WO2012128517A2 - 폴리에스테르계 증착필름 - Google Patents
폴리에스테르계 증착필름 Download PDFInfo
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- WO2012128517A2 WO2012128517A2 PCT/KR2012/001940 KR2012001940W WO2012128517A2 WO 2012128517 A2 WO2012128517 A2 WO 2012128517A2 KR 2012001940 W KR2012001940 W KR 2012001940W WO 2012128517 A2 WO2012128517 A2 WO 2012128517A2
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- WIPO (PCT)
- Prior art keywords
- film
- polyester
- layer
- label
- deposition
- Prior art date
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Classifications
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- G—PHYSICS
- G09—EDUCATION; CRYPTOGRAPHY; DISPLAY; ADVERTISING; SEALS
- G09F—DISPLAYING; ADVERTISING; SIGNS; LABELS OR NAME-PLATES; SEALS
- G09F3/00—Labels, tag tickets, or similar identification or indication means; Seals; Postage or like stamps
- G09F3/02—Forms or constructions
- G09F3/0291—Labels or tickets undergoing a change under particular conditions, e.g. heat, radiation, passage of time
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/14—Metallic material, boron or silicon
- C23C14/20—Metallic material, boron or silicon on organic substrates
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- G—PHYSICS
- G09—EDUCATION; CRYPTOGRAPHY; DISPLAY; ADVERTISING; SEALS
- G09F—DISPLAYING; ADVERTISING; SIGNS; LABELS OR NAME-PLATES; SEALS
- G09F23/00—Advertising on or in specific articles, e.g. ashtrays, letter-boxes
- G09F23/06—Advertising on or in specific articles, e.g. ashtrays, letter-boxes the advertising matter being combined with articles for restaurants, shops or offices
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- G—PHYSICS
- G09—EDUCATION; CRYPTOGRAPHY; DISPLAY; ADVERTISING; SEALS
- G09F—DISPLAYING; ADVERTISING; SIGNS; LABELS OR NAME-PLATES; SEALS
- G09F3/00—Labels, tag tickets, or similar identification or indication means; Seals; Postage or like stamps
- G09F3/04—Labels, tag tickets, or similar identification or indication means; Seals; Postage or like stamps to be fastened or secured by the material of the label itself, e.g. by thermo-adhesion
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/13—Hollow or container type article [e.g., tube, vase, etc.]
- Y10T428/1328—Shrinkable or shrunk [e.g., due to heat, solvent, volatile agent, restraint removal, etc.]
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
- Y10T428/24802—Discontinuous or differential coating, impregnation or bond [e.g., artwork, printing, retouched photograph, etc.]
- Y10T428/24851—Intermediate layer is discontinuous or differential
- Y10T428/24868—Translucent outer layer
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
- Y10T428/24802—Discontinuous or differential coating, impregnation or bond [e.g., artwork, printing, retouched photograph, etc.]
- Y10T428/24851—Intermediate layer is discontinuous or differential
- Y10T428/24868—Translucent outer layer
- Y10T428/24884—Translucent layer comprises natural oil, wax, resin, gum, glue, gelatin
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
- Y10T428/24802—Discontinuous or differential coating, impregnation or bond [e.g., artwork, printing, retouched photograph, etc.]
- Y10T428/24917—Discontinuous or differential coating, impregnation or bond [e.g., artwork, printing, retouched photograph, etc.] including metal layer
Definitions
- the present invention relates to a deposition film comprising a polyester-based film layer having a heat shrinkage property and a use thereof as a label of a film material that can replace a label of a paper material attached to a glass bottle.
- PET bottles and glass bottles have been collected and reused.
- 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.
- 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.
- 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.
- the labels attached to the labeler are separated and transported one by one by adsorption, and then the adhesive is applied to the back of the label by gravure printing, and then the container is transported by a conveyor belt.
- the method of adhering a label to is commonly used.
- the curling of the label itself is severe, so it may be difficult to easily apply a process of attaching a conventional paper label.
- the general label is insufficient printing effect, and if the label is a film material, there is a lack in the highlight 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.
- 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.
- 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 and the application of adhesive to the label warpage layer despite applying the label of the film material.
- the heat-shrinkable polyester film substrate A metal deposition layer on the substrate; A print layer on the metal deposition layer; And it provides a polyester-based deposited film on the other side of the substrate, comprising a bending prevention layer.
- polyester-based deposition film may include a protective layer on the printed layer.
- a primer layer may be included between the metal deposition layer and the printing layer.
- the bending characteristic value defined in the detailed description may be 5.0 mm or less.
- polyester-based deposition film may include a back metal deposition layer between the base layer and the bending prevention layer.
- the opacity (Opacity;%) may be 80% or more.
- the metal deposition layer may be an optical density of 1.0 to 3.0
- the back metal deposition layer may be an optical density of 0.2 to 0.8.
- the warpage prevention layer may be an uneven layer or a white pigment coating layer formed by physically or chemically treating the surface of the heat-shrinkable polyester film substrate.
- the warpage prevention layer is selected from polyamide resin, acrylic resin, polyurethane, PVC resin, ketone resin, rubber chloride, vinyl acetate resin and ethylene-vinylacetate copolymer At least one resin selected; At least one solvent selected from aromatic hydrocarbon-based, ketone-based, acetate-based and chlorine-based solvents; And it may be a layer formed from a composition comprising one or more additives selected from white pigments and precipitation inhibitors, thickeners, color separation agents and pigment dispersants.
- the protective layer is a copolyester, acrylic copolymer, styrene copolymer, methacrylate copolymer, polystyrene, vinyl acetate, polyamide, alkyl acrylate, urea Water consisting of single or mixtures thereof selected from formaldehyde, epoxidized soybean oil, ethylene-vinyl acetate copolymers, tallow oleamides, polyethylene glycol distearates, polyvinylidene, polyolefin copolymers, urethanes and vinyl resins It may be strata.
- the heat-shrinkable polyester film base material may include a polyester-based resin containing a butylene terephthalate repeating unit.
- 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 component 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.
- Dicarboxylic acid component containing at least one dicarboxylic acid such as naphthalenedicarboxylic acid, dipheny
- the copolyester contains 80 mol% or more of terephthalic acid units in dicarboxylic acid units, and 12 to 24 mol% of units other than ethylene glycol in diol units. It may be included.
- the heat-shrinkable polyester film substrate may be a uniaxially oriented heat-shrinkable polyester film substrate or a bidirectional heat-shrinkable polyester film substrate.
- the shrinkage in the maximum shrinkage direction may be 40 to 80% 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 / mm It may be
- Polyester-based deposition film according to an embodiment of the present invention may have a total light transmittance of 0.01 to 5.0%.
- the heat-shrinkable polyester film base material may have a haze of 0.3 to 10.0%.
- Such a labeled bottle can be removed from the polyester-based deposition film by immersion in hot water.
- Polyester-based deposition film according to an embodiment of the present invention can double the advertising effect as it can implement a vivid deposition color, while maintaining shrinkage, and has the appropriate opacity of the final product is a printed label on the colored bottle Even if it is applied, the color of the bottle is not projected, so the printing effect is excellent, and the visibility of the printed pattern is increased, which can improve the aesthetics of the advertisement, and it is used to replace the existing paper label.
- the adhesive application of can be performed on one process line so that the existing paper label line can be applied as it is. Also When recycling, only hot water can be used to remove the label, thus preventing wastewater generation.
- Example 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 is a heat-shrinkable polyester film substrate; A metal deposition layer on the substrate; A protective layer on the printed layer; And it provides a polyester-based deposited film on the other side of the substrate, comprising a bending prevention layer.
- Polyester-based deposition film is a heat-shrinkable polyester film substrate; A metal deposition layer on the substrate; A print layer on the metal deposition layer; A protective layer on the printed layer; And it provides a polyester-based deposited film on the other side of the substrate, comprising a bending prevention layer.
- Polyester-based deposition film is a heat-shrinkable polyester film substrate; A metal deposition layer on the substrate; A print layer on the metal deposition layer; A primer layer on the printed layer; A protective layer on the primer layer; And it provides a polyester-based deposited film on the other side of the substrate, comprising a bending prevention layer.
- Polyester-based deposition film is a heat-shrinkable polyester film substrate; A metal deposition layer on the substrate; A print layer on the metal deposition layer; And a backside metal deposition layer on the other side of the substrate and a bending preventing layer on the backside metal deposition layer.
- Polyester-based deposition film is a heat-shrinkable polyester film substrate; A metal deposition layer on the substrate; A print layer on the metal deposition layer; A protective layer on the printed layer; And a backside metal deposition layer on the other side of the substrate and a bending preventing layer on the backside metal deposition layer.
- Polyester-based deposition film is a heat-shrinkable polyester film substrate; A metal deposition layer on the substrate; A primer layer on the metal deposition layer; A print layer on the primer layer; A protective layer on the printed layer; And a backside metal deposition layer on the other side of the substrate and a bending preventing layer on the backside metal deposition layer.
- the term "heat-shrinkable polyester film base material” is a polyester-based resin, the main matrix constituting the film, achieves maximum uniaxial or biaxial orientation through low temperature uniaxial or biaxial stretching, and also solves residual stress through heat treatment.
- Molecular chains oriented without the part retain the residual stress and shrink in the final shrinkage process, ie uniaxially oriented shrink film as well as bidirectional shrink film. All are 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
- 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 copoly
- Copolyester itself can be manufactured by the manufacturing method of polyester generally performed.
- 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.
- 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% or more.
- 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.
- the said copolyester itself can be manufactured by the manufacturing method of polyester generally performed.
- 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.
