WO2015102339A1 - Film polyester ayant une résistance élevée à la chaleur - Google Patents

Film polyester ayant une résistance élevée à la chaleur Download PDF

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Publication number
WO2015102339A1
WO2015102339A1 PCT/KR2014/012975 KR2014012975W WO2015102339A1 WO 2015102339 A1 WO2015102339 A1 WO 2015102339A1 KR 2014012975 W KR2014012975 W KR 2014012975W WO 2015102339 A1 WO2015102339 A1 WO 2015102339A1
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WO
WIPO (PCT)
Prior art keywords
film
polyester film
polyester
resin
longitudinal
Prior art date
Application number
PCT/KR2014/012975
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English (en)
Korean (ko)
Inventor
이세철
정다우
김수희
허영민
이장원
기정희
김상일
이득영
Original Assignee
에스케이씨 주식회사
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from KR1020130167005A external-priority patent/KR101594542B1/ko
Priority claimed from KR1020140004741A external-priority patent/KR101647470B1/ko
Priority claimed from KR1020140015977A external-priority patent/KR101605413B1/ko
Priority claimed from KR1020140020456A external-priority patent/KR101605411B1/ko
Priority claimed from KR1020140191073A external-priority patent/KR101647475B1/ko
Application filed by 에스케이씨 주식회사 filed Critical 에스케이씨 주식회사
Publication of WO2015102339A1 publication Critical patent/WO2015102339A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/16—Dicarboxylic acids and dihydroxy compounds
    • C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
    • C08G63/199—Acids or hydroxy compounds containing cycloaliphatic rings
    • 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
    • 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

Definitions

  • Polyester film having high heat resistance Polyester film having high heat resistance
  • the present invention relates to a polyester film that is transparent and excellent in heat resistance and suitable as an optical film.
  • LCDs liquid crystal displays
  • OLED organic light emitting diode
  • a back light unit in the form of a back light source capable of maintaining uniform brightness on the screen premises is required, and the backlight
  • a small fluorescent lamp or a light emitting diode LED
  • the BLU is diverted to a light guide plate that converts it into a uniform surface light source, and a reflector to reduce light loss by reflecting a debt exiting to the lower side of the light guide plate, and to the upper axis of the light guide plate.
  • the polyester film mainly used as an optical film of the conventional display device has a problem of heat resistance due to a low glass transition temperature (Tg), and in particular, at a high temperature, oligomer elution occurs, thereby causing a problem of coating an oligomer blocking layer on the film. .
  • Tg glass transition temperature
  • the tendency of the hydrolysis of the polyester at high temperatures is very important for durability in this application.
  • iodine it has long been known that the lower carboxyl end group content (CEG content) can lower the hydrolysis, but precise process control is required to produce polyesters with low carboxyl end group content. And subsequent solid phase polymerization and the like (US Pat. No. 3,051,212).
  • PCT poly (1,4-cyclohexanedimerylene terephthalate) (PCT) derived from 1,4-cyclohexanedimethanol (CHDM) is a transparent, heat resistant, hydrolytically stable polyester Known as
  • CHDM 1,4-cyclohexanedimethanol
  • polyester film which is excellent in heat resistance, hydrolytically stable, and which is free from physical property deterioration due to crystallization at high temperature.
  • the present invention is 0) the structure derived from a diol component containing 90 mol 0 / ⁇ or more nucleic acid 1,4-cyclohexane dimethanol danwoo i, and ( ⁇ ) 3 to 25 mole 0/0 It comprises a polyester resin comprising a structural unit derived from a dicarboxylic acid component containing isophthalic acid of, has a haze of 2% or less, heat shrinkage after holding for 1 hour at 150 o C both in the longitudinal and transverse directions It provides a polyester film having 3% or less and less than 1% haze defense.
  • a diol component comprising a diethanolamine-hexane to 90 mole 0/0 or more 1,4-cyclohexane, and () 3 to 25 mole% of isophthaloyl ralsan of Preparing a polyester resin by polymerizing a dicarboxylic acid component;
  • the present invention also provides an optical film comprising the polyester film.
  • the present invention also provides a display device comprising the polyester film.
  • the polyester film of the present invention is transparent and excellent in heat resistance, and exhibits excellent hydrolysis resistance such as being able to maintain inherent excellent film properties even when exposed to long periods of time, and even at high temperatures and humidity. It is to provide a polyester film suitable as an optical film for display without deterioration in physical properties.
  • 1 is an SEM image of a film prepared in Example.
  • the polyester film according to the present invention is a polyester comprising a structural unit derived from (0 diol component and (ii) a dicarboxylic acid component. Resin tool is included. Such a polyester resin may be induced by polymerization after the ester exchange reaction between the diol component and the dicarboxylic acid component.
  • the diol component is 90 mol 0/0 over lead i 1,4-cyclohexanedimethanol comprises the constitutional unit derived from methanol (CHDM), preferably CHDM to 98 mole 0/0, more preferably at least 99 mole It comprises 0/0 above.
  • the diol component may further include a diol component other than CHDM.
  • diol component which may be further included as such are ethylene glycol, 1,3-propanediol, 1,2-octanediol, 1,3-octanediol, 2,3-butanediol, 1,3-butanediol , 1,4-butanediol, 1,5-pentanediol, 2,2-dimeryl-1,3-propanediol (neopennylglycol), 2-butyl-2-eryl-1,3-propanediol , 2,2-diaryl-1,5-pentanediol, 2,4-diaryl-1,5-pentanediol, 3-methyl-1,5-pentanediol, 1,1-dimeryl-1, 5-pentanediol and mixtures thereof are mentioned.
