KR20120106368A - Polyester-based metallized film - Google Patents

Abstract

PURPOSE: A polyester deposited film capable of removing a label from a glass bottle for recycling with hot water is provided to embody the clear deposition color of the film when using as the label. CONSTITUTION: A polyester deposited film includes a heat shrinkable polyester based film material, a metal deposition layer located on one side of the film material, a printed layer located on the metal deposition layer, and a rear surface layer located on the other side of the film material. The polyester deposited film additionally includes a primer layer in between the metal deposition layer and the printed layer, and a protective layer on the printed layer. The rear surface layer is obtained by a concavo-convex layer or a white pigment coating layer. The shrinking rate of the polyester deposited film processed in 90 deg C hot water for 10 seconds is 40-80%.

Description

Polyester-based deposition film {Polyester-based metallized film}

The present invention relates to a deposition film comprising a polyester-based film layer having heat shrinkage properties and to the use of the film as a label of a film material that can replace the label of the paper material attached to the glass bottle.

In consideration of environmental requirements and economics, PET bottles and glass bottles have been collected and used again. In addition to PET or glass bottle bodies for recycling, labels with printed product names, ingredient names and other emblems should be removed separately. Paper labels that have been used so far have been removed using industrial water. Specifically, the PET bottle or glass bottle collected is immersed in industrial water at about 80 ° C. containing caustic soda and the label is removed. As a result, environmental wastewater is generated in recycling empty bottles, and environmental regulations are in full swing.

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

An example of a film that can be utilized as a label may include a polyvinyl chloride-based film, but this is not preferable because of environmental problems such as generating dioxin during incineration, and thus, a polyester-based heat-shrinkable film is made of a paper material. It is emerging as a means to replace the label.

What can be considered as a method of applying the polyester-based heat-shrinkable film as a label may be a method of printing on a film like a sticker or a conventional paper label and pasting it using a water-soluble adhesive.

In the method of adhering a label using an adhesive like a paper label, an adhesive may be applied to the back layer of the label using a method such as gravure printing and then attached to the bottle. By the way, in the case of the polyester-based heat-shrinkable film label formed with a print layer is severely curled phenomenon of the label itself may be difficult to easily apply the process of attaching a conventional paper label.

In addition, in a glass bottle colored for the purpose of UV protection, such as beer bottles, the printing effect is insufficient as a general label, and when the label is a film material, there is a shortage in the incidence of the advertising effect using the label.

One embodiment of the present invention provides a polyester-based deposition film that can implement a vivid deposition color when applied for labeling while maintaining shrinkage and can double the advertising effect.

In addition, in one embodiment of the present invention, a label including such a polyester-based deposition film is attached, which can double the advertising effect, and can also remove the label using only hot water when recycling, thereby preventing wastewater generation. We can do it and provide environmentally friendly bottle.

In another aspect, the present invention provides a method for producing a bottle with a label that can be carried out in one process in the transfer of the label, the application of the adhesive and the adhesion to the bottle despite the application of the label of the film material.

In one embodiment of the invention the heat-shrinkable polyester film substrate; A metal deposition layer on the substrate; A print layer on the metal deposition layer; And a back layer on the other side of the substrate.

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

In the polyester-based deposition film according to an embodiment of the present invention, it may include a protective layer on the printed layer.

In the polyester-based deposition film according to an embodiment of the present invention, the protective layer is a copolyester, acrylic copolymer, styrene copolymer, methacrylate copolymer, polystyrene, vinyl acetate, polyamide, alkyl acrylate, urea Formaldehyde, epoxidized soybean oil, ethylene-vinyl acetate copolymer, tallow oleamide, polyethylene glycol distearate, polyvinylidene, polyolefin copolymer, urethane and vinyl resin It may be a resin layer consisting of a single or a mixture thereof selected from.

In the polyester-based deposition film according to an embodiment of the present invention, the back layer may be an uneven layer formed by physically or chemically treating the surface of the heat-shrinkable polyester-based film.

In the polyester-based deposition film according to an embodiment of the present invention, the back layer may be a white pigment coating layer.

In the polyester-based deposition film according to an embodiment of the present invention, the heat-shrinkable polyester film base material may include a polyester-based resin containing a butylene terephthalate repeating unit.

In the polyester-based deposition film according to an embodiment of the present invention, the heat-shrinkable polyester film base material is terephthalic acid, oxalic acid, malonic acid, succinic acid, adipic acid, suveric acid, azelaic acid, sebacic acid, phthalic acid, isophthalic acid Dicarboxylic acid components containing at least one dicarboxylic acid such as naphthalenedicarboxylic acid, diphenyl ether dicarboxylic acid, ethylene glycol, neopentyl glycol, propylene glycol, trimethylene glycol, tetramethylene glycol, At least one copolyester selected from the copolyesters obtained from a diol component comprising at least one diol such as hexamethylene glycol, diethylene glycol, polyalkylene glycol, 1,4-cyclohexane dimethanol It may be.

In a specific embodiment, the copolyester may include at least 80 mol% of terephthalic acid units in the dicarboxylic acid units, and 12 to 24 mol% of units other than ethylene glycol in the diol units.

In the polyester-based deposition film according to an embodiment of the present invention, the heat-shrinkable polyester film substrate may be a uniaxially oriented heat-shrinkable polyester film substrate or a bidirectional heat-shrinkable polyester film substrate.

Polyester-based deposition film according to an embodiment of the present invention may be 40 to 80% shrinkage in the maximum shrinkage direction when treated over 90 seconds in 90 ℃ hot water.

Polyester-based deposition film according to an embodiment of the present invention may be a shrinkage start temperature in the maximum shrinkage direction of 68 to 94 ℃.

Polyester-based deposition film according to an embodiment of the present invention is the maximum shrinkage expression temperature in the maximum shrinkage direction is 80 to 110 ℃, the maximum shrinkage stress may be 0.60 to 1.80kg / mm2.

Polyester-based deposition film according to an embodiment of the present invention may be a total light transmittance of 0.01 to 5%.

In the polyester-based deposition film according to an embodiment of the present invention, the heat-shrinkable polyester film substrate may be a haze of 0.3 to 10%.

In one exemplary embodiment of the present invention provides a bottle labeled with a polyester-based deposition film according to the embodiments.

Labeled bottle according to an embodiment of the present invention can be removed polyester-based deposition film by a method of immersing in hot water.

In one embodiment of the invention the process of applying an adhesive to the back layer of the polyester-based deposition film described in the above embodiments; And attaching a back layer of the heat-shrinkable polyester film to which the adhesive is applied to the bottle.

Polyester-based deposition film according to an embodiment of the present invention can increase the advertising effect as it can implement a vivid deposition color, while maintaining shrinkage, labeling when applied to replace the existing paper label Transfer and adhesive application and attachment to the bottle can be performed on one process line, and the existing paper label line can be applied as it is.The resulting bottle has a heat-shrinkable polyester label attached to it for beautiful printing appearance and concealment. It is very environmentally friendly because it is excellent in performance and waste water can be prevented as the label can be removed using only hot water when recycling.

1 is a graph illustrating a change in the shrinkage stress value in the maximum shrinkage direction according to a temperature change of a polyester-based deposited film obtained according to Example 1 using a thermal stress meter.

Polyester-based deposition film according to an embodiment of the present invention is a heat-shrinkable polyester film substrate; A metal deposition layer on the substrate; A print layer on the metal deposition layer; And a back layer on the other side of the substrate.