- the melting point of the copolyester (Melting Point; °C) is 190 ⁇ 220 °C, 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 manufacture the polymer, and the intrinsic viscosity may vary depending on the degree of polymerization.
- the melting point (Melting Point; ° C.) Copolyesters with intrinsic viscosity and in the above range can be used.
- polytriethylene terephthalate may be used instead of or in combination with polybutylene terephthalate as a homopolyester.
- lubricants such as silicon dioxide, titanium dioxide, silica powder, and calcium carbonate may be added to improve the slipperiness, and if necessary, antistatic agents, anti-aging agents, ultraviolet rays, and the like. Inhibitor, Various additives such as pigments may also be added.
- 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.
- '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.
- 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.
- 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 in-line coating layer to minimize the amount of foreign substances generated by friction during the printing process, tubing process and heat shrinkage process to improve the fairness and antistatic performance May be preferred.
- 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 and may be selected in consideration of the solubility by the solvent during the tubing process.
- binder resin 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.
- Such a heat-shrinkable polyester film base material is preferably in terms of achieving a vivid deposition color when forming a metal deposition layer. Haze may be to satisfy 0.3 to 10.0%.
- the thickness of the heat-shrinkable polyester film base material is not particularly limited, and usually 35 to 65 ⁇ m, preferably 40 to 60 ⁇ m, satisfies the rigidity, and when the deposition and printing is completed, the label on the final finished product is attached to the bottle It may be advantageous in terms of feeding stability of the label and uniformity of adhesion of the label to the bottle.
- 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. In the aspect it may be more advantageous to be a bidirectional shrink film.
- the polyester-based deposition film of the present invention includes a metal deposition layer on the heat-shrinkable polyester film base material described above.
- it may further include a back metal deposition layer.
- the metal deposition layer located on the surface is a layer for doubling the advertising effect when forming the printing layer
- the other back metal deposition layer is a function to prevent the bending of the deposition film Has
- the bending characteristic value defined as follows including a metal deposition layer on both surfaces of a base material is 5 mm.
- the anti-bending layer is a coating layer containing a solvent such as a white pigment coating layer, it may be preferable that the bending property value as defined below is 5 mm or less.
- the finished heat-shrink polyester deposited film place it on a flat glass plate, cut it on the deposited film and cut the film 20 cm in the horizontal direction without damage using a knife to form a first incision.
- the film is cut by 20 cm in the vertical direction (the direction perpendicular to the first incision line) without using a knife to form a second incision line, so as to form a second incision line.
- Four incisions each having a length of 10 cm in the horizontal and vertical directions were formed based on the intersection points.
- the incision state is confirmed by lifting the deposited film in the vertical direction to confirm that the incision is completed. This is again placed on a flat glass plate, and the vertical height of the four corners corresponding to the intersection point of the incision line is raised and raised from the flat surface. At this time, two cases where the upper surface of the deposition layer and the lower surface of the deposition layer are respectively measured, and the value indicating the highest height is called a “bending characteristic value”. Negative values of bending characteristics are defined as the vertical height in the direction corresponding to the vertical height being bent.
- the bending characteristic value defined as above In the case of 5mm or less, the adhesion process may be facilitated when the deposition film according to one embodiment of the present invention is applied as a label.
- the bending characteristic value does not exceed 2 mm.
- a metal deposition layer is formed on a surface of the substrate with an optical density of 1.0 to 3.0, which is a metal deposition layer located on the surface, hereinafter referred to as "surface metal deposition layer".
- the film thickness of the surface metal deposition layer is 20 to 90nm, preferably 40 to 70nm may be advantageous in terms of the deposition process stability and shielding effect implementation.
- a metal deposition layer having a thickness of 0.2 to 0.8 optical density which is a metal deposition layer located on the back of the substrate hereinafter referred to as "back metal deposition layer”.
- the film thickness of the backside metal deposition layer is preferably 5 to 25 nm, preferably 10 to 20 nm, in view of maintaining the flatness of the label.
- Examples of the metal that can be used for the surface metal deposition layer to the back metal deposition layer include Al, Zn, Mg, Sn, Ti, In, Cr, Ni, Cu, Pb, Fe, and the like, and preferably Al, Zn, Mg, and 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.
- the heat-shrinkable polyester base film is preferably transparent in order to realize a clear deposition color.
- the metal deposition layer is formed on the transparent substrate, light appears to be blocked due to the reflective effect of the metal deposition layer, but there is a limit to substantially preventing projection by only the metal deposition layer.
- the deposited film according to the embodiment of the present invention has an opacity of 80% or more, preferably 90 to 100%, because the color of the bottle is not projected, and the printing effect is excellent, and the visibility of the print pattern is increased. This is optimal in that the aesthetics can be improved.
- the polyester-based deposition film according to an embodiment of the present invention includes a printing layer on a 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.
- 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 ⁇ m in view of sufficient printing layer and preventing the printed layer from breaking.
- 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 the 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 do.
- Such primer layer may be appropriately selected in consideration of the printing layer, but is not limited thereto.
- Such primer layer may be appropriately selected in consideration of the printing layer, but is not limited thereto.
- corona treatment, flame treatment, plasma treatment, glow discharge treatment, roughening treatment, and the like may be performed on the surface of the heat-shrinkable polyester film substrate before the metal deposition layer is formed to obtain adhesion strength.
- 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 aldehydes, epoxidized soybean oil, ethylene-vinyl acetate copolymers, tallow oleamides, polyethylene glycol distearates, polyvinylidene, polyolefin copolymers and sole or mixtures thereof selected from urethane and vinyl resins Can be.
- the protective layer may have a thickness of 0.1 to 5.0 ⁇ m, preferably 0.3 to 1.0 ⁇ m, in terms of coating stability and drying process stability of the protective layer.
- the polyester-based deposition film of the present invention in order to apply the polyester-based deposition film of the present invention to the label application it is applied to the back of the label and then adhered to the container.
- the label should be flat and easy to dry after the adhesive It is necessary to satisfy the concealment of the titration.
- the anti-bending layer may be an uneven layer or a white pigment coating layer formed by physically or chemically treating the surface of the heat-shrinkable polyester film substrate.
- the anti-bending layer may be a separate coating layer other than the uneven layer, and specifically, may be a white pigment coating layer.
- the white pigment coating layer When the white pigment coating layer is formed, the concealability of the deposited film is enhanced, and the fine concavo-convex effect is obtained by the roughness of the surface, so that the drying efficiency of the adhesive applied to the film can be improved, and the drying time can be shortened.
- a label of a predetermined standard having a printing layer is separated and transported from the labeler by adsorption, and then an adhesive is applied to the back of the label by gravure printing. Then, the process of adhering the labels to the containers carried by the conveyor belt is carried out continuously (this is called "online bonding process").
- the anti-bending layer may include at least one resin selected from a resin such as polyamide resin, PVC resin, ketone resin, rubber chloride, acrylic resin, polyurethane resin, ethylene-vinylacetate copolymer, and vinyl resin; At least one solvent selected from aromatic hydrocarbon-based, ketone-based, acetate-based and chlorine-based solvents; And a layer formed from a composition comprising a white pigment and additives such as precipitation inhibitors, thickeners, color separation agents and pigment dispersants.
- a resin such as polyamide resin, PVC resin, ketone resin, rubber chloride, acrylic resin, polyurethane resin, ethylene-vinylacetate copolymer, and vinyl resin
- At least one solvent selected from aromatic hydrocarbon-based, ketone-based, acetate-based and chlorine-based solvents At least one solvent selected from aromatic hydrocarbon-based, ketone-based, acetate-based and chlorine-based solvents
- a white pigment and additives such as precipitation inhibitors, thicken
- Forming the anti-bending layer on the other side of the base film with such a composition may be preferable in view of the proper concealability and easy control of the warpage phenomenon of the heat-shrinkable polyester film base material.
- the anti-bending layer may have a thickness of 0.1 to 5.0 ⁇ m, preferably 0.4 to 2.0 ⁇ m, in terms of coating stability, drying process stability, and prevention of warpage of labels due to solvent.
- the deposition film including the anti-bending layer according to the embodiment of the present invention may have a bending property value of 5.0 mm or less as defined below.
- the finished heat-shrink polyester deposited film place it on a flat glass plate, cut it on the deposited film and cut the film 20 cm in the horizontal direction without damage using a knife to form a first incision.
- the film is cut by 20 cm in the vertical direction (the direction perpendicular to the first incision line) without using a knife to form a second incision line, so as to form a second incision line.
- Four incisions each having a length of 10 cm in the horizontal and vertical directions were formed based on the intersection points.
- the incision state is confirmed by lifting the deposited film in the vertical direction to confirm that the incision is completed. This is again placed on a flat glass plate, and the vertical height of the four corners corresponding to the intersection point of the incision line is raised and raised from the flat surface. At this time, two cases where the upper surface of the deposition layer and the lower surface of the deposition layer are respectively measured, and the value indicating the highest height is called a “bending characteristic value”.
- the adhesion process may be facilitated.
- 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 °C.
- Such shrinkage range of the hot water shrinkage film is attached to the heat-shrinkable film with a label on the bottle, etc., using an adhesive, and then the bottle is recovered, and the shrink film peeled into the empty bottle while facilitating the peeling of the label using hot water during recycling.
- This is advantageous in that it can be rolled up and then easily pulled out.
- the shrinkage ratio in the maximum shrinkage direction is less than 40%, the time required for shrinking becomes longer and the shrinkage stress generated when shrinking is weakened.
- the removal efficiency of the label for the reuse of the bottle is not only lowered, but also an increase in energy costs may occur because an additional process is required to remove the label that has not been peeled off.
