JP2010128038A - Heat shrinkable label and method for manufacturing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a label using a preferable heat shrinkable polyester film that can achieve initial adhesion without any problem when mounting the same on a container and has finish property and sufficient adhesion strength. <P>SOLUTION: A heat shrinkable label is molded into a continuous body by winding a heat shrinkable polyester film, which is at least uniaxially oriented, around a container, applying an active energy ray-curable adhesive to a part of the film and irradiating the film with active energy rays, wherein the active energy ray-curable adhesive contains a high molecular weight polyester resin containing an aliphatic dicarboxylic acid and having a number average molecular weight of 20,000-50,000. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a heat-shrinkable label, and more particularly to a heat-shrinkable label for coating bottles such as PET bottles (polyethylene terephthalate (PET) bottles) and glass bottles and a method for producing the same.

  In recent years, heat from various resins has been used for exterior packaging to improve the appearance of packages, packaging to avoid direct collision of contents, label packaging that protects glass bottles or plastic bottles and displays products. Shrinkable plastic films are widely used. Among these heat-shrinkable plastic films, stretched films made of polyvinyl chloride resin, polystyrene resin, polyester resin, etc. are used in various containers such as PET containers, polyethylene containers, glass containers, labels, cap seals or Used for integrated packaging purposes.

  However, although the polyvinyl chloride film has excellent shrinkage properties, it has low heat resistance and also has problems such as generation of hydrogen chloride gas during incineration and causing dioxins. In addition, when a polyvinyl chloride film is used as a shrink label for a PET container or the like, there is also a problem that when the container is recycled, the label and the container must be separated. On the other hand, polystyrene-based films have a good finished appearance after shrinkage, but have poor solvent resistance, so that there is a problem that an ink having a special composition must be used for printing. In addition, the polystyrene film needs to be incinerated at a high temperature and has a problem that a large amount of black smoke is generated with a strange odor during incineration.

  For this reason, polyester films having high heat resistance, easy incineration, and excellent solvent resistance have come to be widely used as heat-shrinkable labels, which increases the circulation of PET containers. Along with this, usage tends to increase.

  Up to now, as the heat-shrinkable polyester film, those which are largely shrunk in the width direction have been widely used. The heat-shrinkable polyester film whose width direction is the main shrinkage direction is stretched at a high magnification in the width direction in order to develop shrinkage characteristics in the width direction. In many cases, low-stretching is only performed, and some are not stretched. Such a film that has been stretched at a low magnification in the longitudinal direction or a film that has been stretched only in the width direction has a disadvantage that the mechanical strength in the longitudinal direction is inferior.

  In addition, since the label of the bottle must be circular and heat-shrinked in the circumferential direction after being attached to the bottle, when the heat-shrinkable film that heat-shrinks in the width direction is attached as a label, the width direction of the film is After an annular body (tube) is formed so as to be in the circumferential direction, the annular body must be cut into predetermined lengths and attached to the bottle. Therefore, it becomes more difficult to attach a label made of a heat-shrinkable film that heat-shrinks in the width direction to the bottle as the production speed increases.

  For this reason, recently, there has been a demand for a film that is heat-shrinkable in the longitudinal direction and can be mounted directly around the bottle from a film roll. Furthermore, in recent years, a wrapping method has been developed in which a container is closed by covering the periphery of a synthetic resin single-open container such as a lunch box with a strip-shaped film. It is also suitable for such packaging applications. Therefore, the demand for the film shrinking in the longitudinal direction is expected to increase dramatically in the future.

  In order to form a film continuum (label) by attaching a film shrinking in the longitudinal direction to a container such as a bottle, one end of a film of an appropriate length is stuck on the container, and the film is wound around the outer periphery of the container. In addition, a method is used in which the film ends are overlapped and bonded so that the other film end is on top (for example, Patent Document 1). Examples of the adhesion between these containers and films, or film edges include adhesion with an adhesive, adhesion with an adhesive, adhesion with a solvent, and adhesion with a heat seal.

However, as a sticking method used in the process of attaching these films to a container, sufficient adhesive strength cannot be obtained when a pressure sensitive adhesive is used, and label displacement or peeling occurs during heat treatment for shrinkage. Resulting in. Further, since the label is wound in a state where the container is standing, there is a problem that the viscosity of the solvent is too low in the solvent adhesion, and the coating becomes uneven due to dripping or scattering, or the surroundings are contaminated. Also, considering high-speed mounting from the viewpoint of improving productivity, it is important to perform the bonding process in a short time, but it is difficult to perform high-speed and uniform processing with heat sealing. Furthermore, for example, when a hot melt adhesive is used as the adhesive, there is a problem that label distortion due to the heat of the adhesive, shrinkage insufficiency in the subsequent process, etc. are likely to occur.
JP 2005-292195 A

  In order to solve these problems, it is considered that it is effective to use an active energy ray-curable adhesive as a method for bonding the container and the film or film ends. By using these adhesives, the adhesive is instantly cured by ultraviolet irradiation or electron beam irradiation after application of the adhesive, and by imparting strong adhesive force, film displacement or Since the film can withstand peeling and does not require a large amount of heat at the time of curing, it can be bonded without impairing the shrinkage force of the film.

  Furthermore, even when these active energy ray-curable adhesives are used, in order to wind a film around a container for the purpose of improving productivity, the initial adhesiveness (tack property) between the container and the film is weak, It is expected that the film may not fit well due to slipping or peeling during winding. In addition, it is effective to increase the viscosity of the adhesive to improve tackiness, but in continuous production, the so-called stringing or foam biting of the adhesive occurs during winding due to the increase in viscosity, resulting in poor appearance of the adhesive part or process contamination. May cause problems. Further, it was considered preferable to increase the adhesive strength after curing with active energy rays.

  The present invention provides a label using a good heat-shrinkable polyester film that solves the above-mentioned problems, can be bonded to the container without any major problem when it is attached to the container, and has sufficient adhesive strength as well as finish. It is an issue. It is another object of the present invention to provide a label using a heat-shrinkable polyester film whose main shrinkage direction is a longitudinal direction suitable for mounting while being wrapped around a container.

That is, the present invention has the following configuration.
1. A heat-shrinkable polyester film stretched at least uniaxially is wound around a container, an active energy ray-curable adhesive is applied to a part of the film, and an active energy ray is irradiated to form a continuous body. A heat-shrinkable label, wherein the active energy ray-curable adhesive contains a high-molecular-weight polyester resin having a number average molecular weight of 20,000 to 50,000 containing an aliphatic dicarboxylic acid.
2. The heat-shrinkable label according to the first aspect, wherein the heat-shrinkable polyester film is drawn and cut from a heat-shrinkable polyester film roll whose longitudinal direction is the main shrinkage direction.
3. A step of winding a heat-shrinkable polyester film stretched at least uniaxially around a container, a step of applying an active energy ray-curable adhesive to a part of the film, and a continuous irradiation of active energy rays A method for producing a heat-shrinkable label including a step of forming into a body, wherein the active energy ray-curable adhesive contains a high-molecular weight polyester resin having an aliphatic dicarboxylic acid and having a number average molecular weight of 20,000 to 50,000. A method for producing a heat-shrinkable label.
4). Thirdly, the method includes a step of previously applying an active energy ray-curable adhesive to a part of a container or / and a heat-shrinkable polyester film, and pasting the container and the heat-shrinkable polyester film. The manufacturing method of the heat-shrinkable label of description.

  According to the present invention, it was possible to provide a label using a heat-shrinkable polyester film that can be bonded at high speed when mounted on a container and has good finish. Furthermore, it was also possible to provide a label using a heat-shrinkable polyester film whose main shrinkage direction is the longitudinal direction suitable for mounting while being wrapped around a container. Therefore, it is useful as a heat-shrinkable label for bottles such as PET bottles and glass bottles.

  In the present invention, a heat-shrinkable polyester film stretched at least uniaxially is wound around a container, and then an active energy ray-curable adhesive is applied to a part of the film and irradiated with active energy rays. It relates to a heat-shrinkable label formed into a continuum by

  The dicarboxylic acid component constituting the polyester used as a raw material for the heat-shrinkable polyester film used in the present invention includes terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid, orthophthalic acid and other aromatic dicarboxylic acids, adipic acid, and azelaic acid. And aliphatic dicarboxylic acids such as sebacic acid and decanedicarboxylic acid, and alicyclic dicarboxylic acids.