  • the polyester resin of the present invention contains isopral acid as the dicarboxylic acid component to lower the crystallization rate.
  • the crystallization rate which is excessively high as CHDM is included, may be lowered, and the handleability of the polymerizer may be increased by lowering the melting temperature (Tm) of the polymerizing agent.
  • Tm melting temperature
  • the dicarboxylic acid component is the isophthalic acid with 3 to 25 mol%, relief write down to 5 to 20 mole 0/0, and if in more relief typically 5 to 18 moles of even more specifically 5 0/0, 15 mole May contain%.
  • the dicarboxylic acid component is the isophthaloyl LAL acid 10 mol 0/0 or less, remedies typically 0 mol 0/0 larger than 7 mole 0/0 or less, and more relief typically 0 mol 0/0 ultrahigh a 5 mol It can comprise an amount of not more than 0/0.
  • the dicarboxylic acid component may also include terephthalic acid.
  • the dicarboxylic acid component is 75 to 97 mol%, terephthalic acid.
  • the expulsion of 80 to 95 mole 0/0, more particularly 82 to 95 mole 0/0, than ever relief may further comprise 85 to 95 mole%.
  • the dicarboxylic acid component is 90 mol of the rim Lev ralsan 80 mole 0/0 or more, or 90 mol 0/0 or more, for example 80 mole 0/0 100 mole 0 / less than 0, more relief enemy % or more and less than 100 mole 0/0, can be more specifically hamhal included by 93 mol% or more and 100 mole 0 / less than 0, more typically relief 95 mole 0/0 100 mol is less than 0/0.
  • the polyester resin may be a copolyester resin.
  • said dicarboxylic acid component Aromatic dicarboxylic acid, such as a diaryl terephthalic acid, naphthalenedicarboxylic acid, orthophthalic acid; Aliphatic dicarboxylic acids such as adipic acid, azelaic acid, sebacic acid, and decanedicarboxylic acid; Alicyclic dicarboxylic acid; And it may further include one or more selected from the group consisting of these esterified products.
  • the polyester resin may include 1,4-cyclohexanedimerylene terephthalate, or 1,4-cyclonucleic acid dimethylene isophthalate terephthalate as a main repeating unit.
  • the polyester film according to the invention has an intrinsic viscosity (at 25 ° C) of 6 to 1.2 for filming and preferably has a weight average molecular weight of 30,000 to 50,000 g / mol, in particular 30,000 to 40,000 g / mol. Do.
  • the polyester film may be one containing fine particles in a polyester resin.
  • the fine particles may be, for example, inorganic particles such as colloidal silica, titanium oxide, aluminum oxide, coral zirconia or calcium carbonate, or organic particles such as crosslinked polyester particles, crosslinked polystyrene particles, or other crosslinked polymer particles. , 1 type may be used, or 2 or more types may be used together.
  • the polyester resin may comprise 200 to 3,000 ppm, preferably 400 to 1,500 ppm of spherical monodisperse particles.
  • spherical monodisperse particles By including the spherical monodisperse particles to increase the sulphability of the polyester film, self-contacting of the polyester film It can solve the difficulty of winding up.
  • the friction coefficient of the film can be appropriately lowered without excessive rise in haze, and thus the winding property of the film can be improved.
  • the spherical monodisperse particles is from 0.1 to 2.5 ⁇ , preferably from 0.1 to 2.0 ⁇ (may have a mean particle size of ⁇ , a ratio of the lead 5 to 1.2, preferably from 0.8 to 1.2, more Wook preferably 0.8
  • the particle diameter ratio may be expressed as the ratio of the long diameter I average value of the spherical monodispersed particles to the average value of the short diameter.
  • the coefficient of friction of the film can be set to 0.8 or less while preventing pinholes from occurring and breaking or dispersing to increase the haze.
  • the spherical monodisperse particles may be inorganic particles or organic particles, but preferably inorganic particles, for example, may be at least one selected from the group consisting of spherical silica, spherical titanium oxide, and spherical zirconium.
  • the polyester film of the present invention includes spherical monodisperse particles having an average particle diameter and a particle size in the above range. The problem can be solved. Therefore, the spherical monodisperse particles may be added in the middle of the polymerization of the polyester resin, or may be included in the polyester film by being added to the finished polyester resin and compounded.
  • an application layer may be formed on one or both surfaces.
  • the coating layer may be formed on one side or both sides of the polyester film, it can improve the post-processing and blocking properties of the film.
  • the applicator may include at least one resin selected from the group consisting of polyester resins, acral resins, polyurethane resins, melamine resins, and oxazoline resins, and the coating liquid composition wool comprising the resin. It may be formed by coating on one or both sides of the polyester film and then curing.
  • the coating liquid composition may include a photoinitiator, a solvent, and the like, and the kind thereof is not particularly limited.
  • Polyester-based resin used in the coating layer is an ester grain in the main chain black side chain It may be a polyester resin having a sum.
  • the glass transition temperature (Tg) of the polyester resin may be 50 ⁇ 170 ° C, preferably 50 ⁇ 150 ° C. When the Tg is 50 ° C or more, it is possible to exert a proper moisture resistance, and when the Tg is 17CTC or less, the resin is excellent in coating property and the resin can be uniformly applied.
  • the polyester resin may contain a component having a naphthalene and / or fluorene skeleton, or may contain an aromatic dicarboxylic acid component.
  • the polyester resin is the premise is applied to liquid compositions based on the solid content in the range of 0.1 to 50 parts by weight 0 / o, preferably from 1 to 30 parts by weight 0/0, and more preferably may be used in a 5 to 20% by weight.
