KR101475837B1 - Polyester-based metallized film - Google Patents

Abstract

The present invention relates to an application of a vapor deposition film comprising a polyester film layer having heat shrinkage properties and a label of a film material which can replace the label of a paper material adhered to a glass bottle, , A metal deposition layer on a substrate, a print layer on a metal deposition layer, and a bending prevention layer on the other side of the substrate, and a bottle-attached bottle comprising the same.

Description

BACKGROUND OF THE INVENTION [0001] Polyester-based metallized film [0002]

The present invention relates to the application of a vapor deposition film comprising a polyester film layer having heat shrinkage characteristics and a label of a film material which can replace the label of a paper material adhered to a glass bottle.

PET bottles and glass bottles have been collected and reused in consideration of environmental requirements and economic feasibility. In case of recycling, the label on which the product name, component name and other patterns are printed and attached in addition to the PET bottle or glass bottle body should be removed and removed. For paper labels that have been used so far, use industrial water to remove them. Specifically, the collected PET bottles or glass bottles are immersed in industrial water containing caustic soda at a temperature of about 80 ° C. to remove the label. As a result, environmental wastewater is generated in the recycling of engineers, and environmental regulations are becoming serious.

Thus, there is an increasing demand for labels of film materials rather than paper labels.

On the other hand, an example of a film that can be used as a label is a polyvinyl chloride-based film, but this is not preferable due to environmental problems such as generation of dioxin upon incineration, so that a polyester-based heat- It has become a means to replace labels.

As a method of applying a polyester-based heat-shrinkable film to a label, a method of printing on a film such as a sticker type or a conventional paper label and sticking it using a water-soluble adhesive may be considered.

In the method of adhering labels with an adhesive such as a paper label, the labels attached to the labeler are separated and transferred one by one by an adsorption method, and then the adhesive is applied to the backside of the label by a gravure printing method, A method in which a label is adhered to a label is usually used. However, in the case of a polyester-based heat-shrinkable film label having a print layer formed thereon, since the label itself is curled, it may be difficult to easily apply a conventional process for attaching a paper label.

In addition, in a glass bottle colored for the purpose of ultraviolet ray shielding such as a beer bottle, the printing effect is insufficient with a general label, and in the case where the label is a film material, there is a deficiency in the incidence of an advertising effect using a label.

In one embodiment of the present invention, there is provided a polyester-based evaporated film that can achieve a clear deposition color when applied to a label application while maintaining shrinkage, can double the advertising effect, and has processability in on-line adhesion process.

Further, in an embodiment of the present invention, a label including such a polyester-based evaporated film is attached, which can double the advertising effect. Moreover, since the label can be removed using only hot water when recycling, And provide environmentally friendly bottles.

In addition, the present invention provides a method of manufacturing a label-attached bottle in which labeling of the label sheet and application of the adhesive to the label coat layer can be performed through one process, even though the label of the film is applied.

In one embodiment of the present invention, a heat-shrinkable polyester film substrate; A metal deposition layer on a substrate; A printing layer on the metal deposition layer; And a bending prevention layer on the other surface of the base material.

In the polyester-based deposited film according to an embodiment of the present invention, the bending prevention layer may be formed of a polyamide resin, an acrylic resin, a polyurethane, a PVC resin, a ketone resin, a chlorinated rubber, a vinyl acetate resin, and an ethylene-vinyl acetate copolymer One or more resins selected; At least one solvent selected from aromatic hydrocarbon type, ketone type, acetate type and chlorinated solvents; And a composition comprising a white pigment and at least one additive selected from a precipitation inhibitor, a thickener, a color separation preventing agent and a pigment dispersant.

In the polyester-based deposited film according to an embodiment of the present invention, a primer layer may be included between the metal deposition layer and the print layer.

In the polyester-based evaporated film according to one embodiment of the present invention, a protective layer may be included on the printing layer.

Wherein the protective layer comprises at least one of a copolymerized polyester, an acrylic copolymer, a styrene copolymer, a methacrylate copolymer, polystyrene, vinyl acetate, polyamide, alkyl acrylate, urea formaldehyde, epoxidized soybean oil, ethylene- A polyolefin-based copolymer, a urethane, and a vinyl-based resin, or a mixture thereof.

In the polyester-based evaporated film according to one embodiment of the present invention, the heat-shrinkable polyester-based film substrate may include a polyester-based resin containing a repeating unit of butylene terephthalate.

In the polyester-based evaporated film according to an embodiment of the present invention, the heat-shrinkable polyester film substrate may be formed of a material selected from the group consisting of terephthalic acid, oxalic acid, malonic acid, succinic acid, adipic acid, suberic acid, azelaic acid, sebacic acid, phthalic acid, , Naphthalene dicarboxylic acid, diphenyl ether dicarboxylic acid, and a dicarboxylic acid component containing at least one dicarboxylic acid component such as ethylene glycol, neopentyl glycol, propylene glycol, trimethylene glycol, tetramethylene glycol, At least one copolyester selected from co-polyesters obtained from a diol component comprising at least one diol such as hexamethylene glycol, diethylene glycol, polyalkylene glycol, 1,4-cyclohexanedimethanol, Lt; / RTI >

In the polyester-based evaporated film according to one embodiment of the present invention, the copolyester contains 80 mol% or more of terephthalic acid units in the dicarboxylic acid unit and 12 to 24 mol% of units other than ethylene glycol in the diol unit, May be included.

In one embodiment of the present invention, the heat-shrinkable polyester film substrate may be a uniaxially oriented heat-shrinkable polyester film base or a bidirectional heat-shrinkable polyester film base.

The polyester-based evaporated film according to one embodiment of the present invention has a shrinkage ratio of 40% to 80% with respect to the maximum shrinkage direction when treated for 10 seconds in hot water at 90 ° C.

The polyester-based evaporated film according to one embodiment of the present invention may have a shrinkage starting temperature in the maximum shrinkage direction of 68 to 94 ° C.

The polyester-based evaporated film according to one embodiment of the present invention may have a maximum shrinkage and development temperature in the maximum shrinkage direction of 80 to 110 ° C and a maximum shrinkage stress of 0.60 to 1.80 kg / mm 2.

The polyester-based evaporated film according to an embodiment of the present invention may have a total light transmittance of 0.01 to 5.0%.

In the polyester-based evaporated film according to one embodiment of the present invention, the heat-shrinkable polyester-based film substrate may have a haze of 0.3 to 10.0%.

The polyester-based deposited film according to one embodiment of the present invention may have a bending property value of 5.0 mm or less as defined in the following detailed description.

An exemplary embodiment of the present invention provides a label attached bottle comprising a polyester based deposition film according to one of the above embodiments.

The polyester-based evaporated film can be removed by immersing the bottle with such a label in hot water.

According to an embodiment of the present invention, there is provided a method of manufacturing a polyester-based evaporated film, comprising the steps of: applying an adhesive to a bending prevention layer of a polyester- And adhering a heat-shrinkable polyester-deposited film coated with an adhesive to a container.

Since the polyester based evaporated film according to one embodiment of the present invention can realize a clear deposition color while maintaining shrinking property, the advertising effect can be doubled, and the opacity of the advertisement can be appropriately adjusted so that the final printed product, Even if applied, the color of the bottle is not projected, the printing effect is excellent, the visibility of the printing pattern is increased, and the aesthetics of the advertisement can be improved. When the label is used for replacing the conventional paper label, Can be performed on one process line, so that existing paper label lines can be applied as they are. Also The label can be removed using only hot water when recycling, which makes it possible to prevent the generation of waste water and is environmentally friendly.

FIG. 1 is a graph showing changes in shrinkage stress values in the maximum shrinkage direction of the polyester-based evaporated film obtained according to Example 1 with temperature change using a thermal stress measuring instrument.

The polyester-based evaporated film according to one embodiment of the present invention is a heat-shrinkable polyester-based film substrate; A metal deposition layer on a substrate; And a printing layer on the metal deposition layer, and a bending prevention layer on the other surface of the substrate.

Here, the term "heat-shrinkable polyester film substrate" means that the main matrix constituting the film is a polyester-based resin, and the film is uniaxially or biaxially oriented through low-temperature uniaxial stretching or biaxial stretching, Refers to both a film substrate prepared by the principle that the molecular chains oriented without exclusion remain as they are, and a shrink film with uniaxial orientation produced by the principle that shrinkage occurs under the force of residual stress in the final shrinkage process, as well as the bidirectional shrink film .