  It is preferable not to use a trivalent or higher polyvalent carboxylic acid (for example, trimellitic acid, pyromellitic acid, and their anhydrides). The heat-shrinkable polyester film obtained using the polyester containing these polyvalent carboxylic acids is difficult to achieve the necessary high shrinkage rate.

  Examples of the diol component constituting the polyester used in the present invention include aliphatic diols such as ethylene glycol, 1-3 propanediol, 1-4 butanediol, neopentyl glycol, and hexanediol, and 1,4-cyclohexanedimethanol. Examples thereof include aromatic diols such as alicyclic diols and bisphenol A.

  The polyester used in the heat-shrinkable polyester film of the present invention is a cyclic diol such as 1,4-cyclohexanedimethanol, or a diol having 3 to 6 carbon atoms (for example, 1-3 propanediol, 1-4 butanediol). , Neopentyl glycol, hexanediol, and the like), and a polyester having a glass transition point (Tg) adjusted to 60 to 80 ° C. is preferable.

  Further, in the polyester used for the heat-shrinkable polyester film, the total of at least one diol component that can be an amorphous component in 100 mol% of the diol component is preferably 15 mol% or more, and 17 mol% or more. More preferably, it is more preferably 20 mol% or more. Here, examples of the diol that can be an amorphous component include neopentyl glycol and 1,4-cyclohexanediol. Moreover, since isophthalic acid can also be an amorphous component, 15 mol% or more of isophthalic acid may be used in 100 mol% of the dicarboxylic acid component.

  When synthesizing a polyester used for a heat-shrinkable polyester film, a diol having 8 or more carbon atoms (for example, octanediol) or a trihydric or higher polyhydric alcohol (for example, trimethylolpropane, trimethylolethane, glycerin). , Diglycerin and the like) are preferably not used. The heat-shrinkable polyester film obtained by using polyesters containing these diols or polyhydric alcohols is difficult to achieve the necessary high shrinkage rate.

  Moreover, it is preferable not to contain diethylene glycol, triethylene glycol, and polyethylene glycol as much as possible in the polyester used for the heat-shrinkable polyester film. In particular, although diethylene glycol is likely to be present because it is a by-product component during polyester polymerization, it is preferable that the content of diethylene glycol is less than 4 mol% in the polyester used in the present invention.

When the heat-shrinkable polyester film is treated in warm water at 90 ° C. for 10 seconds in a no-load state, the heat shrinkage rate in the longitudinal direction of the film calculated by the following formula 1 from the length before and after shrinkage ( That is, it is preferable that the 90 ° C. hot water heat shrinkage ratio is 15% or more and 80% or less.
Thermal shrinkage rate = {(length before shrinkage−length after shrinkage) / length before shrinkage} × 100 (%) Formula 1

  If the hot water thermal contraction rate in the longitudinal direction at 90 ° C. is less than 15%, the shrinkage amount is small, and therefore, it is not preferable because wrinkles and tarmi are generated on the label after thermal contraction. If the hot-water heat shrinkage rate in the direction exceeds 80%, it is not preferable because when used as a label, shrinkage tends to occur during heat shrinkage, or so-called “jumping” occurs. The hot water heat shrinkage in the longitudinal direction at 90 ° C. is preferably 20% or more, more preferably 30% or more, and particularly preferably 40% or more. Further, the hot water heat shrinkage in the longitudinal direction at 90 ° C. is preferably 75% or less, more preferably 70% or less, and particularly preferably 65% or less.

  The heat-shrinkable polyester film has a hot-water heat shrinkage ratio in the width direction of the film calculated by the above equation 1 from the length before and after shrinkage when treated in warm water at 90 ° C. for 10 seconds without load. , Preferably from -5% to 20%.

  It is not preferable that the hot water heat shrinkage in the width direction at 90 ° C. is less than −5% because it is difficult to obtain a good shrink appearance when used as a bottle label. When the shrinkage rate exceeds 20%, it is not preferable because when used as a label, distortion tends to occur during heat shrinkage. The hot water heat shrinkage in the width direction at 90 ° C. is preferably −2% or more, more preferably 0% or more, and particularly preferably 2% or more. Moreover, the hot water heat shrinkage in the width direction at 90 ° C. is preferably 17% or less, more preferably 14% or less, and particularly preferably 11% or less.

  A heat-shrinkable polyester film was subjected to 10% shrinkage in the longitudinal direction in warm water at 80 ° C., and then the right-angled tear strength in the width direction was obtained when the transverse tear strength per unit thickness was determined by the following method. The strength is preferably 100 N / mm or more and 300 N / mm or less.

[Measurement method of right-angle tear strength]
The film before heat shrinkage is cut so that the main shrinkage direction is the longitudinal direction, and both ends in the longitudinal direction are fixed to a rectangular frame. At this time, the sample is loosened and fixed to the frame so as to be 10% longer than the length of the frame. The sample is immersed in warm water of 80 ± 0.5 ° C. for each frame, and the film is contracted by 10% in the main contraction direction for about 5 seconds until the loose film becomes a tension state in the frame. Then, after immersing in 25 degreeC water, it may take out and may wipe off moisture.

Then, it samples as a test piece of a predetermined | prescribed magnitude | size according to JISK-7128-3 from the film after the said shrinkage | contraction. Thereafter, both ends of the test piece are gripped with a universal tensile tester, and the strength (N) at the time of tensile fracture in the width direction of the film is measured under the condition of a tensile speed of 200 mm / min. Then, the right angle tear strength (N / mm) per unit thickness (mm) is calculated using the following formula 2.
Right angle tear strength = strength at tensile fracture ÷ thickness Equation 2

  If the right-angled tear strength after shrinking 10% in the longitudinal direction in warm water at 80 ° C is less than 100 N / mm, when used as a label, it may be easily broken by an impact such as dropping during transportation. On the other hand, if the right-angled tear strength is greater than 300 N / mm, the cutability (ease of tearing) when tearing the label becomes unfavorable. The right-angled tear strength is preferably 125 N / mm or more, more preferably 150 N / mm or more, and particularly preferably 175 N / mm or more. The right-angled tear strength is preferably 275 N / mm or less, more preferably 250 N / mm or less, and particularly preferably 225 N / mm or less.

  A heat-shrinkable polyester film was subjected to 10% shrinkage in the longitudinal direction in warm water at 80 ° C., and then the Elmendorf tear load in the longitudinal direction and the width direction was determined by the following method. The Elmendorf ratio is preferably 0.15 or more and 1.5 or less.

[Measurement method of Elmendorf ratio]
The film is shrunk by 10% in the longitudinal direction in the same manner as in the case of the right angle tear strength. Thereafter, the Elmendorf tearing force is measured according to JIS K 7128-2. The Elmendorf tear load (N) in the longitudinal direction and the width direction of the film is measured, and the Elmendorf ratio is calculated using Equation 3 below.
Elmendorf ratio = Elmendorf tear load in the longitudinal direction ÷ Elmendorf tear load in the width direction Equation 3

  When the Elmendorf ratio is less than 0.15, it is not preferable because the Elmendorf ratio is difficult to tear straight along a notch (notch) when used as a label. On the other hand, if the Elmendorf ratio exceeds 1.5, it is not preferable because it easily tears at an obliquely shifted position. The Elmendorf ratio is preferably 0.20 or more, more preferably 0.25 or more, and particularly preferably 0.3 or more. The Elmendorf ratio is preferably 1.4 or less, more preferably 1.3 or less, and particularly preferably 1.2 or less.

The heat shrinkable polyester film preferably has a natural shrinkage ratio of 0.05% or more and 1.5% or less after aging (storage) in an atmosphere of 40 ° C. and 65% RH for 700 hours or more. The natural shrinkage rate can be calculated using the following equation 4.
Natural shrinkage rate = {(length before aging−length after aging) / length before aging} × 100 (%) Formula 4

  When the natural shrinkage rate is 1.5% or less, when a product wound in a roll shape is stored, winding tightening occurs and wrinkles are easily formed in the film, which is not preferable. The smaller the natural shrinkage rate, the better. However, from the viewpoint of measurement accuracy, about 0.05% is considered to be the lower limit. The natural shrinkage rate is preferably 1.3% or less, more preferably 1.1% or less, and particularly preferably 1.0% or less.