- the shrinkage ratio in the maximum shrinkage direction exceeds 80%, the draw ratio in the width direction must be increased in order to improve the shrinkage rate in manufacturing the base film, so that breakage frequently occurs, and the yield of the base film film formation is drastically reduced, resulting in economical efficiency.
- 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 °C in the label application.
- 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.
- thermo stress tester Thermal Stress Tester
- 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.
- FIG. 1 An example of a measurement graph by such a method is illustrated in FIG. 1.
- the initial time point on the graph is an initially set load value Ls.
- the film is tightened and shrinks when a certain temperature is reached.
- 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).
- the shrinkage start temperature in the maximum shrinkage direction is 68 to 94 ° C. If the shrinkage start temperature is lower than 68 °C, during the summer distribution and storage of the finished product, the label is partly detached from the bottle may drop the aesthetics of the finished product, if the shrinkage start temperature is higher than 94 °C remove the label by hot water Since the process requires a long time of high temperature, a process cost may be high.
- 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 °C 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.
- 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.
- the polyester-based deposited film of the present invention advantageously has a low maximum shrinkage stress expression temperature in the main shrinkage direction of 80 to 110 °C, 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.
- the polyester-based deposition film of the present invention preferably has a total light transmittance of 0.01 to 5.0% 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 deposition 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.
- a printing layer is formed on the metal deposition layer.
- the printing layer may be formed by printing at 5 degrees in a gravure printing press.
- the above-described protective layer forming composition is coated or metal deposited on the printing layer, for example, using a gravure printing machine.
- a printed layer can be formed.
- the other side of a heat-shrinkable polyester film base material can apply the crude liquid for anti-bending layers mentioned above, and can form an anti-bending layer.
- the deposition temperature is generally performed at 1200 ° C. or higher, where the metal may be vaporized, and the chamber in which the deposition is performed may preferably maintain a vacuum degree of 10 ⁇ 2 torr or more.
- a conventional apparatus can be used as a vapor deposition method, and well-known methods, such as a crucible system and a boat system, can be applied.
- a conventional apparatus can be used, and for example, a known method such as gravure printing or flexographic printing can be applied.
- 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.
- a conventional method of attaching a label of a paper material may be applied.
- water-soluble adhesives can be applied in consideration of the film material and environmental aspects as adhesives. The water-soluble adhesive is applied to the coated surface of the polyester-based deposition film label transferred in the form of a sheet label, and then transferred by the conveyor belt.
- polyester-based deposition film in the form of a single label Attached bottles can be prepared.
- 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.
- the evaluation method used in the present invention is as follows.
- Heat Shrinkage (%) (300mm-Length after Shrinkage / 300mm) ⁇ 100
- 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.
- the thickness of the film base material 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 and minimum values.
- 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.
- 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 anti-warp 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.
- the measurement method was measured based on ASTM D-1003, and the polyester-based deposition film was randomly extracted from 7 parts at 2 sides and 1 center, and then sliced into 5cm ⁇ 5cm sizes to measure an opacity meter (Film Opacity Meter Series 6000) and set the measuring method to ASTM, and mount the sample so that the light is incident in the direction of the metal deposition layer and the light is transmitted through the bending prevention layer, and then measure the maximum and minimum values by measuring the opacity (%).
- Opacity (%) was calculated by calculating the average of the five values excluded.
- 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.
- the shrinkage stress 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.
- 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).
- T (Smax) the maximum contraction expression temperature
- Smax the stress value at this time
- 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 °C / sec.
- 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).
- the produced sample was displayed in a general product display state and examined by 10 people, and it was determined whether the printing of the deposition label was clearly seen regardless of the color of the glass plate.
- the finished film is cut into a rectangle of 15 cm (MD) ⁇ 5 cm (TD) in the longitudinal direction (MD) and the width direction (TD) of the finished polyester-deposited film, and the adhesive force is constant on the printed layer of the cut film.
- the transparent tape (Nitto Tape, 31-B) is attached without bubbles and rubbed 10 times at a pressure of 3Kg / cm 2 for the entire area so that the transparent tape is firmly attached to the polyester-based deposition film using a rubber roller. Fully glued.
- the transparent tape attached to the printing layer was peeled off, and the number of samples peeling off the printing on the polyester-based deposition film was measured and evaluated as good, normal, or bad.
- Good is 0; ⁇ , usually 1 or more; ⁇ , bad is three or more; It evaluated by x.
- 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 parts by weight of a disinfectant, and 4.1 parts by weight of water is applied to the warpage layer of the polyester-based deposition film label with a thickness of 5 ⁇ m, and a labeler is 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.
- a water-soluble adhesive prepared by mixing 45 parts by weight of styrene-butadiene rubber latex, 40 parts by weight of an acrylic emulsion, 10 parts by weight of an ethylene-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 added to the bottle in a thickness of 5 ⁇ m.
- the label is applied to the adhesive-coated glass bottle so that the printing layer of the label is located on the outermost surface, and 10 times at a pressure of 3Kg / cm2 for the entire area of the label so that the label is firmly attached to the glass bottle using a rubber roller.
- the label was fixed to the vial by reciprocating and rubbing and standing at room temperature for 2 days to solidify the adhesive.
- 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.
- the finished polyester-based deposited film it was placed on a polished glass plate having a refractive index of 1.567, and cut on the deposited film with a knife to cut the film by 20 cm in the horizontal direction without damage to form a first cut line.
- the ruler as a reference to the center point of the first incision, the film is cut by 20 cm in the vertical direction (the direction perpendicular to the first incision) using a ruler to form a second incision.
- Four incisions each having a length of 10 cm in the horizontal and vertical directions were formed based on the intersection points of the second incisions.
- the incision state is confirmed by lifting the deposited film in the vertical direction to confirm that the incision is completed. This is again placed on a flat glass plate, and the vertical height of the four corners corresponding to the intersection point of the incision line is raised and raised from the flat surface. At this time, two cases where the upper surface of the deposition layer and the lower surface of the deposition layer are respectively measured, and the value indicating the highest height is called a bending characteristic value. Negative values of bending characteristics are defined as the vertical height in the direction corresponding to the vertical height being bent.
- 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 ⁇ m, 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.
- polyester heat-shrink film aluminum having a purity of 99.9% was evaporated at a top vacuum degree of 1.09 ⁇ 10 -4 mbar, a bottom vacuum degree of 2.23 ⁇ 10 -2 mbar, and a crucible temperature of 1400 ° C. using a crucible evaporator. And a cooling roll temperature of -16 DEG C and a deposition rate of 400 m / min to form a metal deposition layer having an optical density of 2.1 (metal: Al, metal deposition layer thickness 53 nm).
- the printed film was prepared by forming a warpage layer having a thickness of 1.1 ⁇ m by printing at 2 degrees.
- the obtained deposition film was evaluated by the above method, and the results are shown in Tables 1 and 2 below.
- a deposition film having the same structure as in Example 1 when preparing the base film, 100 mol% of terephthalic acid as a dibasic acid component, 106 mol% of ethylene glycol and neopentyl glycol content as a glycol component using 18 mol% as a catalyst It was polycondensed by direct esterification using 0.05 mole of antimony trioxide (relative to acid component).
- the polymer thus obtained contained 500 ppm of silicon dioxide powder having an average particle diameter of 2.7 ⁇ m 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.
- a metal deposition layer was formed under the same conditions as in Example 1 to have a metal deposition layer thickness of 53 nm, a printing layer thickness of 2.2 ⁇ m, a protective layer thickness of 0.3 ⁇ m, and a bending prevention layer thickness of 1.1 ⁇ m.
- a film was prepared.
- the obtained deposition film was evaluated by the above method, and the results are shown in Tables 1 and 2 below.
- a deposition film having the same structure as in Example 1 when preparing the base film, 100 mol% of terephthalic acid as a dibasic acid component, 96 mol% of ethylene glycol and 28% by weight of neopentyl glycol as a glycol component and as a catalyst It was polycondensed by direct esterification using 0.05 mole of antimony trioxide (relative to acid component).
- the polymer thus obtained contained 50 ppm of silicon dioxide powder having an average particle diameter of 2.7 ⁇ m 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.
- a metal deposition layer was formed under the same conditions as in Example 1 to have a metal deposition layer thickness of 53 nm, a printing layer thickness of 2.2 ⁇ m, a protective layer thickness of 0.3 ⁇ m, and a bending prevention layer thickness of 1.1 ⁇ m.
- a film was prepared.
- the obtained deposition film was evaluated by the above method, and the results are shown in Tables 1 and 2 below.
- the polymer thus obtained contained 500 ppm of silicon dioxide powder having an average particle diameter of 2.7 ⁇ m 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 ⁇ ⁇ .
- the copolyester was extruded from an extruder at 270 ° C. and then rapidly cooled 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 ⁇ m was produced through a heat treatment section at room temperature.
- a metal deposition layer was formed under the same conditions as in Example 1 to have a metal deposition layer thickness of 53 nm, a printing layer thickness of 2.2 ⁇ m, a protective layer thickness of 0.3 ⁇ m, and a bending prevention layer thickness of 1.1 ⁇ m.
- a film was prepared.
- the obtained deposition film was evaluated by the above method, and the results are shown in Tables 1 and 2 below.
- a metal deposition layer was formed under the same conditions as in Example 1 to deposit a metal deposition layer having a thickness of 41 nm, a printing layer thickness of 2.2 ⁇ m, a protective layer thickness of 0.3 ⁇ m, and a bending prevention layer thickness of 1.1 ⁇ m.
- a film was prepared.
- the obtained deposition film was evaluated by the above method, and the results are shown in Tables 1 and 2 below.
- a deposition film having a metal deposition layer thickness of 66 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 was prepared under the same conditions as in Example 1. .