Such a heat-shrinkable polyester film substrate is not particularly limited in its composition, and examples thereof include terephthalic acid, oxalic acid, malonic acid, succinic acid, adipic acid, suberic acid, azelaic acid, sebacic acid, phthalic acid, Naphthalene dicarboxylic acid, diphenyl ether dicarboxylic acid, and the like, with a dicarboxylic acid component containing at least one known dicarboxylic acid such as ethylene glycol, neopentyl glycol, propylene glycol, trimethylene glycol, tetramethylene At least one selected from copolyesters obtained from a diol component comprising at least one known diol such as glycols, hexamethylene glycol, diethylene glycol, polyalkylene glycols, 1,4-cyclohexanedimethanol, ester; Or a mixture of homopolyester and copolyester.

The copolyester itself can be produced by a commonly used process for producing a polyester. For example, a direct esterification method in which a diol is directly reacted with a dicarboxylic acid, and an ester exchange method in which a diol is reacted with a dimethyl ester of a dicarboxylic acid.

The copolyester may be a copolyester in which the terephthalic acid unit constitutes at least 80 mol% of the dicarboxylic acid unit and the unit other than ethylene glycol in the diol unit constitutes 12 to 24 mol% or more. Among the copolyesters, the units other than the ethylene glycol units have the function of increasing the shrinkage ratio by lowering the crystallinity of the polyester polymer. The proportion of the monomer units falling within the above range is preferable for controlling the drying process, May be advantageous in terms of controlling the melting characteristics and physical properties.

In the present invention, the copolyester itself can be produced by a general production process of a polyester. For example, a direct esterification method in which a diol is directly reacted with a dicarboxylic acid, and an ester exchange method in which a dimethyl ester diol of a dicarboxylic acid acts.

According to an embodiment of the present invention, the melting point (° C) of the copolyester is from 190 to 220 ° C and the intrinsic viscosity is from 0.60 to 0.75 dl / g. In this case, the melting point (° C) can be controlled according to the composition of the monomers used for preparing the polymer, and the intrinsic viscosity can be changed according to the degree of polymerization. In the present invention, the melting point (° C) And a copolyester having an intrinsic viscosity within the above range can be used.

On the other hand, polytetraethylene terephthalate may be used instead of or in addition to polybutylene terephthalate as the homopolyester.

In producing such a heat-shrinkable polyester film base material, a lubricant such as silicon dioxide, titanium dioxide, silica powder, or calcium carbonate may be added in order to improve slipperiness. If necessary, an antistatic agent, an antioxidant, Various additives such as pigments, pigments, and the like may be added.

On the other hand, the heat-shrinkable polyester-based film substrate is required to run at a high speed or at a high speed to be made into a film roll in order to improve the productivity in the film forming step and the post-processing step. In-line coating layer.

Herein, the term 'in-line coating layer' will be understood as a layer formed by a coating process in any of the processes of extruding and forming a polyester resin to those having ordinary skill in the art.

When the in-line coating layer including the antistatic agent is formed on the surface layer of the film as described above, the static electricity generated by the friction is relieved, thereby eliminating the phenomenon that the films adhere to each other during the process of winding the film roll, It can be advantageous in that it can facilitate the escape of the introduced air in the process to be taken. In addition, it is possible to prevent defective printing due to static electricity caused by friction between the printing roll and the film during the printing process, and to prevent defective feeding by removing the phenomenon that the film sticks due to static electricity during the post-process .

Examples of the antistatic agent include, but not limited to, quaternary ammonium compounds, alkylsulfonate compounds categorized as RSO ₃ Na, alkylsulfate compounds categorized as ROSO ₃ Na, and alkylphosphate compounds. The content thereof is 0.1 to 1.5% by weight based on the active ingredient in the coating liquid for forming an in-line coating layer, which minimizes the amount of foreign matter generated by friction during the printing process, the tubing process and the heat shrinking process, Lt; / RTI >

On the other hand, the binder resin may be included in the inline coating layer in consideration of binding force and adhesive force. The binder resin is not particularly limited and may be selected in consideration of the solubility of the solvent in the tubing process.

Examples of binder resins that can be considered include polyester-based, acrylic-polyester copolymers, and copolyester-based resins.

Such a heat-shrinkable polyester film substrate may have a haze of 0.3 to 10.0% in view of being able to realize a clear vapor deposition color upon formation of a metal deposition layer.

The thickness of the heat-shrinkable polyester film base material is not particularly limited, and it is usually 35 to 65 占 퐉, preferably 40 to 60 占 퐉, when the rigidity is satisfied and deposition and printing are completed, Can be advantageous in terms of the feeding stability and the uniformity of label attachment to the bottle.

As described above, one embodiment of the present invention includes not only a uniaxially oriented heat-shrinkable film but also a bidirectionally shrinkable film, but there is no particular limitation, but it is possible to further reduce the curling phenomenon in a process of attaching the label to a bottle, It may be more advantageous to be a bi-directional shrink film.

On the other hand, the polyester-based evaporated film of the present invention includes a metal evaporated layer on the above heat-shrinkable polyester-based film substrate.

Examples of metals usable for the metal deposition layer include Al, Zn, Mg, Sn, Ti, In, Cr, Ni, Cu, Pb and Fe, Al may be most preferable in terms of productivity.

The thickness of the metal deposition layer is preferably 20 to 90 nm, and more preferably 40 to 70 nm, which may be advantageous in view of the stability of the deposition process and the shielding effect.

The method of forming the metal deposition layer is not particularly limited, but a physical vapor deposition method such as a vacuum deposition method, a sputtering method, an ion plating method, or a chemical vapor deposition method such as CVD can be applied.

The polyester-based deposited film according to an embodiment of the present invention includes a print layer on a metal deposition layer.

The printed layer is printed with letters and figures, and the contents of the container, advertising and warning phrases are printed and promoted. As a method for forming such a printing layer, a known method can be used, and examples thereof include gravure printing, flexographic printing, and screen printing. The print layer may have a thickness of 0.3 to 20 占 퐉, preferably 0.5 to 10 占 퐉, which may be preferable in terms of being sufficient for the print layer and preventing the print layer from being broken.

If necessary, a primer layer may further be provided between the metal deposition layer and the print layer. The primer layer can increase the adhesion strength between the metal deposition layer and the printing layer, thereby not only imparting scratch resistance to the printing layer but also preventing the contamination due to the peeling of the printing layer in the bottle-cleaning process for removing the label from the bottle can do. The primer layer may be selected in consideration of the print layer, and is not limited thereto.

In addition, the surface of the heat-shrinkable polyester film substrate may be subjected to a corona treatment, a flame treatment, a plasma treatment, a glow discharge treatment, a roughening treatment or the like before the formation of the metal deposition layer in order to obtain the adhesion strength.

Further, a protective layer may be further formed on the printing layer, which may be an object for protecting the printing layer, and also for imparting weather resistance or durability of the metal deposition layer. The protective layer is not particularly limited in its composition. For example, the protective layer may be a copolymerized polyester, an acrylic copolymer, a styrene copolymer, a methacrylate copolymer, polystyrene, vinyl acetate, polyamide, alkyl acrylate, urea form A resin layer made of a single material selected from among aldehyde, epoxidized soybean oil, ethylene-vinyl acetate copolymer, tallow oleamide, polyethylene glycol distearate, polyvinylidene, polyolefin copolymer, urethane and vinyl resin, Lt; / RTI >

The thickness of the protective layer may be 0.1 to 5.0 탆, preferably 0.3 to 1.0 탆 in terms of coating stability of the protective layer and stability of the drying process.

In order to apply the polyester-based deposited film of the present invention to a label, the adhesive is applied to the rear surface of the label, and then the adhesive is adhered to the container. In order to facilitate the adhesive process, the label must be flat, It is necessary to satisfy an appropriate concealment.

And the other side of the heat-shrinkable polyester film substrate includes a bending prevention layer.

As an example of a known method of attaching a paper label, particularly a sheet label, to a glass bottle or the like, a label of a predetermined standard on which a print layer is formed is separated and transferred from a labeler by an adsorption method, and then an adhesive is applied on the back of the label by a gravure printing method The process of adhering the label to the container conveyed by the next conveyor belt is performed continuously (this is referred to as "on-line bonding process"). In the case of a paper material label, proper flatness is maintained even after the printing layer is formed, whereas in the case of a heat-shrinkable polyester film, when the printing layer is formed on one side of the substrate, the curling of the film is increased due to the solvent for diluting the pigment . Therefore, bottles makers and alcohol manufacturers that have applied conventional paper labeling may have difficulties in applying the labeling of the film material.