  The heat-shrinkable polyester film can be obtained by melt-extruding the above-described polyester raw material with an extruder to form an unstretched film, and biaxially stretching the unstretched film by the method shown below and heat-treating it. it can. The polyester can be obtained by polycondensing the above-described preferred dicarboxylic acid component and diol component by a known method. Usually, two or more kinds of chip-like polyester are mixed and used as a raw material for the film.

  When the raw material resin is melt-extruded, the polyester raw material is preferably dried using a dryer such as a hopper dryer or a paddle dryer, or a vacuum dryer. After the polyester raw material is dried in such a manner, it is melted at a temperature of 200 to 300 ° C. and extruded into a film using an extruder. In extruding, any existing method such as a T-die method or a tubular method can be employed.

  And an unstretched film can be obtained by rapidly cooling the sheet-like molten resin after extrusion. In addition, as a method of rapidly cooling the molten resin, a method of obtaining a substantially unoriented resin sheet by casting the molten resin from a die onto a rotating drum and rapidly solidifying it can be suitably employed.

  Further, as will be described later, the obtained unstretched film is stretched in the width direction under predetermined conditions, and then once heat-treated, and then stretched in the longitudinal direction (longitudinal stretching) under the predetermined conditions. By rapidly cooling the subsequent film, a heat-shrinkable polyester film used for the label of the present invention is obtained. Hereinafter, a preferable biaxial stretching / heat treatment method for obtaining a heat-shrinkable polyester film will be described in detail in consideration of differences from the conventional biaxial stretching / heat treatment method of a heat-shrinkable polyester film.

[Preferable stretching and heat treatment method for heat-shrinkable polyester film]
A normal heat-shrinkable polyester film is produced by stretching an unstretched film in the direction in which it is desired to shrink. Although there was a high demand for heat-shrinkable polyester films that shrink in the longitudinal direction from the past, simply stretching an unstretched film in the longitudinal direction makes it impossible to produce a wide film, resulting in poor productivity and thickness. A film with good spots cannot be produced. Moreover, if the method of extending | stretching to a longitudinal direction after extending | stretching previously to the width direction is employ | adopted, the shrinkage | contraction amount to a longitudinal direction will become inadequate, or it will shrink | contract unnecessarily in the width direction.

  For example, JP-A-8-244114 discloses a method of stretching an unstretched film in the order of length-width-length under predetermined conditions in order to improve the mechanical properties in the longitudinal direction. According to their pilot test, it was not possible to obtain a film with sufficient shrinkage in the longitudinal direction, which is the main shrinkage direction, and wrinkles in the width direction were produced on the produced film roll. It became clear that it became easy to do. In addition, if the longitudinal stretching ratio (the first stage longitudinal stretching ratio or the second stage longitudinal stretching ratio) is increased to increase the contractibility in the longitudinal direction, the film is finally stretched in the longitudinal direction. It has also been found that it is difficult to carry out a continuous and stable production due to frequent breaks. Moreover, the film obtained by the additional test had a large natural shrinkage rate, wrinkles in the longitudinal direction were generated in the produced film roll, and the notch opening property was also poor.

In order to finally increase the amount of contraction in the longitudinal direction, the present inventors have disadvantaged the method of stretching in the longitudinal direction after biaxial stretching in the longitudinal direction and the width direction as disclosed in JP-A-8-244114. It was considered that it would be more advantageous to simply stretch in the width direction and then stretch in the longitudinal direction. And in such a method of stretching in the longitudinal direction after stretching in the width direction (hereinafter, simply referred to as a transverse-longitudinal stretching method), the hot water temperature shrinkage rate in the longitudinal direction of the film, the natural shrinkage rate, depending on the conditions in each stretching step, We intensively studied how the notch openability changes. As a result, the present inventors have found out that when the film is manufactured by the transverse-longitudinal stretching method, the following measures are taken to increase the amount of shrinkage in the longitudinal direction, thereby enabling continuous and stable production. In addition, when the following measures are taken, the natural shrinkage rate of the film is reduced, the film roll after manufacture is less likely to wrinkle, and the notch opening property of the film is dramatically improved. It turns out that there is a surprising side effect of becoming. The means (1) to (4) will be described in detail below.
(1) Control of shrinkage stress after stretching in the width direction (2) Blocking of heating between stretching in the width direction and intermediate heat treatment (3) Trimming of film edge before stretching in the longitudinal direction (4) Control of Cooling Rate of Film after Longitudinal Drawing Hereinafter, each of the above-described means will be described in order.

(1) Control of shrinkage stress after stretching in the width direction In the production of a film by the transverse-longitudinal stretching method of the present invention, after stretching an unstretched film in the width direction, the temperature is 100 ° C. or more and less than 170 ° C. It is preferable to perform heat treatment (hereinafter, referred to as intermediate heat treatment) for a period of time between 0.0 seconds and 10.0 seconds. By performing this intermediate heat treatment, it is possible to obtain a label having good notch opening and no shrinkage spots. The reason why it becomes possible to obtain a film with good notch opening and no shrinkage by performing a specific intermediate heat treatment after transverse stretching is not clear, but by applying a specific intermediate heat treatment, It is considered that it is possible to reduce the shrinkage stress in the width direction while leaving some molecular orientation in the direction. The heat treatment temperature is preferably 110 ° C. or higher, and more preferably 115 ° C. or higher. Further, the heat treatment temperature is preferably 165 ° C. or lower, and more preferably 160 ° C. or lower. On the other hand, the heat treatment time may be appropriately adjusted in accordance with the raw material composition within a range of 1.0 second to 10.0 seconds.

  Stretching of the unstretched film in the width direction is a ratio of 2.5 times or more and 6.0 times or less at a temperature of Tg + 5 ° C. or more and Tg + 40 ° C. or less in a state where both ends of the width direction are held by clips in the tenter. It is preferable to do so. If the stretching temperature is lower than Tg + 5 ° C., it is not preferable because breakage is likely to occur during stretching. On the other hand, if it exceeds Tg + 40 ° C., thickness unevenness in the width direction is deteriorated, which is not preferable. The transverse stretching temperature is preferably Tg + 10 ° C. or higher, and more preferably Tg + 15 ° C. or higher. Further, the transverse stretching temperature is preferably Tg + 35 ° C. or lower, and more preferably Tg + 30 ° C. or lower. On the other hand, if the draw ratio in the width direction is less than 2.5 times, not only the productivity is deteriorated but also the thickness unevenness in the width direction is deteriorated, and on the contrary, if it exceeds 6.0 times, breakage occurs at the time of drawing. In addition, it is not preferable because a large amount of energy and a large apparatus are required for relaxation, and productivity deteriorates. The transverse draw ratio is preferably 3.0 times or more, and more preferably 3.5 times or more. The transverse draw ratio is preferably 5.5 times or less and more preferably 5.0 times or less.

(2) Interruption of heating between stretching in the width direction and intermediate heat treatment In the production of a film by the transverse-longitudinal stretching method of the present invention, it is preferable to perform an intermediate heat treatment after transverse stretching as described above. Between the transverse stretching and the intermediate heat treatment, it is preferable to pass through an intermediate zone in which an aggressive heating operation is not performed over a period of 0.5 seconds to 3.0 seconds. That is, in consideration of production cost, it is preferable to perform transverse stretching and intermediate heat treatment in the same tenter, but in the production of the film of the present invention, between the transverse stretching zone and the heat treatment zone in the tenter. It is preferable to provide an intermediate zone. In addition, in the intermediate zone, when the strip-shaped paper piece is hung in a state where the film is not passed, the hot air from the drawing zone and the heat treatment zone is blocked so that the paper piece hangs almost completely in the vertical direction. Is preferred. And in manufacture of a film, it is preferable to guide the film after transverse stretching to an intermediate zone, and let the intermediate zone pass over predetermined time. If the time for passing through the intermediate zone is less than 0.5 seconds, the hot air in the transverse stretching zone flows into the heat fixing zone due to the accompanying flow of the passing film, which makes it difficult to control the temperature of the intermediate heat treatment in the heat fixing zone. . On the contrary, it is sufficient that the time for passing through the intermediate zone is 3.0 seconds, and setting it longer than that is not preferable because it wastes equipment. The time for passing through the intermediate zone is preferably 0.7 seconds or more, and more preferably 0.9 seconds or more. The time for passing through the intermediate zone is preferably 2.5 seconds or less, and more preferably 2.0 seconds or less.