  • the acrylic resin used in the coating layer may be a colloidal acrylic-ester copolymer resin.
  • the coating layer includes an acrylic resin, it may further include an isocyanate, epoxy or melamine-based curing agent for durability and solvent resistance improvement.
  • the acrylic resin may be used in total based on solids in the coating of 0.1 to 60 parts by weight 0/0 solution of the composition, preferably 1 to 50 parts by weight 0/0, more preferably 10 to 40 wt. 0/0.
  • the polyurethane resin used in the coating layer may be prepared by copolymerizing dicarboxylic acid and glycol component.
  • dicarboxylic acid component include aromatics such as terephthalic acid, isophthalic acid, 1,4-napralene dicarboxylic acid, 2.5-naphthalene dicarboxylic acid, 2,5-methylcarboxylic acid and dimetal isophthalic acid.
  • Dicarboxylic acid Dicarboxylic acid; Alicyclic dicarboxylic acids such as 1,3-cyclopentane dicarboxylic acid, 1,2-cyclonucleic acid dicarboxylic acid, 1,3-cyclohexane dicarboxylic acid, and 1,4-cyclonucleic acid dicarboxylic acid mountain; And aliphatic dicarboxylic acids such as adipic acid, sebacic acid, and the like, with aromatic dicarboxylic acids being particularly preferred.
  • Alicyclic dicarboxylic acids such as 1,3-cyclopentane dicarboxylic acid, 1,2-cyclonucleic acid dicarboxylic acid, 1,3-cyclohexane dicarboxylic acid, and 1,4-cyclonucleic acid dicarboxylic acid mountain
  • aliphatic dicarboxylic acids such as adipic acid, sebacic acid, and the like, with aromatic dicarboxylic acids being particularly preferred.
  • the glykul component is preferably an aliphatic glycol having 2 to 8 carbon atoms and an alicyclic glycol having 6 to 12 carbon atoms, for example, ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4 Butanediol, neophenyl glycol, 1,6-hexanediol, 1,2-cyclohexanemethanol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanediethanol, p-xylene glycol, diethylene Glycol, triethylene glycol, polyether glycol, polyethylene glycol, polytetramethylene glycol, and the like, and among these, ethylene glycol is preferable.
  • the polyurethane-based resin may be used as ⁇ to 50 parts by weight 0/0, preferably from 1 to 40 parts by weight 0/0, more preferably from 5 to 30 parts by weight 0/0 based on the solids content of the coating liquid composition premise.
  • the melamine-based resin used in the coating layer may be a melamine-based crosslinking agent, special Although not limited to this, for example, a melylated delamine inducer obtained by condensation of melamine, melaminegoform formaldehyde, a methylolated delamin reaction with a lower alcohol, or a partial black is a completely etherified compound thereof, or Mixtures and the like can be used.
  • the condensate which consists of a monomer, a dimer or more multimer, black, a mixture thereof, etc. can be used as a melamine type crosslinking agent.
  • the tie lamin-based resin may be used in 0.1 to 50% by weight based on the solids content of the coating solution assumes the composition, preferably 1 to 30 parts by weight 0/0, more preferably 5 to 20% by weight.
  • the oxazoline-based resin used in the coating layer may be an oxazoline group-containing polymer, and the oxazoline group-containing polymer may include at least one monomer having an oxazoline group, and may be obtained by copolymerization with at least one other monomer. It may be.
  • the oxazoline group-containing polymer may be cured by heat reaction of functional groups such as hydroxyl group and carboxyl group by heat.
  • the oxazoline-based resins to the premise coating liquid composition based on solids in the range of 0.1 to 70 parts by weight 0/0, preferably from 1 to 60 parts by weight 0/0, more preferably in the can be used in the range of 10 to 50% by weight.
  • the coating layer may have a thickness of 0.01 to 2 ⁇ , preferably 0.01 to 1.5 ⁇ . When the thickness is in the range of 0.01 / jm to 2 ⁇ it can exhibit the function of a sufficient coating layer.
  • the coating layer may be formed by an in-line coating method or an offline coating method, and the application of the coating liquid for forming the coating layer may be performed by applying a reverse coater, a gravure coater, a rod coater, an air doctor coater, or other methods. It can be done by wrapping paper. In order to improve the applicability and / or tackiness of the coating liquid for forming the coating layer on the surface of the polyester film on which the coating layer is formed, a chemical treatment or a corona discharge treatment is performed before the coating liquid is applied. Can be made.
  • the polyester film of the present invention may include a hard coat layer formed on one side of the film to improve brittleness.
  • the hard coating layer may be made of a resin such as a thermoplastic resin, a thermosetting resin, an ionizing radiation (ultraviolet or electron radiation) curable resin, preferably (a) a bifunctional or higher acrylate monomer having ethylene glycol, and (b Multifunctional Urethane Acrylate-based Oligomer and Multifunctional Acrylate-Based Parenter without Eylene Glycol
  • the hard coating composition including at least one of the monomers may be cured.
  • the number of functional groups is n
  • the number of ethylene glycol (EO) contained is n to 2n
  • the number average molecular weight is 100 to 200 ⁇ . It is specified.
  • a bifunctional acrylate monomer it may include 2 to 4 ethylene glycol, the number average molecular weight may be 200 to 400.
  • the number average molecular weight may be 300 to 600.
  • Preferred examples of the bifunctional or higher acrylate-based monomers include, but are not limited to, the compounds of Table 1 or a mixture thereof.
  • the content of the bifunctional or higher acrylate monomer having ethylene glycol is preferably 50 to 85% by weight, more preferably 60 to 80% by weight 0 / ⁇ , based on the solids content of the hard coating composition.