In view of this, the bending prevention layer may be formed of one or more resins selected from resins such as polyamide resin, acrylic resin, polyurethane, PVC resin, ketone resin, chlorinated rubber, vinyl acetate resin and ethylene-vinyl acetate copolymer; At least one solvent selected from aromatic hydrocarbon type, ketone type, acetate type and chlorinated solvents; And a composition comprising a white pigment and additives such as a precipitation inhibitor, a thickener, a color separation preventing agent and a pigment dispersant.

When a bending prevention layer is formed on the other surface of the base film with such a composition, it may be preferable from the viewpoint that the bending phenomenon of the heat-shrinkable polyester film base can be easily controlled while exhibiting proper concealment.

The thickness of the bending prevention layer may be 0.1 to 5.0 μm, preferably 0.4 to 2.0 μm, in view of coating stability of the bending prevention layer, stability of the drying process, and prevention of warpage of the label by the solvent.

In the meantime, it is preferable that the film having such a bending prevention layer according to an embodiment of the present invention has a bending property value as defined below of not more than 5.0 mm.

Flexural properties:

The heat-shrinkable polyester vapor deposited film was placed on a flat glass plate, cut on the vapor-deposited film, and cut by 20 cm in the transverse direction without damaging the film using a knife to form a first section improvement. Using the ruler as a reference, the film was cut so as to have a length of 20 cm in the longitudinal direction (direction perpendicular to the first section improvement) without damaging the knife to form a second section improvement, and the first incision line and the second section improvement Four incisions were made with the distance in the horizontal and the vertical directions being 10 cm, respectively, based on the intersection. In order to confirm that the incision is completed, the incision is confirmed by lifting the deposited film in a vertical direction on the inner surface, the four incision improvement films developed in the horizontal and vertical directions. This is placed on a flat glass plate and the vertical height of the four corners corresponding to the intersection of the incision is measured by elevating the corners from the flat surface. In this case, the two cases in which the deposition layer is the upper surface and the deposition layer is the lower surface are measured, respectively, and the value indicating the maximum height is called "bending characteristic value ".

When the deflection characteristic value defined as described above is 3 mm or less, it is possible to facilitate the adhesion process when the evaporated film according to one embodiment of the present invention is applied with a label.

The polyester-based evaporated film according to one embodiment of the present invention that satisfies the above-described configuration has a shrinkage ratio of 40 to 80% with respect to the maximum shrinkage direction when treated in hot water at 90 캜 for 10 seconds.

Such a range of the heat shrinkage ratio is obtained by attaching a heat-shrinkable film to a bottle or the like using an adhesive, collecting the bottles, and in the process of peeling the label using hot water at the time of recycling, the shrinkable film It is advantageous in terms of being able to get out easily after being dried.

Specifically, when the shrinkage ratio with respect to the maximum shrinkage direction is 40% or less when treated for 10 seconds in hot water at 90 ° C, the time required for shrinkage is prolonged and the shrinkage stress generated upon shrinkage is weakened, It is not possible to remove the label for removing the label for reuse of the bottle when the label is applied. In addition to this, in addition to the detachment efficiency, an additional process is required to remove the un-peeled label, On the other hand, when the shrinkage ratio with respect to the maximum shrinkage direction is more than 80%, the stretching ratio in the width direction must be increased in order to improve the shrinkage ratio in the production of the substrate film, so that the occurrence of breakage is frequent, It is very difficult to maintain and the substrate film may have a too high shrinkage rate It has a label in the process of curling is severe separating and removing the labels separated from the bottles during the process three bottles of a film can cause problems get out of difficult separation process for removing it into the empty bottles.

In addition, the polyester-based evaporated film of the present invention can be easily removed in a short time in removing the label for reuse of the bottle when the label has a shrinkage starting temperature in the maximum shrinkage direction of 68 to 94 ° C. The shrinkage initiation temperature may be defined as follows.

Shrinkage starting temperature: When the film is shaken while heating at a constant heating rate after fixing the film at room temperature and a certain initial load, when the shrinkage stress according to the temperature is plotted, the film shrinks to the same shrinkage stress as the initial load Initial temperature for stress.

An example of a measuring instrument capable of implementing such a graph is a thermal stress tester.

For example, in order to confirm the shrinkage characteristics of the evaporated film in the heat shrinkage stress tester, the film is first fixed with a predetermined load, and then heat is applied at a constant temperature elevation rate to change the stress due to shrinkage .

An example of a measurement graph by such a method is shown in FIG. 1, which will be described with reference to FIG. 1. The initial point on the graph is a load value Ls initially set, Is lower than the initial load (Ls), and when it reaches a certain temperature, the film is stretched and contraction starts. At this time, a shrinkage stress value equal to the initial load (Ls) is observed, and this point is defined as the shrinkage starting temperature (Ts).

The heat-shrinkable polyester film of the present invention has a shrinkage starting temperature in the maximum shrinkage direction of 68 to 94 ° C. If the shrinkage onset temperature is lower than 68 ° C, the label may be partially removed from the bottle during the process of circulating and storing the finished product in the summer. If the shrinkage starting temperature is higher than 94 ° C, It is necessary to carry out the treatment at a high temperature and a long time in the process, so that the process cost may become high.

In addition, the polyester-based evaporated film according to the present invention has a maximum shrinkage development temperature in the maximum shrinkage direction within a range of 80 to 110 ° C, wherein the maximum shrinkage temperature can be defined as follows: The first temperature which shows the maximum shrinkage stress value when the film is shrunk while the film is fixed at room temperature and constant initial load, and then the film is shrunk by heating at a constant heating rate and is plotted against shrinkage stress according to temperature.

The shrinkage stress at this time is defined as the maximum shrinkage stress, which may be 0.60 to 1.80 kg / mm < 2 >.

 Referring to the graph of the change in the shrinkage stress value according to the temperature change by the heat shrinkage stress tester shown in FIG. 1, when the shrinkage of the shrinkable film starts to be started, the shrinkage stress increases to a certain temperature. After the temperature (T (Smax)) indicating the shrinkage stress value (Smax), the value draws a downward curve.

If the temperature (T (Smax)) at which the maximum shrinkage stress value Smax is expressed is high, a high temperature or long heat treatment is required in the hot water treatment for removing the label.

From this point of view, it is advantageous that the polyester-based evaporated film of the present invention has a low maximum shrinkage stress-inducing temperature of 80 to 110 DEG C in the maximum shrinkage direction, and the maximum shrinkage stress in terms of the peeling force of the label to the container is from 0.60 to 1.80 kg / Mm < 2 >.

In addition, the polyester-based evaporated film of the present invention preferably has a total light transmittance of 0.01 to 5.0% in order to enhance the printing effect by the side and the hiding characteristics for protecting the material inside the container from light.

There is no particular limitation on the method for producing the polyester-based evaporated film according to one embodiment of the present invention. For example, a metal such as aluminum is vacuum-deposited on one surface of the heat-shrinkable polyester film substrate, . Next, a printing layer is formed on the metal vapor deposition layer. For example, a printing layer may be formed by performing printing at 5 degrees in a gravure type printing machine. On the other hand, in order to improve the scratch resistance of the print layer and to prevent the print layer from being peeled off from the metal vapor deposition layer, the protective layer formation composition described above is further coated on the print layer using a gravure type printing machine as an example, After forming a protective layer on the layer, a print layer can be formed. Further, on the other surface of the heat-shrinkable polyester film substrate, the above-described bath liquid for bending prevention layer may be applied to form the bending prevention layer.

In the case of metal deposition on one side of a polyester film having heat shrinkage characteristics, the deposition temperature is usually 1200 ° C. or higher at which the metal can be vaporized, and it is preferable to maintain a vacuum of 10 ^-2 torr or more in the chamber where vapor deposition is performed have. As a deposition method, a conventional apparatus can be used, and known methods such as a crucible method and a boat method can be applied.

As a device for forming the print layer, a usual device can be used. For example, known methods such as gravure printing and flexo printing can be applied.