(3) Trimming of film edge before stretching in the longitudinal direction In the production of the film by the horizontal-longitudinal stretching method of the present invention, before stretching the film subjected to the intermediate heat treatment in the longitudinal direction, It is preferable to trim a thick portion that is not sufficiently stretched laterally (mainly a clip gripping portion during transverse stretching). That is, since there is a portion (thick portion) about 1.1 to 1.3 times as thick as the central portion in the vicinity of the left and right edges of the film, this film can be used with a tool such as a cutter. It is preferable that only the remaining portion is stretched in the longitudinal direction while cutting and removing the thick portion at the end. When trimming the film edge, it is preferable to cool the film so that the surface temperature of the film before trimming is 50 ° C. or lower. By cooling the film in this way, trimming can be performed without disturbing the cut surface. In addition, trimming of the film edge can be performed using a normal cutter or the like, but if a round blade having a circumferential cutting edge is used, a situation in which the cutting edge is locally dulled does not occur, and the film edge is This is preferable because it can continue to be cut sharply over a long period of time and does not cause a breakage during stretching in the longitudinal direction.

  By trimming the end of the film before stretching in the longitudinal direction in this way, it becomes possible to stretch the heat-fixed film uniformly in the longitudinal direction, and for the first time, it is possible to continuously produce a stable film without breaking for the first time. It becomes. In addition, it is possible to obtain a film having a large shrinkage in the longitudinal direction (main shrinkage direction). Furthermore, since the film can be uniformly stretched in the longitudinal direction, a film having a small thickness unevenness in the longitudinal direction can be obtained. In addition, by trimming the end of the film, bowing during stretching in the longitudinal direction is avoided, and a film having a small difference in physical properties between the left and right can be obtained.

(4) Control of cooling rate of film after longitudinal stretching In the production of the film by the transverse-longitudinal stretching method of the present invention, as described above, the film is stretched in the longitudinal direction after being subjected to an intermediate heat treatment after the transverse stretching. After the longitudinal stretching, the film is preferably cooled at a cooling rate of 30 ° C./second or more and 70 ° C./second or less until the surface temperature becomes 45 ° C. or more and 75 ° C. or less. Thus, cooling the film at an appropriate rate is effective in reducing the natural shrinkage rate. If the cooling rate is lower than 30 ° C./second or the surface temperature after cooling is higher than 75 ° C., it is not preferable because a low natural shrinkage rate cannot be obtained. On the other hand, if the cooling rate is so rapid that the cooling rate exceeds 70 ° C./second, the degree of shrinkage in the width direction of the film (so-called neck-in) increases, and the film surface is easily damaged, which is not preferable. .

  In addition, by using the above-mentioned means (1) to (4) in appropriate combination, the heat shrinkability in the longitudinal direction, the notch unsealing property, the low natural shrinkage rate, and the stable film-forming property are expressed very efficiently. Can be made.

  Although the thickness of the heat-shrinkable polyester film is not particularly limited, the heat-shrinkable film for labels is preferably 10 to 200 μm, and more preferably 20 to 100 μm.

  Next, the active energy ray curable adhesive will be described. In the present invention, an active energy ray-curable adhesive is used to bond the ends of the heat-shrinkable polyester film wound around the container for high-speed bonding. The adhesive used in the present invention is an adhesive using a solvent-free liquid resin that can be cured using active energy rays, particularly ultraviolet rays or electron beams, and includes urethane (meth) acrylate, epoxy The composition which mixed the acrylate resin which can be hardened | cured with active energy rays, such as (meth) acrylate and polyester (meth) acrylate, and the high molecular weight polyester resin of molecular weight 20000-50000 is mentioned. The high molecular weight polyester resin is preferably non-curable to active energy rays.

  Among these, in the present invention, an active energy curable adhesive composed of urethane (meth) acrylate and high molecular weight polyester is particularly preferable from the viewpoint of adhesion to a heat-shrinkable polyester film. Urethane (meth) acrylate obtained by using is preferable.

Most preferably, the number of repeating units of component (1) obtained by reacting the following (1) to (3) is 2 or more and 2.7 to 11 urethane bonds per component unit of component (1) Urethane acrylate (A) having a molecular weight of 1000 to 20000 having a group and / or a urea bond group, tetrahydrofurfuryl (meth) acrylate, phenoxyethyl (meth) acrylate, phenoxyethylene glycol acrylate, toluyloxyethyl (meth) acrylate, Active energy containing one or more radically polymerizable monomers (B) selected from the group consisting of N-vinylpyrrolidone and (meth) acryloylmorpholine, high molecular weight polyester (C), and photopolymerization initiator (D) A wire curable adhesive is preferred.
(1) Copolyester polyol having a constitutional unit derived from an aromatic dicarboxylic acid, containing 40 mol% or more of 100 mol% in the constitutional unit derived from dicarboxylic acid, and having a molecular weight of 1000 to 10,000
(2) Polyisocyanate compound
(3) Compounds having one or more (meth) acryloyloxy groups and one or more hydroxyl groups

  The copolymer polyester polyol (1) is obtained from a dicarboxylic acid component and a glycol component. The aromatic dicarboxylic acid which is an essential component is a dicarboxylic acid having an aromatic group in the molecule, for example, phthalic anhydride, terephthalic acid, isophthalic acid, orthophthalic acid, 1,5-naphthalic acid, etc. It is mentioned as a typical thing. If necessary, a small amount of tri- and tetracarboxylic acids such as trimellitic acid, trimesic acid and pyromellitic acid may be contained. Examples of dicarboxylic acids that can be copolymerized other than aromatic dicarboxylic acids include aliphatic dicarboxylic acids such as succinic acid, adipic acid, azelaic acid, sebacic acid, and dodecanedicarboxylic acid, 1,2-hexahydrophthalic acid, 1,3- Hexahydrophthalic acid, 1,4-hexahydrophthalic acid, alicyclic dicarboxylic acids such as perhydronaphthalenedicarboxylic acid, fumaric acid, maleic acid, itaconic acid and other unsaturated dicarboxylic acids, tetrahydrophthalic acid, cyclobutene dicarboxylic acid And unsaturated alicyclic dicarboxylic acids such as p-hydroxyethyloxybenzoic acid and ε-caprolactone.

  Examples of the glycol component include ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,9-nonanediol, and neopentyl. Glycol, diethylene glycol, dipropylene glycol, 2,2,4-trimethyl-1,3-pentanediol, 1,4-cyclohexanedimethanol, spiroglycol, 1,4-phenylene glycol, 1,4-phenylene glycol ethylene oxide Adducts, ethylene oxide adducts and propylene oxide adducts of bisphenol A, ethylene oxide adducts and propylene oxide adducts of hydrogenated bisphenol A, polyethylene glycol, polypropylene glycol There are diols such as polytetramethylene glycol. If necessary, it may contain a small amount of triol or tetraol such as trimethylolethane, trimethylolpropane, glycerin or pentaerythritol.

In order to obtain a copolyester polyol from such a dicarboxylic acid component and a glycol component, the glycol raw material may be synthesized in excess relative to the dicarboxylic acid raw material. At this time, it is desirable to synthesize so that the carboxyl group terminal is less than 50 eq / 10 ⁶ g in the copolyester. When it becomes 50 eq / 10 ⁶ g or more, when synthesizing the urethane acrylate (A) described later, the number of inactive terminals in the reaction with the polyisocyanate compound (2) increases so that the desired urethane acrylate cannot be obtained. There exists a possibility that the sclerosis | hardenability with respect to active energy ray may fall. Carboxyl terminus or less, more preferably 30eq / 10 ⁶ g, more preferably not more than 20eq / 10 ⁶ g. In the reaction, a known esterification catalyst may be used if necessary.

  The polyester polyol (1) used in the present invention contains a constituent unit derived from an aromatic dicarboxylic acid in an amount of 40 mol% or more in 100 mol% of a constituent unit derived from a dicarboxylic acid, and a molecular weight in the range of 1,000 to 10,000 is preferable. . If the aromatic dicarboxylic acid component is less than 40 mol%, the adhesiveness is lowered, and the heat resistance of the cured product is also lowered, which is not preferable. On the other hand, if the molecular weight is less than 1000, the adhesiveness is lowered and the flexibility of the cured product may be insufficient. When the molecular weight exceeds 10,000, the urethanization reactivity may be lowered, and the viscosity becomes high, so that the handling property may be lowered.

