WO2018124830A1 - Heat shrinkable polyester-based film, manufacturing method therefor, and label comprising same - Google Patents

Heat shrinkable polyester-based film, manufacturing method therefor, and label comprising same Download PDF

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Publication number
WO2018124830A1
WO2018124830A1 PCT/KR2017/015772 KR2017015772W WO2018124830A1 WO 2018124830 A1 WO2018124830 A1 WO 2018124830A1 KR 2017015772 W KR2017015772 W KR 2017015772W WO 2018124830 A1 WO2018124830 A1 WO 2018124830A1
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WO
WIPO (PCT)
Prior art keywords
acid
heat
shrinkable polyester
polyester film
glycol
Prior art date
Application number
PCT/KR2017/015772
Other languages
French (fr)
Korean (ko)
Inventor
김동진
김윤조
백상현
한재일
Original Assignee
코오롱인더스트리 주식회사
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Publication of WO2018124830A1 publication Critical patent/WO2018124830A1/en

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C55/00—Shaping by stretching, e.g. drawing through a die; Apparatus therefor
    • B29C55/005—Shaping by stretching, e.g. drawing through a die; Apparatus therefor characterised by the choice of materials
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C55/00—Shaping by stretching, e.g. drawing through a die; Apparatus therefor
    • B29C55/02—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets
    • B29C55/04—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets uniaxial, e.g. oblique
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B31—MAKING ARTICLES OF PAPER, CARDBOARD OR MATERIAL WORKED IN A MANNER ANALOGOUS TO PAPER; WORKING PAPER, CARDBOARD OR MATERIAL WORKED IN A MANNER ANALOGOUS TO PAPER
    • B31D—MAKING ARTICLES OF PAPER, CARDBOARD OR MATERIAL WORKED IN A MANNER ANALOGOUS TO PAPER, NOT PROVIDED FOR IN SUBCLASSES B31B OR B31C
    • B31D1/00—Multiple-step processes for making flat articles ; Making flat articles
    • B31D1/02—Multiple-step processes for making flat articles ; Making flat articles the articles being labels or tags
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B32B27/308—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising acrylic (co)polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/043—Improving the adhesiveness of the coatings per se, e.g. forming primers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/046—Forming abrasion-resistant coatings; Forming surface-hardening coatings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/08—Heat treatment
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
    • C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2433/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
    • C08J2433/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters

Definitions

  • the present invention relates to a uniaxially oriented heat shrinkable polyester film having a heat shrink characteristic, a method for preparing the same, and a label including the same.
  • PET bottles and glass bottles have been collected and used again.
  • the label on which the product name, ingredient name and other patterns are printed and attached should be removed separately.
  • the heat shrinkable film is used as a whole coating, shrink wrap and shrink label of plastic or glass bottles and general packaging containers, such as PVC, PS, PET-based heat shrink film is used.
  • the heat shrinkable film of PS material has excellent shrinkage process stability but has a weak chemical resistance, which makes it inconvenient to use a special ink, and has a high storage temperature at room temperature.
  • Heat-shrink films made of PVC are classified as environmentally regulated such as generation of hydrogen chloride gas when incinerated, and it is inconvenient to separate the label and the container because they are heterogeneous materials when the PET container is recycled.
  • polyester shrink films that have no environmental problems and excellent chemical resistance but do not require a separate separation process when recycled.
  • polyester heat-shrink films there is a problem of using an explosive limited adhesive solvent. have.
  • Japanese Patent No. 2771598 discloses a polyester resin prepared by containing a dicarboxylic acid component and isophthalic acid, including terephthalic acid, but has a problem of using a limited adhesive solvent, and therefore, There is an urgent need for research.
  • the main object of the present invention is to provide a heat-shrinkable polyester film having excellent adhesion to solvents (especially THF) that are easy to handle.
  • the present invention also provides a heat shrinkable polyester film having excellent post-processing processability and remarkably low finished product defect rate through ILC treatment of the surface.
  • the present invention also provides a sticker label and seaming label made of the heat-shrinkable polyester film.
  • the present invention is a preferred embodiment, the glass transition temperature of 70 to 80 °C, the intrinsic viscosity of 0.60 to 0.75dl / g and the molecular weight distribution of the base film comprising a copolyester resin of 2.0 to 4.0 and the base film It comprises a primer coating layer formed on one side or both sides, the copolyester resin is copolymerized including a dicarboxylic acid monomer, isophthalic acid and diol monomer, the shrinkage in the main shrinkage direction is measured in hot water at 90 °C 40 It is to provide a heat-shrinkable polyester film having a% or more and an adhesive force of tetrahydrofuran (THF) is 0.65 to 1 Kgf.
  • THF tetrahydrofuran
  • the copolyester resin is copolymerized by including a dicarboxylic acid monomer and isophthalic acid in a molar ratio of 85 to 95: 5 to 15.
  • the dicarboxylic acid monomers are terephthalic acid, oxalic acid, malonic acid, succinic acid, adipic acid, suberic acid, azelaic acid, sebacic acid, phthalic acid, naphthalenedicarboxylic acid, diphenyl ether dicarboxylic acid and the group consisting thereof It is at least one selected from.
  • the diol monomer is selected from the group consisting of ethylene glycol, neopentyl glycol, propylene glycol, trimethylene glycol, tetramethylene glycol, hexamethylene glycol, diethylene glycol, polyalkylene glycol, 1,4-cyclohexane dimethanol It is two kinds or more.
  • the primer coating layer has a thickness of 5 to 50 nm, the friction coefficient is 0.20 or less.
  • the primer coating layer includes an acrylic binder and a slip agent.
  • the primer coating layer is based on 100 parts by weight of the acrylic binder, it includes 150 to 250 parts by weight of the slip agent.
  • Copolyester resin in the step S1 is a dicarboxylic acid monomer, isophthalic acid and diol monomer is prepared by the polycondensation reaction including a molar ratio of 85 to 95: 5 to 15: 100.
  • the dicarboxylic acid monomers are terephthalic acid, oxalic acid, malonic acid, succinic acid, adipic acid, suberic acid, azelaic acid, sebacic acid, phthalic acid, naphthalenedicarboxylic acid, diphenyl ether dicarboxylic acid and the group consisting thereof It is at least one selected from.
  • the diol monomer is selected from the group consisting of ethylene glycol, neopentyl glycol, propylene glycol, trimethylene glycol, tetramethylene glycol, hexamethylene glycol, diethylene glycol, polyalkylene glycol, 1,4-cyclohexane dimethanol It is two kinds or more.
  • the primer coating layer is a thickness of 5 to 50 nm.
  • the primer coating layer composition includes an acrylic binder and a slip agent.
  • the primer coating layer composition is based on 100 parts by weight of the acrylic binder, it will contain 150 to 250 parts by weight of the slip agent.
  • a label comprising a polyester-based film produced by the above-described manufacturing method.
  • the present invention it is possible to provide a polyester heat-shrinkable film that can use a solvent which is easy to handle without environmental problems, and a sticker label and seaming label having excellent post-processing processability and low defect rate in the final product. .
  • the glass transition temperature is 70 to 80 °C
  • the intrinsic viscosity is 0.60 to 0.75dl / g
  • the molecular weight distribution of the base film comprising a copolyester resin of 2.0 to 4.0 and one side of the base film or It includes a primer coating layer formed on both sides
  • the copolyester resin is copolymerized including a dicarboxylic acid monomer, isophthalic acid and a diol monomer
  • the shrinkage in the main shrinkage direction measured at 90 °C hot water 40% or more It is to provide a heat-shrinkable polyester film having an adhesion force of tetrahydrofuran (THF) is 0.65 to 1 Kgf.
  • THF tetrahydrofuran
  • the said copolyester resin is copolymerized including dicarboxylic acid monomer and isophthalic acid in the molar ratio of 85-95: 5-15.
  • the molar ratio of the dicarboxylic acid monomer to isophthalic acid is within the above range, the shrinkage behavior can be easily expressed by suppressing the crystallization phenomenon due to stretching, and in particular, the molar ratio of isophthalic acid is within the above range. If present, the structure of the final film may be more bulky, thereby facilitating swelling of the solvent to improve adhesion to the solvent.
  • Copolyester resin copolymerized in the molar ratio comprises a unit structure derived from isophthalic acid in a content of 5.0 to 15.0 mol%, preferably 6.0 to 12.5 mol%, 12 mol%, 8 mol%, 3 mol% It may be included in such a content.
  • the content of the unit structure derived from isophthalic acid is less than 5.0 mol%, it may be difficult to realize sufficient adhesive strength with a solvent, and when it exceeds 15.0 mol%, chips between chips in a precrystallization process using a vacuum dryer or hot water Fusion may occur.
  • polyester is a crystalline polymer, and surface crystallization occurs in the precrystallization step, so that there is no phenomenon of sticking between chips (raw material).
  • the copolyester it becomes an amorphous polymer, and if the proper conditions are not given in the precrystallization step, fusion between chips occurs.
  • This is related to the amount of copolymer contained in the raw material, and if a certain level of copolymer is included, the pre-crystallization can be carried out by using a vacuum dryer, and if the amount of the copolymer exceeds a certain level, a hydrothermal precrystallization system using hot water is used. Precrystallization can proceed. However, if the amount of the copolymer is too high, even if given the optimum conditions or using a separate process, the surface crystallization does not occur in the pre-crystallization step, the drying process itself to remove the moisture in the chip is impossible.
  • the heat-shrinkable polyester-based film including the copolyester resin described above may satisfy 0.65 to 1 Kgf, preferably 0.68 to 0.87 Kgf, more preferably 0.82 to 0.87 Kgf, with tetrahydrofran (THF). Can be.
  • Shrink film is made in the form of a sleeve (Sleeve) through a process called "seaming (Seaming) after printing on the fabric.
  • Sleeve a sleeve
  • Seaming a process called "seaming” after printing on the fabric.
  • After putting the sleeve on the bottle (Bottle) through the shrinking tunnel is contracted by the shrinkage rate of the fabric itself is fixed to the bottle.
  • the adhesive force with THF as the solvent is within the above range, it has an effect of preventing the occurrence of defects, and when out of the above range, not only the defect occurs but also the application to the product becomes impossible.
  • the dicarboxylic acid monomers are terephthalic acid, oxalic acid, malonic acid, succinic acid, adipic acid, suberic acid, azelaic acid, sebacic acid, phthalic acid, naphthalenedicarboxylic acid, diphenyl ether dicarboxylic acid and the group consisting thereof One or more selected from may be mentioned.
  • the diol monomer is selected from the group consisting of ethylene glycol, neopentyl glycol, propylene glycol, trimethylene glycol, tetramethylene glycol, hexamethylene glycol, diethylene glycol, polyalkylene glycol, 1,4-cyclohexane dimethanol 2 or more types of things are mentioned.
  • the primer coating layer preferably includes an acrylic binder and a slip agent.
  • acrylic binder resin methyl acrylate, methyl acrylate, isopropyl acrylate, n-propyl acrylate, n-butyl acrylate (n -butyl acrylate), isobornyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, isopropyl methacrylate Isopropyl methacrylate, n-propyl methacrylate, tert-butyl methacrylate, n-butyl methacrylate, n-butyl methacrylate, isobutyl methacrylate (isobutyl methacrylate), cyclohexyl methacrylate, isobornyl methacrylate, diethylene glycol monomethyl ether ether methacrylate), 2-ethylhexyl methacrylate, benzyl methacrylate, 1-naphthylmethyl methacrylate
  • the slip agent is any one selected from Stearamidopropyldimethyl-2-hydroxyethyl ammonium nitrate, Steramidopropyldimethyl-2-hydroxyethyl ammonium dihydrogen phosphate, N, N-bis (2-hydroxyethyl) -N- (3-dodecyloxy-2-hydroxypropyl) methyl ammonium methosulfate It may include one or more.
  • the slip property can be imparted, and more preferably, the friction coefficient may have a physical property of 0.2 or less. By providing such slip property, it is possible to reduce the occurrence of scratches generated during the post-processing process.
  • the blocking defect may be prevented by including the acrylic binder and the slip agent described above.
  • the primer coating layer is preferably based on 100 parts by weight of the acrylic binder, 150 to 250 parts by weight, preferably 160 to 210 parts by weight.
  • Including the acrylic binder resin and the slip agent can improve the blocking resistance (blocking), it can be given slip properties. By providing such slip property, it is possible to reduce scratches that may occur during post-processing and to reduce process defects.
  • the blocking resistance is improved by applying an acrylic binder having excellent heat resistance and water resistance.
  • the transfer is not slippery slip, and if it exceeds 250 parts by weight there is a problem that blocking occurs.
  • the primer coating layer may be a thickness of 5 to 50nm, preferably 10 to 20nm.
  • the coating layer is uniformly formed on the surface of the final film, thereby achieving a uniform slip and having a stable anti-blocking property.
  • the coating uniformity does not come out when the thickness of the primer coating layer is less than 5nm, blocking resistance may be lowered when it exceeds 50nm.
  • the primer coating layer of the present invention comprising the above-described configuration is a friction coefficient of 0.20 or less.
  • the above-mentioned copolyester resin has a glass transition temperature of 70-80 degreeC, intrinsic viscosity 0.60-0.75 dl / g, and molecular weight distribution 2.0-4.0.
  • the thermal stability is excellent, so that natural shrinkage does not occur during long-term storage.
  • the slip between the polymer chains is suppressed to have an advantage of maintaining the shrinkage in the main shrinkage direction given during film production for a long time.
  • the shrinkage in the main shrinkage direction measured at 90 ° C. in hot water is 40% or more, preferably 55% or more, and more preferably 70% or more. If the shrinkage is in the above range has the advantage that can be applied to a variety of containers currently in use.
  • the above-mentioned heat-shrinkable polyester film can be prepared a method according to the following.
  • Another embodiment of the present invention comprises mixing a dicarboxylic acid monomer and a diol monomer, and then adding isophthalic acid to polycondensation to prepare a copolyester resin (S1); Melting the prepared copolyester resin at 255 to 280 °C to prepare an unstretched sheet (S2); Coating a primer coating layer composition on one or both surfaces of the unstretched sheet prepared in step S2 to form a primer coating layer (S3); After applying heat to the unstretched sheet on which the primer coating layer was formed, stretching in one direction at a stretch ratio of 4 to 6 times in the main contraction direction at a stretching speed of 6 to 10 m / sec (S4) and the Film stretched in one direction at 70-80 ° C. It is to provide a method for producing a heat-shrinkable polyester film comprising the step (S5) of the heat treatment.
  • the copolyester resin is prepared by copolymerizing dicarboxylic acid monomer, isophthalic acid and diol monomer in a molar ratio of dicarboxylic acid monomer to isophthalic acid to diol monomer in a molar ratio of 85 to 95: 5 to 15: 100. desirable.
  • the molar ratio of the dicarboxylic acid monomer to the isophthalic acid to the diol monomer is within the above range has the advantage that the shrinkage behavior can be easily expressed by suppressing the crystallization phenomenon by stretching, in particular the molar ratio of isophthalic acid is When in the range can have the advantage of improving the adhesion to the solvent to facilitate the swelling (swelling) of the solvent by making the structure of the final film more (bulky).
  • the dicarboxylic acid monomers are terephthalic acid, oxalic acid, malonic acid, succinic acid, adipic acid, suberic acid, azelaic acid, sebacic acid, phthalic acid, naphthalenedicarboxylic acid, diphenyl ether dicarboxylic acid and the group consisting thereof One or more selected from may be mentioned.
  • the diol monomer is selected from the group consisting of ethylene glycol, neopentyl glycol, propylene glycol, trimethylene glycol, tetramethylene glycol, hexamethylene glycol, diethylene glycol, polyalkylene glycol, 1,4-cyclohexane dimethanol 2 or more types of things are mentioned.