- the obtained deposition film was evaluated in the above manner, and the results are shown in Table 1 below.
- Example 2 To prepare a deposited film having the same structure as in Example 1, before forming a printed layer to form a primer layer on the metal deposition layer.
- a silane coupling agent (3-glycidoxy propyltrimethoxy silane, 3-Glycidoxypropyltrimethoxy silane) was diluted in methyl ethyl ketone at a concentration of 0.5% by weight using a gravure roll on a metal deposition layer and a primer layer having a thickness of 0.4 ⁇ m.
- a deposited film having a metal deposition layer thickness of 53nm, printing layer thickness of 2.2 ⁇ m, protective layer thickness of 0.3 ⁇ m, bending prevention layer thickness of 1.1 ⁇ m.
- the obtained deposition film was evaluated in the above manner, and the results are shown in Table 1 below.
- Example 2 To prepare a deposited film having the same structure as in Example 1, before forming a printed layer to form a primer layer on the metal deposition layer.
- a mixed varnish consisting of 10% by weight of urethane (urethane varnish) and 90% by weight of vinyl chloride (vinyl chloride varnish) was diluted with methyl ethyl ketone (MEK) using a gravure roll on a metal deposition layer.
- MEK methyl ethyl ketone
- a coating solution of% was prepared to form a primer layer having a thickness of 0.4 ⁇ m to prepare a deposited film having a thickness of 53 nm of metal deposition layer, 2.2 ⁇ m of printing layer, 0.3 ⁇ m of protective layer thickness, and 1.1 ⁇ m of anti-warp layer thickness.
- the obtained deposition film was evaluated in the above manner, and the results are shown in Table 1 below.
- a deposition film having the same structure as 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) Yellow pigment (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 (R-100, KPIA was printed at 4 degrees using a gravure roll from four crude liquids containing 10 wt% of each colorant selected in the present invention and the total amount thereof was adjusted to 100 wt% to form a printed layer (print layer thickness of 1.2 ⁇ m).
- MEK methyl ethyl ketone
- a deposition film having a metal deposition layer thickness of 53 nm, a printed layer thickness of 1.2 ⁇ m, a protective layer thickness of 0.3 ⁇ m, and a warpage preventing layer thickness of 1.1 ⁇ m 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.
- a deposition film having the same structure as 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) Yellow pigment (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 (R-100, KPIA was printed at 8 degrees using a gravure roll from 8 kinds of crude liquids containing 10 wt% of each colorant selected in the present invention and the total amount was adjusted to 100 wt% to form a printed layer (print layer thickness of 7.5 ⁇ m).
- the obtained deposition film was evaluated in the above manner, and the results are shown in Table 1 below.
- methyl ethyl ketone (MEK) of the copolymer polyester resin (copolyester having a number average molecular weight of 5000 made by mixing two or more polyhydric alcohol and polybasic acid) on the printed layer
- a metal deposition layer thickness of 53 nm, a printing layer thickness of 2.2 ⁇ m, and a protective layer thickness of 1.0 were prepared in the same manner except that a protective layer was formed using a gravure roll from a crude liquid having a solid concentration of 25% by dilution in A deposited film having a thickness of 1.1 ⁇ m and a bending preventing layer was prepared.
- the obtained deposition film was evaluated in the above manner, and the results are shown in Table 1 below.
- a deposition film having the same structure as in Example 1 was prepared, but the polyolefin copolymer varnish was diluted in methyl ethyl ketone (MEK) on the printed layer to form a protective layer using a gravure roll from a crude liquid having a solid concentration of 25% by weight (protection).
- MEK methyl ethyl ketone
- a deposited film having a metal deposition layer thickness of 53 nm, a printed layer thickness of 2.2 ⁇ m, a protective layer thickness of 0.3 ⁇ m, and a warpage prevention layer thickness of 1.1 ⁇ m was prepared in the same manner except that the layer thickness was 0.4 ⁇ m).
- the obtained deposition film was evaluated in the above manner, and the results are shown in Table 1 below.
- Example 1 In the roller group conveyed in the mechanical direction with respect to the unstretched film obtained in the same manner as in Example 1 in Example 1 stretched 1.6 times in the longitudinal direction of the film at 70 °C temperature through a preheating section of the temperature 65 °C Next, after cooling through a cooling roll at room temperature, the film was continuously stretched in the width direction under the same conditions as in Example 1 in a tenter, so that the shrinkage ratio in the film length direction MD was 37.5%, and in the width direction TD.
- a film was prepared.
- the obtained deposition film was evaluated in the above manner, and the results are shown in Table 1 below.
- Example 13 In the roller group conveyed in the mechanical direction in Example 13 was stretched 2.0 times in the longitudinal direction of the film at 75 °C temperature through a preheating section of the temperature 75 °C, and then cooled through a cooling roll of room temperature, and then continuously Stretching in the width direction under the same conditions as in Example 1 in the tenter, the shrinkage ratio in the film length direction (MD) is 41.7%, the shrinkage ratio in the width direction (TD) 71.3% bidirectional thermal shrinkage polyester film
- the obtained deposition film was evaluated in the above manner, and the results are shown in Table 1 below.
- Example 2 Prepare a deposited film having the same structure as in Example 1, except that the protective layer is formed in the same manner to prepare a deposited film having a metal deposition layer thickness 53nm, printed layer thickness 2.2 ⁇ m, bending prevention layer thickness 1.1 ⁇ m It was.
- the obtained deposition film was evaluated in the above manner, and the results are shown in Table 1 below.
- 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 ⁇ m 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 ⁇ ⁇ .
- a metal deposition layer was formed under the same conditions as in Example 1 to have a metal deposition layer thickness of 53 nm, a printing layer thickness of 2.2 ⁇ m, a protective layer thickness of 0.3 ⁇ m, and a bending prevention layer thickness of 1.1 ⁇ m.
- a film was prepared.
- the deposition film was evaluated in the above manner, and the results are shown in Tables 1 and 2 below.
- a deposition film having the same structure as in Example 1 was prepared, except that PET film 50 ⁇ m (CI series, Kolon Industries Co., Ltd.) was applied as the base film, and the metal deposition layer thickness was 53 nm and the print layer thickness 2.2, respectively.
- a deposited film having a protective layer thickness of 0.3 ⁇ m and a bending prevention layer thickness of 1.1 ⁇ m was prepared.
- the obtained deposition film was evaluated by the above method, and the results are shown in Tables 1 and 2 below.
- a deposition film having the same structure as in Example 1 was prepared, except that the formation of the bending prevention layer was performed in the same manner, except that the thickness of the metal deposition layer was 53 nm, the printing layer thickness was 2.2 ⁇ m, the protective layer thickness was 0.3 ⁇ m, and the bending prevention layer thickness was 1.1 ⁇ m.
- a deposited film was prepared.
- the obtained deposition film was evaluated by the above method, and the results are shown in Tables 1 and 2 below.
- a deposition film having a metal deposition layer thickness of 11 nm, a printed layer thickness of 2.2 ⁇ m, a protective layer thickness of 0.3 ⁇ m, and a warpage prevention layer thickness of 1.1 ⁇ m was prepared under the same conditions as in Example 1. .
- the obtained deposition film was evaluated by the above method, and the results are shown in Tables 1 and 2 below.
- the label 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.
- 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, but in the case of Examples 13 and 14, the label is separated from 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.
- Comparative Example 1 which does not use a heat-shrinkable polyester-based film, it can be seen that the peeling of the label in the simple hot water is substantially impossible.
- Example 15 without applying the protective layer, the adhesiveness and peeling characteristics are not a problem, but the phenomenon that the metal deposition layer and the printing layer of the printing label is peeled off during the printing label peeling process, the print peeling water is This may cause a problem of contaminating the present invention, 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.
- Example 16 satisfies the visibility and exhibits proper label peelability, some of the printing labels are adhered to the bottles when the printing labels are removed from the bottles. It can be confirmed that economic efficiency may be reduced. This is caused by a high shrinkage start temperature and a low maximum shrinkage stress, it can be seen that the shrinkage characteristics are preferably controlled to optimize the peelability of the label.
- the heat-shrinkable polyester film substrate includes a metal deposition layer, and it can be seen that the printability of the deposition film that satisfies a predetermined opacity is excellent.
- 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 ⁇ m, 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.
- polyester-based heat-shrink film aluminum having a purity of 99.9% was evaporated at a top vacuum degree of 1.08 ⁇ 10 ⁇ 4 mbar, a bottom vacuum degree of 2.18 ⁇ 10 ⁇ 2 mbar, and a crucible temperature of 1400 ° C. using a crucible evaporator. And a cooling roll temperature of -16 DEG C and a deposition rate of 400 m / min to form a metal deposition layer having an optical density of 2.1 (metal: Al, metal deposition layer thickness 52 nm).
- a metal deposition layer having an optical density of 0.5 was formed on the other side of the base film in the same manner except that the deposition rate was 600 m / min (referred to as a back metal deposition layer.
- Metal Al, metal deposition layer thickness 15 nm).
- the obtained deposition film was evaluated by the above method, and the results are shown in the following Tables 3 and 4.
- a deposition film having the same structure as in Example 17 was prepared, but 100 mol% of terephthalic acid was used as a dibasic acid component, 106 mol% of ethylene glycol and neopentyl glycol were used as a catalyst, and 18 mol% of a catalyst was used as a catalyst. It was polycondensed by direct esterification using 0.05 mole of antimony trioxide (relative to acid component).
- the polymer thus obtained contained 500 ppm of silicon dioxide powder having an average particle diameter of 2.7 ⁇ m 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.