  • the polyfunctional acrylate monomer is a general agent for bifunctional or higher polyfunctional acrylate monomers having no ethylene glycol, preferably at least trifunctional.
  • polyfunctional acrylate monomers examples include 1,6-hexanediol diacrylate and 1,6-hex Acid Diol Dimethacrylate, Butanediol Diacrylate, Butanediol Dimethacrylate, Tricyclodecane Diacrylate, Cyclonucleic Acid Diacrylate, Tris (2-Hydroxyeryl) Isocyanurate Diac Lallylate, hydroxyl pivalaldehyde modified trimerylolpropane diacrylate, 1,4-butanediol diacrylate, meralic diacrylate, modified metallic diacrylate, acrylate ester, cyclonucleic acid di Methanol Dimethacrylate, 1,4-Butanediol Dimethacrylate, Merallic Dimethacrylate, Trimethylolpropane Triacrylate, Trimetalol Propane Trimethacrylate, Pentaerythritol Triacrylate, Tris ( 2-hydroxyethyl
  • the polyfunctional urethane acrylate-based oligomer is a mixture of bifunctional or higher polyfunctional urethane acrylate oligomers, and includes, for example, all aliphatic or aromatic urethane acrylate oligomers, preferably at least trifunctional and at least tetrafunctional. More preferred.
  • the polyfunctional urethane acrylate oligomers include bifunctional urethane acrylate oligomers having a number average molecular weight of 1,400 to 25,000, trifunctional urethane acrylate oligomers having a number average molecular weight of 1,700 to 16,000, and tetrafunctional urethane acrates having a number average molecular weight of 1,000.
  • Late oligomers number average molecular weights 818 to 2,600 I 6 functional urethane acrylate oligomers, 9 functional urethane acrylate oligomers having a number average molecular weight of 3,500 to 5,500, 10 functional urethane acrylate oligomers having a number average molecular weight of 3,200 to 3,900, 15 functional urethane acrylate oligomers having an average molecular weight of 2,300 to 20,000 can be used.
  • the polyfunctional acrylate monomer and / or polyfunctional urethane acrylate oligomer content is preferably 9 to 50% by weight, based on the solid content of the hard coating composition, 15 to 40 weight 0 / More preferably.
  • the hard coating composition may include a photoinitiator, a solvent and the like, the type is not particularly limited.
  • the hard coating layer may have a thickness of about 0.1 ⁇ m to about 5 ⁇ m, and preferably about 0.5 ⁇ m to about 3 ⁇ m. ⁇ , more preferably 1 to 2 ⁇ .
  • the hardness of the hard coating layer may be H to 5H.
  • the polyester film of the present invention is prepared by the conventional method of biaxially stretching and heat setting the unstretched sheet in the longitudinal and transverse directions after producing a sheet by melt extruding and engraving the polyester resin of the specific composition. Can be.
  • Melt extrusion is preferably made at a temperature of Tm + 30 ° C to Tm + 60 ° C of the polyester resin. If the temperature of the extruder during the melt extrusion is less than Tm + 30 ° C, smooth melt does not occur, the viscosity of the extrudate is high, productivity is reduced, on the contrary, in the case of Tm + 60 ° C, depolymerization by thermal decomposition of the resin The molecular weight may drop and problems with oligomers may occur.
  • the incidence is preferably made at a temperature of 30 ° C or less, more preferably at 15 ° C to 30 ° C.
  • the polyester film of the present invention may be biaxially stretched in the longitudinal and transverse directions.
  • the defect is mostly due to the decomposition of the polyester chains due to hydrolysis, and particularly the brittleness of the film produced by using the same, even in the length of the jaws, can no longer withstand mechanical deformation such as elongation or bending. . Therefore, as a method for slowing down the decomposition rate, the resistance to the decomposition rate can be greatly increased by providing an orientation to the molecular chain by adjusting the stretching conditions, that is, the stretching rate and the stretching ratio.
  • the stretching temperature is in the range of the glass transition temperature (Tg) + 5 ° C to Tg + 50 ° C of the polyester resin, Preferably it may range from Tg + 10 ° C. to Tg + 40 ° C. At this time, the lower the better the ductility, but breakage may occur.
  • Tg glass transition temperature
  • Tg + 40 ° C the stretching temperature is particularly in the range of Tg + 10 ° C to Tg + 40 ° C, the brittleness of the produced film can be improved. have.
  • the draw ratio may be 2 to 5 times, preferably 2.5 to 5 times, more preferably 2.5 to 4.0 times in the longitudinal direction, 2.5 to 5 times in the transverse direction, preferably 3 to 4.5 times, more preferably.
  • the longitudinal and transverse draw ratios of Class I (MDxTD) may be 4 to 16, preferably 7 to 14, more preferably 8 to 12.
  • the longitudinal drawing speed may be 22 to 500 m / min, preferably 25 to 400 m / min, more preferably 25 to 200 m / min.
  • the longitudinal stretching speed is 22 m / min or more, it is advantageous to maintain the desired orientation in the present invention, and since the crystallinity is given according to the longitudinal stretching speed and the stretching ratio, the transverse stretching speed varies depending on the longitudinal stretching conditions.
  • the film is heat fixed after stretching, the film is relaxed in the longitudinal and / or transverse direction after starting the heat fixing, the heat setting temperature range is preferably 200 ⁇ 260 ° C.
  • the polyester film of the present invention prepared as described above may have a thickness of 12 / jm to 400 ⁇ .