  • the polycondensation reaction may be carried out by a conventional method well known in the present invention, which is well known and a detailed description thereof will be omitted.
  • the prepared copolyester resin is melted at 255 to 280 ° C to prepare an unstretched sheet.
  • the melting temperature is less than 255 °C there is a possibility that incomplete melting may occur process trouble, if it exceeds 280 °C thermal decomposition lowers the inherent viscosity of the final film and the molecular weight distribution is widened to mechanical properties Deterioration, deterioration of long-term physical properties, etc. occur, and the die shear pressure is lowered, making it difficult to control thickness during film production.
  • a sheet manufacturing method commonly used in the field of the present invention can be arbitrarily selected and used, for example, a sheet manufacturing method using a T die, blown production using an annular die The method etc. are mentioned.
  • the primer coating layer is coated on one or both surfaces of the prepared unstretched sheet to form a primer coating layer (S2).
  • the primer coating layer composition includes an acrylic binder and a slip agent.
  • the acrylic binder resin is the same as described in the above-described primer coating layer.
  • the slip agent is the same as described in the primer coating layer described above.
  • the primer coating layer composition is based on 100 parts by weight of the acrylic binder, 150 to 250 parts by weight, preferably 160 to 210 parts by weight.
  • Including the acrylic binder resin and the slip agent can improve the blocking resistance, it can be given a slip resistance. By providing such slip property, it is possible to reduce scratches that may occur during post-processing and to reduce process defects.
  • the blocking resistance is improved by applying an acrylic binder having excellent heat resistance and water resistance.
  • the transfer is not slippery slip, and if it exceeds 250 parts by weight may cause blocking.
  • the primer coating layer composition according to the present invention may further include a wetting agent in addition to the acrylic binder and the slip agent.
  • the wetting agent may be used to improve coating properties, such as silicone-based wetting agent, modified silicone-based wetting agent, and the like. Specifically, for example, Dow Corning Co., Ltd., QE-5212, ENDOBIC Co., Ltd. Can be used but is not limited thereto.
  • the wetting agent may be included in an amount of 20 to 100 parts by weight, preferably 20 to 60 parts by weight based on 100 parts by weight of the acrylic binder.
  • the content of the wetting agent is less than 20 parts by weight, the coating appearance is poor due to lack of wetting (wetting), and when it exceeds 100 parts by weight, coating stains may occur due to impurities such as a wetting agent remaining after the drying process.
  • the acrylic binder resin and the slip (Slip) agent can improve the blocking resistance, it can be given a slip resistance. By providing such slip properties, it is possible to reduce scratches that may occur during post processing and to reduce process defects.
  • the blocking resistance is improved by applying an acrylic binder having excellent heat resistance and water resistance.
  • the primer coating layer is preferably formed to a thickness of 5 to 50nm, preferably 10 to 20nm. When the thickness of the primer coating layer is less than 5nm, coating uniformity does not come out, and when it exceeds 50nm, blocking resistance may be lowered.
  • the above-described primer coating layer is a friction coefficient of 0.20 or less.
  • a process of forming a primer coating layer by coating the primer coating layer composition it can be used to arbitrarily select a method commonly used in the field to which the present invention belongs, for example, coating method using M-bar, gravure coating method Etc. can be mentioned.
  • the stretch ratio in the main shrinkage direction was 4 to 6 times at a stretching speed of 6 to 10 m / sec, and stretched in one direction to uniaxially oriented heat-shrinkable polyester film To prepare.
  • the unstretched sheet on which the primer coating layer is formed it is preferable to heat the unstretched sheet on which the primer coating layer is formed to a preheating temperature of 85 to 110 ° C and a stretching temperature of 70 to 90 ° C.
  • a preheating temperature 85 to 110 ° C
  • a stretching temperature 70 to 90 ° C.
  • the shrinkage rate of the final film at the heat treatment temperature is controlled by controlling the shrinkage rate of the final film at the heat treatment temperature, the shrinkage rate in the main water extraction direction is lowered physically, and the maximum shrinkage rate that can be physically realized can be obtained to apply to various containers. .
  • the film stretched in one direction is heat-treated at 70 to 80 ° C.
  • the resin When the heat treatment temperature is within the above range, the resin has a relatively low residual stress and structurally has a certain level of crystallization, thereby improving the resistance to changes in appearance over time, thereby eliminating the problem that the appearance of the film is inhibited even when stored for a long time.
  • a label comprising a polyester-based film produced by the above-described manufacturing method.
  • the label is preferably a sticker label and a seaming label.
  • TPA terephthalic acid
  • EG ethylene glycol
  • NPG neopentyl glycol
  • IPA isophthalic acid
  • the prepared copolyester resin was melted in an ETR heated to 260 ° C. and an unstretched sheet was prepared using a T die.
  • 200 parts by weight of a slip agent (Stearamidopropyldimethyl-2-hydroxyethyl ammonium nitrate) based on 100 parts by weight of an acrylic binder (PK-8012P, Nippon Carbibe) on one surface of the prepared unstretched sheet, a silicone-based wetting agent (polyester siloxane) as a wetting agent Copolymer QE-5212, Dow Coating Co.)
  • 50 parts by weight of the primer coating layer composition was coated using M-Bar to form a primer coating layer having a thickness of 20nm.
  • the unstretched sheet having the primer coating layer formed on one surface thereof was preheated to 95 ° C., the drawn temperature was heated to 83 ° C., stretched to 4.0 times the width direction at a stretch rate of 8 m / sec, and then heat treated at 75 ° C. to uniaxially.
  • An oriented heat shrinkable polyester based film was prepared.
  • the prepared copolyester resin has a glass transition temperature of 73 °C, intrinsic viscosity 0.70dl / g, DEG 1.8wt%, carboxyl terminal group 26.7 meq / kg, molecular weight distribution 3.0, IPA content 8 mol
  • a copolyester resin of% was prepared.
  • a heat-shrinkable polyester film was produced in the same manner as in Example 1 except that the preheating temperature was 87 ° C. and the stretching temperature was 85 ° C., and the stretching speed was 10 m / sec.
  • the prepared copolyester resin has a glass transition temperature of 71 °C, intrinsic viscosity 0.71dl / g, DEG 1.5wt%, carboxyl terminal group 25.8meq / kg, molecular weight distribution 3.3, IPA content 12mol
  • a copolyester resin of% was prepared.
  • TPA terephthalic acid
  • EG ethylene glycol
  • NPG neopentyl glycol
  • IPA isophthalic acid
  • the prepared copolyester resin has a glass transition temperature of 75 °C, intrinsic viscosity 0.71dl / g, DEG 1.41wt%, carboxyl terminal group 29.3meq / kg, molecular weight distribution 2.8, IPA content 5mol% Phosphorous copolyester resin was prepared.
  • a heat-shrinkable polyester film was prepared in the same manner as in Example 1 except that the stretched temperature was applied at 67 ° C. in the unstretched sheet.
  • the prepared copolyester resin has a glass transition temperature of 71 °C, intrinsic viscosity 0.70dl / g, DEG 1.42wt%, carboxyl terminal group 27.3 meq / kg, molecular weight distribution 3.1, IPA content 12 mol
  • a copolyester resin of% was prepared.
  • TPA terephthalic acid
  • EG ethylene glycol
  • NPG neopentyl glycol
  • the prepared copolyester resin has a glass transition temperature of 78 °C, intrinsic viscosity 0.70dl / g, DEG 1.33wt%, carboxyl terminal group 28.5meq / kg, molecular weight distribution 3.1, IPA content 0 mol% Phosphorous copolyester resin was prepared.
  • the prepared copolyester resin has a glass transition temperature of 77 °C, intrinsic viscosity 0.71dl / g, DEG 1.41wt%, carboxyl terminal group 29.1meq / kg, molecular weight distribution 2.9, IPA content 1.5mol% Phosphorous copolyester resin was prepared.
  • the prepared copolyester resin has a glass transition temperature of 67 °C, intrinsic viscosity 0.70dl / g, DEG 1.42wt%, carboxyl terminal group 27.6meq / kg, IPA content of 20 mol% Resin was prepared.
  • a heat-shrinkable polyester film was prepared in the same manner as in Example 1 except that the primer coating layer was not formed on the unstretched sheet.
  • the prepared copolyester resin has a glass transition temperature of 71 °C, intrinsic viscosity 0.69dl / g, DEG 1.5wt%, carboxyl terminal group 28.5meq / kg, molecular weight distribution 3.1, IPA content 12mol
  • a copolyester resin of% was prepared.
  • a heat-shrinkable polyester film was prepared in the same manner as in Example 1 except that the unstretched sheet was uniaxially stretched and the heat treatment process was not applied.
  • the prepared copolyester resin has a glass transition temperature of 72 °C, intrinsic viscosity 0.70dl / g, DEG 1.6wt%, carboxyl terminal group 26.9meq / kg, molecular weight distribution 2.9, IPA content 12mol
  • a copolyester resin of% was prepared.
  • a heat-shrinkable polyester film was prepared in the same manner as in Example 1 except that the unstretched sheet was uniaxially stretched and the heat treatment process temperature was applied at 85 ° C.
  • the prepared copolyester resin has a glass transition temperature of 71 °C, intrinsic viscosity 0.69dl / g, DEG 1.5wt%, carboxyl terminal group 26.3meq / kg, molecular weight distribution 3.0, IPA content 12mol
  • a copolyester resin of% was prepared.
  • TPA terephthalic acid
  • EG ethylene glycol
  • NPG neopentyl glycol
  • IPA isophthalic acid
  • DEG diethylene glycol
  • the prepared copolyester resin has a glass transition temperature of 61 °C, intrinsic viscosity 0.69dl / g, DEG 21wt%, carboxyl terminal group 27.6meq / kg, IPA content of 15 mol% Was prepared.
  • Two identical specimens were prepared as films prepared according to Examples and Comparative Examples, respectively. Select one of the prepared specimens and apply it to any one surface of the selected specimens with 0.5 cm thickness in the vertical direction of the main shrinkage direction using tetrahydrofran (THF) as an adhesive solvent (solvent), then one surface of the other specimen And the THF coated surfaces on the THF coated specimens were adhered to each other by pressing with a roller, and then the adhesive strength was evaluated using an Instron equipment after one day. At this time, one surface of the other surface and the THF-coated surface is a primer coating layer.
  • THF tetrahydrofran
  • the specimens were cut into width 15mm and length 100mm and Loaidng in the main shrinkage direction. Then, the head speed was evaluated by applying 300mm / min and Gap 30mm.
  • the shrinkage stress with temperature and the shrinkage stress with time at constant temperature were compared with Kanebo and Testlite instruments.
  • Label shooting machine used in the field of the present invention high-speed contraction labeling machine (SH-5100-S), Saehan Tech Co., Ltd. shooting the label using the film prepared in 100 bottles, the location of the label after shooting) Check and compare the number of seated in the predetermined position.
  • Heat-Gradient equipment (Heat Gradient Tester, TOYOSEIKI) was used to compare the appearances such as tearing or staining after treatment through sticky evaluation and heat resistance water resistance evaluation as follows.
  • the prepared film is wrapped in a roll state and placed in an Aging Room set at 40 ° C. for one week. It is a qualitative evaluation method to check the occurrence of wrinkles observed by naked eye after giving a constant tension by loosening 5m in the roll state after the corresponding period.
  • Intrinsic Viscosity (IV) ⁇ (0.0242 ⁇ Rel) +0.2634 ⁇ ⁇ F
  • a standard chip means a chip selected by a conventional method without the intention of selecting a specific chip when selecting one chip from a group of countless chips.
  • the measurement by the standard operation means that the experimenter measured and proceeded according to a conventional method without a specific intention to derive a predetermined result value.
  • the film was cut to a certain size and the heat flow was measured using a differential scanning calorimeter (TA Instruments, Q20) at room temperature rate of 20 °C per minute from room temperature to 280 °C. The temperature of the endothermic peak was confirmed in the heat flow, and the temperature of the peak was regarded as the glass transition temperature.
  • TA Instruments, Q20 differential scanning calorimeter
  • Example 3 the bulk structure of the final film was removed to partially relieve residual stresses present in the film, thereby improving the adhesion of THF and providing stability over time for long-term storage. Even if it was found that there is no problem in the post-process.
  • the shrinkage stress is lower than that of Examples 1 to 2 can be applied to a relatively soft PE bottle as well as a rigid container, its use can be wider.
  • the adhesive strength is slightly weaker than in Examples 1 to 3, and thus may be differently applied depending on the shape of the container.
  • Example 5 may be used in a shrinkage process using steam because the shrinkage rate measured in hot water at 70 °C high.
  • the heat-shrinkable polyester film prepared according to Comparative Examples 1 to 2 has a poor adhesive strength with THF, thus making it impossible to manufacture a label through the seaming process.
  • the adhesive film has excellent adhesive strength but low Tg of the final film. Stability deteriorates and wrinkles occur with natural shrinkage.
  • Comparative Example 4 it was found that the shooting processability is poor because the surface treatment is not performed through the surface coating is not applicable.
  • steam or hot air is used. When steam is used, the shrinkage rate of 70 ° C. is not important. However, in the case of using hot air, the appearance quality after shrinkage occurs depending on the shrinkage rate.
  • the present invention has a heat shrink property, and can be used for uniaxially oriented heat shrinkable polyester film, a method for preparing the same, and a label including the same.

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Abstract

The present invention relates to a heat shrinkable polyester-based film, a preparation method therefor, and a label comprising the same and, more specifically, can provide: a heat shrinkable polyester film capable of using a solvent which facilitates handling while not being environmentally problematic; and a sticker label and a seaming label, which have excellent post-processability and a low defect rate in final products.

Description

열수축성 폴리에스테르계 필름, 이의 제조방법 및 이를 포함하는 라벨Heat-shrinkable polyester film, method for producing same, and label comprising same
본 발명은 열수축 특성을 가지며, 일축 배향된 열수축성 폴리에스테르계 필름, 이의 제조방법 및 이를 포함하는 라벨에 관한 것이다.The present invention relates to a uniaxially oriented heat shrinkable polyester film having a heat shrink characteristic, a method for preparing the same, and a label including the same.
환경적인 요구 및 경제성 등을 고려하여 PET 병이나 유리병은 수거하여 다시 사용해오고 있다. 이와 같은 재활용시 PET 병이나 유리병 본체 이외에, 제품명, 성분명 및 기타 문양 등이 인쇄되어 부착된 라벨은 분리하여 제거되어야 한다. In consideration of environmental requirements and economic feasibility, PET bottles and glass bottles have been collected and used again. In such recycling, in addition to the PET or glass bottle body, the label on which the product name, ingredient name and other patterns are printed and attached should be removed separately.
지금까지 주로 사용되어온 종이 재질의 라벨인 경우 공업용수를 사용하여 제거한다. 구체적으로는 수거해온 PET 병이나 유리병을 가성소다를 함유하는 80℃ 정도의 공업용수에 담가 라벨을 떼어낸다. 이로 인해 공병을 재활용하는데 있어서 환경폐수가 발생되며, 이에 환경적 규제가 본격화되고 있다. 따라서 종이 라벨이 아닌 필름 재질의 라벨에 대한 요구가 증가하고 있다.In the case of paper labels which have been mainly used until now, remove them using industrial water. Specifically, the PET bottle or glass bottle collected is immersed in industrial water at about 80 ° C. containing caustic soda and the label is removed. As a result, environmental wastewater is generated in recycling empty bottles, and environmental regulations are in full swing. Therefore, there is an increasing demand for labels of film materials rather than paper labels.
한편 열수축성 필름은 플라스틱이나 유리병 등과 일반적인 포장 용기의 전체 피복, 수축 포장 및 수축 라벨 등으로 사용되고 있는데, 이러한 열수축성 필름으로는 PVC, PS, PET계 열수축 필름이 사용되고 있다. On the other hand, the heat shrinkable film is used as a whole coating, shrink wrap and shrink label of plastic or glass bottles and general packaging containers, such as PVC, PS, PET-based heat shrink film is used.