- a metal deposition layer was formed under the same conditions as in Example 17, and the upper metal deposition layer thickness was 52 nm, the lower metal deposition layer thickness was 15 nm, the print layer thickness was 2.0 ⁇ m, the protective layer thickness was 0.4 ⁇ m, A deposited film having a thickness of 1.0 ⁇ m of the anti-bending layer was manufactured.
- the obtained deposition film was evaluated by the above method, and the results are shown in the following Tables 3 and 4.
- a deposition film having the same structure as in Example 17 was prepared, but 100 mol% of terephthalic acid was used as the dibasic acid component, 96 mol% of ethylene glycol as the glycol component and 28 mol% of neopentyl glycol were used as a catalyst. It was polycondensed by direct esterification using 0.05 mole of antimony trioxide (relative to acid component).
- the polymer thus obtained contained 50 ppm of silicon dioxide powder having an average particle diameter of 2.7 ⁇ m 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.
- a metal deposition layer was formed under the same conditions as in Example 17, and the upper metal deposition layer thickness was 52 nm, the lower metal deposition layer thickness was 15 nm, the print layer thickness was 2.0 ⁇ m, the protective layer thickness was 0.4 ⁇ m, A deposited film having a thickness of 1.0 ⁇ m of the anti-bending layer was manufactured.
- the obtained deposition film was evaluated by the above method, and the results are shown in the following Tables 3 and 4.
- a deposition film having the same structure as in Example 17 was prepared, but 100 mol% of terephthalic acid was used as a dibasic acid component, and 80 mol% of ethylene glycol and 20 mol% of 1,4-cyclohexane dimethanol were used as a glycol component. And polycondensation by direct esterification using 0.05 mol of antimony trioxide (relative to acid component) as a catalyst.
- the polymer thus obtained contained 500 ppm of silicon dioxide powder having an average particle diameter of 2.7 ⁇ m 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 ⁇ ⁇ .
- the copolyester was extruded from an extruder at 270 ° C. and then rapidly cooled 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 ⁇ m was produced through a heat treatment section at room temperature.
- a metal deposition layer was formed under the same conditions as in Example 17, and the upper metal deposition layer thickness was 52 nm, the lower metal deposition layer thickness was 15 nm, the print layer thickness was 2.0 ⁇ m, the protective layer thickness was 0.4 ⁇ m, A deposited film having a thickness of 1.0 ⁇ m of the anti-bending layer was manufactured.
- the obtained deposition film was evaluated by the above method, and the results are shown in the following Tables 3 and 4.
- a metal deposition layer having an optical density of 0.7 was formed on the remaining surface of the base film in the same manner except that the deposition rate was 550 m / min (referred to as a back metal deposition layer.
- Metal Al, metal deposition layer thickness of 19 nm).
- a metal deposition layer was formed under the same conditions as in Example 17, and the upper metal deposition layer thickness was 44 nm, the lower metal deposition layer thickness was 19 nm, the print layer thickness was 2.0 ⁇ m, the protective layer thickness was 0.4 ⁇ m, A deposited film having a thickness of 1.0 ⁇ m of the anti-bending layer was manufactured.
- the obtained deposition film was evaluated by the above method, and the results are shown in the following Tables 3 and 4.
- a metal deposition layer having an optical density of 0.4 was formed on the remaining surface of the base film in the same manner except that the deposition rate was 630 m / min (referred to as a back metal deposition layer.
- Metal Al, metal deposition layer thickness 10 nm).
- a metal deposition layer was formed under the same conditions as in Example 17 to form an upper metal deposition layer thickness of 41 nm, a lower metal deposition layer thickness of 20 nm, a printing layer thickness of 2.0 ⁇ m, a protective layer thickness of 0.4 ⁇ m, A deposited film having a thickness of 1.0 ⁇ m of the anti-bending layer was manufactured.
- the obtained deposition film was evaluated by the above method, and the results are shown in the following Tables 3 and 4.
- a deposition film having the same structure as in Example 17 was prepared, but before forming the print layer, a primer layer was formed on the metal deposition layer.
- a silane coupling agent (3-glycidoxy propyltrimethoxy silane, 3-Glycidoxypropyltrimethoxy silane) was diluted in methyl ethyl ketone at a concentration of 0.5% by weight using a gravure roll on a metal deposition layer, and a primer layer having a thickness of 0.4 ⁇ m.
- a deposited film having an upper metal deposition layer thickness 52nm, a lower metal deposition layer thickness 15nm, a printing layer thickness of 2.0 ⁇ m, a protective layer thickness of 0.4 ⁇ m, a bending prevention layer thickness of 1.0 ⁇ m.
- the obtained deposition film was evaluated by the above method, and the results are shown in the following Tables 3 and 4.
- a deposition film having the same structure as in Example 17 was prepared, but before forming the print layer, a primer layer was formed on the metal deposition layer.
- a mixed varnish consisting of 10% by weight of urethane (urethane varnish) and 90% by weight of vinyl chloride (vinyl chloride varnish) using a gravure roll on a metal deposition layer was diluted with methyl ethyl ketone (MEK) to give a solid content of 25
- MEK methyl ethyl ketone
- a coating film was prepared to form a primer layer having a thickness of 0.4 ⁇ m to form a primer layer having a thickness of 0.4 ⁇ m, a deposition film having an upper metal deposition layer thickness of 52 nm, a lower metal deposition layer thickness of 15 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.
- the obtained deposition film was evaluated by the above method, and the results are shown in the following Tables 3 and 4.
- a deposition film having the same structure as in Example 17 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) Yellow pigment (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 (R-100, KPIA was printed at 4 degrees using a gravure roll from four crude liquids containing 10 wt% of each colorant selected in the present invention and the total amount thereof was adjusted to 100 wt% to form a printed layer (print layer thickness of 1.2 ⁇ m).
- MEK methyl ethyl ketone
- a deposition film having a thickness of 52 nm, a thickness of 15 nm, a thickness of a printed layer of 1.2 ⁇ m, a thickness of 0.4 ⁇ m of a protective layer, and a thickness of 1.0 ⁇ m of a warpage prevention layer was prepared in the same manner as above.
- the obtained deposition film was evaluated by the above method, and the results are shown in the following Tables 3 and 4.
- a deposition film having the same structure as in Example 17 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) Yellow pigment (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 (R-100, KPIA was printed at 7 degrees using a gravure roll from 7 kinds of crude liquids including 10 wt% of each colorant selected in the present invention and the total amount was adjusted to 100 wt% to form a printed layer (print layer thickness of 7.0 ⁇ m).
- MEK methyl ethyl ketone
- a deposition film having a thickness of 52 nm, a thickness of 15 nm, a thickness of 7.0 ⁇ m, a thickness of 0.4 ⁇ m of a protective layer, and a thickness of 1.0 ⁇ m of a deflection prevention layer was prepared by the same method as above.
- the obtained deposition film was evaluated by the above method, and the results are shown in the following Tables 3 and 4.
- a deposition film having the same structure as in Example 17 was prepared, but copolymerized polyester resin (copolyester having a number average molecular weight of 5000 produced by mixing two or more polyhydric alcohols and polybasic acids) on the printing layer was methyl ethyl ketone (MEK).
- the upper metal deposition layer thickness was 52 nm
- the lower metal deposition layer thickness was 15 nm
- the printing layer was prepared in the same manner except that a protective layer was formed using a gravure roll from a crude liquid having a solid concentration of 25% by dilution in A deposited film having a thickness of 8.0 ⁇ m, a protective layer thickness of 0.7 ⁇ m, and a warpage preventing layer thickness of 1.0 ⁇ m was prepared.
- the obtained deposition film was evaluated by the above method, and the results are shown in the following Tables 3 and 4.
- a deposition film having the same structure as in Example 17 was prepared, but the polyolefin copolymer varnish was diluted with methyl ethyl ketone (MEK) on the printed layer to form a protective layer using a gravure roll from a crude liquid having a solid concentration of 25% by weight.
- MEK methyl ethyl ketone
- a deposition film having a thickness of 52 nm, a thickness of 15 nm, a thickness of 8.0 ⁇ m, a thickness of 0.6 ⁇ m of a protective layer, and a thickness of 1.0 ⁇ m of a warpage prevention layer was prepared in the same manner except that the thickness of the layer was 0.6 ⁇ m). It was.
- the obtained deposition film was evaluated by the above method, and the results are shown in the following Tables 3 and 4.
- Example 17 in the roller group conveyed in the mechanical direction with respect to the unstretched film obtained in the same manner as in Example 17, the film was stretched 1.7 times in the longitudinal direction of the film at 70 ° C. through a preheating section having a temperature of 65 ° C. Next, after cooling through a cooling roll at room temperature, the film was continuously stretched in the width direction under the same conditions as in Example 17 in a tenter, so that the shrinkage in the film length direction MD was 38.3%, and in the width direction TD.
- a 50 nm thick bidirectional thermal shrink polyester film having a shrinkage rate of 75.1% was prepared, the upper metal deposited layer thickness was 52 nm, the lower metal deposited layer thickness was 15 nm, the printed layer thickness was 2.0 ⁇ m, the protective layer thickness was 0.4 ⁇ m, A deposited film having a thickness of 1.0 ⁇ m of the anti-bending layer was manufactured.
- the obtained deposition film was evaluated by the above method, and the results are shown in the following Tables 3 and 4.
- Example 29 In the roller group conveyed in the mechanical direction in Example 29 was stretched 2.3 times with respect to the longitudinal direction of the film at 75 °C temperature through a preheating section of the temperature 75 °C, then cooled through a cooling roll of room temperature, and then continuously
- the tenter was stretched in the width direction under the same conditions as in Example 17, so that the shrinkage ratio in the film length direction (MD) was 44.1%, and the shrinkage ratio in the width direction (TD) was 71.3%.