  Examples of the polyisocyanate compound (2) used in the present invention include 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, p-phenylene diisocyanate, biphenylmethane diisocyanate, m-phenylene diisocyanate, hexamethylene diisocyanate, tetra Methylene diisocyanate, 3,3′-dimethoxy-4,4′-biphenylene diisocyanate, 2,4-naphthalene diisocyanate, 3,3′-dimethyl-4,4′-biphenylene diisocyanate, 4,4′-diphenylene diisocyanate, 4, , 4'-diisocyanate diphenyl ether, 1,5'-naphthalene diisocyanate, p-xylylene diisocyanate, m-xylylene diisocyanate, 1,3-diisocyanate methylcyclo Diisocyanate compounds such as xane, 1,4-diisocyanate dicyclohexane, 4,4′-diisocyanate dicyclohexane, 4,4′-diisocyanate dicyclohexylmethane, isophorone diisocyanate, or 2,4- Examples include triisocyanate compounds such as tolylene diisocyanate trimer and hexamethylene diisocyanate trimer. Of these isocyanate compounds, isophorone diisocyanate and hexamethylene diisocyanate are particularly preferred in terms of weather resistance.

  Examples of the compound (3) having one or more (meth) acryloyloxy groups and one or more hydroxyl groups used in the present invention include mono (meth) acrylates of glycols such as ethylene glycol, diethylene glycol and hexamethylene glycol, 2-hydroxyethyl (meth) acrylate, 2-hydroxy-1,3-dimethacryloxypropane, 3-hydroxypropyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, trimethylolpropane, glycerin, Mono (meth) acrylate, di (meth) acrylate, di (meth) acrylate, tri (mono) methacrylate and di (meth) acrylate of triol compounds such as trimethylolethane, tetravalent or higher polyols such as pentaerythritol and dipentaerythritol (Meth) acrylate, glycerol monoallyl ether, hydroxyl group-containing acrylic compounds such as glycerol diacrylate ether.

  In the urethane acrylate (A) used in the present invention, polyols and / or polyamines (4) other than the above (1) may be used as a chain extender as necessary. Examples of polyols other than the above (1) include glycol components of the above (1) copolymer polyester polyol such as ethylene glycol and propylene glycol. Examples of the polyamine include high molecular weight polyamines such as hexamethylenediamine, diaminodiphenylmethane, N-methyldiethanolamine, and terminal aminated polybutadiene having two or more primary or secondary amino groups in the molecule. Further, water may be used in the same manner as these compounds.

  The urethane acrylate (A) of the present invention is obtained by reacting the copolymer polyester polyol (1) and the polyisocyanate compound (2) with [NCO] / [OH] <2 to obtain an isocyanate-terminated urethane prepolymer. It can be obtained by reacting a compound (3) having one or more (meth) acryloyloxy groups and one or more hydroxyl groups. As another production method, the copolymerized polyester polyol (1) and the polyisocyanate compound (2) are reacted with [NCO] / [OH] ≧ 2 to obtain an isocyanate-terminated prepolymer, and then one or more ( It can be obtained by reacting a compound (3) having a (meth) acryloyloxy group and one or more hydroxyl groups with a polyol and / or polyamine (4) other than the above (1). The urethane acrylate (A) can also be obtained by a method in which the raw material compounds (1) to (3) (if necessary (4)) are charged and reacted together at a constant ratio. In addition, you may add a well-known catalyst as needed at the time of reaction.

  The molecular weight of the urethane acrylate (A) of the present invention thus obtained is preferably in the range of 1000 to 20000, the number of repeating units in the molecule is 2 or more, and 2.7 to 11 urethane bonding groups per structural unit. And / or having a urea linking group. When the molecular weight is less than 1000, the strain at the time of curing increases, and the adhesiveness may be deteriorated, which is not preferable. When the molecular weight exceeds 20000, the compatibility with the later-described radical polymerizable monomer (B) is deteriorated, and as a result, the viscosity becomes too high, which may cause problems such as difficulty in use. When the number of repeating units is 1, the strength and adhesiveness of the cured product may be insufficient. Further, even if the number of repeating units is 2 or more, if the number of urethane bonding groups and / or urea bonding groups in the molecule is less than 2.7 per unit of the constituent polyester polyol (1), the adhesiveness is lowered. Further, the toughness of the cured product may be insufficient. Exceeding 11 is not preferable because the adhesiveness is lowered and the viscosity may increase due to urethane bonding or the like.

  The active energy ray-curable adhesive contains a radical polymerizable monomer (B). The radical polymerizable monomer (B) is selected from the group consisting of tetrahydrofurfuryl (meth) acrylate, phenoxyethyl (meth) acrylate, phenoxydiethylene glycol acrylate, toluyloxyethyl (meth) acrylate, N-vinylpyrrolidone and (meth) acryloylmorpholine. One or more selected monomers. Although other known radically polymerizable monomers may be added, the above-mentioned radically polymerizable monomer (B) is preferably used because of its excellent adhesion to polyester.

  Active energy ray-curable adhesives using these compounds are preferred because they are excellent in curability for active energy rays, adhesion to polyester, flexibility, weather resistance, water resistance, heat resistance and chemical resistance.

  The active energy ray-curable adhesive used in the present invention preferably contains a high molecular weight polyester resin (C) having a molecular weight of 20,000 to 50,000. The high molecular weight polyester resin (C) is preferably non-curable to active energy rays. By including such a high molecular weight polyester resin, it is possible to impart initial adhesion (tackiness) before curing between the container and the film or between the films. When the molecular weight is less than 20,000, tackiness is insufficient, and when the molecular weight exceeds 50,000, the viscosity becomes high, so that handling properties at the time of preparing and using the adhesive are deteriorated.

  Such a high molecular weight polyester resin is obtained from a dicarboxylic acid component and a glycol component, contains an aromatic dicarboxylic acid as an essential component, and further contains an aliphatic dicarboxylic acid. Aromatic dicarboxylic acid is a dicarboxylic acid having an aromatic group in the molecule. For example, phthalic anhydride, terephthalic acid, isophthalic acid, orthophthalic acid, 1,5-naphthalic acid and the like are representative. Can be mentioned. There are many aliphatic dicarboxylic acids essential for the present invention, and preferred aliphatic dicarboxylic acids include adipic acid, azelaic acid, and sebacic acid. If necessary, a small amount of tri- and tetracarboxylic acids such as trimellitic acid, trimesic acid and pyromellitic acid may be contained. In the dicarboxylic acid component, the molar ratio of aromatic dicarboxylic acid to aliphatic dicarboxylic acid is preferably 70:30 to 30:70, more preferably 60:40 to 40:60. Outside this range, it is difficult to achieve both initial adhesiveness (tackiness) to polyester and adhesiveness after curing. Moreover, it is preferable that the glass transition point (Tg) is -20 degreeC-20 degreeC from the point of handling property, initial stage adhesion | attachment, and the adhesive provision after hardening.

  Examples of preferable glycol components include diols such as ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, and neopentyl glycol. is there.

  The active energy ray-curable adhesive of the present invention preferably contains a photopolymerization initiator (D). Examples of the photopolymerization initiator include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2,2-dimethoxy-1,2-diphenylethane-1-one, benzyldimethyl ketal, 1 -(4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 4- (2-hydroxyethoxy) phenyl- (2-hydroxy-2-propyl) ketone, 1-hydroxycyclohexyl-phenylketone, Acetophenones such as 2-methyl-2-morpholino (4-thiomethylphenyl) propan-1-one, benzoin ethers such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzophenone, o -Benzoy Methyl benzoate, 4-phenylbenzophenone, hydroxybenzophenone, 4-benzoyl-4′-methyl-diphenyl sulfide, alkylated benzophenone, 3,3 ′, 4,4′-tetra (t-butylperoxycarbonyl) benzophenone, 4 -Benzophenones such as benzoyl-N, N-dimethyl-N- [2- (1-oxo-2-propenyloxy) ethyl] benzenemethananium bromide, (4-benzoylbenzyl) trimethylammonium croid, 2-isopropylthioxanthone Thioxanthones such as 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, and 2,4-dichlorothioxanthone. These may be used alone or in combination.