Here, the term "heat-shrinkable polyester film base material" means that the main matrix constituting the film is a polyester-based resin, and has a maximum uniaxial or biaxial orientation through low temperature uniaxial or biaxial stretching, and a solution of residual stress through heat treatment. Not only the film base material, uniaxially oriented shrink film, but also bidirectional shrink film, manufactured on the principle that the molecular chains oriented by exclusion retain the residual stress and shrink under the force of the residual stress in the final shrinkage process. It is called.

The heat-shrinkable polyester film base material is not particularly limited in its composition, and examples thereof include terephthalic acid, oxalic acid, malonic acid, succinic acid, adipic acid, suveric acid, azelaic acid, sebacic acid, phthalic acid, isophthalic acid, A dicarboxylic acid component containing at least one known dicarboxylic acid such as naphthalenedicarboxylic acid, diphenyl ether dicarboxylic acid, and the like, ethylene glycol, neopentyl glycol, propylene glycol, trimethylene glycol, tetramethylene At least one copoly selected from copolyesters obtained from diol components comprising one or more known diols such as glycols, hexamethylene glycols, diethylene glycols, polyalkylene glycols, 1,4-cyclohexane dimethanol and the like ester; Or obtained from a mixture of homopolyester and copolyester.

Copolyester itself can be manufactured by the manufacturing method of polyester generally performed. For example, the direct esterification method which reacts diol directly with dicarboxylic acid, the transesterification method which makes diol act on the dimethyl ester of dicarboxylic acid, etc. are mentioned.

In this case, the copolyester may be a copolyester in which terephthalic acid units constitute 80 mol% or more of the dicarboxylic acid units and units other than ethylene glycol in the diol units constitute 12 to 24 mol%. Units other than ethylene glycol units in the copolyester have a function of increasing the shrinkage rate by lowering the crystallinity of the polyester polymer, and the ratio of the units within the above ranges controls drying process, film processability, It may be advantageous in terms of controlling melting characteristics and physical properties.

In this invention, the said copolyester itself can be manufactured by the manufacturing method of polyester generally performed. For example, the direct esterification method which reacts diol directly with dicarboxylic acid, the transesterification method which reacts the dimethyl ester diol of dicarboxylic acid, etc. are mentioned.

According to an embodiment of the present invention, the melting point of the copolyester (Melting Point; ℃) is 190 ~ 220 ℃, the intrinsic viscosity is 0.60 ~ 0.75 dl / g. The melting point (° C.) may be adjusted according to the composition of the monomer used to prepare the polymer, and the intrinsic viscosity may vary depending on the degree of polymerization. In the present invention, the melting point (° C.) is controlled through such adjustment. Copolyesters with intrinsic viscosity and in the above range can be used.

On the other hand, polytriethylene terephthalate may be used instead of or in combination with polybutylene terephthalate as a homopolyester.

In manufacturing such a heat-shrinkable polyester film base material, lubricants such as silicon dioxide, titanium dioxide, silica powder, and calcium carbonate may be added in order to improve slipperiness, and if necessary, antistatic agents, anti-aging agents, ultraviolet rays, and the like. Inhibitor, Various additives such as pigments may also be added.

On the other hand, the heat-shrinkable polyester film base material is required to be made of a film roll by running a long film at high speed or winding at a high speed in view of improving productivity in a film forming process or a post-processing process. It may include an in-line coating layer.

Here, the term 'inline coating layer' will be understood by those skilled in the art as a layer formed by a coating process in any one process of extruding a polyester resin to form a film.

As such, when the in-line coating layer including the antistatic agent is formed on the surface of the film, the static electricity generated by the friction is alleviated, thereby eliminating the phenomenon that the films stick to each other during the process of winding the film roll. It can be advantageous in that it can help to easily escape the introduced air in the intake process. In addition, feeding defects can be controlled by preventing printing defects caused by static electricity generated by the friction of the printing roll and the film during the printing process, and removing the sticking of the film by the static electricity during the post-processing process. .

The type of antistatic agent is not particularly limited, but examples thereof include quaternary ammonium compounds, alkyl sulfonate compounds classified by RSO ₃ Na, alkyl sulfate compounds classified by ROSO ₃ Na, alkyl phosphate compounds and the like. The content is 0.1 to 1.5% by weight based on the active ingredient in the crude liquid for forming the inline coating layer may be preferable in terms of excellent processability and antistatic performance by minimizing the amount of foreign matter generated by the friction during the printing process.

On the other hand, the in-line coating layer may include a binder resin in consideration of the binding force and the adhesive force, wherein the binder resin is not particularly limited.

As an example of the binder resin which can be considered, a polyester type, an acryl- polyester copolymer, a co-polyester type, etc. are mentioned.

The heat-shrinkable polyester film base material may preferably have a haze of 0.3 to 10% in terms of realizing a bright deposition color when forming a metal deposition layer.

The thickness of the heat-shrinkable polyester film base material is 35 to 65 μm, preferably 40 to 60 μm, and the feeding stability of the label and the label for the bottle when the deposition and printing is completed are attached to the bottle. It may be advantageous in terms of uniformity of adhesion.

As described above, in one embodiment of the present invention includes not only uniaxially oriented heat shrink film but also bidirectional shrink film, and is not particularly limited. It may be more advantageous to be a bidirectional shrink film in terms of where possible.

On the other hand, the polyester-based deposition film of the present invention includes a metal deposition layer on the heat-shrinkable polyester film base material described above.

Examples of the metal that can be used for the metal deposition layer include Al, Zn, Mg, Sn, Ti, In, Cr, Ni, Cu, Pb, Fe, and the like, and preferably Al, Zn, Mg, in particular Al may be most preferred in terms of productivity.

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

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

Polyester-based deposition film according to an embodiment of the present invention includes a printed layer on the metal deposition layer.

The printing layer is printed with letters or figures to print out the contents of the container, advertisements and warning texts to promote the product. As a method of forming a printed layer, a well-known method can be used, for example, gravure printing, flexographic printing, screen printing, etc. are mentioned. The thickness of the printed layer may be preferably 0.5 to 10 µm in view of sufficient printing layer and preventing the printed layer from breaking.

If necessary, a primer layer may be further included between the metal deposition layer and the printing layer. The primer layer can increase the adhesion strength between the metal deposition layer and the printing layer, which not only gives scratch resistance to the printing layer but also prevents contamination due to peeling of the printing layer in the thin bottle process of removing the label from the bottle. Can play a role. Such primer layer may be appropriately selected in consideration of the printing layer, but is not limited thereto.

In addition, corona treatment, flame treatment, plasma treatment, glow discharge treatment, roughening treatment, etc. may be performed on the surface of the heat-shrinkable polyester film substrate before forming the metal deposition layer in order to obtain adhesion strength.

In addition, a protective layer may be further included on the printed layer, which may be not only for protecting the printed layer but also for imparting weather resistance or durability of the metal deposition layer. The protective layer is not particularly limited in its composition, and for example, the protective layer may be a copolyester, an acrylic copolymer, a styrene copolymer, a methacrylate copolymer, polystyrene, vinyl acetate, polyamide, alkyl acrylate, or ureaform. Resin layer consisting of aldehyde, epoxidized soybean oil, ethylene-vinyl acetate copolymer, tallow oleamide, polyethylene glycol distearate, polyvinylidene, polyolefin copolymer, urethane and vinyl resin alone or mixtures thereof Can be.

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

In addition, in order to apply the polyester-based deposition film of the present invention for label use, it is necessary to satisfy the ease of drying to the appropriate concealment of the adhesion after the adhesive using an adhesive.

This includes a back layer on the other side of the heat-shrinkable polyester film substrate.

The back layer may be an uneven layer formed by physically or chemically treating the surface of the heat-shrinkable polyester film substrate, or may be a white pigment coating layer.