- a deposition film having a thickness of 52 nm, a thickness of 15 nm, a thickness of a printed layer of 2.0 ⁇ m, a thickness of 0.4 ⁇ m of a protective layer, and a thickness of 1.0 ⁇ m of an anti-bending layer was prepared in the same manner except that the same was manufactured.
- the obtained deposition film was evaluated by the above method, and the results are shown in the following Tables 3 and 4.
- a deposition film having the same structure as in Example 17 was manufactured, except that the protective layer was not formed, and the upper metal deposition layer thickness was 52 nm, the lower metal deposition layer thickness was 15 nm, the printing layer thickness was 2.0 ⁇ m, and the bending prevention layer thickness.
- a deposited film having 1.0 ⁇ m was prepared.
- the obtained deposition film was evaluated by the above method, and the results are shown in the following Tables 3 and 4.
- 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 ⁇ m 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 ⁇ ⁇ .
- a metal deposition layer was formed under the same conditions as in Example 17, and the upper metal deposition layer thickness was 52 nm, the lower metal deposition layer thickness was 15 nm, the print layer thickness was 2.0 ⁇ m, the protective layer thickness was 0.4 ⁇ m, A deposited film having a thickness of 1.0 ⁇ m of the anti-bending layer was manufactured.
- the obtained deposition film was evaluated by the above method, and the results are shown in the following Tables 3 and 4.
- a deposition film having the same structure as in Example 17 was prepared, except that PET film 50 ⁇ m (CE series, Kolon Industries Co., Ltd.) was applied as the base film, and the upper metal deposition layer thickness was 52 nm and the lower metal deposition under the same conditions.
- the obtained deposition film was evaluated by the above method, and the results are shown in the following Tables 3 and 4.
- a metal deposition layer having an optical density of 0.5 was formed on the remaining surface of the base film in the same manner except that the deposition rate was set to 600 m / min (referred to as a back metal deposition layer.
- a metal deposition layer was formed under the same conditions as in Example 17, and an upper metal deposition layer thickness of 121 nm, a lower metal deposition layer thickness of 15 nm, a printed layer thickness of 2.0 ⁇ m, a protective layer thickness of 0.4 ⁇ m, A deposited film having a thickness of 1.0 ⁇ m of the anti-bending layer was manufactured.
- the obtained deposition film was evaluated by the above method, and the results are shown in the following Tables 3 and 4.
- a deposition film having the same structure as in Example 17 was prepared, but aluminum having a purity of 99.9% was deposited on both sides of a polyester-based heat-shrink film base material using a crucible evaporator.
- the upper vacuum degree of the evaporator was 2.01 ⁇ 10 ⁇ 4 mbar, the lower part. Evaporation was carried out at a vacuum degree of 1.89 ⁇ 10 ⁇ 2 mbar and a crucible temperature of 1400 ° C., and a metal deposition layer having an optical density of 0.4 was formed in the same manner at a cooling roll temperature of ⁇ 15 ° C. and a deposition rate of 630 m / min. (Metals: Al, both sides) Metal deposition layer thickness 10nm)
- a metal deposition layer was formed under the same conditions as in Example 17, the upper metal deposition layer thickness was 10 nm, the lower metal deposition layer thickness was 10 nm, the print layer thickness was 2.0 ⁇ m, the protective layer thickness was 0.4 ⁇ m, A deposited film having a thickness of 1.0 ⁇ m of the anti-bending layer was manufactured.
- the obtained deposition film was evaluated by the above method, and the results are shown in the following Tables 3 and 4.
- a deposition film having the same structure as in Example 17 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) Yellow pigment (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 (R-100, Printed by printing at 6 degrees using a gravure roll from six crude liquids, the total amount of the total amount is adjusted to 100% by weight, including 10% by weight of each colorant selected from KPIA) (print layer thickness 12.0 ⁇ m)
- a deposition film having a thickness of 52 nm, a thickness of 15 nm, a thickness of a printed layer of 2.0 ⁇ m, a thickness of 0.4 ⁇ m of a protective layer, and a thickness of 1.0 ⁇ m of a warpage prevention layer was prepared in the same manner as above.
- the obtained deposition film was evaluated by the above method, and the results are shown in the following Tables 3 and 4.
- a deposition film having the same structure as in Example 17 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) Yellow pigment (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 (R-100, KPIA) was printed with two degrees using a gravure roll from two crude liquids containing 10 wt% of each colorant selected in the present invention and the total amount was adjusted to 100 wt% to form a printed layer (print layer thickness 0.2 ⁇ ).
- MEK methyl ethyl ketone
- a deposition film having a thickness of 52 nm, a thickness of 15 nm, a thickness of a printed layer of 2.0 ⁇ m, a thickness of 0.4 ⁇ m of a protective layer, and a thickness of 1.0 ⁇ m of a warpage prevention layer was prepared in the same manner as above.
- the obtained deposition film was evaluated by the above method, and the results are shown in the following Tables 3 and 4.
- the label 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.
- the film curled in the direction of the maximum shrinkage of the film, which causes the pressure or flow rate of the water to increase when the label floats to the top of the bottle, but in the case of Examples 29 and 30, the label is separated from 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.
- Comparative Example 4 which does not use a heat-shrinkable polyester-based film, it can be seen that the peeling of the label in the simple hot water is substantially impossible.
- Example 15 without applying the protective layer, the adhesiveness and peeling characteristics are not a problem, but during the printing label peeling process, the phenomenon that the metal deposition layer and the printing layer of the printing label peel off occurs, This may cause a problem of contaminating the present invention, 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.
- Example 32 shows the appropriate label peelability while satisfying the visibility, but when the printing label is removed from the bottle, the printing label is sometimes adhered to the bottle, so that the printing label is removed several times. It can be confirmed that economic efficiency may be reduced. This is caused by a high shrinkage start temperature and a low maximum shrinkage stress, it can be seen that the shrinkage characteristics are preferably controlled to optimize the peelability of the label.
- 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 ⁇ m, 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.
- polyester-based heat shrink film aluminum having a purity of 99.9% was evaporated at the top vacuum degree of 1.07 ⁇ 10 -4 mbar, the bottom vacuum degree 2.13 ⁇ 10 -2 mbar, and the crucible temperature of 1400 ° C. using a crucible evaporator. And a cooling roll temperature of -16 DEG C 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).
- the deposition film of the present invention was prepared by forming a warp layer having a thickness of 1.0 ⁇ m by controlling the depth of the gravure roll by applying a crude liquid having a total amount adjusted to 100 wt% including a separation inhibitor and a pigment dispersant. It was.
- the obtained deposition film was evaluated by the above-described method, and the results are shown in Tables 5 and 6 below.
- a deposition film having the same structure as in Example 33 was prepared, but 100 mol% of terephthalic acid was used as a dibasic acid component, 106 mol% of ethylene glycol as a glycol component and 18 mol% of neopentyl glycol were used as a catalyst. It was polycondensed by direct esterification using 0.05 mole of antimony trioxide (relative to acid component).
- the polymer thus obtained contained 500 ppm of silicon dioxide powder having an average particle diameter of 2.7 ⁇ m 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.
- a metal deposition layer was formed under the same conditions as in Example 33 to have a metal deposition layer 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.
- a film was prepared.
- the obtained deposition film was evaluated by the above-described method, and the results are shown in Tables 5 and 6 below.
- a deposition film having the same structure as in Example 33 was prepared, but 100 mol% of terephthalic acid was used as a dibasic acid component, 96 mol% of ethylene glycol and 28 wt% of neopentyl glycol were used as a catalyst, and the catalyst was used as a catalyst. It was polycondensed by direct esterification using 0.05 mole of antimony trioxide (relative to acid component).
- the polymer thus obtained contained 50 ppm of silicon dioxide powder having an average particle diameter of 2.7 ⁇ m 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.
- a metal deposition layer was formed under the same conditions as in Example 33 to have a metal deposition layer 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.
- a film was prepared.
- the obtained deposition film was evaluated by the above-described method, and the results are shown in Tables 5 and 6 below.
- a deposition film having the same structure as in Example 33 when preparing the base film, 100 mol% of terephthalic acid as the dibasic acid component, 80 mol% of ethylene glycol and 20 mol% of 1,4-cyclohexane dimethanol as the glycol component And polycondensation by direct esterification using 0.05 mol of antimony trioxide (relative to acid component) as a catalyst.
- the polymer thus obtained contained 500 ppm of silicon dioxide powder having an average particle diameter of 2.7 ⁇ m 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 ⁇ ⁇ .
- the copolyester was extruded from an extruder at 270 ° C. and then rapidly cooled 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 ⁇ m was produced through a heat treatment section at room temperature.
- a metal deposition layer was formed under the same conditions as in Example 33 to have a metal deposition layer 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.
- a deposited film was prepared.
- the obtained deposition film was evaluated by the above-described method, and the results are shown in Tables 5 and 6 below.
- a deposition film having a metal deposition layer thickness of 41 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 was prepared under the same conditions as in Example 33. .
- the obtained deposition film was evaluated by the above-described method, and the results are shown in Tables 5 and 6 below.
- Example 33 Prepare a deposition film having the same structure as in Example 33, on the polyester-based heat-shrink film substrate, using a crucible evaporator vapor deposition of 99.9% of the purity of the vapor deposition unit of the upper vacuum degree 1.83 ⁇ 10 -4 mbar, lower vacuum degree
- the evaporation was carried out at 2.18 ⁇ 10 ⁇ 2 mbar and the crucible temperature of 1400 ° C. to form a metal deposition layer having an optical density of 1.9 with a cooling roll temperature of ⁇ 20 ° C. and a deposition rate of 330 m / min. (Metal: Al, metal deposition layer thickness) 65 nm)
- a deposition film having a metal deposition layer thickness of 65 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 was prepared under the same conditions as in Example 33. .