  In addition to the photopolymerization initiator (D), triethanolamine, methyldiethanolamine, triethanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, benzoic acid ( Photosensitizers such as 2-dimethylamino) ethyl, 4,4′-dimethylaminobenzophenone, 4,4′-diethylaminobenzophenone may be used in combination.

  The active energy ray-curable adhesive of the present invention is a blend of the urethane acrylate (A), the radical polymerizable monomer (B), the high molecular weight polyester resin (C), and the photopolymerization initiator (D). Is preferred. The blending ratio can be arbitrarily set, but the mass ratio is (A) / (B) / (C) / (D) = 10-50 / 10-50 / 10-10-50 / 0-10. preferable. If the component (A) is less than 10% by mass, the properties of the urethane acrylate are lost, resulting in a decrease in adhesive strength and a decrease in flexibility and weather resistance. On the other hand, when the component (A) exceeds 50% by mass, the viscosity becomes so high that it becomes difficult to use, and the curability with respect to active energy rays deteriorates, which is not preferable.

  As a method for producing the active energy ray-curable adhesive of the present invention, there is a method of synthesizing the urethane acrylate (A) by the above method and then blending the radical polymerizable monomer (B). As another method, there is a method of synthesizing urethane acrylate (A) using radically polymerizable monomer (B) as a reaction solvent.

Components other than the components (A) to (D) can be added to the active energy curable adhesive of the present invention as necessary. For example, it is effective to add an epoxy resin or a polyisocyanate compound in order to improve the adhesive strength. In addition, other resins, plasticizers, antifoaming agents, leveling agents, solvents, stabilizers and the like may be added depending on the properties of the adhesive. The active energy rays used for curing in the present invention are ultraviolet rays, electron beams, γ rays, neutron rays and the like. When ultraviolet rays are used, it is desirable to add the aforementioned photopolymerization initiator to the active energy ray-curable adhesive. As the electron beam irradiator, a scanning method or a curtain beam method can be adopted, and the absorbed dose is 1 to 20 Mrad, preferably 2 to 15 Mrad. For ultraviolet irradiation, UV irradiation apparatus having a mercury lamp or a metal halide lamp or the like can be used, the dose is preferably in the range of ^{50~5000mJ / cm 2, 100~1000mJ / cm} 2 is more preferable.

  The active energy ray-curable adhesive may contain an organic solvent. The organic solvent that can be used in the present invention is limited to a volatile one, and it is preferable that most or all of the organic solvent is volatilized by heat drying or the like before curing with active energy rays. Usable solvents include acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone and other ketones, methyl acetate, ethyl acetate and other esters, tetrahydrofuran, dioxane, ethers such as ethylene glycol monomethyl ether, benzene, toluene, xylene, etc. Aromatic hydrocarbons, aliphatic hydrocarbons such as hexane and heptane, alcohols such as methanol, ethanol and isopropyl alcohol, or mixtures thereof. These solvents may be used during the synthesis of the urethane acrylate (A), and in this case, they can be used as they are.

  Next, the manufacturing method of the heat-shrinkable label of this invention is demonstrated. First, a label design is printed on a heat-shrinkable polyester film, if necessary, and wound into a roll. The film is fed from the roll and cut into a predetermined length. Apply the active energy ray-curable adhesive to the whole or part of the film (for example, part or all of the film edge) before, after or while winding the cut film around the container, It is preferable that one end is overlapped to cover the entire circumference of the container. If the adhesive is cured by irradiating the adhesive part with active energy rays, the heat-shrinkable label of the present invention can be obtained. The film may be unwound from a roll, applied with an adhesive while being wound around a container, and then cut. Moreover, when starting to wind around the container, an adhesive may be applied to the container and / or the film in advance in order to fix the film and the container and facilitate the subsequent operation. A known adhesive can be used as the adhesive to be applied first. However, the use of the active energy ray-curable adhesive of the present invention makes it possible to achieve high-speed productivity, curability to active energy rays, adhesion to polyester, flexibility. It is excellent in weather resistance, water resistance, heat resistance and chemical resistance. This operation can be performed continuously.

  The application thickness of the active energy ray-curable adhesive is not particularly limited, but it is preferably as thin as possible from the economical aspect. Therefore, the coating thickness is preferably 5.0 μm or less, and more preferably 3.0 μm or less. It is a major feature of the present invention that the film can be bonded instantaneously and firmly by applying such an extremely thin layer of active energy ray-curable adhesive.

  EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, this invention is not restrict | limited to these Examples at all. First, the evaluation method of the film and label produced in the Example and the comparative example is demonstrated. The evaluation results of the films are summarized in Table 2, and the evaluation results of the labels are summarized in Table 4. In the following description, “part” means “part by mass”.

[Heat shrinkage (hot water heat shrinkage)]
The film was cut into a 10 cm × 10 cm square, and heat-shrinked in hot water at a predetermined temperature ± 0.5 ° C. for 10 seconds under no load. The film was immediately immersed in water at 25 ° C. ± 0.5 ° C. for 10 seconds, and then the vertical and horizontal dimensions of the film were measured. The direction in which the heat shrinkage rate is large was taken as the maximum shrinkage direction.
Thermal shrinkage rate = {(length before shrinkage−length after shrinkage) / length before shrinkage} × 100 (%) Formula 1

[Measurement method of right-angle tear strength]
The film before heat shrinkage is cut so that the main shrinkage direction is the longitudinal direction, and both ends in the longitudinal direction are fixed to a rectangular frame. At this time, the sample is loosened and fixed to the frame so as to be 10% longer than the length of the frame. The sample is immersed in warm water of 80 ± 0.5 ° C. for each frame, and the film is contracted by 10% in the main contraction direction for about 5 seconds until the loose film becomes a tension state in the frame. Then, after immersing in 25 degreeC water, it may take out and may wipe off moisture.

Then, the test piece F of the shape shown in FIG. 1 was cut out from the film after shrinkage according to JIS K-7128-3. When cutting out, the longitudinal direction of the test piece was set as the main shrinkage direction of the film. Then, grip both ends of the test piece with a universal tensile tester (trade name “Tensilon”; manufactured by Toyo Seiki Co., Ltd.), and measure the strength (N) at the time of tensile fracture in the width direction of the film at a tensile speed of 200 mm / min. Went. The right angle tear strength (N / mm) per unit thickness (mm) was calculated using the following formula 2.
Right angle tear strength = strength at tensile fracture ÷ thickness Equation 2

[Measurement method of Elmendorf ratio]
The film is shrunk by 10% in the longitudinal direction in the same manner as in the case of the right angle tear strength. After that, in accordance with JIS K 7128-2, a sample having a length of 63 mm in the main shrinkage direction and a length (width) of 75 mm in the direction perpendicular to the main shrinkage direction is cut out, and perpendicular to the edge from the center of the longitudinal edge. A 20 mm slit (cut) was inserted to make a test piece. Further, a specimen having a length (width) of 75 mm in the main contraction direction and a length of 63 mm in the orthogonal direction was cut out to prepare a test piece having a length and width opposite to those of the test piece. About these test pieces, the Elmendorf tear load (N) in the longitudinal direction and the width direction of the film was measured using a light load tearer (manufactured by Toyo Seiki Co., Ltd.), and the Elmendorf ratio was calculated using the following equation 3. .
Elmendorf ratio = Elmendorf tear load in the longitudinal direction ÷ Elmendorf tear load in the width direction Equation 3

[Natural shrinkage]
The obtained film was cut into a size of main shrinkage direction × orthogonal direction = 200 mm × 30 mm and allowed to stand (aging) in an atmosphere of 40 ° C. × 65% RH for 700 hours, and then the amount of shrinkage in the main shrink direction of the film was measured. Then, the natural shrinkage rate was calculated by Equation 4.
Natural shrinkage rate = {(length before aging−length after aging) / length before aging} × 100 (%) Formula 4

[Tg (glass transition temperature)]
Using a differential scanning calorimeter (model: DSC220) manufactured by Seiko Denshi Kogyo Co., Ltd., in the case of a film, 5 mg of an unstretched film is sampled and heated from −40 ° C. to 120 ° C. at a heating rate of 10 ° C./min. Then, a heat flow rate curve (DSC curve) was measured. A tangent line was drawn before and after the inflection point of the DSC curve, and the intersection was defined as Tg (glass transition temperature). In the case of the resin used for the adhesive, 5 mg of the resin was sampled and Tg was determined in the same manner.