The polyester-based deposited film according to one of the above embodiments is useful as a label for replacing a paper label. In one embodiment of the present invention, a label-attached bottle containing such a polyester-based deposited film is provided.

As a method for attaching a label including a polyester-based deposited film to a glass bottle or the like, a method of attaching a conventional paper material label can be applied. However, it is possible to apply the water-soluble adhesive considering the film material as the adhesive and taking the environment into consideration, and the water-soluble adhesive is applied to the coated surface of the polyester-based evaporated film label transferred in the form of a single label, , A bottle with a polyester-based evaporated film in the form of a single label can be produced.

In this way, recovery of the produced labeled bottle removal of used in polyester deposited film for reproducing is done by immersion of the bottle in hot water, the temperature of hot water may be sufficient if degree of 70 to 90 ℃.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the scope of the present invention is not limited to these Examples.

The evaluation method used in the present invention is as follows.

(1) Heat shrinkage

(MD) x 400 mm (TD) size with respect to the direction of the maximum shrinkage (TD) (width direction) and the direction perpendicular thereto (MD) with respect to the film base material and the deposited film, A specimen with an effective measurement length of 300 mm was prepared by drawing a solid line in the MD direction from the point, and then a point within 50 mm from one end of the specimen was gripped using tweezers or the like without any left and right distinction. The tape was heat-shrunk for 10 seconds in a completely dipped state after being fully immersed, left for 1 minute at room temperature, and then measured at a distance of 300 mm in the TD direction indicated by an initial solid line to measure the film's maximum shrinkage direction (TD The heat shrinkage was calculated according to the following formula (1).

<Formula 1>

(2) Thickness measurement

Immediately after immersing the film specimen in liquid nitrogen and quenching it, the film specimen was broken in liquid nitrogen and its cross section was measured using SEM (Jeol, 6700F). For each layer constituting the film, the magnification was adjusted to adjust the scale bar And the thickness was measured using the same.

The thicknesses of the film base material and the evaporated film were measured at intervals of 5 cm with respect to the entire width using a thickness measuring device, and the average values of the values excluding the maximum value and the minimum value were calculated to calculate the thickness.

(3) Hayes

The measurement method was ASTM D-1003, and 7 pieces were randomly extracted from one central portion of the polyester film at two edges, and then cut into a size of 5 cm × 5 cm. The haze was measured with a haze meter (NDH 5000) And the measurement method was set to ASTM. Then, haze (%) was measured by transmitting light, and the haze was calculated by calculating an average value for five values excluding the maximum value and the minimum value.

(4) Total light transmittance

The measurement method was ASTM D-1003, and seven portions were randomly extracted from two portions of the edge and one central portion of the polyester-deposited film, and the pieces were cut into pieces each having a size of 5 cm x 5 cm. The haze was measured with a haze meter ), And set the measurement method to ASTM. Then, the light was incident in the direction of the metal deposition layer, and the sample was mounted so as to transmit the light to the rear layer. Total transmittance (%) was measured, And the total light transmittance was calculated.

(5) Shrinkage initiation temperature, maximum shrinkage development temperature, maximum shrinkage stress

The definition of the shrinkage initiation temperature, maximum shrinkage development temperature and maximum shrinkage initiation temperature, maximum shrinkage development temperature and maximum shrinkage stress derived from the principle applied to the maximum shrinkage stress analysis in the maximum shrinkage direction of the polyester- Respectively.

1) Principle

Polymer chains undergo orientation and crystallization through a stretching process and have a structure divided into a crystallization region and an amorphous region. When heat is applied to the stretched polymer, the stress relaxation phenomenon remaining in the polymer chain appears, and the shrinkage phenomenon returning to the original shape appears. Such shrinkage force is referred to as shrinkage stress, and as the shrinkage stress is higher, The shrinking force according to the temperature becomes high.

Stress changes due to the expansion and contraction of the sample due to temperature changes can be detected by a linear variable differential transformer (LVDT) when heat is applied at a constant heating rate after fixing the film under normal temperature and constant initial load. . &Lt; / RTI &gt; Information on the shrinkage stress of the film due to the temperature change can be obtained using the above principle. Since the rate of temperature rise depends on the residual stress relaxation rate of the polymer chain, the shrinkage stress value according to the temperature change was measured at a rate of temperature increase of 2.5 ° C / sec in the present invention.

The measured graph shows a pattern as shown in Fig. 1, in which the temperature at the time when the shrinkage stress value such as the initial load value Ls is first observed is the shrinkage start temperature Ts and the value corresponding to the peak of the graph (T (Smax)), and the stress at this time is defined as the maximum shrinkage stress (Smax). As an example of a device implementing the above-mentioned principle, in the following Examples and Comparative Examples, a thermal stress tester

Tester, KE-2, Kanebo Eng.) Was used.

A film specimen having a width of 4 mm (MD direction) and a length of 50 mm (TD direction) was fixed at an initial load of 0.125 kg / mm 2 using a thermal stress tester (KE-2, Kanebo Eng. The graph was obtained by measuring the shrinkage stress according to the temperature while raising the temperature to 占 폚 / sec.

In this graph, the temperature at the time when the initial shrinkage stress value equal to the initial load of 0.125 kg / mm 2 appears at the initial shrinkage starting temperature (Ts) and the temperature at the time when the maximum shrinkage stress value first appears is referred to as the maximum shrinkage temperature (Smax)), and the stress at this time was defined as the maximum shrinkage stress (Smax).

(6) Evaluation of printing adhesion

(MD) × 5 cm (TD) size with respect to the longitudinal direction (MD) and the width direction (TD) of the polyester-based evaporated film after the completion of the above processes and the adhesive force to the printed layer of the cut film The transparent tape (Nitto Tape, 31-B) was stuck so as not to generate air bubbles, and was rubbed and rubbed 10 times at a total pressure of ³ Kg / cm ² with respect to the entire area so that the transparent tape adhered firmly to the polyester- Fully adhered.

Ten samples were prepared by the above-mentioned method, and then the transparent tape adhered to the print layer was peeled off, and the number of peeling-off samples on the polyester-based deposited film was measured and evaluated as good, normal and poor.

0 is good; ○, usually one or more; △, bad three or more; ×.

(7) Flexural property value

The polyester-based evaporated film having been subjected to all processes was placed on a polished glass plate having a refractive index of 1.567. The film was cut on the evaporated film and cut by 20 cm in the transverse direction without damage using a knife, , And the second incision was made by cutting the film in the longitudinal direction (direction perpendicular to the first incision improvement) by 20 cm, using a ruler on the basis of the center point of the incision improvement, In Section 2, four incisions were made with the distance in the horizontal and vertical directions being 10 cm, respectively, based on the intersection of the improvements. In order to confirm that the incision is completed, the incision is confirmed by lifting the deposited film in a vertical direction on the inner surface, the four incision improvement films developed in the horizontal and vertical directions. This is placed on a flat glass plate and the vertical height of the four corners corresponding to the intersection of the incision is measured by elevating the corners from the flat surface. In this case, the two cases in which the deposition layer is the upper surface and the deposition layer is the lower surface are measured, respectively, and the value indicating the maximum height is called the bending characteristic value. The negative value in the bending property is defined as the vertical height in the direction corresponding to the vertical height of the bending.

(8) Evaluation of label adhesiveness during bottle manufacturing process

The polyester-based evaporated film label was cut into a square having a size of 80 mm x 80 mm with respect to the direction of maximum shrinkage and the direction perpendicular thereto, and then 45 parts by weight of styrene-butadiene rubber latex, 40 parts by weight of acrylic emulsion, - A water-soluble adhesive prepared by mixing 10 parts by weight of a vinyl emulsion, 0.8 part by weight of sodium hydroxide, 0.1 part by weight of a germicide and 4.1 parts by weight of water was applied to the back layer of a polyester-based evaporated film label in a thickness of 5 탆, And labeling is performed on 1,000 glass bottles (shochu bottle). The labeled 1,000 glass bottles were allowed to stand at room temperature for 2 days, and then the number of wrinkled or peeled bottles on the label was measured, and the adhesiveness was evaluated by the adhesion failure rate according to the following formula (2).