그러나 PS 재질의 열수축 필름은 수축 공정 안정성은 우수하나 내화학성이 약해 특수 잉크를 사용해야 하는 불편함이 있고, 상온 자연 수축율이 커 보관상 어려움이 있다. However, the heat shrinkable film of PS material has excellent shrinkage process stability but has a weak chemical resistance, which makes it inconvenient to use a special ink, and has a high storage temperature at room temperature.
PVC 재질의 열수축 필름은 소각 시 염화수소 가스 발생 등 환경적으로 규제 대상으로 분류되어 있으며, PET 용기의 재활용 시 이질 재료이기 때문에 라벨과 용기를 분리해야 하는 불편함이 있다. Heat-shrink films made of PVC are classified as environmentally regulated such as generation of hydrogen chloride gas when incinerated, and it is inconvenient to separate the label and the container because they are heterogeneous materials when the PET container is recycled.
이에 환경적으로 문제가 없고 내화학성이 우수하면서도 재활용 시 별도의 분리 공정이 필요없는 폴리에스테르 수축 필름의 수요가 증대되고 있으나, 폴리에스테르 열수축 필름의 경우 폭발성이 있는 한정적인 접착 용제를 사용해야 하는 문제가 있다. There is an increasing demand for polyester shrink films that have no environmental problems and excellent chemical resistance but do not require a separate separation process when recycled. However, in the case of polyester heat-shrink films, there is a problem of using an explosive limited adhesive solvent. have.
일본등록특허 제2781598호에서는 테레프탈산을 포함하는 디카르복실산 성분 및 이소프탈산을 포함하여 제조된 폴리에스테르 수지를 개시하고 있으나, 한정적인 접착 용제를 사용해야 하는 문제를 가지고 있어, 이러한 문제를 해결하기 위한 연구가 절실한 상황이다.Japanese Patent No. 2771598 discloses a polyester resin prepared by containing a dicarboxylic acid component and isophthalic acid, including terephthalic acid, but has a problem of using a limited adhesive solvent, and therefore, There is an urgent need for research.
본 발명의 주된 목적은 취급이 용이한 용제(특히, THF)와의 접착력이 우수한 열수축성 폴리에스테르 필름을 제공하는데 있다.The main object of the present invention is to provide a heat-shrinkable polyester film having excellent adhesion to solvents (especially THF) that are easy to handle.
본 발명은 또한, 표면의 ILC 처리를 통해 후가공 공정성이 우수하고 완제품 불량률이 현저히 낮은 열수축성 폴리에스테르 필름을 제공하는데 있다.The present invention also provides a heat shrinkable polyester film having excellent post-processing processability and remarkably low finished product defect rate through ILC treatment of the surface.
본 발명은 또한, 상기 열수축성 폴리에스테르 필름으로 만든 스티커 라벨 및 시밍 라벨을 제공하는데 있다.The present invention also provides a sticker label and seaming label made of the heat-shrinkable polyester film.
이에 본 발명은 바람직한 일 구현예로서, 유리전이온도가 70 내지 80℃, 고유점도가 0.60 내지 0.75dl/g 및 분자량분포가 2.0 내지 4.0인 코폴리에스테르 수지를 포함하는 기재필름 및 상기 기재필름의 일면 또는 양면에 형성된 프라이머 코팅층을 포함하고, 상기 코폴리에스테르 수지는 디카르복실산 모노머, 이소프탈릭산 및 디올 모노머를 포함하여 공중합된 것이고, 90℃의 온수에서 측정된 주수축방향의 수축율이 40% 이상이고, 테트라하이드로퓨란(THF)와의 접착력이 0.65 내지 1Kgf인 열수축성 폴리에스테르계 필름을 제공하는 것이다.Thus, the present invention is a preferred embodiment, the glass transition temperature of 70 to 80 ℃, the intrinsic viscosity of 0.60 to 0.75dl / g and the molecular weight distribution of the base film comprising a copolyester resin of 2.0 to 4.0 and the base film It comprises a primer coating layer formed on one side or both sides, the copolyester resin is copolymerized including a dicarboxylic acid monomer, isophthalic acid and diol monomer, the shrinkage in the main shrinkage direction is measured in hot water at 90 ℃ 40 It is to provide a heat-shrinkable polyester film having a% or more and an adhesive force of tetrahydrofuran (THF) is 0.65 to 1 Kgf.
상기 코폴리에스테르 수지는 디카르복실산 모노머 및 이소프탈릭산이 85 내지 95 : 5 내지 15의 몰비로 포함하여 공중합된 것을 특징으로 한다.The copolyester resin is copolymerized by including a dicarboxylic acid monomer and isophthalic acid in a molar ratio of 85 to 95: 5 to 15.
상기 디카르복실산 모노머는 테레프탈산, 옥살산, 말론산, 숙신산, 아디프산, 수베르산, 아젤라산, 세바스산, 프탈산, 나프탈렌디카르복실산, 디페닐 에테르 디카르복실산 및 이들로 이루어진 군에서 선택되는 어느 하나 이상인 것이다.The dicarboxylic acid monomers are terephthalic acid, oxalic acid, malonic acid, succinic acid, adipic acid, suberic acid, azelaic acid, sebacic acid, phthalic acid, naphthalenedicarboxylic acid, diphenyl ether dicarboxylic acid and the group consisting thereof It is at least one selected from.
상기 디올 모노머는 에틸렌 글리콜, 네오펜틸 글리콜, 프로필렌 글리콜, 트리메틸렌 글리콜, 테트라메틸렌 글리콜, 헥사메틸렌 글리콜, 디에틸렌 글리콜, 폴리알킬렌 글리콜, 1,4-시클로헥산 디메탄올 및 이들로 이루어진 군에서 선택되는 2종 이상인 것이다.The diol monomer is selected from the group consisting of ethylene glycol, neopentyl glycol, propylene glycol, trimethylene glycol, tetramethylene glycol, hexamethylene glycol, diethylene glycol, polyalkylene glycol, 1,4-cyclohexane dimethanol It is two kinds or more.
상기 프라이머 코팅층은 5 내지 50 ㎚의 두께이며, 마찰계수가 0.20 이하인 것이다. The primer coating layer has a thickness of 5 to 50 nm, the friction coefficient is 0.20 or less.
상기 프라이머 코팅층은 아크릴 바인더 및 슬립제를 포함하는 것이다. The primer coating layer includes an acrylic binder and a slip agent.
상기 프라이머 코팅층은 아크릴 바인더 100 중량부를 기준으로 하여, 슬립제 150 내지 250 중량부를 포함하는 것이다. The primer coating layer is based on 100 parts by weight of the acrylic binder, it includes 150 to 250 parts by weight of the slip agent.
본 발명은 바람직한 다른 일 구현예로서, 디카르복실산 모노머 및 디올 모노머를 혼합한 후, 이소프탈릭산을 첨가하여 축중합 반응시켜 코폴리에스테르 수지를 제조하는 단계(S1); 상기 제조된 코폴리에스테르 수지를 255 내지 280℃에서 용융시켜 미연신 시트를 제조하는 단계(S2); 상기 S2 단계에서 제조된 미연신 시트의 일면 또는 양면에 프라이머 코팅층 조성물을 코팅하여 프라이머 코팅층을 형성하는 단계(S3); 상기 프라이머 코팅층이 형성된 미연신 시트에 열을 가한 후, 6 내지 10m/sec의 연신속도로 주수축 방향의 연신비를 4 내지 6배로 하여 한 방향으로 연신시키는 단계(S4) 및 상기 한 방향으로 연신된 필름을 70 내지 80℃로 열처리하는 단계(S5)를 포함하는 열수축성 폴리에스테르계 필름의 제조방법을 제공하는 것이다.As another preferred embodiment of the present invention, after mixing a dicarboxylic acid monomer and a diol monomer, and adding isophthalic acid to the polycondensation reaction to prepare a copolyester resin (S1); Melting the prepared copolyester resin at 255 to 280 ℃ to prepare an unstretched sheet (S2); Forming a primer coating layer by coating the primer coating layer composition on one or both surfaces of the unstretched sheet prepared in step S2 (S3); After applying heat to the unstretched sheet on which the primer coating layer was formed, stretching in one direction by stretching ratio in the main contraction direction at 4 to 6 times at a stretching speed of 6 to 10 m / sec (S4) and stretching in one direction It provides a method for producing a heat-shrinkable polyester film comprising the step (S5) of heat-treating the film at 70 to 80 ℃.
상기 S1 단계에서 코폴리에스테르 수지는 디카르복실산 모노머, 이소프탈릭산 및 디올 모노머가 85 내지 95 : 5 내지 15 : 100의 몰비로 포함하여 축중합 반응시켜 제조되는 것이다.Copolyester resin in the step S1 is a dicarboxylic acid monomer, isophthalic acid and diol monomer is prepared by the polycondensation reaction including a molar ratio of 85 to 95: 5 to 15: 100.
상기 디카르복실산 모노머는 테레프탈산, 옥살산, 말론산, 숙신산, 아디프산, 수베르산, 아젤라산, 세바스산, 프탈산, 나프탈렌디카르복실산, 디페닐 에테르 디카르복실산 및 이들로 이루어진 군에서 선택되는 어느 하나 이상인 것이다. The dicarboxylic acid monomers are terephthalic acid, oxalic acid, malonic acid, succinic acid, adipic acid, suberic acid, azelaic acid, sebacic acid, phthalic acid, naphthalenedicarboxylic acid, diphenyl ether dicarboxylic acid and the group consisting thereof It is at least one selected from.
상기 디올 모노머는 에틸렌 글리콜, 네오펜틸 글리콜, 프로필렌 글리콜, 트리메틸렌 글리콜, 테트라메틸렌 글리콜, 헥사메틸렌 글리콜, 디에틸렌 글리콜, 폴리알킬렌 글리콜, 1,4-시클로헥산 디메탄올 및 이들로 이루어진 군에서 선택되는 2종 이상인 것이다. The diol monomer is selected from the group consisting of ethylene glycol, neopentyl glycol, propylene glycol, trimethylene glycol, tetramethylene glycol, hexamethylene glycol, diethylene glycol, polyalkylene glycol, 1,4-cyclohexane dimethanol It is two kinds or more.
상기 프라이머 코팅층은 5 내지 50 ㎚의 두께인 것이다. The primer coating layer is a thickness of 5 to 50 nm.
상기 프라이머 코팅층 조성물은 아크릴 바인더 및 슬립제를 포함하는 것이다. The primer coating layer composition includes an acrylic binder and a slip agent.
상기 프라이머 코팅층 조성물은 아크릴 바인더 100 중량부를 기준으로 하여, 슬립제 150 내지 250중량부를 포함하는 것이다. The primer coating layer composition is based on 100 parts by weight of the acrylic binder, it will contain 150 to 250 parts by weight of the slip agent.
본 발명은 바람직한 다른 일 구현예로서, 상술한 제조방법으로 제조된 폴리에스테르계 필름을 포함하는 라벨을 제공하는 것이다. As another preferred embodiment of the present invention, to provide a label comprising a polyester-based film produced by the above-described manufacturing method.
본 발명에 따르면, 환경적으로 문제가 되지 않으면서도 취급이 용이한 용제를 이용할 수 있는 폴리에스테르 열수축성 필름 및 후가공 공정성이 우수하고 최종 제품에서의 불량률이 낮은 스티커 라벨 및 시밍 라벨을 제공할 수 있다. According to the present invention, it is possible to provide a polyester heat-shrinkable film that can use a solvent which is easy to handle without environmental problems, and a sticker label and seaming label having excellent post-processing processability and low defect rate in the final product. .
이하, 본 발명을 보다 상세히 설명한다.Hereinafter, the present invention will be described in more detail.
본 발명의 일 구현예로서, 유리전이온도가 70 내지 80℃, 고유점도가 0.60 내지 0.75dl/g 및 분자량분포가 2.0 내지 4.0인 코폴리에스테르 수지를 포함하는 기재필름 및 상기 기재필름의 일면 또는 양면에 형성된 프라이머 코팅층을 포함하고, 상기 코폴리에스테르 수지는 디카르복실산 모노머, 이소프탈릭산 및 디올 모노머를 포함하여 공중합된 것이고, 90℃의 온수에서 측정된 주수축방향의 수축율이 40% 이상이고, 테트라하이드로퓨란(THF)와의 접착력이 0.65 내지 1Kgf인 열수축성 폴리에스테르계 필름을 제공하는 것이다. In one embodiment of the present invention, the glass transition temperature is 70 to 80 ℃, the intrinsic viscosity is 0.60 to 0.75dl / g and the molecular weight distribution of the base film comprising a copolyester resin of 2.0 to 4.0 and one side of the base film or It includes a primer coating layer formed on both sides, the copolyester resin is copolymerized including a dicarboxylic acid monomer, isophthalic acid and a diol monomer, the shrinkage in the main shrinkage direction measured at 90 ℃ hot water 40% or more It is to provide a heat-shrinkable polyester film having an adhesion force of tetrahydrofuran (THF) is 0.65 to 1 Kgf.
상기 코폴리에스테르 수지는 디카르복실산 모노머 및 이소프탈릭산이 85 내지 95 : 5 내지 15의 몰비로 포함하여 공중합된 것이 바람직하다. 상기 디카르복실산 모노머대 이소프탈릭산의 몰비가 상기 범위 내에 있는 경우 연신에 의한 결정화 현상을 억제함으로써 수축 거동이 용이하게 발현될 수 있게 하는 장점을 가지며, 특히 이소프탈릭산의 몰비가 상기 범위 내에 있는 경우 최종 필름의 구조를 더욱 크게(bulky) 함으로써 용매의 부풀음(swelling)을 용이하게 하여 용매와의 접착력을 향상 시키는 장점을 가질 수 있다. It is preferable that the said copolyester resin is copolymerized including dicarboxylic acid monomer and isophthalic acid in the molar ratio of 85-95: 5-15. When the molar ratio of the dicarboxylic acid monomer to isophthalic acid is within the above range, the shrinkage behavior can be easily expressed by suppressing the crystallization phenomenon due to stretching, and in particular, the molar ratio of isophthalic acid is within the above range. If present, the structure of the final film may be more bulky, thereby facilitating swelling of the solvent to improve adhesion to the solvent.
상기 몰비로 공중합된 코폴리에스테르 수지는 이소프탈릭산으로부터 유래된 단위구조를 5.0 내지 15.0몰%, 바람직하게는 6.0 내지 12.5몰%의 함량으로 포함하고, 12몰%, 8몰%, 3몰% 등의 함량으로 포함할 수 있다. 상기 이소프탈릭산으로부터 유래된 단위구조의 함량이 5.0몰% 미만인 경우 충분한 용매와의 접착력을 구현하기가 어려울 수 있고, 15.0몰%를 초과하는 경우 Vacuum Dryer나 뜨거운 물을 이용한 예비결정화 공정에서 칩 간 융착이 발생할 수 있다. Copolyester resin copolymerized in the molar ratio comprises a unit structure derived from isophthalic acid in a content of 5.0 to 15.0 mol%, preferably 6.0 to 12.5 mol%, 12 mol%, 8 mol%, 3 mol% It may be included in such a content. When the content of the unit structure derived from isophthalic acid is less than 5.0 mol%, it may be difficult to realize sufficient adhesive strength with a solvent, and when it exceeds 15.0 mol%, chips between chips in a precrystallization process using a vacuum dryer or hot water Fusion may occur.