[Tm (melting point)]
Using the above differential scanning calorimeter (model: DSC220), 5 mg of unstretched film was sampled, and the peak of the heat flow rate curve (DSC curve) when the temperature was raised from room temperature (23 ° C) at a rate of temperature rise of 10 ° C / min. Was set to Tm (melting point).

[Initial adhesive strength (tack strength)]
An adhesive is applied to the film in a size of 10 mm width × 20 mm length and a thickness of 10 μm, and a 10 mm width 200 mm length strip made of the same film is overlaid on the applied adhesive, and then the strip film is removed from the adhesive. The peel strength at the time of peeling at a speed of 0.5 m / min was measured with a spring alone, and the maximum strength (N) was measured. Similarly, n = 5 was measured, and the average value was defined as the initial adhesive strength.

[Adhesive strength after UV curing]
An adhesive is applied to the film in a size of 5 mm width × 50 mm length and a thickness of 10 μm, the same film is overlaid from above, and ultraviolet rays are irradiated with a UV irradiator so that the irradiation dose is 100 mJ / cm ² . After that, in the vicinity of the center of 50 mm length, it was cut into a strip shape with a width of 15 mm in the orthogonal direction, and as a test piece, the adhesive strength of the 5 mm × 15 mm adhesive part was measured with a universal tensile testing machine (trade name “Tensilon”; manufactured by Toyo Seiki Co., Ltd.) Both ends of the test piece were gripped, T-shaped peeled at a tensile speed of 200 mm / min, and the maximum peel strength (N) was measured. Similarly, five test pieces were prepared, and the average value of the maximum peel strength measured at n = 5 was defined as the adhesive strength after UV curing.

[Labelability]
For the label attached to the bottle, the attached part does not shift or peel off, and there is no adhesive stringing or foam chewing, and the appearance is neatly wrapped around the bottle. When stringing or foam biting occurred, it was marked as x.

[Adhesiveness of label bonding part]
About the label after heat shrink with which the bottle was mounted | worn, sensory evaluation was carried out about how the film peeled when the film edge which has come out on the surface of the part where films were bonded together was scratched by hand. Those that did not peel off and adhered well were marked with ◯, those that adhered but peeled off with a light force were marked with Δ, and those that did not adhere were marked with ×.

[Shrink finish]
Evaluation of the finish after heat shrinkage attachment to the bottle was performed visually, and the criteria were as follows.
◎: No wrinkles, jumping up, insufficient shrinkage, and no color spots are observed ○: Wrinkles, jumping up, or insufficient shrinkage cannot be confirmed, but some color spots are seen △: Jumping Neither ascending nor insufficient shrinkage has occurred, but spots on the neck are observed. ×: Wrinkles, jumping up, insufficient shrinkage occurred

[Label openability]
A label having a notch with a length of 2 mm in a direction perpendicular to the main shrinkage direction was attached to a PET bottle and thermally shrunk. However, the notch was provided on the upper side of the label when the bottle was erected. Thereafter, the bottle with the label attached was refrigerated at 5 ° C. for 24 hours, and the label of the bottle immediately after being taken out of the refrigerator was torn with a fingertip from the notch portion. The number of bottles that were torn up in the vertical direction and the label could be easily removed from the bottles was counted, and the ratio (%) to 50 samples was calculated.

[Production Method of Polyester Film 1]
90 parts of polyester 1 (IV 0.72 dl / g) composed of 70 mol% of ethylene glycol, 30 mol% of neopentyl glycol and 100 mol% of terephthalic acid and 10 of polyethylene terephthalate (IV 0.75 dl / g: hereinafter, polyester 2) 10 Were mixed and put into an extruder. Thereafter, the mixed resin was melted at 280 ° C., extruded from a T-die, wound around a rotating metal roll cooled to a surface temperature of 30 ° C., and rapidly cooled to obtain an unstretched film having a thickness of 360 μm. At this time, the take-up speed of the unstretched film (the rotation speed of the metal roll) was about 20 m / min. Moreover, Tg of the unstretched film was 67 degreeC. Thereafter, the unstretched film was led to a tenter (first tenter) in which a transverse stretching zone, an intermediate zone, and an intermediate heat treatment zone were continuously provided. In the tenter, the length of the intermediate zone located between the transverse stretching zone and the intermediate heat treatment zone was set to about 40 cm. In addition, in the intermediate zone, when the strip-shaped paper piece is hung in a state where the film is not passed through, the hot air from the stretching zone and the hot air from the heat treatment zone are blown so that the paper piece hangs almost completely in the vertical direction. It was cut off.

  The pre-stretched film led to the tenter was preheated until the film temperature reached 90 ° C., and then stretched 4 times at 75 ° C. in the transverse direction in the transverse stretching zone and passed through the intermediate zone (passing time = About 1.2 seconds), the film was guided to an intermediate heat treatment zone and heat treated at a temperature of 130 ° C. for 2.0 seconds to obtain a transversely uniaxially stretched film having a thickness of 90 μm. Thereafter, using a pair of left and right trimming devices (configured by a round blade having a circumferential cutting edge) provided at the rear of the tenter, both end portions (about 1.. 2 times thick part) was cut, and the end of the film located outside the cut site was continuously removed.

  The film trimmed at the end is guided to a longitudinal stretching machine in which a plurality of roll groups are continuously arranged, preheated on a preheating roll until the film temperature reaches 70 ° C., and then stretched at a surface temperature of 95 ° C. The film was stretched 3 times between rolls. Thereafter, the longitudinally stretched film was forcibly cooled by a cooling roll set at a surface temperature of 25 ° C. The surface temperature of the film before cooling was about 75 ° C., and the surface temperature of the film after cooling was about 25 ° C. The time required for cooling from 70 ° C. to 25 ° C. was about 1.0 second, and the film cooling rate was 45 ° C./second.

  The cooled film was guided to a tenter (second tenter), heat-treated in an atmosphere of 95 ° C. for 2.0 seconds in the second tenter, cooled, and both ends were cut and removed. In this manner, a biaxially stretched film of about 30 μm was continuously formed over a predetermined length to obtain a film roll made of a heat-shrinkable polyester film. The production conditions are summarized in Table 1, and the characteristics of the obtained polyester film 1 are summarized in Table 2.

[Production Method of Polyester Film 2]
A heat-shrinkable film was continuously produced by the same method as for polyester film 1 except that polyester 1 and polyester 2 were mixed at a mass ratio of 70:30 and charged into an extruder. The production conditions are summarized in Table 1, and the characteristics of the obtained polyester film 2 are summarized in Table 2.

[Production Method of Polyester Film 3]
A heat-shrinkable film was continuously produced by the same method as the polyester film 1 except that the temperature of the stretching roll in the longitudinal stretching machine was changed to 92 ° C. and the stretching ratio in the longitudinal direction was changed to 7.0 times. The thickness of this biaxially stretched heat-shrinkable polyester film was about 13 μm. The production conditions are summarized in Table 1, and the characteristics of the obtained polyester film 3 are summarized in Table 2.

[Production method of UV curable adhesive 1]
440 parts of dimethyl terephthalate, 440 parts of dimethyl isophthalate, 412 parts of ethylene glycol, 393 parts of neopentyl glycol and 0.5 part of tetrabutoxy titanate in a reaction vessel equipped with a thermometer, stirrer, distillation column, condenser, and decompression device Was heated at 150 to 230 ° C. for 120 minutes to cause transesterification. Next, the reaction system was depressurized to 10 mmHg, and the reaction was carried out by raising the temperature to 250 ° C. in 30 minutes. Thus, a copolyester polyol 1 was obtained. The molecular weight of the polyester polyol was 2000. Similarly, 260 parts of dimethyl terephthalate, 180 parts of dimethyl isophthalate, 440 parts of azelaic acid, 490 parts of ethylene glycol, 310 parts of neopentyl glycol, and 0.5 part of tetrabutoxy titanate are charged and heated at 150 to 230 ° C. for 120 minutes. The ester exchange reaction was carried out. Next, the reaction system was depressurized to 10 mmHg, and the reaction was carried out by raising the temperature to 250 ° C. over 30 minutes. Thus, high molecular weight polyester 1 was obtained. The molecular weight of the high molecular weight polyester 1 was 37000.