<Formula 2>

Adhesion (%) = 100 - Adhesion failure rate (%)

(9) Evaluation of peelability after bonding with label

A water-soluble adhesive prepared by mixing 45 parts by weight of styrene-butadiene rubber latex, 40 parts by weight of acrylic emulsion, 10 parts by weight of ethylene-vinyl emulsion, 0.8 part by weight of sodium hydroxide, 0.1 part by weight of bactericide and 4.1 parts by weight of water, After the application, the glass bottle to which the adhesive was applied was labeled so that the printed layer of the label was positioned on the outermost surface. Using a rubber roller, the adhesive was applied ten times at a pressure of 3 kg / Rubbed back and rubbed, and allowed to stand at room temperature for 2 days to solidify the adhesive so that the label was firmly fixed to the glass bottle.

Label Adhesion Except for Adhesion to Labeling Adhesion The label for normal products was left in hot water at 80 캜 for 2 minutes and then the number of bottles in which the label was not completely peeled off from the glass bottle was measured to determine the peeling defect rate by the following formula Respectively.

<Formula 3>

Peelability (%) = 100 - Peeling defect rate (%)

EXAMPLES Hereinafter, the present invention will be described in detail with reference to Examples. However, the present invention is not limited to these Examples.

&Lt; Example 1 >

100 mol% of terephthalic acid as a dibasic acid component, 100 mol% of ethylene glycol and 24 mol% of neopentyl glycol as a glycol component and 0.05 mol of antimony trioxide (as an acid component) as a catalyst, Respectively. The polymer thus obtained contained 500 ppm of silicon dioxide powder having an average particle size of 2.7 μm and dried by a conventional method to prepare a copolyester having an intrinsic viscosity of 0.71 dl / g and a melting point of 203 ° C.

On the other hand, 0.015 part by weight of tetrabutyl titanate was added as a catalyst, using 100 mol% of terephthalic acid and 100 mol% of 1,4-butanediol to obtain a polybutylene terephthalate resin (intrinsic viscosity of 0.97 dl / g and melting point of 220 캜).

90 wt% of the above copolyester and 10 wt% of polybutylene terephthalate were blended and extruded from an extruder at 270 캜, followed by rapid cooling and solidification to obtain an unstretched film. The unstretched film was stretched 4.2 times over its width at 72 캜 through a preheating section at a temperature of 85 캜 through a roller conveyed in a mechanical direction, and then a polyester heat-shrinkable film having a thickness of 50 탆 was prepared through a heat treatment section at room temperature . The obtained film had a thickness of 50 mu m, and the heat shrinkage measured by the above method was 77.4% (TD direction) and the haze was 5.3%.

Aluminum having a purity of 99.9% was evaporated on the resulting polyester-based heat shrinkable film using a vaporizer of a crucible evaporation method at an upper vacuum degree of 1.07 x 10 ^-4 mbar, a lower vacuum degree of 2.13 x 10 ^-2 mbar, and a crucible temperature of 1400 ° C , A cooling roll temperature of -16 占 폚 and a deposition rate of 400 m / min to form a metal deposition layer having an optical density of 2.2 (metal: Al, metal deposition layer thickness: 52 nm)

10 wt% of acrylic resin (BPS-5698, Samyoung Toy), 80 wt% of methyl ethyl ketone (MEK, instead of chemical agent) and 10 wt% of a yellow pigment (Yellow 10G, Hyundai Chemical) Red coloring agent (Red-FRN, Hyundai Chemical), green pigment (Green 735, Hyundai Chemical), black pigment (Black # 30, Hyundai Chemical) and white pigment (R-100, A printed layer was formed by printing five sheets of the coarse liquid including the thickener, the color separation preventing agent and the pigment dispersant in the total amount of 100% by weight using a gravure roll (printing layer thickness: 2.0 탆).

The depth of the gravure roll was adjusted on the printing layer from the total amount of the liquid containing Alcohol (E'Vanol ^ⓡ 70-75, Dupont) and polyamide (MO-5336, Motochem) And a protective layer was formed by printing (protective layer thickness: 0.4 탆).

10% by weight of acrylic resin (BPS-5698, Samyoung Toy), 89% by weight of methyl ethyl ketone (MEK, chemical agent instead of ketone solvent), white pigment (R-100, A detergent and a pigment dispersant to adjust the depth of the gravure roll by applying a total amount of 100% by weight to the total amount of the gravure roll, and then printing at 2 to form a bending prevention layer having a thickness of 1.0 탆, Respectively.

The obtained deposited film was evaluated by the above-mentioned method, and the results are shown in the following Tables 1 and 2.

&Lt; Example 2 >

A vapor-deposited film having the same structure as in Example 1 was prepared, except that 100 mol% of terephthalic acid as a dibasic acid component and 106 mol% of ethylene glycol as a glycol component and 18 mol% of neopentyl glycol were used as a catalyst component And polycondensation was carried out by direct esterification using 0.05 mol of antimony trioxide (relative to the acid component). The polymer thus obtained contained 500 ppm of silicon dioxide powder having an average particle size of 2.7 μm and dried by a conventional method to prepare a copolyester having an intrinsic viscosity of 0.63 dl / g and a melting point of 218 ° C.

90 wt% of the above copolyester and 10 wt% of polybutylene terephthalate of Example 1 were blended and extruded from an extruder at 270 캜, followed by rapid cooling to obtain a solidified unoriented film. The unstretched film was stretched to 4.0 times the width at 72 캜 through a preheating section at a temperature of 92 캜 through a roller conveyed in a mechanical direction, and then a polyester heat-shrinkable film having a thickness of 60 탆 was produced through a heat treatment section at 90 캜 Respectively.

A metal vapor deposition layer was formed on the polyester-based heat shrinkable film prepared above under the same conditions as in Example 1 to form a metal vapor deposition layer having a thickness of 52 nm, a printing layer thickness of 2.0 μm, a protective layer thickness of 0.4 μm, A film was prepared.

The obtained deposited film was evaluated by the above-mentioned method, and the results are shown in the following Tables 1 and 2.

&Lt; Example 3 >

A vapor-deposited film having the same structure as in Example 1 was prepared, except that 100 mol% of terephthalic acid was used as a dibasic acid component, 96 mol% of ethylene glycol and 28 mol% of neopentyl glycol were used as a glycol component, And polycondensation was carried out by direct esterification using 0.05 mol of antimony trioxide (relative to the acid component). The thus obtained polymer was dried by a conventional method by containing 50 ppm of silicon dioxide powder having an average particle size of 2.7 μm to prepare a copolyester having an intrinsic viscosity of 0.73 dl / g and a melting point of 193 ° C.

90 wt% of the above copolyester and 10 wt% of polybutylene terephthalate of Example 1 were blended and extruded from an extruder at 270 캜, followed by rapid cooling to obtain a solidified unoriented film. The unstretched film was stretched to 4.0 times the width at 70 DEG C through a preheating section at a temperature of 82 DEG C through a roller conveyed in a mechanical direction, and then a polyester heat-shrinkable film having a thickness of 40 um was produced through a heat treatment section at room temperature .

A metal vapor deposition layer was formed on the polyester-based heat shrinkable film prepared above under the same conditions as in Example 1 to form a metal vapor deposition layer having a thickness of 52 nm, a printing layer thickness of 2.0 μm, a protective layer thickness of 0.4 μm, A film was prepared.

The obtained deposited film was evaluated by the above-mentioned method, and the results are shown in the following Tables 1 and 2.

<Example 4>

A vapor-deposited film having the same structure as in Example 1 was prepared, except that 100 mol% of terephthalic acid was used as a dibasic acid component, 80 mol% of ethylene glycol and 20 mol% of 1,4-cyclohexanedimethanol were used as glycol components And polycondensation was carried out by direct esterification using 0.05 mol of antimony trioxide (as acid component) as a catalyst. The polymer thus obtained contained 500 ppm of silicon dioxide powder having an average particle diameter of 2.7 μm and was dried by a conventional method to prepare a copolyester having an intrinsic viscosity of 0.68 dl / g and a melting point of 205 ° C.

The above copolyester was extruded from an extruder at 270 DEG C and then rapidly cooled and solidified to obtain an unstretched film. The unstretched film was stretched to 4.2 times the width at 72 캜 through a preheating zone at a temperature of 85 캜 through a roller conveyed in a mechanical direction, and then a heat shrinkable film having a thickness of 50 탆 was prepared through a heat treatment zone at room temperature.

A metal vapor deposition layer was formed on the polyester-based heat-shrinkable film prepared above under the same conditions as in Example 1 to form a metal vapor deposition layer having a thickness of 52 nm, a printing layer thickness of 2.0 탆, a protective layer thickness of 0.4 탆 and a bending prevention layer thickness of 1.0 탆 To prepare a deposited film.