이를 구체적으로 설명하면, 폴리에스테르의 경우 용융 과정 상에 수분이 존재할 경우 가수분해에 의해서 분자량이 급격히 감소하고 기계적 물성이 취약해진다. 이를 방지하기 위하여 용융시키기 전에 건조라는 공정을 거치고 해당 건조 공정은 예비결정화와 본건조로 나뉜다. In detail, in the case of polyester, when water is present in the melting process, the molecular weight rapidly decreases due to hydrolysis, and mechanical properties become weak. In order to prevent this, before melting, a drying process is performed, and the drying process is divided into precrystallization and main drying.
일반적인 폴리에스테르는 결정성 고분자로 예비결정화 단계에서 표면결정화가 일어나 칩(원료)간에 들러붙는 현상(칩 간 융착)이 없다. 그러나 공중합 폴리에스테르의 경우 비결정성 고분자가 되어 해당 예비결정화 단계에서 적절한 조건이 부여되지 않을 경우 칩간 들러붙는 융착 현상이 발생된다. 이는 원료에 포함된 공중합물의 양과도 관련되며 일정 수준의 공중합물이 포함된 경우 Vacuum Dryer를 이용하여 예비결정화를 진행할 수 있고 공중합물의 양이 일정 수준을 초과하는 경우 뜨거운 물을 이용한 열수예비결정화 시스템으로 예비결정화를 진행할 수 있다. 그러나 공중합물의 양이 지나치게 높을 경우 최적 조건을 부여하거나 별도의 공정을 이용하더라도 예비결정화 단계에서 표면결정화가 일어나지 않아 칩 내 수분을 제거하는 건조 공정 자체가 불가능하게 된다.In general, polyester is a crystalline polymer, and surface crystallization occurs in the precrystallization step, so that there is no phenomenon of sticking between chips (raw material). However, in the case of the copolyester, it becomes an amorphous polymer, and if the proper conditions are not given in the precrystallization step, fusion between chips occurs. This is related to the amount of copolymer contained in the raw material, and if a certain level of copolymer is included, the pre-crystallization can be carried out by using a vacuum dryer, and if the amount of the copolymer exceeds a certain level, a hydrothermal precrystallization system using hot water is used. Precrystallization can proceed. However, if the amount of the copolymer is too high, even if given the optimum conditions or using a separate process, the surface crystallization does not occur in the pre-crystallization step, the drying process itself to remove the moisture in the chip is impossible.
이러한 점에서 상술한 코폴리에스테르 수지를 포함하는 열수축성 폴리에스테르계 필름은 테트라하이드로프란(THF)와의 접착력이 0.65 내지 1Kgf, 바람직하게는 0.68 내지 0.87Kgf, 보다 바람직하게는 0.82 내지 0.87Kgf을 만족할 수 있다. In this regard, the heat-shrinkable polyester-based film including the copolyester resin described above may satisfy 0.65 to 1 Kgf, preferably 0.68 to 0.87 Kgf, more preferably 0.82 to 0.87 Kgf, with tetrahydrofran (THF). Can be.
수축 필름의 경우 원단에 인쇄를 한 후 "시밍(Seaming)"이라는 공정을 거쳐서 슬리브(Sleeve) 형태로 만들어지게 된다. 해당 슬리브를 병(Bottle)에 씌우고 난 후 수축터널을 거치면서 원단 자체 수축율에 의해 수축이 되면서 병에 고정이 되게 된다. 수축응력이 높은 제품은 수축터널을 지나는 공정에서 용매(Solvent)와의 접착력이 약할 경우 접착 부위가 떨어지면서 불량이 발생하게 된다. 이러한 점에서 상기 용매로서 THF와의 접착력이 상기 범위 내에 있는 경우 불량 발생을 방지하는 효과를 가지는 것이며, 상기 범위를 벗어나는 경우 불량이 발생할 뿐만 아니라 제품으로의 적용이 불가능하게 된다. Shrink film is made in the form of a sleeve (Sleeve) through a process called "seaming (Seaming) after printing on the fabric. After putting the sleeve on the bottle (Bottle) through the shrinking tunnel is contracted by the shrinkage rate of the fabric itself is fixed to the bottle. If the product with high shrinkage stress is weak in adhesiveness with Solvent in the process of passing through the shrinkage tunnel, defects occur due to drop of adhesion site. In this regard, when the adhesive force with THF as the solvent is within the above range, it has an effect of preventing the occurrence of defects, and when out of the above range, not only the defect occurs but also the application to the product becomes impossible.
상기 디카르복실산 모노머는 테레프탈산, 옥살산, 말론산, 숙신산, 아디프산, 수베르산, 아젤라산, 세바스산, 프탈산, 나프탈렌디카르복실산, 디페닐 에테르 디카르복실산 및 이들로 이루어진 군에서 선택되는 어느 하나 이상인 것을 들 수 있다. The dicarboxylic acid monomers are terephthalic acid, oxalic acid, malonic acid, succinic acid, adipic acid, suberic acid, azelaic acid, sebacic acid, phthalic acid, naphthalenedicarboxylic acid, diphenyl ether dicarboxylic acid and the group consisting thereof One or more selected from may be mentioned.
상기 디올 모노머는 에틸렌 글리콜, 네오펜틸 글리콜, 프로필렌 글리콜, 트리메틸렌 글리콜, 테트라메틸렌 글리콜, 헥사메틸렌 글리콜, 디에틸렌 글리콜, 폴리알킬렌 글리콜, 1,4-시클로헥산 디메탄올 및 이들로 이루어진 군에서 선택되는 2종 이상인 것을 들 수 있다. The diol monomer is selected from the group consisting of ethylene glycol, neopentyl glycol, propylene glycol, trimethylene glycol, tetramethylene glycol, hexamethylene glycol, diethylene glycol, polyalkylene glycol, 1,4-cyclohexane dimethanol 2 or more types of things are mentioned.
상기 프라이머 코팅층은 아크릴 바인더 및 슬립(Slip)제를 포함하는 것이 바람직하다. The primer coating layer preferably includes an acrylic binder and a slip agent.
상기 아크릴 바인더 수지로는 메틸아크릴레이트(methyl acrylate), 에틸아크릴레이트(ethyl acrylate), 이소프로필아크릴레이트(isopropyl acrylate), n-프로필아크릴레이트(n-propyl acrylate), n-부틸아크릴레이트(n-butyl acrylate), 이소보르닐아크릴레이트(isobornyl acrylate), 2-에틸헥실아크릴레이트(2-ethylhexyl acrylate), 메틸메타크릴레이트(methyl methacrylate), 에틸메타크릴레이트(ethyl methacrylate), 이소프로필메타크릴레이트(isopropyl methacrylate), n-프로필메타크릴레이트(n-propyl methacrylate), tert-부틸메타크릴레이트(tert-butyl methacrylate), n-부틸메타크릴레이트(n-butyl methacrylate), 이소부틸메타크릴레이트(isobutyl methacrylate), 시클로헥실메타크릴레이트(cyclohexyl methacrylate), 이소보르닐메타크릴레이트(isECOobornyl methacrylate), 디에틸렌 글리콜 모노메틸 에테르 메타크릴레이트(diethylene glycol monomethyl ether methacrylate), 2-에틸헥실메타크릴레이트(2-ethylhexyl methacrylate), 벤질메타크릴레이트(benzyl methacrylate), 1-나프틸메틸메타크릴레이트(1-naphthylmethyl methacrylate), 2-나프틸메틸메타크릴레이트(2-naphthylmethyl methacrylate), 9-안트릴메틸메타크릴레이트(9-anthrylmethyl methacrylate), 1-안트릴메틸메타크릴레이트(1-anthrylmethyl methacrylate) 및 2-안트릴메틸메타크릴레이트(2-anthrylmethyl methacrylate)로 이루어진 군으로부터 하나 이상 선택될 수 있으며, 반드시 이에 제한되지 않는다.As the acrylic binder resin, methyl acrylate, methyl acrylate, isopropyl acrylate, n-propyl acrylate, n-butyl acrylate (n -butyl acrylate), isobornyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, isopropyl methacrylate Isopropyl methacrylate, n-propyl methacrylate, tert-butyl methacrylate, n-butyl methacrylate, n-butyl methacrylate, isobutyl methacrylate (isobutyl methacrylate), cyclohexyl methacrylate, isobornyl methacrylate, diethylene glycol monomethyl ether ether methacrylate), 2-ethylhexyl methacrylate, benzyl methacrylate, 1-naphthylmethyl methacrylate, 2-naphthylmethyl methacrylate (2-naphthylmethyl methacrylate), 9-anthrylmethyl methacrylate, 1-anthrylmethyl methacrylate and 2-anthrylmethyl methacrylate At least one selected from the group consisting of, but is not necessarily limited thereto.
상기 슬립제로는 Stearamidopropyldimethyl-2-hydroxyethyl ammonium nitrate, Steramidopropyldimethyl-2-hydroxyethyl ammonium dihydrogen phosphate, N,N-bis (2-hydroxyethyl)-N-(3-dodecyloxy-2-hydroxypropyl) methyl ammonium methosulfate 중에서 선택되는 어느 하나 이상을 포함할 수 있다. The slip agent is any one selected from Stearamidopropyldimethyl-2-hydroxyethyl ammonium nitrate, Steramidopropyldimethyl-2-hydroxyethyl ammonium dihydrogen phosphate, N, N-bis (2-hydroxyethyl) -N- (3-dodecyloxy-2-hydroxypropyl) methyl ammonium methosulfate It may include one or more.
상기 슬립제를 포함함으로써, 슬립성을 부여할 수 있으며 보다 바람직하게는 마찰계수를 0.2 이하의 물성을 가질 수 있다. 이러한 슬립성을 부여함으로써 후가공 공정 시 발생되는 스크래치 발생을 줄일 수 있다. By including the slip agent, the slip property can be imparted, and more preferably, the friction coefficient may have a physical property of 0.2 or less. By providing such slip property, it is possible to reduce the occurrence of scratches generated during the post-processing process.
일반적으로 공기 중 수분이 필름의 표면에 흡착되게 되고 이로 인해서 인접한 두 장의 필름이 들러붙게 된다. 이러한 현상에 의해서 최종 제품을 포장한 상태에서 하나의 제품을 꺼낼 때 인접한 제품의 라벨이 찢어지는 현상이 발생되는데, 이를 블록킹 불량이라고 한다. 본 발명에서는 상술한 아크릴 바인더 및 슬립제를 포함하여 블록킹 불량을 방지할 수 있다.In general, moisture in the air is adsorbed on the surface of the film, which causes the two adjacent films to stick together. Due to this phenomenon, when one product is taken out while packing the final product, a label of adjacent products is torn, which is called a blocking defect. In the present invention, the blocking defect may be prevented by including the acrylic binder and the slip agent described above.
상기 프라이머 코팅층은 아크릴 바인더 100 중량부를 기준으로 하여, 슬립제 150 내지 250 중량부, 바람직하게는 160 내지 210중량부로 포함하는 것이 좋다. The primer coating layer is preferably based on 100 parts by weight of the acrylic binder, 150 to 250 parts by weight, preferably 160 to 210 parts by weight.
상기 아크릴 바인더 수지와 슬립제를 포함하여 내블록킹(Blocking)성을 향상시킬 수 있으며, 슬립성을 부여할 수 있다. 이러한 슬립성을 부여함으로써, 후가공 시 발생될 수 있는 스크래치를 줄일 수 있으며, 공정상의 불량을 감소시킬 수 있다. 또한 내열내수성 측면에서 우수한 아크릴 바인더를 적용함으로써 내블록킹 성능이 향상되었다. Including the acrylic binder resin and the slip agent can improve the blocking resistance (blocking), it can be given slip properties. By providing such slip property, it is possible to reduce scratches that may occur during post-processing and to reduce process defects. In addition, the blocking resistance is improved by applying an acrylic binder having excellent heat resistance and water resistance.
상기 슬립제의 함량이 150중량부 미만인 경우 전사가 되지 않아 슬립성이 떨어지며, 250중량부를 초과하는 경우 블록킹이 유발되는 문제가 있다.If the content of the slip agent is less than 150 parts by weight, the transfer is not slippery slip, and if it exceeds 250 parts by weight there is a problem that blocking occurs.
상기 프라이머 코팅층은 5 내지 50㎚, 바람직하게는 10 내지 20nm의 두께인 것이 좋다. 상기 프라이머 코팅층의 두께가 상기 범위 내에 있는 경우 최종 필름의 표면에 균일하게 코팅층이 형성됨으로써 균일한 슬립성(Slip)을 구현할 수 있으며 안정적인 블록킹 방지 특성도 구현할 수 있는 효과를 가진다. 또한, 상기 프라이머 코팅층의 두께가 5nm 미만일 경우에는 도포균일성이 나오지 않으며, 50nm를 초과하는 경우에는 내블록킹성이 저하될 수 있다.The primer coating layer may be a thickness of 5 to 50nm, preferably 10 to 20nm. When the thickness of the primer coating layer is within the above range, the coating layer is uniformly formed on the surface of the final film, thereby achieving a uniform slip and having a stable anti-blocking property. In addition, the coating uniformity does not come out when the thickness of the primer coating layer is less than 5nm, blocking resistance may be lowered when it exceeds 50nm.
상술한 구성을 포함하는 본 발명의 프라이머 코팅층은 마찰계수가 0.20 이하인 것이다.The primer coating layer of the present invention comprising the above-described configuration is a friction coefficient of 0.20 or less.
상술한 코폴리에스테르 수지는 유리전이온도가 70 내지 80℃, 고유점도가 0.60 내지 0.75dl/g 및 분자량분포가 2.0 내지 4.0인 것이 바람직하다. It is preferable that the above-mentioned copolyester resin has a glass transition temperature of 70-80 degreeC, intrinsic viscosity 0.60-0.75 dl / g, and molecular weight distribution 2.0-4.0.
상기 유리전이온도가 상기 범위 내에 있는 경우 열적 안정성이 우수하여 장기 보관 시 자연 수축이 발생하지 않는 장점을 가진다.When the glass transition temperature is within the above range, the thermal stability is excellent, so that natural shrinkage does not occur during long-term storage.
상기 고유점도가 상기 범위 내에 있는 경우 고분자 주쇄간에 충분한 엉킴이 존재하여 1축 배향임에도 불구하고 충분한 기계적 강도 및 신도를 구현할 수 있는 장점을 가진다.When the intrinsic viscosity is within the above range, there is sufficient entanglement between the polymer backbones, so that the mechanical strength and elongation can be realized despite the uniaxial orientation.
상기 분자량분포가 상기 범위 내에 있는 경우 고분자 사슬간 슬립을 억제하여 필름 제조 시 부여한 주수축 방향의 수축율을 장기간 유지할 수 있는 장점을 가진다.When the molecular weight distribution is within the above range, the slip between the polymer chains is suppressed to have an advantage of maintaining the shrinkage in the main shrinkage direction given during film production for a long time.
상기 코폴리에스테르 수지를 포함하는 열수축성 폴리에스테르계 필름은 90℃의 온수에서 측정된 주수축방향의 수축율이 40% 이상, 바람직하게는 55% 이상, 보다 바람직하게는 70% 이상인 것이 바람직하다. 상기 수축율이 상기 범위 내에 있는 경우 현재 통용되고 있는 다양한 용기에 적용이 가능한 장점을 가진다. In the heat-shrinkable polyester film containing the copolyester resin, the shrinkage in the main shrinkage direction measured at 90 ° C. in hot water is 40% or more, preferably 55% or more, and more preferably 70% or more. If the shrinkage is in the above range has the advantage that can be applied to a variety of containers currently in use.
상술한 열수축성 폴리에스테르계 필름은 하기에 따른 방법을 제조될 수 있다. The above-mentioned heat-shrinkable polyester film can be prepared a method according to the following.