In the case of forming the uneven layer by physically or chemically treating the surface of the heat-shrinkable polyester film substrate, when the adhesive is applied to the deposited film, the deposited film is adhered to the bottle and dried, the drying efficiency is increased due to the air layer formed on the uneven layer. It can improve and shorten the drying time.

 The back layer may be a separate coating layer instead of the uneven layer, and specifically, may be a white pigment coating layer. When the white pigment coating layer is formed, the concealability of the deposited film may be improved, and the fine concavo-convex effect may be obtained by the roughness of the surface, thereby improving the drying efficiency of the adhesive applied to the film, and reducing the drying time.

On the other hand, as an example of a known method of attaching a label of paper material, especially a sheet label, to a glass bottle, an adhesive is applied by a method such as gravure printing while transferring a label of a predetermined standard on which a printing layer is formed, and the adhesion to the bottle is continuously performed. (This is called an "online bonding process.") In the case of the label of the paper material, even after the printing layer is formed, the flatness of the titration is maintained. In the case of the heat-shrinkable polyester film, the coating solution is formed by forming a white pigment coating layer on one surface of the substrate. This may intensify the curling of the film. Therefore, there may be a difficulty in applying a label of a film material in a bottle maker or a liquor manufacturer that has been applying a conventional paper label.

The white pigment coating layer includes at least one resin selected from resins such as acrylics, polyurethanes, ethylene-vinylacetate copolymers, vinyls, solvents, white pigments, precipitation inhibitors, thickeners, color separation agents, pigment dispersants, and the like. Forming from a composition containing an additive of may be preferable in terms of being able to easily control the warpage phenomenon of the heat-shrinkable polyester film substrate. The solvent for preparing the crude liquid is not particularly limited, but considering at least one solvent used for forming the printed layer, at least one selected from an aromatic hydrocarbon solvent, a ketone solvent, an acetate solvent, a chlorine solvent and an alcohol solvent is selected. Can be used.

The white pigment coating layer may have a thickness of 0.1 to 5.0 탆, preferably 0.4 to 2 탆, which may be advantageous in terms of coating stability of the back layer, stability of the drying process, and prevention of warpage of the label by the solvent.

Polyester-based deposition film according to an embodiment of the present invention that satisfies the above configuration is that the shrinkage in the maximum shrinkage direction is 40 to 80% when treated over 90 seconds in hot water at 90 ℃.

Such a range of shrinkage rate of hot water is easy to peel even in the process of peeling the label using hot water at the time of recovering empty bottles after attaching the heat-shrinkable film to the bottle with a label using an adhesive. It is advantageous in terms of what it can do.

Specifically, in the case of treatment for 10 seconds in hot water at 90 ° C., if the shrinkage ratio in the maximum shrinkage direction is less than 40%, the time required for shrinkage becomes long, and when the label is applied, the label is removed for reuse of the bottle. Not only does the peeling efficiency drop but also the energy cost is high. On the other hand, when the shrinkage rate in the maximum shrinkage direction exceeds 80%, the film is curled due to the excessively high shrinkage rate. Labels are difficult to get into and out of the bottle, causing problems in the separation removal process.

In addition, the polyester-based deposition film of the present invention can be easily removed within a short time in the removal of the label for reuse of the bottle when the shrinkage start temperature of the maximum shrinkage direction is 68 to 94 ℃ in the label application. Here, the shrinkage start temperature may be defined as follows.

Shrink initiation temperature: After fixing the film under normal temperature and constant initial load, the stress when shrinking the film while applying heat at a constant heating rate is measured. Initial temperature at which stress is indicated.

An example of a measuring device that can implement such a graph is a thermal stress tester (Thermal Stress Tester).

For example, in order to check the shrinkage characteristics according to the temperature change of the deposited film in the thermal shrinkage stress tester, first, the film is fixed at a predetermined load, and then the heat is changed at a constant heating rate, and the change of stress due to the shrinkage according to the temperature change is applied. Measure

An example of a measurement graph by such a method is illustrated in FIG. 1. Referring to FIG. 1, the initial time point on the graph is an initially set load value Ls. Compared to the initial load Ls, the film is tightened and shrinks when a certain temperature is reached. At this time, the shrinkage stress value of the same value as the initial load (Ls) is observed, this time is defined as the shrinkage start temperature (Ts).

In the heat-shrinkable polyester film of the present invention, the shrinkage start temperature in the maximum shrinkage direction is 68 to 94 ° C. If the shrinkage start temperature is lower than 68 ℃, during the summer distribution and storage of the finished product, the label may be partially detached from the bottle to drop the aesthetics of the finished product, if the shrinkage start temperature is higher than 94 ℃ remove the label by hot water Since the process requires a long time of high temperature, a process cost may be high.

In addition, the polyester-based deposition film according to the present invention is observed in the maximum shrinkage expression temperature in the maximum shrinkage direction of 80 to 110 ℃ range, where the maximum shrinkage expression temperature can be defined as follows; The first temperature that shows the maximum shrinkage stress value when the film is fixed at room temperature and constant initial load, and then the stress when shrinking the film while applying heat at a constant heating rate is plotted against the shrinkage stress with temperature.

In addition, the shrinkage stress value at this time is defined as the maximum shrinkage stress, and the value may be 0.60 to 1.80kg / mm 2.

 Referring to this with reference to the graph of the change in the shrinkage stress value according to the temperature change by the heat shrinkage stress tester shown in Figure 1, when the shrinkage of the shrinkable film starts to draw a curve that increases the shrinkage stress up to a certain temperature, After the temperature T (Smax) representing the shrinkage stress value Smax, the value becomes a downward curve.

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

In this regard, the polyester-based deposited film of the present invention advantageously has a low maximum shrinkage stress expression temperature in the maximum shrinkage direction of 80 to 110 ℃, the maximum shrinkage stress in terms of peeling force of the label to the container is 0.60 to 1.80kg / It is advantageous that it is mm 2.

In addition, the polyester-based deposition film of the present invention preferably has a total light transmittance of 0.01 to 5% in order to increase the printing effect by the side and concealment properties for protecting the material inside the container from light.

Such a method of manufacturing a polyester-based deposited film according to embodiments of the present invention is not particularly limited, but one example thereof is heat shrinkable A metal deposition layer is formed by vacuum depositing a metal such as aluminum on one surface of the polyester film substrate. Next, a printing layer is formed on the metal deposition layer. For example, the printing layer may be formed by printing at 5 degrees in a gravure printing press. On the other hand, in terms of improving the scratch resistance of the printing layer, and prevents the printing layer from being peeled off from the metal deposition layer, the above-described protective layer forming composition is coated or metal deposited on the printing layer, for example, using a gravure printing machine. After forming a protective layer on the layer, a printed layer can be formed. Finally, on the other side of the heat-shrinkable polyester film substrate, an ink layer in which a white pigment is dispersed using, for example, an alcohol solvent may be coated or physically treated using a gravure printing machine to form a back layer.

The polyester-based deposition film according to the embodiments is useful as a label to replace the paper label, in one embodiment of the present invention provides a labeled bottle containing such a polyester-based deposition film.

As a method of attaching a label including a polyester-based deposition film to a glass bottle or the like, a conventional method of attaching a label of a paper material may be applied. However, water-soluble adhesives can be applied in consideration of the film material and environmental aspects as adhesives, and a water-soluble adhesive is applied to the back layer of the polyester-based deposition film transferred in the form of a single label, and the surface coated with the adhesive is applied to the bottle. When attached, a labeled bottle can be made.

The removal of the polyester-based deposition film in the recovery and recycling of the bottle with the label manufactured as described above is performed by immersing the bottle in hot water, wherein the temperature of the hot water may be about 70 to 90 ° C.