The obtained deposited film was evaluated by the above-mentioned method, and the results are shown in the following Tables 1 and 2.

&Lt; Example 5 >

Aluminum having a purity of 99.9% was vapor-deposited on the polyester-based heat-shrinkable film substrate using a vaporizer of a crucible evaporation type to produce an aluminum film having an upper vacuum degree of 1.52 x 10 ^-4 mbar and a lower vacuum degree 1.97 × 10 ^-2 mbar and a crucible temperature of 1400 ° C., and a metal deposition layer having an optical density of 1.9 was formed at a cooling roll temperature of -16 ° C. and a deposition rate of 450 m / min (metal: Al, metal deposition layer thickness 41 nm)

An evaporated film having a metal deposition layer thickness of 41 nm, a print layer thickness of 2.0 탆, a protective layer thickness of 0.4 탆, and a bending prevention layer thickness of 1.0 탆 was produced on the vapor-deposited polyester thermosetting film prepared above under the same conditions as in Example 1 .

The obtained deposited film was evaluated by the above-mentioned method, and the results are shown in the following Tables 1 and 2.

&Lt; Example 6 >

Aluminum having a purity of 99.9% was vapor-deposited on the polyester-based heat-shrinkable film substrate using a vaporizer of a crucible evaporation type to obtain an upper vacuum degree of 1.83 × 10 ^-4 mbar and a lower vacuum degree 2.18 占^10-2 mbar and a crucible temperature of 1400 占 폚 to form a metal deposition layer having an optical density of 1.9 at a cooling roll temperature of -20 占 폚 and a deposition rate of 330 m / min (Metal: Al, metal deposition layer thickness 65 nm)

An evaporated film having a metal deposition layer thickness of 65 nm, a print layer thickness of 2.0 mu m, a protective layer thickness of 0.4 mu m, and a bending preventive layer thickness of 1.0 mu m was produced on the vapor-deposited polyester thermosetting film prepared above under the same conditions as in Example 1 .

The obtained deposited film was evaluated by the above-mentioned method, and the results are shown in the following Tables 1 and 2.

&Lt; Example 7 >

A vapor deposited film having the same structure as that of Example 1 was prepared, and a primer layer was formed on the metal vapor deposition layer before forming the print layer.

Specifically, a silane coupling agent was diluted with methylketone (MEK) on a metal vapor deposition layer using a gravure roll to form a primer layer having a thickness of 0.4 um to form a metal vapor deposition layer having a thickness of 52 nm, a printing layer thickness of 2.0 m, An evaporated film having a bending prevention layer thickness of 1.0 mu m was prepared.

The obtained deposited film was evaluated by the above-mentioned method, and the results are shown in the following Tables 1 and 2.

&Lt; Example 8 >

A vapor deposition film having the same structure as that of Example 1 was prepared and a primer layer was formed on the metal deposition layer before forming the print layer.

Specifically, a mixed resin of urethane and vinyl chloride was diluted with methyl ketone (MEK) using a gravure roll on the metal deposition layer to form a primer layer having a thickness of 0.4 um to form a metal deposition layer having a thickness of 52 nm, An evaporation film having a thickness of 0.4 [micro] m and a bending prevention layer thickness of 1.0 [micro] m was produced.

The obtained deposited film was evaluated by the above-mentioned method, and the results are shown in the following Tables 1 and 2.

&Lt; Example 9 >

10% by weight of an acrylic resin (BPS-5698, Samyoung Toyot), 80% by weight of methyl ethyl ketone (MEK, a chemical agent in the form of a ketone solvent) on the metal deposition layer, (Yellow 10G, Hyundai Chemical), Red Pigment (Red-FRN, Hyundai Chemical), Green Pigment (Green 735, Hyundai Chemical), Black Pigment (Black # 30, Hyundai Chemical) and White Pigment And a coloring agent, a coloring agent, and a pigment dispersant, and printing was carried out at 3 degrees using a gravure roll from three kinds of coarse liquids, the total amount of which was adjusted to 100 wt% (Printing layer thickness 1.0 mu m), a vapor-deposited film having a metal vapor deposition layer thickness of 52, a printing layer thickness of 1.0 mu m, a protective layer thickness of 0.4 mu m and a bending prevention layer thickness of 1.0 mu m was prepared.

The obtained deposited film was evaluated by the above-mentioned method, and the results are shown in the following Tables 1 and 2.

&Lt; Example 10 >

10% by weight of an acrylic resin (BPS-5698, Samyoung Toyot), 80% by weight of methyl ethyl ketone (MEK, a chemical agent in the form of a ketone solvent) on the metal deposition layer, (Yellow 10G, Hyundai Chemical), Red Pigment (Red-FRN, Hyundai Chemical), Green Pigment (Green 735, Hyundai Chemical), Black Pigment (Black # 30, Hyundai Chemical) and White Pigment And a coloring agent, a coloring agent, and a pigment dispersant, and printing was carried out at 8 degrees using a gravure roll from eight kinds of coarse liquids, the total amount of which was adjusted to 100 wt% (Printing layer thickness 8.0 mu m), a vapor-deposited film having a metal deposition layer thickness of 52 nm, a print layer thickness of 8.0 mu m, a protective layer thickness of 0.4 mu m and a bending prevention layer thickness of 1.0 mu m was prepared.

The obtained deposited film was evaluated by the above-mentioned method, and the results are shown in the following Tables 1 and 2.

&Lt; Example 11 >

A protective film was formed from a coating liquid containing a copolymerized polyester resin on the printing layer and controlled to a total amount of 100% by weight using a gravure roll (protective layer thickness: 0.8 um), a metallized layer thickness of 52 nm, a print layer thickness of 2.0 [mu] m, a protective layer thickness of 0.8 [mu] m, and a bending prevention layer thickness of 1.0 [mu] m.

The obtained deposited film was evaluated by the above-mentioned method, and the results are shown in the following Tables 1 and 2.

&Lt; Example 12 >

A polyolefin-based copolymer was diluted with methyl ethyl ketone (MEK) on a printing layer to prepare an evaporated film having the same structure as in Example 1, and a protective layer was formed on the protective layer using a gravure roll, (Protective layer thickness: 0.4 [micro] m), a metallized layer thickness of 52 nm, a print layer thickness of 2.0 [micro] m, a protective layer thickness of 0.4 [micro] m, and a bending prevention layer thickness of 1.0 [micro] m.

The obtained deposited film was evaluated by the above-mentioned method, and the results are shown in the following Tables 1 and 2.

&Lt; Example 13 >

In Example 1, the unstretched film obtained in the same manner as in Example 1 was stretched 1.6 times in the longitudinal direction of the film at a temperature of 70 占 폚 through a preheating section at a temperature of 65 占 폚 in a roller group conveyed in a mechanical direction The film was then cooled in a tenter in the transverse direction in the same manner as in Example 1 to obtain a shrinkage ratio of 37.3% in the film longitudinal direction (MD) Except that a bidirectional heat-shrinkable polyester film having a shrinkage ratio of 74.9% was produced, a metal vapor deposition layer having a thickness of 52 nm, a printing layer thickness of 2.0 m, a protective layer thickness of 0.4 m, and a bending prevention layer thickness of 1.0 m To prepare a deposited film.

The obtained deposited film was evaluated by the above-mentioned method, and the results are shown in the following Tables 1 and 2.

&Lt; Example 14 >

In the roller group conveyed in the mechanical direction in Example 13, the sheet was stretched 2.5 times in the longitudinal direction of the film at a temperature of 75 DEG C through a preheating section at a temperature of 75 DEG C, cooled through a cooling roll at room temperature, Stretched in the transverse direction under the same conditions as in Example 1 to obtain a bidirectional heat-shrinkable polyester film having a shrinkage ratio of 45.8% in the film longitudinal direction (MD) and a shrinkage ratio of 70.5% in the transverse direction (TD) , A deposited film having a thickness of a metal deposition layer of 52 nm, a print layer thickness of 2.0 mu m, a protective layer thickness of 0.4 mu m and a bending prevention layer thickness of 1.0 mu m was prepared.

The obtained deposited film was evaluated by the above-mentioned method, and the results are shown in the following Tables 1 and 2.