본 발명의 다른 일 구현예는 디카르복실산 모노머 및 디올 모노머를 혼합한 후, 이소프탈릭산을 첨가하여 축중합 반응시켜 코폴리에스테르 수지를 제조하는 단계(S1); 상기 제조된 코폴리에스테르 수지를 255 내지 280℃에서 용융시켜 미연신 시트를 제조하는 단계(S2); 상기 S2 단계에서 제조된 미연신 시트의 일면 또는 양면에 프라이머 코팅층 조성물을 코팅하여 프라이머 코팅층을 형성하는 단계 (S3); 상기 프라이머 코팅층이 형성된 미연신 시트에 열을 가한 후, 6 내지 10m/sec의 연신속도로 주수축 방향의 연신비를 4 내지 6배로 하여 한 방향으로 연신시키는 단계(S4) 및 상기 한 방향으로 연신된 필름을 70 내지 80℃로 열처리하는 단계(S5)를 포함하는 열수축성 폴리에스테르계 필름의 제조방법을 제공하는 것이다. Another embodiment of the present invention comprises mixing a dicarboxylic acid monomer and a diol monomer, and then adding isophthalic acid to polycondensation to prepare a copolyester resin (S1); Melting the prepared copolyester resin at 255 to 280 ℃ to prepare an unstretched sheet (S2); Coating a primer coating layer composition on one or both surfaces of the unstretched sheet prepared in step S2 to form a primer coating layer (S3); After applying heat to the unstretched sheet on which the primer coating layer was formed, stretching in one direction at a stretch ratio of 4 to 6 times in the main contraction direction at a stretching speed of 6 to 10 m / sec (S4) and the Film stretched in one direction at 70-80 ° C. It is to provide a method for producing a heat-shrinkable polyester film comprising the step (S5) of the heat treatment.
[(S1) 단계][(S1) step]
먼저, 디카르복실산 모노머 및 디올 모노머를 혼합한 후, 이소프탈릭산을 첨가하여 축중합 반응시켜 코폴리에스테르 수지를 제조한다. First, after mixing a dicarboxylic acid monomer and a diol monomer, isophthalic acid is added and polycondensation reaction is carried out to manufacture a copolyester resin.
상기 코폴리에스테르 수지는 디카르복실산 모노머, 이소프탈릭산 및 디올 모노머가 디카르복실산 모노머대 이소프탈릭산대 디올 모노머의 몰비로서 85 내지 95 : 5 내지 15 : 100의 몰비로 공중합되어 제조되는 것이 바람직하다. 상기 디카르복실산 모노머대 이소프탈릭산대 디올 모노머의 몰비가 상기 범위 내에 있는 경우 연신에 의한 결정화 현상을 억제함으로써 수축 거동이 용이하게 발현될 수 있게 하는 장점을 가지며, 특히 이소프탈릭산의 몰비가 상기 범위 내에 있는 경우 최종 필름의 구조를 더욱 크게(bulky) 함으로써 용매의 부풀음(swelling)을 용이하게 하여 용매와의 접착력을 향상 시키는 장점을 가질 수 있다. The copolyester resin is prepared by copolymerizing dicarboxylic acid monomer, isophthalic acid and diol monomer in a molar ratio of dicarboxylic acid monomer to isophthalic acid to diol monomer in a molar ratio of 85 to 95: 5 to 15: 100. desirable. When the molar ratio of the dicarboxylic acid monomer to the isophthalic acid to the diol monomer is within the above range has the advantage that the shrinkage behavior can be easily expressed by suppressing the crystallization phenomenon by stretching, in particular the molar ratio of isophthalic acid is When in the range can have the advantage of improving the adhesion to the solvent to facilitate the swelling (swelling) of the solvent by making the structure of the final film more (bulky).
상기 디카르복실산 모노머는 테레프탈산, 옥살산, 말론산, 숙신산, 아디프산, 수베르산, 아젤라산, 세바스산, 프탈산, 나프탈렌디카르복실산, 디페닐 에테르 디카르복실산 및 이들로 이루어진 군에서 선택되는 어느 하나 이상인 것을 들 수 있다. The dicarboxylic acid monomers are terephthalic acid, oxalic acid, malonic acid, succinic acid, adipic acid, suberic acid, azelaic acid, sebacic acid, phthalic acid, naphthalenedicarboxylic acid, diphenyl ether dicarboxylic acid and the group consisting thereof One or more selected from may be mentioned.
상기 디올 모노머는 에틸렌 글리콜, 네오펜틸 글리콜, 프로필렌 글리콜, 트리메틸렌 글리콜, 테트라메틸렌 글리콜, 헥사메틸렌 글리콜, 디에틸렌 글리콜, 폴리알킬렌 글리콜, 1,4-시클로헥산 디메탄올 및 이들로 이루어진 군에서 선택되는 2종 이상인 것을 들 수 있다. The diol monomer is selected from the group consisting of ethylene glycol, neopentyl glycol, propylene glycol, trimethylene glycol, tetramethylene glycol, hexamethylene glycol, diethylene glycol, polyalkylene glycol, 1,4-cyclohexane dimethanol 2 or more types of things are mentioned.
상기 축중합 반응은 본 발명에서 널리 알려진 통상적인 방법으로 실시할 수 있으며, 이는 잘 알려진 바 구체적인 설명은 생략한다.The polycondensation reaction may be carried out by a conventional method well known in the present invention, which is well known and a detailed description thereof will be omitted.
[(S2) 단계][(S2) step]
이어서, 상기 제조된 코폴리에스테르 수지를 255 내지 280℃에서 용융시켜 미연신 시트를 제조한다.Subsequently, the prepared copolyester resin is melted at 255 to 280 ° C to prepare an unstretched sheet.
상기 용융온도의 범위가 255℃ 미만인 경우 불완전 용융이 발생될 여지가 있어 공정 트러블이 발생할 수 있고, 280℃를 초과하는 경우 열분해에 의해 최종 필름의 고유 점도가 낮아지고 분자량 분포가 넓어져 기계적 물성의 저하, 장기 물성 유지 특성의 저하 등이 발생하고 다이 전단 압력이 낮아져 필름 제조 시 두께 제어가 어렵게 된다.If the melting temperature is less than 255 ℃ there is a possibility that incomplete melting may occur process trouble, if it exceeds 280 ℃ thermal decomposition lowers the inherent viscosity of the final film and the molecular weight distribution is widened to mechanical properties Deterioration, deterioration of long-term physical properties, etc. occur, and the die shear pressure is lowered, making it difficult to control thickness during film production.
이 때, 시트를 제조하는 공정으로서, 본 발명이 속한 분야에서 통상적으로 사용되는 시트 제조방법을 임의로 선택하여 사용할 수 있으며, 예를 들어, T 다이를 사용한 시트 제조방법, 환형 다이를 사용한 블로운 제조방법 등을 들 수 있다. At this time, as a process for producing a sheet, a sheet manufacturing method commonly used in the field of the present invention can be arbitrarily selected and used, for example, a sheet manufacturing method using a T die, blown production using an annular die The method etc. are mentioned.
[(S3) 단계][(S3) step]
이어서, 상기 제조된 미연신 시트의 일면 또는 양면에 프라이머 코팅층 조성물을 코팅하여 프라이머 코팅층을 형성한다(S2). Subsequently, the primer coating layer is coated on one or both surfaces of the prepared unstretched sheet to form a primer coating layer (S2).
상기 프라이머 코팅층 조성물은 아크릴 바인더 및 슬립제를 포함하는 것이다. The primer coating layer composition includes an acrylic binder and a slip agent.
상기 아크릴 바인더 수지는 상술된 프라이머 코팅층에서 기재된 바와 동일하다. The acrylic binder resin is the same as described in the above-described primer coating layer.
상기 슬립제는 상술된 프라이머 코팅층에서 기재된 바와 동일하다. The slip agent is the same as described in the primer coating layer described above.
상기 프라이머 코팅층 조성물은 아크릴 바인더 100 중량부를 기준으로 하여, 슬립제 150 내지 250 중량부, 바람직하게는 160 내지 210중량부로 포함하는 것이 좋다. The primer coating layer composition is based on 100 parts by weight of the acrylic binder, 150 to 250 parts by weight, preferably 160 to 210 parts by weight.
상기 아크릴 바인더 수지와 슬립제를 포함하여 내 Blocking 성을 향상시킬 수 있으며, 슬립성을 부여할 수 있다. 이러한 슬립성을 부여함으로써, 후가공 시 발생될 수 있는 스크래치를 줄일 수 있으며, 공정상의 불량을 감소시킬 수 있다. 또한 내열내수성 측면에서 우수한 아크릴 바인더를 적용함으로써 내블록킹 성능을 향상 되었다. Including the acrylic binder resin and the slip agent can improve the blocking resistance, it can be given a slip resistance. By providing such slip property, it is possible to reduce scratches that may occur during post-processing and to reduce process defects. In addition, the blocking resistance is improved by applying an acrylic binder having excellent heat resistance and water resistance.
상기 슬립제의 함량이 150중량부 미만인 경우 전사가 되지 않아 슬립성이 떨어지며, 250중량부를 초과하는 경우 블록킹이 유발될 수 있다.If the content of the slip agent is less than 150 parts by weight, the transfer is not slippery slip, and if it exceeds 250 parts by weight may cause blocking.
본 발명에 따른 프라이머 코팅층 조성물은 상기 아크릴 바인더 및 슬립제 이외에 웨팅제를 더 포함할 수 있다. The primer coating layer composition according to the present invention may further include a wetting agent in addition to the acrylic binder and the slip agent.
상기 웨팅제는 코팅성을 향상시키기 위하여 사용되는 것으로 실리콘계 웨팅제, 변성 실리콘계 웨팅제 등을 사용할 수 있으며, 구체적으로 예를 들면, 다우코닝사에 QE-5212, ENDOBIC사의 TEGO WET250, BYKCHEMIE사에 BYK340 등을 사용할 수는 있으나 이에 한정되는 것은 아니다. The wetting agent may be used to improve coating properties, such as silicone-based wetting agent, modified silicone-based wetting agent, and the like. Specifically, for example, Dow Corning Co., Ltd., QE-5212, ENDOBIC Co., Ltd. Can be used but is not limited thereto.
상기 웨팅제는 아크릴 바인더 100 중량부를 기준으로 하여 20 내지 100 중량부, 바람직하게는 20 내지 60중량부의 함량으로 포함하는 것이 좋다. 상기 웨팅제의 함량이 20중량부 미만인 경우 웨팅(Wetting)성 부족으로 코팅외관이 불량하며, 100중량부를 초과하는 경우 건조공정 이후 잔존하는 웨팅제 등의 불순물로 인하여 코팅얼룩이 발생할 수 있다. 상기 아크릴 바인더 수지와 슬립(Slip)제의 적용을 통하여 내블록킹성을 향상시킬 수 있으며, 슬립성을 부여할 수 있다. 이러한 슬립성을 부여함으로써, 후가공 시 발생될 수 있는 스크래치를 줄일 수 있으며, 공정상의 불량을 감소 시킬수 있다. 또한 내열내수성측면 우수한 아크릴 바인더를 적용함으로써 내블록킹 성능이 향상 되었다. The wetting agent may be included in an amount of 20 to 100 parts by weight, preferably 20 to 60 parts by weight based on 100 parts by weight of the acrylic binder. When the content of the wetting agent is less than 20 parts by weight, the coating appearance is poor due to lack of wetting (wetting), and when it exceeds 100 parts by weight, coating stains may occur due to impurities such as a wetting agent remaining after the drying process. Through the application of the acrylic binder resin and the slip (Slip) agent can improve the blocking resistance, it can be given a slip resistance. By providing such slip properties, it is possible to reduce scratches that may occur during post processing and to reduce process defects. In addition, the blocking resistance is improved by applying an acrylic binder having excellent heat resistance and water resistance.
상기 프라이머 코팅층은 5 내지 50㎚, 바람직하게는 10 내지 20nm의 두께로 형성되는 것이 좋다. 상기 프라이머 코팅층의 두께가 5nm 미만일 경우에는 도포균일성이 나오지 않으며, 50nm을 초과하는 경우에는 내블록킹성이 저하될 수 있다. The primer coating layer is preferably formed to a thickness of 5 to 50nm, preferably 10 to 20nm. When the thickness of the primer coating layer is less than 5nm, coating uniformity does not come out, and when it exceeds 50nm, blocking resistance may be lowered.
상술한 프라이머 코팅층은 마찰계수가 0.20 이하인 것이다. The above-described primer coating layer is a friction coefficient of 0.20 or less.
이때, 프라이머 코팅층 조성물을 코팅하여 프라이머 코팅층을 형성하는 공정으로서, 본 발명이 속한 분야에서 통상적으로 사용되는 방법을 임의로 선택하여 사용할 수 있으며, 예를 들어, M-bar를 사용한 코팅법, 그라비어 코팅법 등을 들 수 있다.At this time, as a process of forming a primer coating layer by coating the primer coating layer composition, it can be used to arbitrarily select a method commonly used in the field to which the present invention belongs, for example, coating method using M-bar, gravure coating method Etc. can be mentioned.
[(S4) 단계][(S4) step]
이어서, 상기 프라이머 코팅층이 형성된 미연신 시트에 열을 가한 후, 6 내지 10m/sec의 연신속도로 주수축 방향의 연신비를 4 내지 6배로 하여 한 방향으로 연신시켜 일축 배향된 열수축성 폴리에스테르계 필름을 제조한다. Subsequently, after applying heat to the unstretched sheet on which the primer coating layer was formed, the stretch ratio in the main shrinkage direction was 4 to 6 times at a stretching speed of 6 to 10 m / sec, and stretched in one direction to uniaxially oriented heat-shrinkable polyester film To prepare.
상기 프라이머 코팅층이 형성된 미연신 시트에 열을 가하는 공정은 상기 프라이머 코팅층이 형성된 미연신 시트에 예열온도 85 내지 110℃, 연신 온도 70 내지 90℃로 가열하는 것이 바람직하다. 상기 예열, 연신 온도의 범위가 상기 범위 내에 있는 경우 연신 시 발생되는 연신응력을 낮춤으로써 최종 필름에 잔류하는 연신응력을 최소화 할 수 있는 효과를 얻을 수 있다. In the process of applying heat to the unstretched sheet on which the primer coating layer is formed, it is preferable to heat the unstretched sheet on which the primer coating layer is formed to a preheating temperature of 85 to 110 ° C and a stretching temperature of 70 to 90 ° C. When the range of the preheating and the stretching temperature is within the range, an effect of minimizing the stretching stress remaining in the final film may be obtained by lowering the stretching stress generated during stretching.
상기 연신비의 범위가 상기 범위 내에 있는 경우 최종 필름의 수축율을 열처리 온도로 제어함으로써 물리적으로 주수추축방향의 수축율이 낮은 것과 더불어 물리적으로 구현 가능한 최대 수축율을 발현함으로써 다양한 용기에 적용 가능한 효과를 얻을 수 있다. When the draw ratio is within the range, by controlling the shrinkage rate of the final film at the heat treatment temperature, the shrinkage rate in the main water extraction direction is lowered physically, and the maximum shrinkage rate that can be physically realized can be obtained to apply to various containers. .
[(S5) 단계][(S5) step]
이어서, 상기 한 방향으로 연신된 필름을 70 내지 80℃로 열처리한다. Subsequently, the film stretched in one direction is heat-treated at 70 to 80 ° C.
상기 한 방향으로 연신 필름을 70 내지 80℃로 추가 연신 없이 필름에 열을 가하여 연신구간에서 발생되는 연신 후 잔류 응력을 일부 해소시킴과 더불어 결정화를 증가시켜 일축 배향된 열수축성 폴리에스테르계 필름을 제조한다. Heat-stretching the stretched film in the direction of 70 to 80 ℃ without further stretching in one direction to relieve some of the residual stress after stretching in the stretching section and to increase the crystallization to produce a monoaxially oriented heat-shrinkable polyester film do.