  • polyester film of the present invention may include various additives such as ordinary electrostatic agent, antistatic agent, sunscreen agent, antiblocking agent and other inorganic lubricants within a range that does not impair the effects of the present invention.
  • the present invention provides an optical film and display paper containing the polyester film.
  • polyester film has (i) a configuration derived from a diol component comprising at least 90 mole 0 / 0. I 1,4- cyclohexyl di methanol danwoo I, and ( ⁇ ) 3 to 25 mol
  • a polyester resin comprising a structural unit derived from a dicarboxylic acid component containing% isophthalic acid, having a haze of 2% or less, and after 1 hour hold at 15 CTC, the heat shrinkage is reduced in both the longitudinal and transverse directions. It is less than% and the haze change is less than 1%.
  • Such a polyester resin may be induced by polymerization after the ester exchange reaction between the diol component and the dicarboxylic acid component.
  • the diol component that comprises a constituent unit derived from at least 90 mole 0/0, 1,4-cyclohexane dimethanol nucleic acid (CHDM), preferably from the CHDM 98 mole 0/0, more preferably 0 to 99 mol / It contains 0 or more.
  • the diol component may further contain a diol component other than CHDM.
  • diol component which may be further included as such are ethylene glycol, 1,3-propanediol, 1,2-octanediol, 1,3-octanediol, 2,3-butanediol, 1,3-butanediol , 1,4—butanediol, 1,5-pentanediol, 2,2-dimeryl-1,3-propanediol (neopennylglycol), 2-buryl-2-eryl-1,3-propanediol, 2,2-diethyl-1,5-pentanediol, 2,4-diethyl-1,5-pentanediol, 3-methyl-1,5-pentanediol, 1,1-dimeryl-1,5 -Pentanediol and mixtures thereof.
  • the polyester resin contains isophthalic acid as the dicarboxylic acid component in order to lower the crystallization rate.
  • the crystallization rate which is too high as CHDM is included, can be lowered, and the polymer's melt temperature (Tm) can be lowered to increase the handleability of the polymer, but when included in excess, the Tg of the polymer Gets lower It is possible to lower thermal characteristics such as thermal properties.
  • the dicarboxylic acid component is in the isophthaloyl ralsan 3 to 25 mole 0/0, relief write down to 5 to 20 mole 0/0, the more relief typically 5 to 18 mole 0/0, more relief than ever 5 It may contain 15 mol%.
  • the dicarboxylic acid component may comprise terephthalic acid.
  • Relief Generally, the dicarboxylic acid component is the terephthalic acid to 75 to 97 mol%, sphere expulsion of 80 to 95 mole 0/0, more relief typically 82 to 95 mole 0/0, more relief typically 85 to 95 It may be included in mol%. That is, the polyester resin may be a copolyester resin.
  • Aromatic dicarboxylic acid such as a dimeryl terephthalic acid, a naphthalenedi butyl carboxylic acid, orthophthalic acid; Aliphatic dicarboxylic acids such as adipic acid, azelaic acid, sebacic acid, and decanedicarboxylic acid; Alicyclic dicarboxylic acid; And it may further include one or more selected from the group consisting of these esterified products.
  • the polyester resin may include 1,4-cyclonucleic acid dimerylene isophthalate terephthalate as a main repeating unit.
  • the polyester film has an I intrinsic viscosity (at 25 ° C.) of 0.6 to 1.2 for filming, and it is preferable to have a weight average molecular weight of 30,000 to 50,000 g / m.
  • the polyester film may include a hard coating layer formed on one side of the film to improve brittleness.
  • the hard coating layer may be made of a resin such as a thermoplastic resin, a thermosetting resin, an ionizing radiation (ultraviolet ray or an electron ray) curable resin, and preferably (a) a bifunctional or higher acrylate monomer having an ethylene glycol (EO).
  • a hard coating composition comprising at least one of a polyfunctional urethane acrylate oligomer and a polyfunctional acrylate monomer having no ethylene glycol may be cured.
  • the bifunctional or higher functional acrylate monomer having ethylene glycol is characterized in that when the number of functional groups thereof is n, the number of ethylene glycol contained is n to 2n, and the number average molecular weight is 100 ⁇ to 200 ⁇ . .
  • a bifunctional acrylate monomer it may include two to four ethylene glycol, and may have a horizontal homogeneous molecular weight of 200 to 400.
  • trifunctional acrylate monomer in this case, it may include 3 to 6 ethylene glycol, the number average molecular weight may be 300 to 600.
  • Preferred examples of the bifunctional or higher acrylate monomer include, but are not limited to, the compounds of Table 1 or mixtures thereof.
  • the tolylene bifunctional or more acrylate monomers coming I content with a glycol and, when based on the solids content of the de-coating composition, and is 50 to 85% by weight, preferably, it is 60 to 80 parts by weight 0/0, more preferably .
  • the polyfunctional acrylate monomer is a general agent for bifunctional or higher polyfunctional acrylate monomers having no ethylene glycol, preferably at least trifunctional.
  • polyfunctional acrylate monomers examples include 1,6-hexanediol diacrylate, 1,6-nucleic acid diol dimethacrylate, butanediol diacrylate, butanediol dimethacrylate, and tricyclodecane diacrylate Latex, cyclohexane diacrylate, tris (2-hydroxyeryl) isocyanurate diacrylate, hydroxyl pivalaldehyde modified trimerylolpropane diacrylate, 1,4-butanediol diacrylate Lateral, Merallic Diacrylate, Modified Meralic Diacrylate, Acrylate Ester, Cyclohexanedi Methanol Dimethacrylate, 1,4-Butanediol Dimethacrylate, Merallic Dimethacrylate, Trimeryl Allpropane triacrylate, trimethylolpropane trimethacrylate, pentaerythrite triacrylate, tris (2—hydroxyether) isocyanur
  • Polyfunctional urethane acrylate oligomers are bifunctional or more .