Hereinafter, the embodiments of the present invention will be described in more detail, 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

For film substrates and evaporated films, cut into a rectangle of 15 mm (MD) × 400 mm (TD) size in the maximum shrinkage direction (TD; width direction) and right angle direction (MD; longitudinal direction), and 50 mm at both ends of the TD direction. Draw a solid line in the direction of MD from the point to make a specimen with 300mm effective measurement length, and then use tweezers or the like to hold a point within 50mm from one end of the sample without using left or right to place the whole sample in hot water of 90 ℃ ± 0.5 ℃. Heat-shrink for 10 seconds in a fully immersed state without load, and then leave it for 1 minute at room temperature, and then measure the reduced length of 300 mm intervals in the TD direction indicated by the solid line at the beginning to determine the maximum shrinkage direction (TD; width direction) of the film. Thermal contraction rate was calculated | required according to following formula 1.

<Formula 1>

(2) thickness measurement

Immediately after immersing the film specimen in liquid nitrogen and quenching, the film specimen was broken in liquid nitrogen and its cross section was measured using SEM (Jeol, 6700F), and the scale bar was adjusted by adjusting the magnification for each layer constituting the film. Thickness was measured.

In addition, the thickness of the film substrate and the deposited film was measured by measuring the thickness at intervals of 5cm with respect to the entire width using a thickness gauge to calculate the average value of the value excluding the maximum value and the minimum value.

(3) Hayes

The measuring method was measured based on ASTM D-1003, and the polyester film was randomly extracted from 7 parts at 2 sides and 1 center, and then sliced into 5cm × 5cm sized haze measuring instruments (Nihonden Shoku NDH 5000). After the measurement method was set to ASTM, the haze (%) was measured by transmitting light, and the average value of five values except the maximum value and the minimum value was obtained to calculate the haze.

(4) total light transmittance

The measurement method was measured based on ASTM D-1003, and the polyester vapor-deposited film was randomly extracted from two parts at one side and one at the center, and then sliced into 5 cm x 5 cm each to have a haze meter (Nihonden Shoku NDH 5000). ), Set the measuring method to ASTM, and mount the sample to inject light in the direction of the metal deposition layer and transmit the light to the back layer, and measure the total transmittance (%) by measuring the maximum and minimum values. The total light transmittance was calculated by obtaining an average of five values except for.

(5) Shrink start temperature, maximum shrinkage expression temperature, maximum shrinkage stress

The principles applied to the analysis of the shrinkage start temperature, the maximum shrinkage expression temperature and the maximum shrinkage stress in the maximum shrinkage direction of the polyester-based deposition film of the present invention and the definition of the shrinkage start temperature, the maximum shrinkage expression temperature and the maximum shrinkage stress Is the same as

1) Principle

The polymer chain is oriented and crystallized through the stretching process, and has a structure roughly divided into a crystalline region and an amorphous region. When heat is applied to the stretched polymer, the relaxation of stress remaining in the polymer chain appears, and the shrinkage phenomenon returns to its original form. The force that hinders the contraction is called a shrinkage stress, and the higher the shrinkage stress, the higher the shrinkage stress. The shrinkage force with temperature becomes high.

When the film is fixed at room temperature and constant initial load and then heated at a constant heating rate, stress changes due to expansion and contraction of the sample according to temperature change are detected by a displacement variable magnetic sensor (LVDT). Derived by the method. Using the above principle, it is possible to obtain information on the shrinkage stress of the film according to the temperature change. At this time, since the temperature increase rate depends on the residual stress relaxation rate of the polymer chain, in the present invention, the shrinkage stress value according to the temperature change was measured at a temperature increase rate of 2.5 ° C / sec.

The measured graph shows the same pattern as shown in FIG. 1, and the temperature corresponding to the shrinkage start temperature (Ts) and the peak of the graph appear when the shrinkage stress value such as the initial load value (Ls) is first observed. The temperature at that time is defined as the maximum contraction expression temperature (T (Smax)) and the stress value at this time as the maximum contraction stress (Smax). As an example of a device that implements the above principle, in the following Examples and Comparative Examples, a thermal shrinkage stress tester (Thermal Stress)

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

Using a thermal stress tester (KE-2, Kanebo Eng.), The 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 / mm2, followed by a temperature increase rate of 2.5 The graph was obtained by measuring the shrinkage stress according to the temperature while raising the temperature to ℃ / sec.

In this graph, the temperature at which the shrinkage stress value equal to the initial load of 0.125kg / mm2 is first shown is the shrinkage start temperature (Ts), and the temperature at the point where the maximum shrinkage stress value is first appeared is the maximum shrinkage expression temperature (T). (Smax)) and the stress value at this time was defined as the maximum shrinkage stress (Smax).

(6) Label adhesive evaluation during bottle manufacturing process

The polyester-based evaporation film label was cut into 80 mm × 80 mm squares in the maximum shrinkage direction and at right angles thereto, and then 45 parts by weight of styrene-butadiene rubber latex, 40 parts by weight of an acrylic emulsion, and ethylene using a gravure printing method. A water-soluble adhesive prepared by mixing 10 parts by weight of a vinyl emulsion, 0.8 parts by weight of sodium hydroxide, 0.1 part by weight of a disinfectant, and 4.1 parts by weight of water was applied to the back layer of the polyester-based deposition film label with a thickness of 5 μm, and a labeler was applied. Labeling is performed on 1,000 glass bottles. After 1,000 labeled glass bottles were left at room temperature for 2 days, the number of bottles with wrinkles or corners peeled off the label was measured, and the adhesion was evaluated by the adhesion failure rate according to Equation 2 below.

<Formula 2>

Adhesiveness (%) = 100-Adhesive Defective Rate (%)

(7) Peelability Evaluation after Labeling on Bottle

In the label adhesive evaluation, the label-adhesive normal product except for label adhesion defects was left at 80 ° C. hot water for 2 minutes, and then the number of bottles in which the label was not completely peeled from the glass bottle was measured and peeled off according to the following Equation 3 The defect rate was calculated | required and peelability was evaluated.

<Formula 3>

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

(8) Evaluation of process applicability of labels

The process applicability of the label is closely related to the adhesiveness and peelability of the label, and even if any one is poor in terms of process applicability, the process applicability becomes worse.

Therefore, the process application of the label evaluated the process applicability by the following formula 4.

<Equation 4>

Process applicability (%) = [Adhesiveness (%) × Peelability (%)] / 100

Hereinafter, the present invention will be described in detail with reference to Examples. The present invention is not limited based on these Examples.

&Lt; Example 1 >

Polycondensation was carried out by direct esterification using 100 mol% of terephthalic acid as a dibasic acid component, 100 mol% of ethylene glycol and 24 mol% of neopentyl glycol as glycol components, and 0.05 mol of antimony trioxide (relative to acid components) as a catalyst. Combined. The polymer thus obtained contained 500 ppm of silicon dioxide powder having an average particle diameter 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 占 폚.

On the other hand, by using 100 mol% terephthalic acid and 100 mol% of 1,4-butanediol, 0.015 parts by weight of tetrabutyl titanate was added as a catalyst to obtain a polybutylene terephthalate resin.

90 wt% of the copolyester and 10 wt% of polybutylene terephthalate were blended and extruded from an extruder at 270 ° C., followed by rapid cooling and solidification to obtain an unstretched film. The unstretched film was stretched 4.2 times with respect to the width at 72 ° C. through a preheating section having a temperature of 85 ° C. via a roller conveyed in a mechanical direction, and then subjected to a heat treatment section at room temperature to prepare a film. The obtained film was 50 micrometers in thickness, the thermal contraction rate measured by the above-mentioned method was 77.4% (TD direction), and haze was 5.3%.