&Lt; Example 15 >

An evaporated film having the same structure as in Example 1 was prepared except that a protective layer was not formed, and a vapor deposited film having a metal deposition layer thickness of 52 nm, a print layer thickness of 2.0 um, and a bending prevention layer thickness of 1.0 um was produced Respectively.

The obtained deposited film was evaluated by the above-mentioned method, and the results are shown in the following Tables 1 and 2.

&Lt; Example 16 >

Aluminum with a purity of 99.9% was vapor-deposited on a polyester-based heat shrinkable film base material by using a vaporizer of a crucible evaporation type to produce an evaporation film having the same structure as that of Example 1, with an upper vacuum degree of 1.79 × 10 ^-4 mbar, 2.03 x 10 &lt; ^{-2 &} gt ^; mbar and a crucible temperature of 1400 DEG C, and a metal deposition layer having an optical density of 1.5 was formed at a cooling roll temperature of -10 DEG C and a deposition rate of 500 m / min. 10 nm)

A vapor-deposited film having a metal deposition layer thickness of 10 nm, a print layer thickness of 2.0 [mu] m, a protective layer thickness of 0.4 [mu] m, and a bending prevention layer thickness of 1.0 [mu] m was prepared on the vapor-deposited polyester- .

The obtained deposited film was evaluated by the above-mentioned method, and the results are shown in the following Tables 1 and 2.

&Lt; Example 17 >

, 100 mol% of terephthalic acid as a dibasic acid component, 110 mol% of ethylene glycol and 14 mol% of neopentyl glycol as glycol components and 0.05 mol of antimony trioxide (as an acid component) as a catalyst, Respectively. The polymer thus obtained contained 500 ppm of silicon dioxide powder having an average particle size of 2.7 μm and was dried by a conventional method to prepare a copolyester having an intrinsic viscosity of 0.71 dl / g and a melting point of 203 ° C.

90 wt% of the above copolyester and 10 wt% of polybutylene terephthalate of Example 1 were blended and extruded from an extruder at 270 캜, followed by rapid cooling and solidification to obtain an unstretched film. The unstretched film was stretched to 4.0 times the width at 80 DEG C through a preheating section at a temperature of 92 DEG C through a roller conveyed in a mechanical direction, and then a heat-shrinkable film having a thickness of 50 mu m was produced through a heat treatment section at 95 DEG C.

A metal vapor deposition layer was formed on the polyester-based heat shrinkable film prepared above under the same conditions as in Example 1 to form a metal vapor deposition layer having a thickness of 52 nm, a printing layer thickness of 2.0 μm, a protective layer thickness of 0.4 μm, The film was evaluated by the above-mentioned method for the coating film, and the results are shown in the following Tables 1 and 2. &lt; tb &gt;&lt; TABLE &gt;

&Lt; Example 18 >

10% by weight of an acrylic resin (BPS-5698, Samyoung Toyot), 80% by weight of methyl ethyl ketone (MEK, a chemical agent in the form of a ketone solvent) on the metal deposition layer, (Yellow 10G, Hyundai Chemical), Red Pigment (Red-FRN, Hyundai Chemical), Green Pigment (Green 735, Hyundai Chemical), Black Pigment (Black # 30, Hyundai Chemical) and White Pigment And a pigment dispersant, and printing was carried out at 6 degrees using a gravure roll from six kinds of coarse liquids, the total amount of which was adjusted to 100% by weight, including a precipitation inhibitor, a thickener, a color separation inhibitor and a pigment dispersant, (Printing layer thickness: 12.0 mu m), a vapor deposited film having a thickness of the metal vapor deposition layer of 52 nm, a printing layer thickness of 12.0 mu m, a protective layer thickness of 0.4 mu m, and a bending prevention layer thickness of 1.0 mu m was prepared.

The obtained deposited film was evaluated by the above-mentioned method, and the results are shown in the following Tables 1 and 2.

&Lt; Example 19 >

10% by weight of an acrylic resin (BPS-5698, Samyoung Toyot), 80% by weight of methyl ethyl ketone (MEK, a chemical agent in the form of a ketone solvent) on the metal deposition layer, (Yellow 10G, Hyundai Chemical), Red Pigment (Red-FRN, Hyundai Chemical), Green Pigment (Green 735, Hyundai Chemical), Black Pigment (Black # 30, Hyundai Chemical) and White Pigment And a pigment dispersant, and printing was carried out at a printing speed of 2 degrees using a gravure roll from two types of coarse liquids, the total amount of which was adjusted to 100% by weight, including a coloring agent, (Printing layer thickness 0.2 탆), a vapor deposition film having a metal deposition layer thickness of 52 nm, a printing layer thickness of 12.0 탆, a protective layer thickness of 0.4 탆, and a bending prevention layer thickness of 1.0 탆 was prepared.

The obtained deposited film was evaluated by the above-mentioned method, and the results are shown in the following Tables 1 and 2.

&Lt; Comparative Example 1 &

Except that a PET film 50um (H34, manufactured by Kolon Industries, Ltd.) was used as a base film to produce a vapor deposited film having the same structure as that of Example 1, except that the thickness of the metal vapor deposition layer was 52 nm, A protective layer having a thickness of 0.4 탆, and a bending prevention layer having a thickness of 1.0 탆.

The obtained deposited film was evaluated by the above-mentioned method, and the results are shown in the following Tables 1 and 2.

&Lt; Comparative Example 2 &

A vapor deposited film having the same structure as that of Example 1 was prepared except that the formation of the bending prevention layer was not carried out. Thus, a vapor deposition film having a metal deposition layer thickness of 52 nm, a printing layer thickness of 2.0 m, Respectively.

The obtained deposited film was evaluated by the above-mentioned method, and the results are shown in the following Tables 1 and 2.

Base film Evaporated film Heat shrinkage
(TD direction,%) Hayes
(%) Analysis by heat shrinkage stress tester Heat shrinkage
(TD direction,%) Total light transmittance (%) Ts
(° C) T _(Smax)
(° C) S _max
(kg / mm2) Example 1 77.4 5.3 82.3 91.3 1.23 77.2 0.20 Example 2 43.0 8.6 92.4 108.7 0.63 42.0 0.15 Example 3 78.7 0.4 70.4 87.3 1.67 78.0 0.23 Example 4 78.5 4.3 88.2 99.7 0.67 75.3 0.20 Example 5 77.4 5.3 83.3 91.7 1.26 77.1 0.28 Example 6 77.7 5.1 82.4 91.6 1.24 77.5 0.13 Example 7 77.3 5.2 82.3 91.5 1.23 77.1 0.19 Example 8 77.4 5.3 82.4 91.4 1.24 77.3 0.21 Example 9 77.4 5.1 82.4 91.3 1.23 77.2 0.20 Example 10 77.3 5.0 82.3 91.3 1.25 77.1 0.21 Example 11 77.3 5.2 82.4 91.4 1.26 77.2 0.20 Example 12 77.4 5.3 82.2 91.3 1.23 77.2 0.20 Example 13 74.9 5.9 83.2 93.5 1.18 71.7 0.20 Example 14 70.5 6.2 84.5 95.7 1.12 68.2 0.20 Example 15 77.4 5.2 82.2 90.9 1.23 77.1 0.21 Example 16 77.4 5.3 82.0 90.9 1.28 77.2 11.31 Example 17 77.2 5.2 82.1 91.0 1.24 76.9 0.22 Example 18 77.4 5.3 82.2 91.3 1.24 77.1 0.20 Example 19 77.3 5.4 82.3 91.3 1.23 77.2 0.19 Comparative Example 1 1.6 2.3 231.7 272.9 0.11 1.4 0.19 Comparative Example 2 77.3 5.3 82.4 91.3 1.22 77.0 9.23