상기 열처리 온도가 상기 범위 내에 있는 경우 상대적으로 낮은 잔류 응력을 가지고 구조적으로 일정 수준의 결정화를 가짐으로써 경시 외관 변화에 대한 저항성이 우수해져 장기 보관하더라도 필름의 외관이 저해되는 문제를 해소할 수 있다.When the heat treatment temperature is within the above range, the resin has a relatively low residual stress and structurally has a certain level of crystallization, thereby improving the resistance to changes in appearance over time, thereby eliminating the problem that the appearance of the film is inhibited even when stored for a long time.
본 발명은 바람직한 다른 일 구현예로서, 상술한 제조방법으로 제조된 폴리에스테르계 필름을 포함하는 라벨을 제공하는 것이다. 상기 라벨은 스티커라벨 및 시밍 라벨이 바람직하다.  As another preferred embodiment of the present invention, to provide a label comprising a polyester-based film produced by the above-described manufacturing method. The label is preferably a sticker label and a seaming label.
이하, 실시예를 통하여 본 발명을 더욱 상세히 설명하고자 한다. 이들 실시예는 오로지 본 발명을 보다 구체적으로 설명하기 위한 것으로서, 본 발명의 범위가 이들 실시예에 의해 제한되지 않는다는 것은 본 발명이 속하는 기술 분야에서 통상의 지식을 가진 자에게 있어 자명할 것이다.Hereinafter, the present invention will be described in more detail with reference to Examples. These examples are only for illustrating the present invention in more detail, it will be apparent to those skilled in the art that the scope of the present invention is not limited by these examples.
실시예 1Example 1
테레프탈산(TPA) 88몰, 에틸렌 글리콜(EG) 84몰 및 네오펜틸 글리콜(NPG) 16몰의 함량으로 혼합하여 반응관에 투입하고, 이소프탈릭산 (IPA) 12몰을 반응관에 투입하여 1.5㎏/㎠로 가압한 후, 부생성물을 제거하면서 240℃까지 승온시키면서 반응시켰다. 에스테르화 반응 후 중합 촉매로서 3산화안티몬을 0.05몰 함량으로, pinning제로서 마그네슘과 나트륨을 200ppm 함량으로, 추가하여 280℃에서 250분 동안 중합하여 유리전이온도가 71℃, 고유점도가 0.71 dl/g, DEG 1.3wt%, 카르복실말단기가 28.3meq/㎏, 분자량분포 3.2, 이소프탈릭산으로부터 유래된 단위구조의 함량(이하, IPA 함량이라 함)이 12몰%인 코폴리에스테르 수지를 제조하였다. 88 moles of terephthalic acid (TPA), 84 moles of ethylene glycol (EG) and 16 moles of neopentyl glycol (NPG) were mixed into the reaction tube, and 12 moles of isophthalic acid (IPA) were added to the reaction tube for 1.5 kg. After pressurization at / cm 2, the reaction was carried out while the temperature was raised to 240 ° C while removing the by-product. After the esterification reaction, an antimony trioxide as a polymerization catalyst was added in a 0.05 mol content, magnesium and sodium as a pinning agent were added in an amount of 200 ppm, and the polymerization was carried out at 280 ° C. for 250 minutes to give a glass transition temperature of 71 ° C. and an intrinsic viscosity of 0.71 dl /. g, DEG 1.3wt%, carboxyl terminal group was 28.3meq / kg, molecular weight distribution 3.2, the copolyester resin having a content of the unit structure derived from isophthalic acid (hereinafter referred to as IPA content) 12 mol% was prepared. .
상기 제조된 코폴리에스테르 수지를 260℃로 가열된 ETR에서 용융시키고 T 다이를 이용하여 미연신 시트를 제조하였다. 상기 제조된 미연신 시트의 일면에 아크릴 바인더(PK-8012P, Nippon Carbibe사) 100중량부에 대하여 슬립제(Stearamidopropyldimethyl-2-hydroxyethyl ammonium nitrate) 200중량부, 웨팅제로서 실리콘계 웨팅제(폴리에스테르실록산 공중합체 QE-5212, 다우코팅사) 50중량부로 혼합된 프라이머 코팅층 조성물을 M-Bar를 이용하여 코팅하여 20㎚ 두께를 가지는 프라이머 코팅층을 형성하였다. The prepared copolyester resin was melted in an ETR heated to 260 ° C. and an unstretched sheet was prepared using a T die. 200 parts by weight of a slip agent (Stearamidopropyldimethyl-2-hydroxyethyl ammonium nitrate) based on 100 parts by weight of an acrylic binder (PK-8012P, Nippon Carbibe) on one surface of the prepared unstretched sheet, a silicone-based wetting agent (polyester siloxane) as a wetting agent Copolymer QE-5212, Dow Coating Co.) 50 parts by weight of the primer coating layer composition was coated using M-Bar to form a primer coating layer having a thickness of 20nm.
상기 일면에 프라이머 코팅층이 형성된 미연신 시트를 예열온도 95℃로 하고, 연신 온도를 83℃로 가열한 후, 8m/sec의 연신속도로 폭 방향의 4.0배로 연신한 후, 75℃로 열처리하여 일축 배향된 열수축성 폴리에스테르계 필름을 제조하였다. The unstretched sheet having the primer coating layer formed on one surface thereof was preheated to 95 ° C., the drawn temperature was heated to 83 ° C., stretched to 4.0 times the width direction at a stretch rate of 8 m / sec, and then heat treated at 75 ° C. to uniaxially. An oriented heat shrinkable polyester based film was prepared.
실시예 2Example 2
테레프탈산(TPA) 92몰, 에틸렌 글리콜(EG) 84몰 및 네오펜틸 글리콜(NPG) 16몰의 함량으로 혼합하여 반응관에 투입하고, 이소프탈릭산(IPA) 8몰을 적용한 것 외에는 실시예 1과 동일한 방법으로 열수축성 폴리에스테르계 필름을 제조하였다.92 mol of terephthalic acid (TPA), 84 mol of ethylene glycol (EG) and 16 mol of neopentyl glycol (NPG) were mixed and introduced into the reaction tube, and 8 mol of isophthalic acid (IPA) was applied. In the same manner, a heat shrinkable polyester film was prepared.
이 때, 상기 제조된 코폴리에스테르 수지는 유리전이온도가 73℃, 고유점도가 0.70dl/g, DEG 1.8wt%, 카르복실말단기가 26.7meq/㎏, 분자량분포가 3.0, IPA 함량이 8몰%인 코폴리에스테르 수지를 제조하였다. At this time, the prepared copolyester resin has a glass transition temperature of 73 ℃, intrinsic viscosity 0.70dl / g, DEG 1.8wt%, carboxyl terminal group 26.7 meq / kg, molecular weight distribution 3.0, IPA content 8 mol A copolyester resin of% was prepared.
실시예 3Example 3
필름 연신 시 예열 온도를 87℃로 하고, 연신 온도를 85℃로 가열한 후, 연신 속도를 10m/sec로 한 것을 제외하고는 실시예 1과 동일한 방법으로 열수축성 폴리에스테르계 필름을 제조하였다.A heat-shrinkable polyester film was produced in the same manner as in Example 1 except that the preheating temperature was 87 ° C. and the stretching temperature was 85 ° C., and the stretching speed was 10 m / sec.
이 때, 상기 제조된 코폴리에스테르 수지는 유리전이온도가 71℃, 고유점도가 0.71dl/g, DEG 1.5wt%, 카르복실말단기가 25.8meq/㎏, 분자량분포가 3.3, IPA 함량이 12몰%인 코폴리에스테르 수지를 제조하였다. At this time, the prepared copolyester resin has a glass transition temperature of 71 ℃, intrinsic viscosity 0.71dl / g, DEG 1.5wt%, carboxyl terminal group 25.8meq / kg, molecular weight distribution 3.3, IPA content 12mol A copolyester resin of% was prepared.
실시예Example 4 4
테레프탈산(TPA) 95몰, 에틸렌 글리콜(EG) 84몰 및 네오펜틸 글리콜(NPG) 16몰의 함량으로 혼합하여 반응관에 투입하고, 이소프탈릭산(IPA) 5몰을 적용한 것 외에는 실시예 1과 동일한 방법으로 열수축성 폴리에스테르계 필름을 제조하였다.95 moles of terephthalic acid (TPA), 84 moles of ethylene glycol (EG) and 16 moles of neopentyl glycol (NPG) were mixed and introduced into the reaction tube, and 5 moles of isophthalic acid (IPA) were applied. In the same manner, a heat shrinkable polyester film was prepared.
이 때, 상기 제조된 코폴리에스테르 수지는 유리전이온도가 75℃, 고유점도가 0.71dl/g, DEG 1.41wt%, 카르복실말단기가 29.3meq/㎏, 분자량분포 2.8, IPA 함량이 5몰%인 코폴리에스테르 수지를 제조하였다. At this time, the prepared copolyester resin has a glass transition temperature of 75 ℃, intrinsic viscosity 0.71dl / g, DEG 1.41wt%, carboxyl terminal group 29.3meq / kg, molecular weight distribution 2.8, IPA content 5mol% Phosphorous copolyester resin was prepared.
실시예 5Example 5
미연신 시트를 연신 온도를 67℃로 적용한 것을 제외하고는 실시예 1과 동일한 방법으로 열수축성 폴리에스테르계 필름을 제조하였다.A heat-shrinkable polyester film was prepared in the same manner as in Example 1 except that the stretched temperature was applied at 67 ° C. in the unstretched sheet.
이 때, 상기 제조된 코폴리에스테르 수지는 유리전이온도가 71℃, 고유점도가 0.70dl/g, DEG 1.42wt%, 카르복실말단기가 27.3meq/㎏, 분자량분포가 3.1, IPA 함량이 12몰%인 코폴리에스테르 수지를 제조하였다. At this time, the prepared copolyester resin has a glass transition temperature of 71 ℃, intrinsic viscosity 0.70dl / g, DEG 1.42wt%, carboxyl terminal group 27.3 meq / kg, molecular weight distribution 3.1, IPA content 12 mol A copolyester resin of% was prepared.
비교예 1Comparative Example 1
테레프탈산(TPA) 100몰, 에틸렌 글리콜(EG) 84몰 및 네오펜틸 글리콜(NPG) 16몰의 함량으로 혼합하여 중합 반응관에 투입하고 1.5㎏/㎠로 가압한 후, 부생성물을 제거하면서 240℃까지 승온시키면서 반응시켰 코폴리에스터를 제조한 것을 제외하고는 실시예 1과 동일한 방법으로 열수축성 폴리에스테르계 필름을 제조하였다. 100 moles of terephthalic acid (TPA), 84 moles of ethylene glycol (EG), and 16 moles of neopentyl glycol (NPG) were mixed and introduced into a polymerization reaction tube, pressurized to 1.5 kg / cm 2, and then 240 ° C. while removing by-products. The reaction was carried out while heating up to produce a heat-shrinkable polyester film in the same manner as in Example 1 except that the copolyester was prepared.
이 때, 상기 제조된 코폴리에스테르 수지는 유리전이온도가 78℃, 고유점도가 0.70dl/g, DEG 1.33wt%, 카르복실말단기가 28.5meq/㎏, 분자량분포 3.1, IPA 함량이 0몰%인 코폴리에스테르 수지를 제조하였다. At this time, the prepared copolyester resin has a glass transition temperature of 78 ℃, intrinsic viscosity 0.70dl / g, DEG 1.33wt%, carboxyl terminal group 28.5meq / kg, molecular weight distribution 3.1, IPA content 0 mol% Phosphorous copolyester resin was prepared.
비교예 2Comparative Example 2
테레프탈산(TPA) 98.5몰, 에틸렌 글리콜(EG) 84몰 및 네오펜틸 글리콜(NPG) 16몰의 함량으로 혼합하여 반응관에 투입하고, 이소프탈릭산(IPA) 1.5몰을 적용한 것 외에는 실시예 1과 동일한 방법으로 열수축성 폴리에스테르계 필름을 제조하였다.It was mixed with the content of 98.5 mol of terephthalic acid (TPA), 84 mol of ethylene glycol (EG) and 16 mol of neopentyl glycol (NPG) into a reaction tube, and 1.5 mol of isophthalic acid (IPA) was applied. In the same manner, a heat shrinkable polyester film was prepared.
이 때, 상기 제조된 코폴리에스테르 수지는 유리전이온도가 77℃, 고유점도가 0.71dl/g, DEG 1.41wt%, 카르복실말단기가 29.1meq/㎏, 분자량분포 2.9, IPA 함량이 1.5몰%인 코폴리에스테르 수지를 제조하였다. At this time, the prepared copolyester resin has a glass transition temperature of 77 ℃, intrinsic viscosity 0.71dl / g, DEG 1.41wt%, carboxyl terminal group 29.1meq / kg, molecular weight distribution 2.9, IPA content 1.5mol% Phosphorous copolyester resin was prepared.
비교예 3Comparative Example 3
테레프탈산(TPA) 80몰, 에틸렌 글리콜(EG) 84몰 및 네오펜틸 글리콜(NPG) 16몰의 함량으로 혼합하여 반응관에 투입하고, 이소프탈릭산(IPA) 20몰을 적용한 것 외에는 실시예 1과 동일한 방법으로 열수축성 폴리에스테르계 필름을 제조하였다.80 mol of terephthalic acid (TPA), 84 mol of ethylene glycol (EG), and 16 mol of neopentyl glycol (NPG) were mixed and introduced into the reaction tube, and 20 mol of isophthalic acid (IPA) was applied. In the same manner, a heat shrinkable polyester film was prepared.
이 때, 상기 제조된 코폴리에스테르 수지는 유리전이온도가 67℃, 고유점도가 0.70dl/g, DEG 1.42wt%, 카르복실말단기가 27.6meq/㎏, IPA 함량이 20몰%인 코폴리에스테르 수지를 제조하였다. At this time, the prepared copolyester resin has a glass transition temperature of 67 ℃, intrinsic viscosity 0.70dl / g, DEG 1.42wt%, carboxyl terminal group 27.6meq / kg, IPA content of 20 mol% Resin was prepared.
비교예 4Comparative Example 4
미연신 시트에 프라이머 코팅층을 형성하지 않은 것을 제외하고는 실시예 1과 동일한 방법으로 열수축성 폴리에스테르계 필름을 제조하였다.A heat-shrinkable polyester film was prepared in the same manner as in Example 1 except that the primer coating layer was not formed on the unstretched sheet.
이 때, 상기 제조된 코폴리에스테르 수지는 유리전이온도가 71℃, 고유점도가 0.69dl/g, DEG 1.5wt%, 카르복실말단기가 28.5meq/㎏, 분자량분포가 3.1, IPA 함량이 12몰%인 코폴리에스테르 수지를 제조하였다. At this time, the prepared copolyester resin has a glass transition temperature of 71 ℃, intrinsic viscosity 0.69dl / g, DEG 1.5wt%, carboxyl terminal group 28.5meq / kg, molecular weight distribution 3.1, IPA content 12mol A copolyester resin of% was prepared.
비교예 5Comparative Example 5
미연신 시트를 일축으로 연신한 후 열처리 공정을 적용하지 않을 것을 제외하고는 실시예 1과 동일한 방법으로 열수축성 폴리에스테르계 필름을 제조하였다.A heat-shrinkable polyester film was prepared in the same manner as in Example 1 except that the unstretched sheet was uniaxially stretched and the heat treatment process was not applied.
이 때, 상기 제조된 코폴리에스테르 수지는 유리전이온도가 72℃, 고유점도가 0.70dl/g, DEG 1.6wt%, 카르복실말단기가 26.9meq/㎏, 분자량분포가 2.9, IPA 함량이 12몰%인 코폴리에스테르 수지를 제조하였다. At this time, the prepared copolyester resin has a glass transition temperature of 72 ℃, intrinsic viscosity 0.70dl / g, DEG 1.6wt%, carboxyl terminal group 26.9meq / kg, molecular weight distribution 2.9, IPA content 12mol A copolyester resin of% was prepared.