On the obtained polyester-based heat-shrink film, aluminum having a purity of 99.9% was deposited on the evaporator of the boat evaporation method at an upper vacuum of 2.3 x 10 ^-2 mbar, a lower vacuum of 5.7 x 10 ^-4 mbar, a cooling roll temperature of -15 deg. A metal deposition layer was formed at a deposition rate of 405 m / min (metal: Al, metal deposition layer thickness 52 nm).

10% by weight of acrylic resin (BPS-5698, Samyoung Toyo), 80% by weight of methyl ethyl ketone (MEK, Daishin Chemical), yellow pigment (Yellow 10G, Hyundai Chemical), red pigment ( Each of the colorants selected from Red-FRN, Hyundai Chemical), Green Pigment (Green 735, Hyundai Chemical), Black Pigment (Black # 30, Hyundai Chemical) and White Pigment (R-100, Kaffei), and Anti-Sedimentation Agent, A printing layer having a thickness of 2 μm was formed by printing at 5 degrees using a gravure roll from five crude liquids including a thickener, a color separation agent, and a pigment dispersant, in which the total amount was adjusted to 100% by weight.

On the printed layer, a mixed layer of urethane and vinyl chloride was diluted with methyl ethyl ketone (MEK) using a gravure roll to form a protective layer. (Protective layer thickness 0.4 mu m)

Meanwhile, the deposition film of the present invention was manufactured by forming a back layer having a thickness of 1.5 μm by applying a crude solution containing a white pigment (R-100, Kpia) in a printing layer forming crude solution and printing it with 1 degree using a gravure roll. .

The obtained deposition film was evaluated in the above manner, and the results are shown in Table 1 below.

<Example 2>

Polycondensation was carried out by direct esterification using 100 mol% of terephthalic acid as a dibasic acid component, 106 mol% of ethylene glycol and 18 mol% of neopentyl glycol as glycol components, and 0.05 mol of antimony trioxide (relative to acid components) as a catalyst. Combined. The polymer thus obtained contained 500 ppm of silicon dioxide powder having an average particle diameter 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 占 폚.

90 wt% of the copolyester and 10 wt% of the polybutylene terephthalate of Example 1 were blended and extruded from an extruder at 270 ° C., followed by rapid cooling and solidification to obtain an unstretched film. The unstretched film was stretched 4.0 times with respect to the width at 72 ° C. through a preheating section having a temperature of 92 ° C. via a roller conveyed in a mechanical direction, and then a heat shrink film having a thickness of 60 μm was produced through a heat treatment section at 90 ° C.

The obtained polyester-based heat shrinkable film was subjected to the same conditions as in Example 1 to produce the evaporated film of the present invention having a metal deposition layer thickness of 52 nm, a print layer thickness of 2 탆, a protective layer thickness of 0.4 탆 and a rear layer thickness of 1.5 탆 .

The obtained deposition film was evaluated in the above manner, and the results are shown in Table 1 below.

<Example 3>

Polycondensation was carried out by direct esterification using 100 mol% of terephthalic acid as the dibasic acid component, 96 mol% of ethylene glycol and 28 mol% of neopentyl glycol as the glycol component, and 0.05 mol of antimony trioxide (relative to the acid component) as a catalyst. Combined. The polymer thus obtained contained 50 ppm of silicon dioxide powder having an average particle diameter of 2.7 μm, and dried by a conventional method to prepare a copolyester having an intrinsic viscosity of 0.73 dl / g and a melting point of 193 ° C.

90 wt% of the copolyester and 10 wt% of the polybutylene terephthalate of Example 1 were blended and extruded from an extruder at 270 ° C., followed by rapid cooling and solidification to obtain an unstretched film. The unstretched film was stretched 4.0 times with respect to the width at 70 ° C. through a preheating section of a temperature of 82 ° C. via a roller conveyed in a mechanical direction, and then a heat shrink film having a thickness of 40 μm was prepared through a heat treatment section at room temperature.

On the obtained polyester heat-shrink film, it carried out on the conditions similar to Example 1, and produced the vapor deposition film of this invention which has a metal deposition layer thickness of 52 nm, a printing layer thickness of 2 micrometers, a protective layer thickness of 0.4 micrometer, and a back layer thickness of 1.5 micrometer. .

The obtained deposition film was evaluated in the above manner, and the results are shown in Table 1 below.

<Example 4>

100 mole% of terephthalic acid as the dibasic acid component, 80 mole% of ethylene glycol and 20 mole% of 1,4-cyclohexane dimethanol as the glycol component, and 0.05 mole of antimony trioxide (relative to the acid component) as catalysts It polycondensed by the esterification method. The polymer thus obtained contained 500 ppm of silicon dioxide powder having an average particle diameter of 2.7 µm and dried by a conventional method to prepare a copolyester having an intrinsic viscosity of 0.68 dl / g and a melting point of 205 占 폚.

The copolyester was extruded from an extruder at 270 ° C. followed by rapid cooling and solidified to yield an unstretched film. The unstretched film was stretched 4.2 times with respect to the width at 72 ° C. through a preheating section having a temperature of 85 ° C. via a roller which is transferred in a mechanical direction, and then a heat shrinkable film having a thickness of 50 μm was produced through a heat treatment section at room temperature.

On the obtained polyester heat-shrink film, it carried out on the conditions similar to Example 1, and produced the vapor deposition film of this invention which has a metal deposition layer thickness of 52 nm, a printing layer thickness of 2 micrometers, a protective layer thickness of 0.4 micrometer, and a back layer thickness of 1.5 micrometer. .

The obtained deposition film was evaluated in the above manner, and the results are shown in Table 1 below.

<Example 5>

Polycondensation was carried out by direct esterification using 100 mol% of terephthalic acid as a dibasic acid component, 100 mol% of ethylene glycol and 24 mol% of neopentyl glycol as glycol components, and 0.05 mol of antimony trioxide (relative to acid components) as a catalyst. Combined. The polymer thus obtained contained 500 ppm of silicon dioxide powder having an average particle diameter 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 占 폚.

The copolyester was extruded from an extruder at 270 ° C. followed by rapid cooling and solidified to yield an unstretched film. The unstretched film was stretched to 4.0 times the width at 72 캜 through a preheating section at a temperature of 90 캜 through a roller conveyed in a mechanical direction, and then a heat shrinking film having a thickness of 50 탆 was produced through a heat treatment section at 88 캜.

On the obtained polyester heat-shrink film, it carried out on the conditions similar to Example 1, and produced the vapor deposition film of this invention which has a metal deposition layer thickness of 52 nm, a printing layer thickness of 2 micrometers, a protective layer thickness of 0.4 micrometer, and a back layer thickness of 1.5 micrometer. .

The obtained deposition film was evaluated in the above manner, and the results are shown in Table 1 below.

<Example 6>

In Example 1, the film was stretched 4.2 times with respect to the width at 72 ° C through a preheating section of a temperature of 90 ° C. through a roller conveyed in the mechanical direction, and then a film having a thickness of 50 μm was produced through a heat treatment section of 88 ° C. Except for the same heat shrink film was prepared.

On the obtained polyester-based heat-shrink film, aluminum having a purity of 99.9% was deposited on the evaporator of the boat evaporation method, and the upper vacuum degree of the vapor deposition machine was 1.0 × 10 ^-2 mbar, the lower vacuum degree was 3.5 × 10 ^-4 mbar, the cooling roll temperature -15 ° C, A metal deposition layer was formed at a deposition rate of 490 m / min. (Metal: Al, thickness of metal deposition layer 32 nm).