Evaporated film Evaluation of warpage (mm)
(Measured at four corners) Bending property value
(mm) print
Adhesiveness On the label
Adhesiveness
(%) On the label
Peelability
(%) Example 1 1.2 / 0.8 / 0.4 / 0.4 1.2 ○ 99.9 99.9 Example 2 2.0 / 1.3 / 1.0 / 0.5 2.0 ○ 100.0 99.8 Example 3 0.7 / 0.6 / 1.6 / 1.4 1.6 ○ 100.0 100.0 Example 4 0.6 / 1.3 / 0.2 / 1.4 1.4 ○ 99.9 100.0 Example 5 1.1 / 1.0 / 1.2 / 1.1 1.2 ○ 100.0 100.0 Example 6 1.3 / 0.7 / 0.8 / 1.2 1.3 ○ 99.9 100.0 Example 7 1.5 / 1.2 / 1.4 / 0.8 1.5 ○ 100.0 100.0 Example 8 1.6 / 0.4 / 1.2 / 1.3 1.6 ○ 100.0 99.9 Example 9 1.2 / 1.5 / 1.7 / 1.1 1.7 ○ 100.0 99.9 Example 10 2.1 / 1.8 / 1.7 / 2.3 2.3 ○ 99.9 100.0 Example 11 1.2 / 1.5 / 1.3 / 1.6 1.6 ○ 100.0 100.0 Example 12 1.3 / 1.7 / 1.2 / 1.4 1.7 ○ 100.0 99.9 Example 13 1.8 / 2.2 / 1.8 / 1.2 1.8 ○ 100.0 99.9 Example 14 1.7 / 2.8 / 3.0 / 0.8 3.0 ○ 100.0 100.0 Example 15 1.1 / 1.3 / 2.1 / 0.6 2.1 △ 100.0 100.0 Example 16 3.9 / 3.8 / 4.5 / 3.1 3.1 ○ 92.1 100.0 Example 17 2.3 / 3.2 / 1.8 / 4.1 4.1 ○ 99.9 85.1 Example 18 2.2 / 3.1 / 4.7 / 3.5 4.7 ○ 95.1 99.7 Example 19 -2.7 / -3.5 / -2.4 / -3.3 -3.5 ○ 93.9 99.9 Comparative Example 1 0.4 / 1.7 / 1.3 / 1.1 1.7 ○ 99.8 2.2 Comparative Example 2 -5.3 / -6.7 / -4.7 / -4.9 -6.7 ○ 87.9 99.8

From the results of Tables 1 and 2, it can be seen that the examples according to the present invention are excellent in shrinkage stress, shrinkability, total light transmittance, print adhesion and label adhesiveness and peelability, It can be seen that the label can be removed. Particularly, in Examples 13 and 14 in which stretching was performed both in the longitudinal direction and in the width direction of the film in the above Examples, the adhesiveness and peeling property of the label were excellent and the applicability of the label was excellent, It is relatively easy to separate the separated label and the bottle from the other embodiments. In particular, in three stages of a float type in which water is introduced into three stages and the label is lifted to the water level by using water pressure and the separated labels are collected from the upper stage by using hooks, The pressure and flow rate of the water must be increased when the label is floated to the upper part of the three stages. In the case of Examples 13 and 14, however, the label is separated from the bottle It is possible to separate the label by floating the label on the upper part of the three stages in comparison with other embodiments, which is advantageous in terms of water consumption and energy saving.

On the other hand, in the case of Comparative Example 1 in which the heat-shrinkable polyester base material film is not used, it can be seen that peeling of the label is practically impossible in the case of simple hot water.

Also, as in Comparative Example 2, it can be confirmed that the adhesive property of the label is deteriorated in the absence of the bending prevention layer.

In addition, from the results of Examples 16 to 19, it can be confirmed that controlling the thicknesses of the metal deposition layer and the print layer is more preferable in terms of improving the adhesiveness of the label.

Also, when the thickness of the metal vapor deposition layer is thin as in the case of Example 16, the total light transmittance of the heat-shrinkable deposited film is high, so that the color of the bottle is projected on application of the final finished product to a colored bottle, And thus the aesthetics of the advertisement may be deteriorated as a result. Therefore, it is necessary to control the thickness of the metal deposition layer in consideration of visibility.

In addition, when the shrinkage starting temperature is high and the maximum shrinkage stress is low as in Example 17, when the printing label is removed from the bottle, a part of the printing label adhered to the bottle is partially generated, It can be confirmed that the shrinkage initiation temperature, the maximum shrinkage stress and the like are more preferably controlled.

In the case of Example 15 in which the protective layer is not applied, the adhesive property and peeling property are not a problem, but a phenomenon occurs in which the metal deposition layer and the print layer of the print label peel off during the printing label peeling process, It may cause a problem of contaminating the bottle, and may cause secondary contamination of the bottle resulting from the contamination, resulting in a problem of further cleaning of the bottle. There is no problem with the overall fairness, but since the cleaning process of the bottle must be added after peeling off the printing label, there is a problem of increase in the process cost when applying the printing label.

Claims (17)

A heat-shrinkable polyester film substrate;
A metal deposition layer on a substrate;
A printing layer on the metal deposition layer; And
And a bending prevention layer on the other surface of the substrate,
Wherein the bending prevention layer comprises at least one resin selected from the group consisting of polyamide resin, acrylic resin, polyurethane, PVC resin, ketone resin, chlorinated rubber, vinyl acetate resin and ethylene-vinyl acetate copolymer; At least one solvent selected from aromatic hydrocarbon type, ketone type, acetate type and chlorinated solvents; And a layer formed from a composition comprising a white pigment and at least one additive selected from a precipitation inhibitor, a thickener, a color separation inhibitor and a pigment dispersant,
The first incision is cut by 20 cm in the transverse direction on the evaporated film to form the first incision and the incision is cut by 20 cm in the vertical direction perpendicular to the first incision to form the second incision, Four incisions were made in which the distance in the transverse direction and the transverse direction were respectively 10 cm on the basis of the intersection points of the incision incisions and the four corners corresponding to the intersection points of the incision incisions were bent and raised from the flat surface Wherein a warp characteristic value expressed by a vertical height that comes up is 5.0 mm or less. delete The method according to claim 1,
A polyester-based deposition film comprising a primer layer between a metal deposition layer and a print layer. The method according to claim 1 or 3,
A polyester-based evaporated film comprising a protective layer on a printing layer. 5. The method of claim 4,
The protective layer may be a copolymerized polyester, an acrylic copolymer, a styrene copolymer, a methacrylate copolymer, polystyrene, vinyl acetate, polyamide, alkyl acrylate, urea formaldehyde, epoxidized soybean oil, ethylene- Wherein the resin layer is a resin layer composed of a resin selected from the group consisting of oleamide, polyethylene glycol distearate, polyvinylidene, polyolefin copolymer, urethane, and vinyl resin, or a mixture thereof. The method according to claim 1,
Wherein the heat-shrinkable polyester-based film substrate comprises a polyester-based resin containing a repeating unit of butylene terephthalate. The method according to claim 6,
The heat-shrinkable polyester film substrate is at least one of terephthalic acid, oxalic acid, malonic acid, succinic acid, adipic acid, suberic acid, azelaic acid, sebacic acid, phthalic acid, isophthalic acid, naphthalene dicarboxylic acid and diphenyl ether dicarboxylic acid And at least one dicarboxylic acid component selected from the group consisting of ethylene glycol, neopentyl glycol, propylene glycol, trimethylene glycol, tetramethylene glycol, hexamethylene glycol, diethylene glycol, polyalkylene glycol, 1,4-cyclohexane di And at least one copolyester selected from among copolyesters obtained from a diol component containing at least one or more selected from the group consisting of methanol and methanol. The polyester-based evaporated film according to claim 7, wherein the copolyester comprises 80 mol% or more of terephthalic acid units in the dicarboxylic acid unit and 12 to 24 mol% of units other than ethylene glycol in the diol unit. The method according to claim 1,
Wherein the shrinkage ratio with respect to the maximum shrinkage direction is 40 to 80% when the film is treated in hot water at 90 占 폚 for 10 seconds. The method according to claim 1,
And the shrinkage starting temperature in the maximum shrinkage direction is 68 to 94 占 폚. The method according to claim 1,
A maximum shrinkage development temperature in the maximum shrinkage direction of 80 to 110 DEG C and a maximum shrinkage stress of 0.60 to 1.80 kg / mm &lt; 2 &gt;. The polyester-based vapor deposited film according to claim 1, wherein the total light transmittance is 0.01 to 5.0%. The polyester-based evaporated film according to claim 1, wherein the heat-shrinkable polyester film substrate has a haze of 0.3 to 10.0%. delete A bottle-attached bottle comprising the polyester-based evaporated film of claim 1. The bottle according to claim 15, wherein the polyester-based deposited film is removed by immersion in hot water. A step of applying an adhesive to the bending prevention layer of the polyester-based evaporated film according to claim 1; And
And adhering a polyester-based evaporated film coated with an adhesive to a container.

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