비교예 6Comparative Example 6
미연신 시트를 일축으로 연신한 후 열처리 공정 온도를 85℃로 적용한 것을 제외하고는 실시예 1과 동일한 방법으로 열수축성 폴리에스테르계 필름을 제조하였다.A heat-shrinkable polyester film was prepared in the same manner as in Example 1 except that the unstretched sheet was uniaxially stretched and the heat treatment process temperature was applied at 85 ° C.
이 때, 상기 제조된 코폴리에스테르 수지는 유리전이온도가 71℃, 고유점도가 0.69dl/g, DEG 1.5wt%, 카르복실말단기가 26.3meq/㎏, 분자량분포가 3.0, IPA 함량이 12몰%인 코폴리에스테르 수지를 제조하였다. At this time, the prepared copolyester resin has a glass transition temperature of 71 ℃, intrinsic viscosity 0.69dl / g, DEG 1.5wt%, carboxyl terminal group 26.3meq / kg, molecular weight distribution 3.0, IPA content 12mol A copolyester resin of% was prepared.
비교예 7Comparative Example 7
테레프탈산(TPA) 85몰, 에틸렌 글리콜(EG) 60몰 및 네오펜틸 글리콜(NPG) 20몰의 함량으로 혼합하여 반응관에 투입하고, 이소프탈릭산(IPA) 15몰과 디에틸렌 글리콜 (DEG) 20몰을 적용한 것 외에는 실시예 1과 동일한 방법으로 열수축성 폴리에스테르계 필름을 제조하였다.85 mol of terephthalic acid (TPA), 60 mol of ethylene glycol (EG) and 20 mol of neopentyl glycol (NPG) were mixed and introduced into the reaction tube, and 15 mol of isophthalic acid (IPA) and diethylene glycol (DEG) 20 were added. A heat-shrinkable polyester film was prepared in the same manner as in Example 1 except that moles were applied.
이 때, 상기 제조된 코폴리에스테르 수지는 유리전이온도가 61℃, 고유점도가 0.69dl/g, DEG 21wt%, 카르복실말단기가 27.6meq/㎏, IPA 함량이 15몰%인 코폴리에스테르 수지를 제조하였다. At this time, the prepared copolyester resin has a glass transition temperature of 61 ℃, intrinsic viscosity 0.69dl / g, DEG 21wt%, carboxyl terminal group 27.6meq / kg, IPA content of 15 mol% Was prepared.
<특성평가 방법><Characteristic evaluation method>
(1) 수축율 측정(1) Shrinkage rate measurement
필름의 길이방향(MD)과 폭방향(TD)에 대해 15mm(MD)× 400mm(TD) 크기의 직사각형으로 재단하고, TD 방향 양 끝단 50mm 지점에서 MD 방향으로 실선을 그어 유효측정길이가 300mm인 시편을 제작한 후, 핀셋 등을 이용하여 좌우 구분없이 시료의 한쪽 끝단에서 50mm이내의 지점을 잡아 전체 시료를 70℃ 및 90℃의 온수 중에 무하중 상태로 하여 완전히 담근 상태에서 10초간 열수축시킨 후, 상온에서 1분간 방치한 후, 초기의 실선으로 표시된 TD방향의 300mm 간격의 줄어든 길이를 측정하여 필름 폭 방향(TD)의 70℃ 및 90℃ 열수축율을 하기 식 1에 따라 구하였다.Cut into 15mm (MD) × 400mm (TD) rectangles in the length direction (MD) and width direction (TD) of the film, and draw a solid line in the MD direction at 50mm at both ends of the TD direction, and the effective measuring length is 300mm. After fabricating the specimen, use a tweezer, etc. to grasp the point within 50mm from one end of the sample without distinction between left and right, and heat-shrink for 10 seconds in a completely immersed state in the entire sample is unloaded in hot water at 70 ℃ and 90 ℃ After being left at room temperature for 1 minute, the reduced length of the 300 mm interval in the TD direction indicated by the solid line at the beginning was measured to obtain 70 ° C. and 90 ° C. thermal shrinkage in the film width direction (TD) according to the following Equation 1.
<식 1><Equation 1>
Figure PCTKR2017015772-appb-I000001
Figure PCTKR2017015772-appb-I000001
(2) 용매와의 접착력 측정(2) Adhesion Measurement with Solvent
실시예 및 비교예에 따라 제조된 필름으로서 동일한 시편 2장을 각각 준비한다. 상기 준비된 시편 중 어느 하나를 선택하여 상기 선택된 시편의 어느 일면에 접착 용제(solvent)로 테트라하이드로프란(THF)를 사용하여 주수축 방향의 수직 방향으로 0.5cm 굵기로 도포한 후, 다른 시편의 일면과 상기 THF가 도포된 시편에서의 THF 도포면을 서로 붙여서 롤러로 압착하여 접착시킨 후, 하루 방치 후 인스트론 장비로 접착 강도를 평가 하였다. 이 때, 상기 다른 시편의 일면과 THF가 도포된 면 중 어느 하나의 면은 프라이머 코팅층으로 한다. Two identical specimens were prepared as films prepared according to Examples and Comparative Examples, respectively. Select one of the prepared specimens and apply it to any one surface of the selected specimens with 0.5 cm thickness in the vertical direction of the main shrinkage direction using tetrahydrofran (THF) as an adhesive solvent (solvent), then one surface of the other specimen And the THF coated surfaces on the THF coated specimens were adhered to each other by pressing with a roller, and then the adhesive strength was evaluated using an Instron equipment after one day. At this time, one surface of the other surface and the THF-coated surface is a primer coating layer.
평가 시 시편은 폭 15mm, 길이 100mm로 절단하여 주수축 방향으로 Loaidng 한 후 Head speed는 300mm/min, Gap 30mm를 적용하여 접착 강도를 평가하였다. After evaluation, the specimens were cut into width 15mm and length 100mm and Loaidng in the main shrinkage direction. Then, the head speed was evaluated by applying 300mm / min and Gap 30mm.
(3) 수축응력 측정(3) Shrinkage stress measurement
가네보 및 테스트라이트 기기로 온도에 따른 수축응력 및 항온에서 시간에 따른 수축응력을 비교하였다. The shrinkage stress with temperature and the shrinkage stress with time at constant temperature were compared with Kanebo and Testlite instruments.
(4) 슈팅(Shooting) 공정성 측정(4) Shooting fairness measurement
본 발명이 속한 분야에서 사용되는 라벨 슈팅기(고속형 수축라벨러(SH-5100-S), (주)새한테크를 이용하여 100개의 바틀에 상기 제조된 필름을 이용한 라벨을 슈팅하여 슈팅 후 라벨의 위치를 확인하여 정해진 위치에 안착된 개수를 확인하여 비교하였다. Label shooting machine used in the field of the present invention (high-speed contraction labeling machine (SH-5100-S), Saehan Tech Co., Ltd. shooting the label using the film prepared in 100 bottles, the location of the label after shooting) Check and compare the number of seated in the predetermined position.
(5) 내블록킹성 측정(5) Blocking resistance measurement
Heat-Gradient 장비(Heat Gradient Tester, TOYOSEIKI)를 사용하여 아래와 같은 방법으로 Sticky 평가 및 내열내수 평가를 통한 처리 후 찢어짐이나 얼룩 등 외관으로 비교하였다. Heat-Gradient equipment (Heat Gradient Tester, TOYOSEIKI) was used to compare the appearances such as tearing or staining after treatment through sticky evaluation and heat resistance water resistance evaluation as follows.
-두 장의 필름을 로딩(Loading)한 상태에서 일정한 압력과 온도로 필름을 눌러주는 것이고 일정 시간 후에 해당 필름을 꺼내서 붙은 면을 관찰하여 블러킹 특성을 평가한다. 내열내수의 경우 실제 병(Bottle)에 끓는 물을 넣고 두 개의 병(Bottle)을 단단하게 묶은 후 시간의 경과에 따라 라벨의 손상 여부를 확인하는 정성적 평가 방법이다.-Pressing the film at a constant pressure and temperature while loading two sheets of film. After a certain time, take out the film and observe the attached surface to evaluate the blocking characteristics. In the case of heat-resistant water, it is a qualitative evaluation method that checks whether a label is damaged over time after putting boiling water in an actual bottle and tightly tying the two bottles.
외관은 아래와 같은 기호로 표시하였다.The appearance is indicated by the following symbols.
◎: 들러붙음 없음. 얼룩 발생 없음◎: No sticking. No staining
○: 들러붙음 없음. 약한 얼룩 발생○: no sticking. Weak spots occur
△: 약한 들러붙음 발생, 강한 얼룩 발생△: weak adhesion, strong staining
X: 강한 들러붙음 발생, 강한 얼룩 발생X: Strong adhesion, strong staining
상술한 방법으로 측정된 물성을 하기 표 1과 표2에 기재하였다.Physical properties measured by the above-described method are shown in Tables 1 and 2 below.
(6) 가속경시 주름 발생 측정(6) Measurement of wrinkles during acceleration
제조된 필름을 Roll 상태로 포장하여 40℃로 설정된 Aging Room에 넣고 1주일 Aging을 시킨다. 해당 기간 경과 후 Roll 상태에서 5m 풀어서 일정한 장력을 주어 편 다음 육안상 관찰되는 주름의 발생 정도를 확인하는 정성적 평가 방법이다.The prepared film is wrapped in a roll state and placed in an Aging Room set at 40 ° C. for one week. It is a qualitative evaluation method to check the occurrence of wrinkles observed by naked eye after giving a constant tension by loosening 5m in the roll state after the corresponding period.
외관은 아래와 같은 기호로 표시하였다.The appearance is indicated by the following symbols.
○: 주름 발생 없음.○: no wrinkles.
△: 약한 주름 발생. 후공정 사용 문제 없음.(Triangle | delta): A weak wrinkle generate | occur | produces. No post-process use problems.
X: 강한 주름 발생. 후공정 사용 불가X: Strong wrinkles occur. Post process not available
(7) 고유점도 측정(7) intrinsic viscosity measurement
필름을 160± 2℃에서 OCP (Ortho Chloro Phenol)로 녹인 후, 25℃의 조건에서 자동점도 측정기(Skyvis-4000)를 이용하여 점도관에서의 시료 점도를 측정하여 하기 계산식 2로 시료의 고유 점성도(intrinsic viscosity, IV)를 구하였다. After dissolving the film with OCP (Ortho Chloro Phenol) at 160 ± 2 ° C, the sample viscosity in the viscous tube was measured by using an automatic viscosity meter (Skyvis-4000) at 25 ° C. (intrinsic viscosity, IV) was obtained.
[계산식 2] [Calculation 2]
고유점성도(IV) = {(0.0242× Rel)+0.2634}× F Intrinsic Viscosity (IV) = {(0.0242 × Rel) +0.2634} × F
Figure PCTKR2017015772-appb-I000002
Figure PCTKR2017015772-appb-I000002
Figure PCTKR2017015772-appb-I000003
Figure PCTKR2017015772-appb-I000003
상기 계산식 2에서 표준칩(Standard chip)이란 무수한 칩(chip)의 집단에서 하나의 칩을 선별할 경우 특정의 칩을 선정하고자 하는 의도를 가지지 않고 통상의 방법으로 선별된 칩을 의미한다. 또한, 표준동작으로 측정한 것이란 실험자가 소정의 결과값을 도출하려는 특정한 의도 없이 통상의 방법에 따라 측정하여 진행한 것을 의미한다. In the formula 2, a standard chip means a chip selected by a conventional method without the intention of selecting a specific chip when selecting one chip from a group of countless chips. In addition, the measurement by the standard operation means that the experimenter measured and proceeded according to a conventional method without a specific intention to derive a predetermined result value.
(8) 유리전이온도 측정(8) glass transition temperature measurement
필름을 일정 크기로 절단하여 상온에서부터 280℃까지 분당 20℃ 승온 속도 조건에서 시차주사열량계(TA Instruments社, Q20)를 이용하여 열 흐름을 측정하였다. 해당 열 흐름 중에서 흡열 Peak의 온도를 확인하여 해당 Peak의 온도를 유리전이온도로 하였다.The film was cut to a certain size and the heat flow was measured using a differential scanning calorimeter (TA Instruments, Q20) at room temperature rate of 20 ℃ per minute from room temperature to 280 ℃. The temperature of the endothermic peak was confirmed in the heat flow, and the temperature of the peak was regarded as the glass transition temperature.
(9) 분자량분포 측정(9) Molecular weight distribution measurement
시료 25mg을 0.5mL HFIP에 녹인 후 Eluent 9.5mL 희석을 시킨다. 표준물은 5mg을 0.25mL HFIP에 녹인 후 Eluent 4.75mL에 희석시킨다. 해당 표준물을 이용하여 측정 기기인 GPC(영린, GPC AutoChro)에서 영점 조정을 한 후 시료를 희석시킨 용액을 기기에 투입하여 측정한다. 측정 시 Column은 μStyragel 103 + 104+ 105A을 사용하고 Flow Rate 1.0mL/min, 40℃로 유지한다. Dissolve 25 mg of sample in 0.5 mL HFIP and dilute Eluent 9.5 mL. The standard is dissolved in 5 mL of 0.25 mL HFIP and diluted in 4.75 mL of Eluent. Using the standard, zero-point calibration is performed on the measuring device GPC (English, GPC AutoChro), and the diluted solution is added to the device for measurement. For measurement, use a column of μStyragel 10 3 + 10 4 + 10 5 A and maintain the flow rate at 1.0mL / min and 40 ℃.
상술한 방법으로 측정된 물성을 하기 표 1과 표 2에 기재하였다.Physical properties measured by the above-described method are shown in Tables 1 and 2 below.
THF 접착력(Kgf)THF Adhesion (Kgf) 수축응력(Kg/㎟)Shrinkage Stress (Kg / ㎡) 슈팅공정성(Ea.)Shooting Fairness (Ea.) 내블록킹성Blocking resistance 마찰계수Coefficient of friction
실시예 1Example 1 0.870.87 1.321.32 100100 ◎◎ 0.180.18
실시예 2Example 2 0.820.82 1.231.23 9999 ◎◎ 0.200.20
실시예 3Example 3 0.820.82 1.191.19 100100 ◎◎ 0.180.18
실시예 4Example 4 0.680.68 1.291.29 100100 ◎◎ 0.190.19
실시예 5Example 5 0.850.85 1.551.55 100100 ◎◎ 0.180.18
비교예 1Comparative Example 1 0.570.57 1.521.52 100100 ◎◎ 0.170.17
비교예 2Comparative Example 2 0.620.62 1.381.38 9898 ◎◎ 0.180.18
비교예 3Comparative Example 3 필름 제조 불가No film production
비교예 4Comparative Example 4 0.840.84 1.331.33 7676 XX 0.450.45
비교예 5Comparative Example 5 0.920.92 1.621.62 9999 ◎◎ 0.190.19
비교예 6Comparative Example 6 0.550.55 1.091.09 100100 ◎◎ 0.200.20
비교예 7Comparative Example 7 1.321.32 1.021.02 8686 ◎◎ 0.190.19
70℃열수축율(%)70 ℃ Heat Shrinkage (%) 90℃열수축율(%)90 ℃ Heat Shrinkage (%) 가속 경시 주름 발생Accelerated aging wrinkles
실시예 1Example 1 2424 7676 ○○
실시예 2Example 2 2525 7575 ○○
실시예 3Example 3 2727 7575 ○○
실시예 4Example 4 2626 7575 ○○
실시예 5Example 5 4747 7676 ○○
비교예 1Comparative Example 1 2525 7676 ○○
비교예 2Comparative Example 2 2525 7575 ○○
비교예 3Comparative Example 3 필름 제조 불가No film production
비교예 4Comparative Example 4 2525 7575 ○○
비교예 5Comparative Example 5 2626 7676 XX
비교예 6Comparative Example 6 2525 7575 ○○
비교예 7Comparative Example 7 3838 7777 XX
상기 표 1과 2에 나타난 바와 같이, 실시에 1 내지 4는 최종 필름의 구조를 벌키하게 하면서 필름 내 존재하는 잔류 응력을 일부 해소 시켜줌으로써 THF의 접착력을 향상시킴과 더불어 경시 안정성을 부여함으로써 장기 보관을 하더라도 후공정에 문제가 없음을 알 수 있었다. 특히 실시예 3의 경우 실시예 1 내지 2에 비해 수축응력이 더 낮아 딱딱한 용기뿐 아니라 상대적으로 연질인 PE Bottle에도 적용할 수 있어 그 용도가 더 넓을 수 있다. 또한, 실시예 4의 경우 실시예 1 내지 3에 비하여 접착력이 다소 약하여 용기의 형태에 따라 달리 적용될 수 있다. 또한, 실시예 5는 70℃의 온수에서 측정된 수축율이 높아 스팀을 이용하는 수축 공정에 이용될 수 있다. As shown in Tables 1 and 2, in Examples 1 to 4, the bulk structure of the final film was removed to partially relieve residual stresses present in the film, thereby improving the adhesion of THF and providing stability over time for long-term storage. Even if it was found that there is no problem in the post-process. In particular, in the case of Example 3, the shrinkage stress is lower than that of Examples 1 to 2 can be applied to a relatively soft PE bottle as well as a rigid container, its use can be wider. In addition, in the case of Example 4, the adhesive strength is slightly weaker than in Examples 1 to 3, and thus may be differently applied depending on the shape of the container. In addition, Example 5 may be used in a shrinkage process using steam because the shrinkage rate measured in hot water at 70 ℃ high.