- the obtained deposition film was evaluated by the above-described method, and the results are shown in Tables 5 and 6 below.
- a deposition film having the same structure as in Example 33 was prepared, but before the printing layer was formed, a primer layer was formed on the metal deposition layer.
- a silane coupling agent (3-glycidoxy propyltrimethoxy silane, 3-Glycidoxypropyltrimethoxy silane) was diluted in methyl ethyl ketone at a concentration of 0.5% by weight using a gravure roll on a metal deposition layer, and a primer layer having a thickness of 0.4 ⁇ m.
- a deposited film having a metal deposition layer thickness of 52nm, printed layer thickness of 2.0 ⁇ m, protective layer thickness of 0.4 ⁇ m, bending prevention layer thickness 1.0 ⁇ m.
- the obtained deposition film was evaluated by the above-described method, and the results are shown in Tables 5 and 6 below.
- a deposition film having the same structure as in Example 33 was prepared, but before forming a printing layer, a primer layer was formed on the metal deposition layer.
- a mixed varnish consisting of 10% by weight of urethane (urethane varnish) and 90% by weight of vinyl chloride (vinyl chloride varnish) using a gravure roll on a metal deposition layer was diluted with methyl ethyl ketone (MEK) to give a solid content of 25
- MEK methyl ethyl ketone
- a coating solution of% was formed to form a primer layer having a thickness of 0.4 ⁇ m to prepare a deposited film having a metal deposition layer thickness of 52 nm, a printed layer thickness of 2.0 ⁇ m, a protective layer thickness of 0.4 ⁇ m, and a bending prevention layer thickness of 1.0 ⁇ m.
- the obtained deposition film was evaluated by the above-described method, and the results are shown in Tables 5 and 6 below.
- Example 33 To prepare a deposition film having the same structure as in Example 33, 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) Yellow pigment (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 (R-100, KPIA was printed at 3 degrees using a gravure roll from three crude liquids, each containing 10 wt% of each colorant selected from 100 wt%, to form a printed layer (print layer thickness 1.0 mu m).
- MEK methyl ethyl ketone
- a deposition film having a metal deposition layer thickness of 52 nm, a printed layer thickness of 1.0 ⁇ m, a protective layer thickness of 0.4 ⁇ m, and a warpage preventing layer thickness of 1.0 ⁇ m was prepared in the same manner except that.
- the obtained deposition film was evaluated by the above-described method, and the results are shown in Tables 5 and 6 below.
- Example 33 To prepare a deposition film having the same structure as in Example 33, 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) Yellow pigment (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 (R-100, KPIA was printed at 8 degrees using a gravure roll from 8 kinds of crude liquids including 10 wt% of each colorant selected in the present invention and the total amount was adjusted to 100 wt% to form a printed layer (print layer thickness 8.0 ⁇ ).
- MEK methyl ethyl ketone
- a deposition film having a metal deposition layer thickness of 52 nm, a printed layer thickness of 8.0 ⁇ m, a protective layer thickness of 0.4 ⁇ m, and a bending prevention layer thickness of 1.0 ⁇ m was prepared in the same manner except that.
- the obtained deposition film was evaluated by the above-described method, and the results are shown in Tables 5 and 6 below.
- methyl ethyl ketone (MEK) of the copolymer polyester resin (copolyester having a number average molecular weight of 5000 made by mixing two or more polyhydric alcohol and polybasic acid) on the printed layer
- a metal deposition layer thickness of 52 nm, a printing layer thickness of 2.0 mu m, and a protective layer thickness of 0.8 were prepared in the same manner except that a protective layer was formed (gravure layer thickness 0.8 mu m) using a gravure roll from a crude liquid having a solid content concentration of 25% by diluting to.
- a vapor deposition film having a thickness of 1.0 ⁇ m and a warpage prevention layer was prepared.
- the obtained deposition film was evaluated by the above-described method, and the results are shown in Tables 5 and 6 below.
- a deposition film having the same structure as in Example 33 but diluting the polyolefin copolymer varnish in methyl ethyl ketone (MEK) on the printed layer to form a protective layer using a gravure roll from a crude liquid of 25% by weight solid content concentration (protection A deposited film having a metal deposition layer thickness of 52 nm, a printed layer thickness of 2.0 ⁇ m, a protective layer thickness of 0.4 ⁇ m, and a bending prevention layer thickness of 1.0 ⁇ m was prepared in the same manner except that the layer thickness was 0.4 ⁇ m).
- MEK methyl ethyl ketone
- the obtained deposition film was evaluated by the above-described method, and the results are shown in Tables 5 and 6 below.
- Example 33 in the roller group conveyed in the mechanical direction with respect to the unstretched film obtained in the same manner as in Example 33, stretched 1.6 times in the longitudinal direction of the film at a temperature of 70 °C through a preheating section of the temperature 65 °C After cooling through a cooling roll at room temperature, the film was continuously stretched in the width direction under the same conditions as in Example 33 in a tenter, so that the shrinkage in the film length direction MD was 37.3%, and in the width direction TD.
- the metal deposition layer had a thickness of 52 nm, a printed layer thickness of 2.0 ⁇ m, a protective layer thickness of 0.4 ⁇ m, and a bending prevention layer thickness of 1.0 ⁇ m.
- a deposited film was prepared.
- the obtained deposition film was evaluated by the above-described method, and the results are shown in Tables 5 and 6 below.
- Example 45 In the roller group conveyed in the mechanical direction in Example 45 was stretched 2.5 times in the longitudinal direction of the film at a temperature of 75 °C through a preheating section of the temperature 75 °C, then cooled through a cooling roll of room temperature, and then continuously The tenter was stretched in the width direction under the same conditions as in Example 33, so that the shrinkage in the film length direction (MD) was 45.8%, and the shrinkage in the width direction (TD) was 70.5%.
- a deposition film having a metal deposition layer thickness of 52 nm, a printed layer thickness of 2.0 ⁇ m, a protective layer thickness of 0.4 ⁇ m, and a warpage preventing layer thickness of 1.0 ⁇ m was prepared in the same manner except that was prepared.
- the obtained deposition film was evaluated by the above-described method, and the results are shown in Tables 5 and 6 below.
- Example 33 Prepare a deposited film having the same structure as in Example 33, except for not forming a protective layer in the same manner to prepare a deposited film having a metal deposition layer thickness 52nm, printed layer thickness 2.0 ⁇ m, bending prevention layer thickness 1.0 ⁇ m It was.
- the obtained deposition film was evaluated by the above-described method, and the results are shown in Tables 5 and 6 below.
- a deposition film having a metal deposition layer thickness of 10 nm, a printed layer thickness of 2.0 ⁇ m, a protective layer thickness of 0.4 ⁇ m, and a bending prevention layer thickness of 1.0 ⁇ m was prepared under the same conditions as in Example 33. .
- the obtained deposition film was evaluated by the above-described method, and the results are shown in Tables 5 and 6 below.
- 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 ⁇ m 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 ⁇ ⁇ .
- a metal deposition layer was formed under the same conditions as in Example 33 to have a metal deposition layer 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.
- a film was prepared. The composite film was evaluated in the above manner, and the results are shown in Tables 5 and 6 below.
- a deposition film having the same structure as in Example 33 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) Yellow pigment (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 (R-100, Printed by printing at 6 degrees using a gravure roll from six crude liquids, the total amount of the total amount is adjusted to 100% by weight, including 10% by weight of each colorant selected from KPIA) (print layer thickness 12.0 ⁇ m) A deposition film having a metal deposition layer thickness of 52 nm, a printed layer thickness of 12.0 ⁇ m, a protective layer thickness of 0.4 ⁇ m, and a warpage prevention layer thickness of 1.0 ⁇ m was prepared in the same manner.
- MEK methyl ethyl ketone
- the obtained deposition film was evaluated by the above-described method, and the results are shown in Tables 5 and 6 below.
- a deposition film having the same structure as in Example 33 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) Yellow pigment (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 (R-100, KPIA) was printed with two degrees using a gravure roll from two crude liquids containing 10 wt% of each colorant selected in the present invention and the total amount was adjusted to 100 wt% to form a printed layer (print layer thickness 0.2 ⁇ ).
- the obtained deposition film was evaluated by the above-described method, and the results are shown in Tables 5 and 6 below.
- a deposition film having the same structure as in Example 33 was prepared, except that PET film 50 ⁇ m (H34, Kolon Industries Co., Ltd.) was applied as a base film, and the metal deposition layer thickness was 52 nm and the print layer thickness was 2.0 ⁇ m. , A protective film thickness 0.4 ⁇ m, a bending film having a thickness of 1.0 ⁇ m anti-warp layer was prepared.
- the obtained deposition film was evaluated by the above-described method, and the results are shown in Tables 5 and 6 below.
- Example 33 Prepare a deposited film having the same structure as in Example 33, except for not forming a warpage prevention layer to prepare a deposited film having a metal deposition layer thickness 52nm, printed layer thickness 2.0 ⁇ m, protective layer thickness 0.4 ⁇ m It was.
- the obtained deposition film was evaluated by the above-described method, and the results are shown in Tables 5 and 6 below.
- the label 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.
- the film curled in the direction of the maximum shrinkage of the film, which causes the pressure or flow rate to increase when the label floats on the top of the bottle, but in the case of Examples 45 and 46, the label is separated from 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.