  Next, 100 parts of the copolymer polyester polyol 1 and 150 parts of phenoxydiethylene glycol acrylate were charged into a reaction vessel equipped with a thermometer, a stirrer, and a reflux condenser, and after dissolution, 15 parts of isophorone diisocyanate and 0.1 part of dibutyltin dilaurate were added. After charging 05 parts and reacting at 70 to 80 ° C. for 2 hours, 5 parts of 2-hydroxyethyl acrylate was added and reacted at 70 to 80 ° C. to obtain a phenoxydiethylene glycol acrylate solution of urethane acrylate. Furthermore, 120 parts of high molecular weight polyester 1 was added and stirred at 80 ° C. for 2 hours to obtain a mixed liquid of urethane acrylate and high molecular weight polyester. Furthermore, 100 parts of this solution was subjected to 2,2-dimethoxy-1,2-diphenylethane-1-one (Irgacure (registered trademark) 651: manufactured by Ciba Specialty Chemicals) as a photopolymerization initiator immediately before use. 2 parts by mass was added to obtain an active energy ray (UV) curable adhesive 1. The composition of the adhesive is summarized in Table 3.

  The above molecular weights are all number average molecular weights, and are the results (polystyrene conversion) measured using GPC150c (manufactured by Waters) with tetrahydrofuran as an eluent. The column temperature was 35 ° C. and the flow rate was 1 ml / min.

[Production method of UV curable adhesive 2]
A UV curable adhesive 2 was obtained in the same manner as the UV curable adhesive 1 except that the high molecular weight polyester 2 obtained using 440 parts of sebacic acid instead of 440 parts of azelaic acid was used. The molecular weight of the high molecular weight polyester 2 was 27000. The composition of the adhesive is summarized in Table 3.

[Production method of UV curable adhesive 3]
The UV curable adhesive 3 was prepared in the same manner as the active energy ray curable adhesive 1 except that 5 parts of 2-hydroxy-1,3-dimethacryloxypropane was used instead of 5 parts of 2-hydroxyethyl acrylate. Obtained. The composition of the adhesive is summarized in Table 3.

[Method for producing UV curable adhesive 4]
Instead of high molecular weight polyester 1, 49 mol parts of terephthalic acid, 49 mol parts of isophthalic acid as acid components, 2 mol parts of trimellitic acid (having three carboxyl groups in the structural formula), 50 mol of ethylene glycol as glycol components UV curing type in the same manner as in the active energy ray curable adhesive 1 except that high molecular weight polyester 2 having a molecular weight of 30000 consisting of 140 parts by mole of neopentyl glycol and 140 parts by mole of polycaprolactone was used as the soft segment component. Adhesive 4 was obtained. The composition of the adhesive is summarized in Table 3.

[Production method of UV curable adhesive 5]
Instead of using the high molecular weight polyester 1, a polyester having a molecular weight of 10,000 consisting of 50 mol% terephthalic acid and 50 mol% isophthalic acid as the acid component, 50 mol% ethylene glycol and 50 mol% neopentyl glycol as the glycol component, The UV curable adhesive 5 was obtained in the same manner as the active energy ray curable adhesive 1. The composition of the adhesive is summarized in Table 3.

Example 1
Using the polyester film 1 roll, three-color printing is performed with grass, gold, and white ink from Toyo Ink Manufacturing Co., Ltd., and the film roll is cut out into a length of 230 mm x width 150 mm so that the longitudinal direction of the film roll is vertical. It was. Using a labeling machine LH101H manufactured by Koyo Automatic Co., Ltd., a 500 ml PET bottle (height 210 mm, maximum barrel diameter 68 mm), while winding the film so that one of the long sides of the cut film is along the bottom of the bottle Wrapping the film while applying the UV curable adhesive 1 to the bottle at the upper and lower ends (10 mm width × 20 mm length) of one end of the short side of the bottle on the short side of the bottle, Furthermore, the other end of the wound film is coated with UV curable adhesive 1 having a width of about 10 mm over the entire length of the film, and this one end is overlapped by 15 mm on one end previously fixed to the bottle so as to sandwich the adhesive layer. Together, the film was wrapped around the bottle. The winding was performed at an adhesive temperature of 80 ° C. and a speed of 30 m / min.

A heat-shrinkable label is obtained by irradiating ultraviolet rays with a 3 kW (120 W / cm) × 1 lamp air-cooled mercury lamp to 100 mJ / cm ^{2 on} the adhesive portion of the bottle around which the film is wound, and curing and bonding both ends of the film. A bottle with a stick was created.

  Subsequently, the label with the heat-shrinkable label was shrunk immediately after being attached to the steam furnace shrink tunnel, which was 3 m long and kept at 92 ° C., and allowed to pass for 10 seconds. It was made to contact | adhere to the outer periphery of a bottle and the package (a container with a label after shrinkage | contraction) was obtained. The package had good shrinkage finish and good adhesion at the label bonding part. The evaluation results are shown in Table 4.

Example 2
A package was obtained in the same manner as in Example 1 except that the polyester film 2 was used as the heat-shrinkable polyester film. The evaluation results are shown in Table 4.

Example 3
A package was obtained in the same manner as in Example 1 except that the polyester film 3 was used as the heat-shrinkable polyester film. The evaluation results are shown in Table 4.

Example 4
A package was obtained in the same manner as in Example 1 except that the UV curable adhesive 2 was used as an adhesive for attaching the film, the bottle, and the film ends. The evaluation results are shown in Table 4.

Example 5
A package was obtained in the same manner as in Example 1 except that the UV curable adhesive 3 was used as an adhesive for pasting the film, the bottle, and the film ends. The evaluation results are shown in Table 4.

Comparative Example 1
A package was obtained in the same manner as in Example 1 except that the UV curable adhesive 4 was used as an adhesive for attaching the film, the bottle, and the film ends. There was a lot of threading of the adhesive at the time of winding the film, and it could be wound, but there was a part where the adhesive protruded from the bonded part by threading, and it was not possible to wind it cleanly in appearance. The evaluation results are shown in Table 4.

Comparative Example 2
A package was obtained in the same manner as in Example 1 except that the UV curable adhesive 5 was used as an adhesive for sticking the film, the bottle, and the film ends. Since the initial adhesion was weak, the label was greatly displaced during winding and could not be wound neatly. The evaluation results are shown in Table 4.

Comparative Example 3
The same method as in Example 1 except that a commercially available ethylene-vinyl acetate hot melt adhesive (softening point 85 ° C.) is used at 100 ° C. as an adhesive for attaching the film and the bottle and the film ends to each other. A package was obtained. Due to the heat at the time of applying the hot melt adhesive, the shrinkage finish was deteriorated, and the label bonded portion was also lightly peeled off by hand, so that sufficient adhesiveness was not obtained.

  The heat-shrinkable label of the present invention is suitable for bottle labels such as PET bottles and glass bottles.

It is explanatory drawing which shows the shape of the test piece at the time of measuring a right-angled tear strength.

Claims (4)

  A heat-shrinkable polyester film stretched at least uniaxially is wound around a container, an active energy ray-curable adhesive is applied to a part of the film, and an active energy ray is irradiated to form a continuous body. A heat-shrinkable label, wherein the active energy ray-curable adhesive contains a high-molecular-weight polyester resin having a number average molecular weight of 20,000 to 50,000 containing an aliphatic dicarboxylic acid.   The heat-shrinkable label according to claim 1, wherein the heat-shrinkable polyester film is drawn from a heat-shrinkable polyester film roll whose longitudinal direction is the main shrinkage direction and cut.   A step of winding a heat-shrinkable polyester film stretched at least uniaxially around a container, a step of applying an active energy ray-curable adhesive to a part of the film, and a continuous irradiation of active energy rays A method for producing a heat-shrinkable label including a step of forming into a body, wherein the active energy ray-curable adhesive contains a high-molecular weight polyester resin having an aliphatic dicarboxylic acid and having a number average molecular weight of 20,000 to 50,000. A method for producing a heat-shrinkable label.   The method according to claim 3, comprising a step of applying an active energy ray-curable adhesive to a container or / and a part of the heat-shrinkable polyester film in advance and bonding the container and the heat-shrinkable polyester film. The manufacturing method of the heat-shrinkable label of description.

Images