The deposited film of the present invention was prepared on the metal deposition layer under the same conditions as in Example 1, having a printed layer thickness of 2 m, a protective layer thickness of 0.4 m, and a back layer thickness of 1.5 m.

The obtained deposition film was evaluated in the above manner, and the results are shown in Table 1 below.

&Lt; Example 7 >

In Example 1, the film was stretched 4.2 times with respect to the width at 72 ° C through a preheating section of a temperature of 82 ° C. via a roller conveyed in a mechanical direction, and then a film having a thickness of 50 μm was produced through a heat treatment section at room temperature. In the same manner to prepare a heat shrink film.

On the obtained polyester-based heat-shrink film, aluminum having a purity of 99.9% was deposited on the evaporator of the boat evaporation method at an upper vacuum degree of 3.5 x 10 ^-2 mbar, lower vacuum degree of 8.1 x 10 ^-4 mbar, a cooling roll temperature of -20 deg. A metal deposition layer was formed at a deposition rate of 315 m / min. (Metal: Al, metal deposition layer thickness of 85 nm).

The deposited film of the present invention was prepared on the metal deposition layer under the same conditions as in Example 1, having a printed layer thickness of 2 m, a protective layer thickness of 0.4 m, and a back layer thickness of 1.5 m.

The obtained deposition film was evaluated in the above manner, and the results are shown in Table 1 below.

&Lt; Example 8 >

In Example 1, 10% by weight of acrylic resin (BPS-5698, Samyoung Toyo) on the metal deposition layer, 80% by weight of methyl ethyl ketone (MEK, chemical instead of ketone) and yellow pigment (Yellow 10G, Hyundai) Chemicals), Red Pigment (Red-FRN, Hyundai Chemical), Green Pigment (Green 735, Hyundai Chemical), Black Pigment (Black # 30, Hyundai Chemical), Blue Pigment (Blue 501, Hyundai Chemical), Pink Pigment (Pink E) , Hyundai Chemicals), brown pigments (Brown HFR, Hyundai Chemicals) and white pigments (R-100, KPIA), and the total amount of the total amount, including precipitation inhibitors, thickeners, color separation agents and pigment dispersants. A protective layer and a rear layer were formed under the same conditions as in Example 1 except that a printing layer having a thickness of 3.5 μm was formed by printing at 8 degrees using a gravure roll from eight kinds of crude liquids adjusted to 100% by weight. The deposited film of the present invention was prepared.

The obtained deposition film was evaluated in the above manner, and the results are shown in Table 1 below.

&Lt; Example 9 >

In Example 1, the film was stretched 4.2 times with respect to the width at 70 ° C through a preheating section at a temperature of 80 ° C. through a roller conveyed in a mechanical direction, and then a film having a thickness of 50 μm was produced through a heat treatment section at room temperature. In the same manner, a heat shrink film was prepared.

On the obtained polyester type heat shrink film, a metal deposition layer having a thickness of 52 nm was formed under the same conditions as in Example 1.

10% by weight of acrylic resin (BPS-5698, Samyoung Toyo), 80% by weight of methyl ethyl ketone (MEK, Daishin Chemical), red pigment (Red-FRN, Hyundai Chemical), green pigment on metal deposition layer (Green 735, Hyundai Chemical) and white pigment (R-100, KPIA), each colorant selected from 3, and the total amount is adjusted to 100% by weight, including precipitation inhibitor, thickener, color separation agent, pigment dispersant The gravure roll was used to print 3 degree | times from the crude liquid of the seed, and the printed layer of thickness 1.0micrometer was formed.

The deposition film of the present invention was prepared on the printed layer under the same conditions as in Example 1, having a protective layer thickness of 0.4 µm and a rear layer thickness of 1.5 µm.

The obtained deposition film was evaluated in the above manner, and the results are shown in Table 1 below.

&Lt; Example 10 >

In Example 1, 10% by weight of acrylic resin (BPS-5698, Samyoung Toyo) on the metal deposition layer, 80% by weight of methyl ethyl ketone (MEK, chemical instead of ketone) and yellow pigment (Yellow 10G, Hyundai) Chemicals), Red Pigment (Red-FRN, Hyundai Chemical), Green Pigment (Green 735, Hyundai Chemical), Black Pigment (Black # 30, Hyundai Chemical), Blue Pigment (Blue 501, Hyundai Chemical), Pink Pigment (Pink E) , Hyundai Chemicals), brown pigments (Brown HFR, Hyundai Chemicals) and white pigments (R-100, KPIA), and the total amount of the total amount, including precipitation inhibitors, thickeners, color separation agents and pigment dispersants. A vapor deposition film of the present invention was prepared in the same manner, except that a printing layer having a thickness of 8.0 μm was formed by printing at 8 degrees using a gravure roll from eight crude liquids adjusted to 100 wt%.

The obtained deposition film was evaluated in the above manner, and the results are shown in Table 1 below.

<Example 11>

The present invention was carried out in the same manner as in Example 1 except that a mixed layer of urethane and vinyl chloride was diluted in methyl ethyl ketone (MEK) using a gravure roll on a printed layer to form a protective layer having a thickness of 2.5 μm. The deposited film was prepared.

The obtained deposition film was evaluated in the above manner, and the results are shown in Table 1 below.

&Lt; Example 12 >

In the same manner as in Example 1 except that a mixed layer of an acrylic copolymer and a styrene copolymer was diluted in methyl ethyl ketone (MEK) using a gravure roll on a printed layer to form a protective layer having a thickness of 2.0 μm. To prepare a deposited film of the present invention.

The obtained deposition film was evaluated in the above manner, and the results are shown in Table 1 below.

&Lt; Example 13 >

The deposition film of the present invention in the same manner as in Example 1 except that a protective layer having a thickness of 3.5 μm was formed by diluting the copolyester resin with methyl ethyl ketone (MEK) using a gravure roll on the printed layer. Was prepared.

The obtained deposition film was evaluated in the above manner, and the results are shown in Table 1 below.

&Lt; Example 14 >

In Example 1, the thickness of the printed layer forming crude liquid was printed by two degrees using a gravure roll from two kinds of crude liquids including yellow pigment (Yellow 10G, Hyundai Chemical) and white pigment (R-100, KPAI). A vapor deposition film of the present invention was prepared in the same manner except that a rear layer of 3.0 μm was formed.

The obtained deposition film was evaluated in the above manner, and the results are shown in Table 1 below.

 &Lt; Example 15 >

In Example 1, the thickness of the heat-shrink film was 40 μm, and a yellow pigment (Yellow 10G, Hyundai Chemical), a red pigment (Red-FRN, Hyundai Chemical) and a white pigment (R-100, KPI) in the printing layer forming solution. A vapor deposition film of the present invention was prepared in the same manner except that the back layer having a thickness of 3.5 μm was formed by printing at 3 degrees using a gravure roll from three kinds of crude liquids including I).

The obtained deposition film was evaluated in the above manner, and the results are shown in Table 1 below.

 &Lt; Example 16 >

In Example 1, the thickness of the heat-shrinkable film was set to 55 μm, and a printing solution containing white pigment (R-100, KPIA) was applied to the printing layer-forming solution to print 1 degree using a gravure roll, and the thickness was 0.7. A deposited film of the present invention was prepared in the same manner except that a back layer having a thickness of µm was formed.

The obtained deposition film was evaluated in the above manner, and the results are shown in Table 1 below.

 <Example 17>

A deposition film of the present invention was prepared in the same manner as in Example 1, except that the back layer was formed using an embossing roll.