  • a general function of the polyfunctional urethane acrylate oligomer is to include all aliphatic or aromatic urethane acrylate oligomers, trifunctional or higher functional is preferable, and tetrafunctional or higher is more preferable.
  • Examples of the polyfunctional urethane acrylate oligomers include bifunctional urethane acrylate oligomers having a number average molecular weight of 1,400 to 25,000, trifunctional urethane acrylate oligomers having a number average molecular weight of 1,700 to 16,000, and tetrafunctional four number molecular weights of 1,000.
  • the polyfunctional arc barrels rate-based monomer and / or polyfunctional urethane arc barrels hitting rate based come meoeu i content and the like a hard coating based on solids with 9 to 50% by weight of the composition preferably 15 to 40 parts by weight 0/0 More preferably.
  • the hard coating composition may include a photoinitiator, a solvent and the like, the type is not particularly limited.
  • the thickness of the hard coat layer may be 0.1 to 5 ⁇ ( ⁇ , preferably 0.5 to 3 ⁇ , more preferably 1 to 2.
  • the thickness of the hard coating layer is within the above preferred range, It is advantageous to prevent cracks in the hard coat layer material while preventing cracks or chipping points of the film, and the hardness of the hard coat layer may be H to 5H.
  • Melt extrusion may be performed by a conventional method of melt extruding and engraving a polyester resin of a composition to prepare a sheet, and then biaxially stretching and heat setting the unstretched sheet in the longitudinal and transverse directions. it is preferably Tm + 30 ° C to Tm + 60 o C coming from being made in i temperature.
  • the nyaenggak is 30 o C or less is preferably formed at a temperature of, and takes place in more bar preferably from 15 ° C to 30 o C.
  • the polyester film may be biaxially stretched in the longitudinal and transverse directions. At this time, the draw ratio may be 2 to 5 times, preferably 2.5 to 5 times, more preferably 2.5 to 4.0 times in the longitudinal direction, 2.5 to 5 times in the transverse direction, preferably 3 to 4.5 times, more preferably. Preferably 3.2 to 4.2 times.
  • the film is heat fixed after stretching, the film is relaxed in the longitudinal and / or transverse direction after starting the heat fixing, the heat setting temperature range is preferably 200 ⁇ 260 ° C.
  • the polyester film thus prepared may have a thickness of 12 ⁇ to 400 ⁇ .
  • the polyester film may include various additives such as a conventional electrostatic agent, an antistatic agent, a sunscreen, an antiblocking agent, and other inorganic lubricants within a range that does not impair the above effects.
  • Such a polyester film is 3% or less in both the longitudinal direction (length or machine direction, MD) and the transverse direction (width direction, TD) after holding for 30 minutes at 150 ° C. and further maintaining for 1 hour.
  • the haze change after 1 hour of holding is less than 1%.
  • the polyester film may have a heat shrinkage of 1.5% or less in both the longitudinal and transverse directions and a haze law of less than 1% after holding at 150 ° C. for 1 hour.
  • the polyester film may have a wavelength of 400 to 700 nm.
  • the permeability in can be 90% or more.
  • the polyester film may be 50% or more to maintain the elongation after 72 hours at 120 ° C and 1.2 atm.
  • the polyester film such as iodine, is transparent and excellent in heat resistance, and exhibits excellent hydrolysis resistance such as being able to maintain inherent excellent film properties even when exposed to long periods of time, and even at high temperatures and humidity. Since there is no degradation in physical properties, it can be usefully used as an optical film for display.
  • the reaction product was transferred to a second reactor equipped with a vacuum equipment, and then polymerized at 300 ° C. for 180 minutes to give a poly (1,4-cyclonucleoside di) having an intrinsic viscosity (IV) of 075 and a weight average molecular weight of 35,000.
  • Merylene isophthalate terephthalate) (PCT) copolymer resin was obtained.
  • the PCT resin obtained from 150 o C Drying 4 hours, 280 ⁇ 290 o C to obtain a non-stretched sheet and then melt-extruded through an extruder equipped with a screw and brought into close contact with the nyaeng gakreul nyaenggak to 20 ° C at.
  • the pre-stretched sheet was immediately preheated to 60 ° C., and then stretched 2.9 and 3.4 times in the longitudinal and transverse directions at 110 ° C., respectively, with longitudinal and transverse stretching speeds of 29 m / min and 30 m, respectively. / Min. Subsequently, the stretched sheet was heat-set at 230 ° C. to prepare a 50-thick copolymer PCT biaxially oriented film.
  • Comparative Example A1 100 mol parts of erylian glycol and 100 mol parts of terephthalic acid were added to an autoclave equipped with a stirrer and a distillation column, and manganese acetate was used as a transesterification catalyst. After the addition of 0.01% by weight of deoxidation, transesterification was performed at 280 ° C. After the transesterification reaction was completed, 0.01 parts by weight 0/0 In the tin oxide as a polymerization catalyst, and stirred for 10 minutes, the hair rente Lev LAL rate (PET) resin was obtained in the IV is 0.61, and a 34,000 weight average molecular weight. The prepared PET resin was dried at 150 ° C.
  • PET hair rente Lev LAL rate
  • the unstretched sheet was immediately preheated to 6 C C and then stretched 2.9 times and 3.4 times in the longitudinal and transverse directions, respectively, at 110 ° C., with longitudinal and transverse stretching speeds of 290 m / min and 300 m /, respectively. It was minutes. Subsequently, the stretched sheet was heat fixed at 230 ° C. to prepare a PET biaxially stretched film having a thickness of 50 ⁇ . 74 wt .