- the thickness of the metal deposition layer is thin, as in Example 48, the total light transmittance of the heat shrinkable deposition film is high, so that the color of the bottle is projected when applied to colored bottles in the printing label, which is the final product, and the printing effect is reduced. As a result, it may be confirmed that the aesthetics of the advertisement may be reduced. Therefore, when considering the visibility it can be seen that the thickness control of the metal deposition layer is required.
- the shrinkage start temperature is high and the maximum shrinkage stress is low, as in Example 49, the printing label is sometimes adhered to the bottle when the printing label is removed from the bottle, and thus the printing label is removed several times. Since economic efficiency may be reduced, it may be confirmed that the shrinkage start temperature, the maximum shrinkage stress, and the like are more preferably controlled.
- Example 47 without the protective layer, the adhesiveness and peeling properties are not a problem, but the printing film peeled off due to the phenomenon that 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 the present invention, 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.
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Abstract
Description
Claims (26)
- 열수축성 폴리에스테르계 필름 기재;기재 상의, 금속증착층;금속증착층 상의 인쇄층; 및기재의 다른 일면 상의, 휨방지층을 포함하는폴리에스테르계 증착필름.
- 제 1항에 있어서,상기 인쇄층 상의 보호층을 포함하는 폴리에스테르계 증착필름.
- 제 2 항에 있어서,상기 금속증착층과 인쇄층 사이에 프라이머층을 포함하는 폴리에스테르계 증착필름.
- 제 1 항에 있어서,상세한 설명에서 정의된 휨특성치가 5.0mm이하인 폴리에스테르계 증착필름.
- 제 1항 내지 제 4항에서 선택되는 어느 한 항에 있어서,상기 기재층과 휨방지층의 사이에 후면 금속증착층을 포함하는 폴리에스테르계 증착필름.
- 제 1 항에 있어서,불투명도(Opacity; %)가 80% 이상인 폴리에스테르계 증착필름.
- 제 6 항에 있어서,불투명도가 90 내지 100%인 폴리에스테르계 증착필름.
- 제 4 항에 있어서,휨특성치가 2.0mm 이하인 폴리에스테르계 증착필름.
- 제 5 항에 있어서,금속증착층은 광학밀도 1.0 내지 3.0이고, 후면 금속증착층은 광학밀도 0.2 내지 0.8인 폴리에스테르계 증착필름.
- 제 1 항에 있어서,휨방지층은 열수축성 폴리에스테르계 필름 기재의 표면을 물리적 또는 화학적으로 처리하여 형성된 요철층 또는 백색 안료 코팅층인 것인 폴리에스테르계 증착필름.
- 제 10 항에 있어서,휨방지층은 폴리아마이드 수지, 아크릴 수지, 폴리우레탄, PVC계 수지, 케톤 수지, 염화고무, 비닐아세테이트 수지 및 에틸렌-비닐아세테이트 코폴리머 중에서 선택되는 1종 이상의 수지; 방향족 탄화수소계, 케톤계, 아세테이트계 및 염소계 용매 중에서 선택되는 1종 이상의 용매; 및 백색안료와 침전방지제, 증점제, 색분리방지제 및 안료분산제 중에서 선택되는 1종 이상의 첨가제를 포함하는 조성으로부터 형성된 층인 열수축성 폴리에스테르계 증착 필름.
- 제 1 항에 있어서,보호층은 공중합 폴리에스테르, 아크릴공중합체, 스티렌공중합체, 메타크릴레이트 공중합체, 폴리스티렌, 비닐아세테이트, 폴리아미드, 알킬아크릴레이트, 우레아포름알데히드, 에폭시화 대두유, 에틸렌-비닐 아세테이트 공중합체, 우지계 올레아미드, 폴리에틸렌 글리콜 디스테아레이트, 폴리비닐리덴, 폴리올레핀계 공중합물, 우레탄 및 비닐계 수지 중에서 선택되는 단독 또는 이들의 혼합물로 이루어진 수지층인 폴리에스테르계 증착필름.
- 제 1 항에 있어서,열수축성 폴리에스테르계 필름 기재는 부틸렌테레프탈레이트 반복단위를 포함하는 폴리에스테르계 수지를 포함하는 것인 폴리에스테르계 증착필름.
- 제 13 항에 있어서,열수축성 폴리에스테르 필름 기재는 테레프탈산, 옥살산, 말론산, 숙신산, 아디프산, 수베르산, 아젤라산, 세바스산, 프탈산, 이소프탈산, 나프탈렌디카르복실산, 디페닐 에테르 디카르복실산과 같은 디카르복실산을 1개 이상 포함하는 디카르복실산 성분과, 에틸렌 글리콜, 네오펜틸 글리콜, 프로필렌 글리콜, 트리메틸렌 글리콜, 테트라메틸렌 글리콜, 헥사메틸렌 글리콜, 디에틸렌 글리콜, 폴리알킬렌 글리콜, 1,4-시클로헥산 디메탄올과 같은 디올을 1개 이상 포함하는 디올 성분으로부터 수득되는 코폴리에스테르 중 선택된 적어도 1종의 코폴리에스테르를 포함하는 것인 폴리에스테르계 증착필름.
- 제 14 항에 있어서,코폴리에스테르는 디카르복실산 단위체 중 테레프탈산 단위체가 80몰% 이상 포함되고, 디올 단위체 중 에틸렌 글리콜 이외의 단위체가 12 내지 24 몰% 포함되는 것인 폴리에스테르계 증착필름.
- 제 1 항에 있어서,열수축성 폴리에스테르 필름 기재는 일축배향 열수축성 폴리에스테르 필름 기재 또는 양방향 열수축성 폴리에스테르 필름 기재인 것인 폴리에스테르계 증착필름.
- 제 1 항에 있어서,90℃의 온수 중에서 10초간에 걸쳐서 처리한 경우에 있어서 최대수축방향에 대한 수축율이 40 내지 80%인 폴리에스테르계 증착필름.
- 제 1 항에 있어서,최대수축방향의 수축개시온도가 68 내지 94℃, 최대수축발현온도가 80 내지 110℃이고, 최대수축응력이 0.60 내지 1.80kg/㎟인 폴리에스테르계 증착필름.
- 제 1 항에 있어서,전광선투과율이 0.1 내지 5.0%인 폴리에스테르계 증착필름.
- 제 1 항에 있어서,열수축성 폴리에스테르계 필름 기재는 헤이즈가 0.3 내지 10.0%인 폴리에스테르계 증착필름.
- 제 1 항 내지 제 4 항에서 선택되는 어느 한 항의 폴리에스테르계 증착필름을 포함하는 라벨이 부착된 병.
- 제 21 항에 있어서,열수 중에 침지시키는 방법으로 폴리에스테르계 증착필름이 제거되는 라벨이 부착된 병.
- 라벨이 부착될 위치에 접착제를 도포하는 공정; 및접착제가 도포된 면에 제 1 항 내지 제 4 항에서 선택되는 어느 한 항에 기재된 폴리에스테르계 증착필름을 부착시키는 공정을 포함하는 라벨이 부착된 병의 제조방법.
- 제 5 항의 폴리에스테르계 증착필름을 포함하는 라벨이 부착된 병.
- 제 24 항에 있어서,열수 중에 침지시키는 방법으로 폴리에스테르계 증착필름이 제거되는 라벨이 부착된 병.
- 라벨이 부착될 위치에 접착제를 도포하는 공정; 및접착제가 도포된 면에 제 5 항에 기재된 폴리에스테르계 증착필름을 부착시키는 공정을 포함하는 라벨이 부착된 병의 제조방법.
Priority Applications (4)
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CN201280024003.8A CN103534087B (zh) | 2011-03-18 | 2012-03-19 | 聚酯类金属化薄膜 |
EP12760541.8A EP2687369B1 (en) | 2011-03-18 | 2012-03-19 | Polyester-based deposited film |
JP2014500987A JP5872020B2 (ja) | 2011-03-18 | 2012-03-19 | ポリエステル系蒸着フィルム |
US14/005,744 US9418577B2 (en) | 2011-03-18 | 2012-03-19 | Polyester-based metalizing film |
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KR10-2011-0024487 | 2011-03-18 | ||
KR10-2011-0024455 | 2011-03-18 | ||
KR1020110024510A KR101475841B1 (ko) | 2011-03-18 | 2011-03-18 | 폴리에스테르계 증착필름 |
KR1020110024455A KR101475837B1 (ko) | 2011-03-18 | 2011-03-18 | 폴리에스테르계 증착필름 |
KR1020110024487A KR20120106400A (ko) | 2011-03-18 | 2011-03-18 | 폴리에스테르계 증착필름 |
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EP (1) | EP2687369B1 (ko) |
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- 2012-03-19 JP JP2014500987A patent/JP5872020B2/ja active Active
- 2012-03-19 EP EP12760541.8A patent/EP2687369B1/en not_active Not-in-force
- 2012-03-19 WO PCT/KR2012/001940 patent/WO2012128517A2/ko active Application Filing
- 2012-03-19 US US14/005,744 patent/US9418577B2/en active Active
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Also Published As
Publication number | Publication date |
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CN103534087A (zh) | 2014-01-22 |
US20140065333A1 (en) | 2014-03-06 |
EP2687369B1 (en) | 2018-03-07 |
JP2014514973A (ja) | 2014-06-26 |
JP5872020B2 (ja) | 2016-03-01 |
WO2012128517A3 (ko) | 2012-12-27 |
CN103534087B (zh) | 2016-02-03 |
EP2687369A4 (en) | 2014-11-05 |
EP2687369A2 (en) | 2014-01-22 |
US9418577B2 (en) | 2016-08-16 |
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