Specifically, in the formation of the rear layer, the heat shrink film passes between the roller having the planar surface and the embossing roll having the uneven structure having a height of 50 μm on the surface, wherein the embossing pressure is 20Kg / cm ² and the unevenness is formed on the rear layer. The structure was formed.

The obtained deposition film was evaluated in the above manner, and the results are shown in Table 1 below.

 &Lt; Example 18 >

After forming the primer layer on the metal deposition layer in Example 1, to form a printed layer, the deposition film of the present invention was prepared in the same manner except that the protective layer coating was not performed.

Specifically, the silane coupling agent was diluted in methyl ethyl ketone (MEK) using a gravure roll on the metal deposition layer to form a primer layer having a thickness of 0.4 μm.

The obtained deposition film was evaluated in the above manner, and the results are shown in Table 1 below.

&Lt; Example 19 >

The present invention was carried out in the same manner as in Example 18, except that a mixed resin of urethane and vinyl chloride was diluted in methyl ethyl ketone (MEK) using a gravure roll on a metal deposition layer to form a primer layer having a thickness of 0.4 μm. The deposited film was prepared.

The obtained deposition film was evaluated in the above manner, and the results are shown in Table 1 below.

Example 20

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 DEG C through a preheating section at a temperature of 65 DEG C in a roller group conveyed in a mechanical direction Subsequently, the film was cooled through a cooling roll at room temperature and then stretched in the transverse direction in the tenter in the same manner as in Example 1 continuously to obtain a shrinkage ratio of 37.3% in the longitudinal direction (MD) of the film, A printed layer, a protective layer and a rear layer were formed in the same manner as in Example 1, except that a bidirectional heat-shrinkable polyester film having a thickness of 50 m and a shrinkage ratio of 74.9% was produced.

The obtained deposition film was evaluated in the above manner, and the results are shown in Table 1 below.

&Lt; Example 21 >

In the roller group conveyed in the mechanical direction in Example 20 was stretched 2.5 times in the longitudinal direction of the film at a temperature of 75 ℃ through a preheating section of the temperature 75 ℃, and then cooled through a cooling roll of room temperature, then continuous In the tenter in the width direction under the same conditions as in Example 1, with a shrinkage rate of 45.8% in the film length direction (MD) and a shrinkage rate in the width direction (TD) of 70.5%, a bidirectional thermal shrinkage polyester having a thickness of 50 µm. A deposition film of the present invention was prepared by forming a metal deposition layer, a print layer, a protective layer and a back layer in the same manner except that the film was prepared.

The obtained deposition film was evaluated in the above manner, and the results are shown in Table 1 below.

<Example 22>

In Example 1, on the polyester-based heat-shrink film, aluminum having a purity of 99.9% was deposited using a boat evaporator evaporator at an upper vacuum degree of 0.4 × 10 ^-2 mbar, a lower vacuum degree of 1.0 × 10 ^-4 mbar, and a cooling roll. A deposition film of the present invention was prepared in the same manner as the metal deposition layer having a thickness of 10 nm at a temperature of −10 ° C. and a deposition rate of 500 m / min. The obtained deposition film was evaluated in the above manner, and the results are shown in Table 1 below.

<Example 23>

In Example 1, yellow pigment (Yellow 10G, Hyundai Chemical), red pigment (Red-FRN, Hyundai Chemical), green pigment (Green 735, Hyundai Chemical) of the print layer forming solution of Example 10 was formed. ), A back layer having a thickness of 5.5 μm was formed by printing 5 degrees using a gravure roll from five kinds of crude liquids including black pigment (Black # 30, Hyundai Chemical) and white pigment (R-100, KPIA). A deposition film of the present invention was prepared in the same manner except that.

The obtained deposition film was evaluated in the above manner, and the results are shown in Table 1 below.

<Example 24>

Polycondensation was carried out by direct esterification using 100 mole% of terephthalic acid as the dibasic acid component, 110 mole% of ethylene glycol and 14 mole% of neopentyl glycol as the glycol component, and 0.05 mole of antimony trioxide (relative to the acid component) as a catalyst. Combined. The polymer thus obtained contained 500 ppm of silicon dioxide powder having an average particle diameter 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 占 폚.

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

After forming a metal deposition layer, a printing layer, and a protective layer on the obtained polyester type heat-shrink film on the same conditions as Example 1, yellow pigment (Yellow 10G, Hyundai Chemical) and white pigment (R-) in a printing layer formation crude liquid. 100, KPIA)) was prepared in the same manner as the deposition method of the present invention except that a two-layer printing using a gravure roll to form a back layer having a thickness of 3.0㎛ from two kinds of crude liquids.

The obtained deposition film was evaluated in the above manner, and the results are shown in Table 1 below.

<Example 25>

A deposited film of the present invention was prepared in the same manner as in Example 1 except that no protective layer was formed on the printed layer.

The obtained deposition film was evaluated in the above manner, and the results are shown in Table 1 below.

Reference Example 1

In Example 1, the polybutylene terephthalate and titanium oxide particles (particle size 0.3㎛) particles of Example 1 were melt-kneaded in a twin screw extruder to prepare a masterbatch chip having a content of 50% by weight titanium oxide. The unstretched film was prepared by blending 90 wt% of the copolyester of Example 1 and 10 wt% of the masterbatch chip, except that no processing was performed on the back layer, and a deposition film was prepared in the same manner.

The obtained deposition film was evaluated in the above manner, and the results are shown in Table 1 below.

Base film Vapor deposition film Hydrothermal
Reduction
(Maximum shrinkage direction; TD,%)
Hayes
(%) Analysis by heat shrink stress tester Hydrothermal
Reduction
(maximum
Shrink
direction; TD,%)
Total light transmittance
(%)
Adhesive of label
(%)
Peelability of Label
(%)
Of label
fair
Applicability
(%) Ts
(℃) T _(Smax)
(℃) S _max
(kg / ㎡) Example 1 77.4 5.3 82.3 91.3 1.23 77.2 0.20 100 100 100 Example 2 43.0 8.6 92.4 108.7 0.63 42.0 0.15 99.5 99.6 99.1 Example 3 78.7 0.4 70.4 87.3 1.67 78.0 0.23 100 100 100 Example 4 78.5 4.3 88.2 99.7 0.67 75.3 0.20 100 99.7 99.7 Example 5 64.5 6.5 88.1 97.9 0.86 63.2 0.20 100 100 100 Example 6 67.5 6.8 87.5 97.0 0.89 65.9 3.35 100 100 100 Example 7 77.5 5.4 82.2 90.9 1.34 77.3 0.05 100 100 100 Example 8 77.4 5.3 83.5 92.4 1.20 76.2 0.18 100 100 100 Example 9 78.2 5.7 78.2 89.7 1.51 77.3 0.36 100 100 100 Example 10 77.4 5.3 85.3 94.1 1.15 73.4 0.12 99.5 100 99.5 Example 11 77.4 5.3 83.2 92.2 1.19 77.0 0.19 100 100 100 Example 12 77.4 5.3 82.1 91.6 1.20 76.8 0.19 100 100 100 Example 13 77.4 5.3 85.3 94.2 1.10 74.1 0.18 99.5 100 99.5 Example 14 77.4 5.3 83.4 92.3 1.17 75.5 0.15 100 100 100 Example 15 76.7 4.1 85.7 93.5 1.08 72.5 0.17 99.5 100 99.5 Example 16 77.2 7.2 81.3 90.2 1.35 77.1 0.27 100 100 100 Example 17 77.4 5.3 80.9 90.5 1.25 77.2 0.35 98.7 100 98.7 Example 18 77.4 5.3 82.1 91.4 1.22 77.1 0.20 100 100 100 Example 19 77.4 5.3 82.0 91.5 1.24 77.2 0.21 100 100 100 Example 20 74.9 5.9 83.2 93.5 1.18 71.7 0.20 100 100 100 Example 21 70.5 6.2 84.5 95.7 1.12 68.2 0.20 100 100 100 Example 22 77.4 5.3 82.0 90.9 1.28 77.2 10.23 100 100 100 Example 23 77.4 5.3 87.2 94.3 1.02 70.2 0.12 92.5 100 92.5 Example 24 38.5 6.8 94.3 111.9 0.52 38.1 0.15 100 85.1 85.1 Example 25 77.4 5.3 82.1 92.1 1.25 77.2 0.21 100 100 100 Reference Example 1 77.4 90.2 81.7 90.8 1.33 77.1 0.30 56.3 95.5 53.8