  • the hard coating composition is applied to one surface of the PCT biaxially stretched film by a die coating method, and after passing the drying chamber at 70 ° C. for about 1 minute to dry the solvent, from a UV lamp such as a high pressure mercury lamp or a xenon lamp. Irradiated ultraviolet rays were cured by irradiating with 1,000 mJ / cm 2 of I light quantity to complete a polyester film having a hard coating layer having a thickness of 5 ⁇ ).
  • Comparative Example A2 100 mol parts of ethylene glycol and 100 mol parts of terephthalic acid were charged into an autoclave equipped with a stirrer and a distillation column, and manganese acetate was added in an amount of 0.01% by weight of terephthalic acid as a transesterification catalyst, followed by 280 °. The transesterification was carried out in C. After the transesterification reaction was completed, the tin oxide ⁇ weight 0/0 added as a polymerization catalyst, and stirred for 10 minutes, and the IV is 0.61 to give the hair terephthalate (PET) resin to the poly 34,000 weight average molecular weight.
  • PET hair terephthalate
  • the reaction product was transferred to a second reaction device equipped with a vacuum facility, and then polymerized at 260 ° C. for 180 minutes to give a polyylene terephthalate (PET) having an IV of 0.75 and a weight average molecular weight of 45,300. Resin was obtained. Thereafter, using the obtained PET resin, in the same manner as in Comparative Example A1, the film was manufactured by drying, melt extrusion, molding and biaxial stretching to form a hard coating layer on one surface.
  • PET polyylene terephthalate
  • a pep resin was prepared in the same manner as in Example 1, and a hard coat layer was formed on two surfaces of I, one surface of which was prepared by drying, melt extrusion, molding, and biaxial stretching. .
  • Comparative Example A4 Except that no isophthalic acid was used, the per resin was prepared in the same manner as in Example 1, and the film was prepared by drying, melt extrusion, molding, and biaxial stretching. Formed.
  • the films of Examples A1 to A4 not only have excellent thermal contraction rate and permeability, but also have very low number of cases of haze.
  • the substrate for heat-resistant optics or the heat-resistant material film should not be eluted with oligomers like the films of Examples A1 to A4, which is advantageous for post processing, optically transparent and oligomers should not be eluted.
  • the oligomer is eluted at the time of post-processing, since it acts as a foreign material in and and the film reduces production efficiency, a film with little oligomer elution (haze change) is required.
  • a ⁇ substrate or an ITO protective film or the like undergoes heat preservation during processing for ITO crystallization, and thus oligomers are generated on the surface of a general PET film.
  • the film of Comparative Example A1 is a general optical PET film
  • the film of Comparative Example A2 solidifies the polyester resin prepared in Comparative Example A1 to raise Tg and Tm to improve heat resistance.
  • the films of Comparative Examples A1 and A2 were relatively large in the number of haze P ⁇ , indicating that a large amount of oligomer elution occurred at high temperature. Specifically, the oligomer elutes to the film surface after the heat resistance test in the oven, thereby raising the haze. The film surface at this time
  • the polyester film has a constituent unit derived from a diol component comprising hexane dimethanol (i) at least 90 mol% 1,4-cyclohexane, and (ii) on the Te Lev 90 mole 0/0 Polyester resin comprising a structural unit derived from a dicarboxylic acid component containing lactic acid, the heat shrinkage after holding for 30 minutes at 150 o C is less than or equal to 3% in both the longitudinal and transverse directions, 120 ° C. And elongation retention after 72 hours at 1.2 atm is more than 50%.
  • Such a polyester resin may be induced by polymerization after the ester exchange reaction between the diol component and the dicarboxylic acid component.
  • the diol component comprises structural units derived from 90 mole 0/0 or more 1,4-cyclohexanedimethanol (CHDM), preferably CHDM to 98 mole 0/0, more preferably at least 99 mol% Include.
  • the diol component may further contain a diol component other than CHDM.
  • diol component which may be further included as such are ethylene glycol, 1,3-propanediol, 1,2-octanediol, 1,3-octanediol, 2,3-butanediol, 1,3- Butanediol, 1,4-butanediol, 1,5—pentanediol, 2,2-dimeryl-1,3-propanediol (neopentylglycol), 2-butyl-2-ethyl-1,3-propanediol , 2,2-diaryl-1,5-pentanediol, 2,4-diethal-1,5-pentanediol, 3-metal-1,5-pentanediol, 1,1-dimeryl-1, 5-pentanediol and mixtures thereof are mentioned.
  • the crystallization rate which is too high as CHDM is included, may be lowered, and the polymer meltability may be lowered by lowering the melting temperature (Tm) of the polymer, but when included in an excessive amount, The Tg may be lowered to lower thermal characteristics such as heat resistance.
  • the dicarboxylic acid component may include The isophthaloyl ralsan to less than 10 mol 0/0.
  • Aromatic dicarboxylic acid such as dimethyl terephthalic acid, naphthalenedicarboxylic acid, orthophthalic acid; Adipic acid, azela mountain, sebacic acid, Aliphatic dicarboxylic acids such as decanedicarboxylic acid; Alicyclic dicarboxylic acid; And it may further include one or more selected from the group consisting of these esterified products.
  • the polyester resin may include 1,4—cyclonucleic acid dimethyllian terephthalate as the main repeating unit.