그러나 비교예 1 내지 2에 따라 제조된 열수축성 폴리에스테르계 필름은 THF와의 접착력 특성이 저하되어 시밍공정을 통한 라벨 제조가 불가하고 비교예 3의 경우 접착력은 우수하나 최종 필름의 낮은 Tg로 인해 치수 안정성이 저하되어 자연수축에 의한 경시 주름이 발생된다. 비교예 4의 경우 표면 코팅을 통한 표면처리가 되지 않음으로 인해 슈팅 공정성이 불량하여 적용이 불가함을 알 수 있었다. 수축 공정의 경우 스팀을 이용하거나 열풍을 이용하게 되는데 스팀을 이용하는 경우 70℃ 수축율이 중요하지 않으나 열풍을 이용하는 경우 수축되는 속도에 따라 수축 후 외관 품질의 차이가 발생한다. 본 발명이 속한 분야의 업계에서는 수축속도가 느릴수록 수축 후 외관 품질이 우수하다고 알려져 있으며, 비교예 5의 경우 필름을 제조한 시점에는 육안으로 주름이 확인되지 않으나 일정 시간 경과 후에는 필름 내에 존재하는 잔류 응력에 의한 수치 변화가 발생되고 해당 수치 변화에 의해 표면에 주름이 발생된다. 필름에 주름이 발생될 경우 인쇄 공정 및 시밍 공정에서 불량이 발생되어 사용할 수 없게 된다. 비교예 6의 경우 과도한 열처리에 의해 필름의 결정화가 증가하고 이로 인해 THF의 스웰링 현상이 줄어 들어 THF와의 접착력 특성이 떨어져 슬리브를 제조할 수 없게 된다. 비교예 7의 경우 과도한 공중합 공중합물을 적용함에 따라 접착력은 매우 높으나 접착 용매의 투과 현상이 발생되어 최종 라벨에서 라벨간 접착이 발생되어 슈팅 공정성이 저하됨은 물론 매우 낮은 Tg로 인해 치수 안정성이 저하되어 자연수축에 의한 경시 주름이 발생된다. However, the heat-shrinkable polyester film prepared according to Comparative Examples 1 to 2 has a poor adhesive strength with THF, thus making it impossible to manufacture a label through the seaming process. In Comparative Example 3, the adhesive film has excellent adhesive strength but low Tg of the final film. Stability deteriorates and wrinkles occur with natural shrinkage. In the case of Comparative Example 4 it was found that the shooting processability is poor because the surface treatment is not performed through the surface coating is not applicable. In the contraction process, steam or hot air is used. When steam is used, the shrinkage rate of 70 ° C. is not important. However, in the case of using hot air, the appearance quality after shrinkage occurs depending on the shrinkage rate. In the industry to which the present invention belongs, the slower the shrinkage rate, the better the appearance quality after shrinkage. In the case of Comparative Example 5, the wrinkles are not visually confirmed at the time of manufacturing the film, but present in the film after a certain time. Numerical changes occur due to residual stress, and wrinkles appear on the surface due to the numerical change. When wrinkles are generated in the film, defects occur in the printing process and the seaming process, and thus they cannot be used. In Comparative Example 6, the crystallization of the film is increased due to excessive heat treatment, which reduces the swelling phenomenon of the THF, thereby making it impossible to manufacture the sleeve due to poor adhesion to THF. In the case of Comparative Example 7, the adhesive strength is very high as the excessive copolymerization is applied, but the permeation phenomenon of the adhesive solvent is generated, resulting in adhesion between the labels in the final label, resulting in poor shooting processability and low dimensional stability due to very low Tg. Wrinkles occur over time due to natural shrinkage.
본 발명의 단순한 변형 또는 변경은 모두 이 분야의 통상의 지식을 가진 자에 의하여 용이하게 실시될 수 있으며 이러한 변형이나 변경은 모두 본 발명의 영역에 포함되는 것으로 볼 수 있다.　All simple modifications or changes of the present invention can be easily carried out by those skilled in the art, and all such modifications or changes can be seen to be included in the scope of the present invention.
본 발명은 열수축 특성을 가지며, 일축 배향된 열수축성 폴리에스테르계 필름, 이의 제조방법 및 이를 포함하는 라벨에 이용가능하다.The present invention has a heat shrink property, and can be used for uniaxially oriented heat shrinkable polyester film, a method for preparing the same, and a label including the same.

Claims (15)

  1. 유리전이온도가 70 내지 80℃, 고유점도가 0.60 내지 0.75dl/g 및 분자량분포가 2.0 내지 4.0인 코폴리에스테르 수지를 포함하는 기재필름 및 상기 기재필름의 일면 또는 양면에 형성된 프라이머 코팅층을 포함하고, It includes a base film comprising a copolyester resin having a glass transition temperature of 70 to 80 ℃, intrinsic viscosity 0.60 to 0.75dl / g and molecular weight distribution of 2.0 to 4.0 and a primer coating layer formed on one or both sides of the base film ,
    상기 코폴리에스테르 수지는 디카르복실산 모노머, 이소프탈릭산 및 디올 모노머를 포함하여 공중합된 것이고, The copolyester resin is copolymerized including a dicarboxylic acid monomer, isophthalic acid and a diol monomer,
    90℃의 온수에서 측정된 주수축방향의 수축율이 40% 이상이고, 테트라하이드로퓨란(THF)와의 접착력이 0.65 내지 1Kgf인 열수축성 폴리에스테르계 필름.A heat shrinkable polyester film having a shrinkage ratio of 40% or more in the main shrinkage direction measured at 90 ° C. in hot water, and an adhesion force of tetrahydrofuran (THF) of 0.65 to 1 Kgf.
  2. 제1항에 있어서, 상기 코폴리에스테르 수지는 디카르복실산 모노머 및 이소프탈릭산이 85 내지 95 : 5 내지 15의 몰비로 포함하여 공중합된 것을 특징으로 하는 열수축성 폴리에스테르계 필름.The heat-shrinkable polyester film of claim 1, wherein the copolyester resin is copolymerized by including a dicarboxylic acid monomer and isophthalic acid in a molar ratio of 85 to 95: 5 to 15.
  3. 제1항에 있어서, 상기 디카르복실산 모노머는 테레프탈산, 옥살산, 말론산, 숙신산, 아디프산, 수베르산, 아젤라산, 세바스산, 프탈산, 나프탈렌디카르복실산, 디페닐 에테르 디카르복실산 및 이들로 이루어진 군에서 선택되는 어느 하나 이상인 것을 특징으로 하는 열수축성 폴리에스테르계 필름.The dicarboxylic acid monomer according to claim 1, wherein the dicarboxylic acid monomer is terephthalic acid, oxalic acid, malonic acid, succinic acid, adipic acid, suveric acid, azelaic acid, sebacic acid, phthalic acid, naphthalenedicarboxylic acid, diphenyl ether dicarboxylic acid. Heat-shrinkable polyester film, characterized in that any one or more selected from the group consisting of acids and these.
  4. 제1항에 있어서, 상기 디올 모노머는 에틸렌 글리콜, 네오펜틸 글리콜, 프로필렌 글리콜, 트리메틸렌 글리콜, 테트라메틸렌 글리콜, 헥사메틸렌 글리콜, 디에틸렌 글리콜, 폴리알킬렌 글리콜, 1,4-시클로헥산 디메탄올 및 이들로 이루어진 군에서 선택되는 2종 이상인 것을 특징으로 하는 열수축성 폴리에스테르계 필름. The method of claim 1 wherein the diol monomer is ethylene glycol, neopentyl glycol, propylene glycol, trimethylene glycol, tetramethylene glycol, hexamethylene glycol, diethylene glycol, polyalkylene glycol, 1,4-cyclohexane dimethanol and Heat-shrinkable polyester film, characterized in that two or more selected from the group consisting of these.
  5. 제1항에 있어서, 상기 프라이머 코팅층은 5 내지 50㎚의 두께이며, 마찰계수가 0.20 이하인 것을 특징으로 하는 열수축성 폴리에스테르계 필름.The heat-shrinkable polyester film of claim 1, wherein the primer coating layer has a thickness of 5 to 50 nm and a coefficient of friction of 0.20 or less.
  6. 제1항에 있어서, 상기 프라이머 코팅층은 아크릴 바인더 및 슬립제를 포함하는 것을 특징으로 하는 열수축성 폴리에스테르계 필름. The heat-shrinkable polyester film of claim 1, wherein the primer coating layer comprises an acrylic binder and a slip agent.
  7. 제6항에 있어서, 상기 프라이머 코팅층은 아크릴 바인더 100 중량부를 기준으로 하여, 슬립제 150 내지 250 중량부를 포함하는 것을 특징으로 하는 열수축성 폴리에스테르계 필름. The heat-shrinkable polyester film of claim 6, wherein the primer coating layer comprises 150 to 250 parts by weight of the slip agent based on 100 parts by weight of the acrylic binder.
  8. 디카르복실산 모노머 및 디올 모노머를 혼합한 후, 이소프탈릭산을 첨가하여 축중합 반응시켜 코폴리에스테르 수지를 제조하는 단계(S1);Mixing the dicarboxylic acid monomer and the diol monomer, and then adding isophthalic acid to polycondensation to prepare a copolyester resin (S1);
    상기 제조된 코폴리에스테르 수지를 255 내지 280℃에서 용융시켜 미연신 시트를 제조하는 단계(S2); Melting the prepared copolyester resin at 255 to 280 ℃ to prepare an unstretched sheet (S2);
    상기 S2 단계에서 제조된 미연신 시트의 일면 또는 양면에 프라이머 코팅층 조성물을 코팅하여 프라이머 코팅층을 형성하는 단계(S3); Forming a primer coating layer by coating the primer coating layer composition on one or both surfaces of the unstretched sheet prepared in step S2 (S3);
    상기 프라이머 코팅층이 형성된 미연신 시트에 열을 가한 후, 6 내지 10m/sec의 연신속도로 주수축 방향의 연신비를 4 내지 6배로 하여 한 방향으로 연신시키는 단계(S4); 및 Applying heat to the unstretched sheet on which the primer coating layer is formed, and stretching in one direction at a stretch ratio of 4 to 6 times in the main contraction direction at a stretch speed of 6 to 10 m / sec (S4); And
    상기 한 방향으로 연신된 필름을 70 내지 80℃로 열처리 하는 단계(S5)를 포함하는 열수축성 폴리에스테르계 필름의 제조방법.Method for producing a heat-shrinkable polyester film comprising the step (S5) of heat-treating the film stretched in one direction at 70 to 80 ℃.
  9. 제8항에 있어서, 상기 S1 단계에서 상기 코폴리에스테르 수지는 디카르복실산 모노머, 이소프탈릭산 및 디올 모노머가 85 내지 95 : 5 내지 15 : 100의 몰비로 포함하여 축중합 반응시켜 제조되는 것을 특징으로 하는 열수축성 폴리에스테르계 필름의 제조방법. The method of claim 8, wherein the copolyester resin in the step S1 is a dicarboxylic acid monomer, isophthalic acid and diol monomers are prepared by the polycondensation reaction including a molar ratio of 85 to 95: 5 to 15: 100 Method for producing a heat-shrinkable polyester film characterized in that.
  10. 제8항에 있어서, 상기 디카르복실산 모노머는 테레프탈산, 옥살산, 말론산, 숙신산, 아디프산, 수베르산, 아젤라산, 세바스산, 프탈산, 나프탈렌디카르복실산, 디페닐 에테르 디카르복실산 및 이들로 이루어진 군에서 선택되는 어느 하나 이상인 것을 특징으로 하는 열수축성 폴리에스테르계 필름의 제조방법.The dicarboxylic acid monomer according to claim 8, wherein the dicarboxylic acid monomer is terephthalic acid, oxalic acid, malonic acid, succinic acid, adipic acid, suveric acid, azelaic acid, sebacic acid, phthalic acid, naphthalenedicarboxylic acid, diphenyl ether dicarboxyl. A method of producing a heat-shrinkable polyester film, characterized in that any one or more selected from the group consisting of acids and these.
  11. 제8항에 있어서, 상기 디올 모노머는 에틸렌 글리콜, 네오펜틸 글리콜, 프로필렌 글리콜, 트리메틸렌 글리콜, 테트라메틸렌 글리콜, 헥사메틸렌 글리콜, 디에틸렌 글리콜, 폴리알킬렌 글리콜, 1,4-시클로헥산 디메탄올 및 이들로 이루어진 군에서 선택되는 2종 이상인 것을 특징으로 하는 열수축성 폴리에스테르계 필름의 제조방법.The method of claim 8, wherein the diol monomer is ethylene glycol, neopentyl glycol, propylene glycol, trimethylene glycol, tetramethylene glycol, hexamethylene glycol, diethylene glycol, polyalkylene glycol, 1,4-cyclohexane dimethanol and A method for producing a heat-shrinkable polyester film, characterized in that two or more selected from the group consisting of these.
  12. 제8항에 있어서, 상기 프라이머 코팅층은 20 내지 100㎚의 두께로 형성되는 것을 특징으로 하는 열수축성 폴리에스테르계 필름의 제조방법.The method of claim 8, wherein the primer coating layer is formed of a thickness of 20 to 100nm method of producing a heat-shrinkable polyester film.
  13. 제8항에 있어서, 상기 프라이머 코팅층 조성물은 아크릴 바인더 및 슬립제를 포함하는 것을 특징으로 하는 열수축성 폴리에스테르계 필름의 제조방법.The method of claim 8, wherein the primer coating layer composition comprises an acrylic binder and a slip agent.
  14. 제12항에 있어서, 상기 프라이머 코팅층 조성물은 아크릴 바인더 100중량부를 기준으로 하여 슬립제 150 내지 250중량부를 포함하는 것을 특징으로 하는 열수축성 폴리에스테르계 필름의 제조방법.The method of claim 12, wherein the primer coating layer composition comprises 150 to 250 parts by weight of a slip agent based on 100 parts by weight of the acrylic binder.
  15. 제1항 내지 제7항 중에서 어느 한 항의 열수축성 폴리에스테르계 필름을 포함하는 라벨.A label comprising the heat-shrinkable polyester film of any one of claims 1 to 7.
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