In Examples 20 and 21 in which both of the films were stretched in both the longitudinal direction and the width direction, the labels were excellent in the adhesiveness and peeling property, and thus the processability of the label was excellent. The process of separating the peeled label and the bottle is relatively easy compared to other embodiments. In particular, in the type of floating type bleaching machine where water is introduced into the bottle and the label is raised to the surface using water pressure, and the label separated using a hook from the top of the bottle is stretched only in the width direction of the film. In other embodiments of the present invention, a label curling phenomenon occurs in the direction of the maximum shrinkage of the film, thereby increasing the pressure or flow rate of the water when the label floats to the top of the bottle. Since shrinkage occurs in both directions at the time to mitigate labeling, the label can be easily floated to the top of the bottle when compared to other embodiments to separate the label, which is advantageous in terms of water consumption and energy saving.

In the case of Example 22 of the above examples, the work processability is good, but the thickness of the metal deposition layer is thin, so that the total light transmittance of the heat shrinkable deposition film is high, the color of the bottle is projected when applied to the colored bottle in the final printed label The printing effect is reduced, and the visibility of the print pattern is lowered, and as a result, the aesthetics of the advertisement may be reduced.

In the case of Example 23, in which the thickness of the back layer is thick, the heat shrinkable deposition film is stiff (stiff) and after the printing label adhesion, it can be seen that the phenomenon that the partial peeling from the bottle occurs, the adhesion performance is reduced.

In Example 24, when the shrinkage start temperature was high and the maximum shrinkage stress was low, the printing label was partially adhered to the bottle when the printing label was removed from the bottle. In such a case, the economic efficiency may be lowered because the printing label is removed several times.

 In the case of Example 25 without applying the protective layer or the primer layer, the adhesiveness and the peeling characteristics are not a problem, but the peeling process occurs because the metal deposition layer and the printing layer of the printing label peel off during the printing label peeling process. This may cause a problem of contaminating water, which may cause secondary contamination of the bottle, resulting in a problem of additional cleaning of the bottle. The overall fairness is not a problem, but since the cleaning process of the bottle must be added after peeling off the printing label, it may cause an increase in process cost when the printing label is applied.

In the case of Reference Example 1 without the back layer, when the printing label was adhered to the bottle, the printing label was not fixed to the bottle and slipped a lot, causing different labeling positions or a large portion of the printing label peeling off the bottle. As a result, adhesion stability was lowered, and in the printing label removal process, the penetration of water between the bottle and the printing label was difficult. In the printing label removal process, since the water penetration time between the bottle and the printing label is relatively long, the label separation time may be slightly longer during the bottle washing process.

Therefore, the heat-shrinkable polyester film substrate according to the present invention; A metal deposition layer on the substrate; A print layer on the metal deposition layer; And the most preferred example of the polyester-based deposition film including the back layer on the other side of the substrate is 40 to 80% in the maximum shrinkage direction when treated over 90 seconds in hot water at 90 ° C. The shrinkage start temperature in the maximum shrinkage direction is 68 to 94 ° C, the maximum shrinkage expression temperature is 80 to 110 ° C, the maximum shrinkage stress is 0.60 to 1.80kg / mm2, and the total light transmittance is 0.01 to 5%. It can be seen that the appearance, adhesiveness and peeling properties are excellent.

Claims (18)

Heat-shrinkable polyester film base material;
A metal deposition layer on the substrate;
A print layer on the metal deposition layer; And
Comprising a back layer, on the other side of the substrate
Polyester vapor deposition film. The method of claim 1,
Polyester-based deposition film comprising a primer layer between the metal deposition layer and the printing layer. The method according to claim 1 or 2,
Polyester-based deposition film comprising a protective layer on the printed layer. The method of claim 3, wherein
The protective layer is copolyester, acrylic copolymer, styrene copolymer, methacrylate copolymer, polystyrene, vinyl acetate, polyamide, alkyl acrylate, urea formaldehyde, epoxidized soybean oil, ethylene-vinyl acetate copolymer, tallow type A polyester-based deposition film which is a resin layer composed of oleamide, polyethylene glycol distearate, polyvinylidene, polyolefin copolymer, urethane and vinyl resin alone or a mixture thereof. The method of claim 1,
The back layer is a polyester-based deposited film that is an uneven layer formed by physically or chemically treating the surface of the heat-shrinkable polyester film. The method of claim 1,
The back layer is a polyester-based deposition film that is a white pigment coating layer. The method of claim 1,
The heat-shrinkable polyester film base material is a polyester-based deposition film comprising a polyester resin containing a butylene terephthalate repeat unit. The method of claim 1, wherein the heat-shrinkable polyester film substrate is terephthalic acid, oxalic acid, malonic acid, succinic acid, adipic acid, suveric acid, azelaic acid, sebacic acid, phthalic acid, isophthalic acid, naphthalenedicarboxylic acid, diphenyl ether A dicarboxylic acid component containing at least one dicarboxylic acid such as dicarboxylic acid, ethylene glycol, neopentyl glycol, propylene glycol, trimethylene glycol, tetramethylene glycol, hexamethylene glycol, diethylene glycol, polyalkyl A polyester-based deposition film comprising at least one copolyester selected from the copolyesters obtained from a diol component containing at least one diol such as ethylene glycol and 1,4-cyclohexane dimethanol. The polyester-based deposition film of claim 8, wherein the copolyester includes 80 mol% or more of terephthalic acid units in the dicarboxylic acid units, and 12 to 24 mol% of units other than ethylene glycol in the diol units. The method of claim 1,
The heat-shrinkable polyester film base material is a polyester-based deposited film that is a uniaxially orientated heat-shrinkable polyester film base material or a bidirectional heat-shrinkable polyester film base material. The method of claim 1,
A polyester-based deposited film having a shrinkage ratio in the maximum shrinkage direction of 40 to 80% when treated over 90 seconds in hot water at 90 ° C. The method of claim 1,
A polyester-based deposited film having a shrinkage start temperature in the maximum shrinkage direction of 68 to 94 ° C. The method of claim 1,
A polyester-based deposition film having a maximum shrinkage expression temperature in the maximum shrinkage direction of 80 to 110 ℃, the maximum shrinkage stress is 0.60 to 1.80kg / ㎜. The polyester-based deposition film according to claim 1, wherein the total light transmittance is 0.01 to 5%. The polyester-based deposition film of claim 1, wherein the heat-shrinkable polyester film substrate has a haze of 0.3 to 10%. Labeled bottle comprising a polyester-based deposition film of claim 1. The bottle with a label according to claim 16, wherein the polyester-based deposition film is removed by immersion in hot water. Applying an adhesive to the back layer of the polyester-based deposition film according to claim 1; And attaching a back layer of the polyester-based deposition film to which the adhesive is applied to the bottle.

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