratio of the number of fractured test pieces to the total number of test pieces is 25% or less. 2. The heat-shrinkable polyester film according to claim 1, wherein the main component constituting the film is ethylene terephthalate, and the content of the recycled plastic bottle material in the film is 25 to 45% by weight. The heat-shrinkable polyester film according to claim 1 or 2 , wherein the film can be solvent-bonded with tetrahydrofuran. The heat-shrinkable polyester film according to any one of claims 1 to 3 , wherein the intrinsic viscosity of the film is 0.61 dl / g or more. The heat-shrinkable label produced from the heat-shrinkable polyester-type film in any one of the said Claims 1-4 .