  • the polyester film has an intrinsic viscosity (at 25 0 C) of 0.6 to 1.2 for filming, and preferably has a weight average molecular weight of 30,000 to 50,000 g / mol, especially 30,000 to 40,000 g / m.
  • the polyester film is a polyester resin comprising a dicarboxylic acid component and a diol component comprising at least 90 mol% to 90 mol Pohang 0/0 or more nucleic acid 1,4-cyclohexane dimethanol terephthalic and melt extrusion nyaenggak
  • the sheet may be produced by a method including biaxially stretching and heat setting the sheet in the longitudinal and transverse directions.
  • the melt-extrusion is preferably be a luer at the temperature of the polyester to build Tm + 30 ° C to I Tm + 60 o C.
  • the angle is preferably made at a temperature of 30 ° C or less, more preferably from 15 0 C to 30 ° C.
  • the defect is mostly due to the decomposition of the polyester chains due to hydrolysis, especially the minimum grip length of the film produced by using it, which is no longer able to withstand mechanical deformation such as elongation or bending. .
  • the resistance to the decomposition rate can be greatly increased by providing the orientation to the molecular procedure by adjusting the stretching conditions, that is, the stretching rate and the stretching ratio.
  • Stretching conditions and with respect to a longitudinal and is performed is biaxially stretched in both the transverse direction, the stretching-on to turn the glass transition temperature of the polyester resin (Tg) + the range of 5 ° C to Tg + 50 o C, preferably from Tg It may range from + 10 ° C to Tg + 40 ° C.
  • the stretching temperature is in the range of Tg + 10 ° C.
  • the product of longitudinal and transverse draw ratios may be 4 to 16, preferably 7 to 14, more preferably 8 to 12.
  • the longitudinal drawing speed may be 22 to 500 m / min, preferably 25 to 400 m / min. In this case, when the longitudinal stretching speed is 22 m / min or more, it is advantageous to maintain the desired orientation, and since the crystallinity is given according to the longitudinal stretching speed and the stretching ratio, the transverse stretching speed varies depending on the longitudinal stretching conditions.
  • the film is heat fixed after stretching, the film is relaxed in the longitudinal and / or transverse direction after starting the heat fixing, the heat setting temperature range is preferably 200 ⁇ 260 ° C.
  • the polyester film prepared as described above may have a thickness of 12 / jm to 400 ⁇ .
  • the polyester film may include various additives such as a conventional electrostatic agent, an antistatic agent, a sunscreen, an antiblocking agent, and other inorganic lubricants within a range that does not impair the above effects.
  • a conventional electrostatic agent such as a conventional electrostatic agent, an antistatic agent, a sunscreen, an antiblocking agent, and other inorganic lubricants within a range that does not impair the above effects.
  • a relatively long durability of up to several years is required under the application temperature of about 78 0 C, the vitrification temperature range of polyester polyylene terephthalate (PET). do.
  • the polyester film had a heat shrinkage ratio of 3% or less in both the longitudinal direction (length or machine direction, MD) and transverse direction (width direction, TD) after 30 minutes at 15 CTC, and 72 hours at 120 ° C. and 1.2 atm. After elongation retention is more than 50%.
  • the polyester film may have a transmittance of 88% or more at a wavelength of 400 to 700 nm, and an intrinsic viscosity (IV) retention after 72 hours at 120 ° C. and 1.2 atm may be 70% or more.
  • Polyester films such as IOS have excellent hydrolysis resistance, such as transparency and long term, and even excellent exposure to high temperature and humidity, and excellent hydrolysis resistance. Under the circumstances, it can be usefully used as a film for solar, electric insulation and retort packaging.
  • the polyester resin preparation according to the above-described control examples are described.
  • PCT Leprolatate
  • the prepared PCT resin was melt-extruded through an extruder at 280 ° C., and then adhered to the angle of angle at 20 ° C. to obtain an unstretched sheet.
  • the sheet thus obtained was immediately preheated to 60 ° C. and then stretched 2.9 times and 3.4 times in the longitudinal and transverse directions at 110 ° C., respectively, where the longitudinal and transverse stretching speeds were 29 m / min and 28 m / min. Subsequently, the stretched sheet was heat-set at 240 ° C. to prepare a PCT biaxially stretched film having a thickness of 50 ⁇ .
  • Example B1 While using a PCT resin prepared in a similar manner to Example B1, the same as Example B1, except that the longitudinal and transverse draw ratios and the longitudinal draw speeds were varied as described in Table 3 below. The process was performed to produce a PCT biaxially oriented film.
  • PET polyethylene terephthalate
  • IV group 0 IV group 0
  • weight average molecular weight of 34,000 34,000. It was.
  • the PET resin was melt-extruded through an extruder at 265 0 C, and then adhered to the angle of angle at 20 ° C. to obtain an unstretched sheet.
  • the sheet thus obtained was immediately preheated to 60 ° C., and then 110 ° C. longitudinal direction and the number of rows were respectively 3.4 times and 4.0 times stretched in the transverse direction at, the [for all the longitudinal and transverse stretching been velocity are each 34 m / min and 33 m / min. Subsequently, the stretched sheet was heat-set at 220 ° C. to produce a PET biaxially stretched film having a thickness of 125 ⁇ .
  • the polyester film has (i) 1,4- cyclohexanedimethanol methanol structural units derived from a diol component containing 90 mol 0/0 or more, and (ii) terephthalic acid 80 mol 0 / Structural unit derived from a dicarboxylic acid component containing 0 or more Including a polyester resin containing, the vitrification temperature of the polyester resin is 88 ° C. or more, after maintaining at 150 ° C. for 30 minutes, heat shrinkage is less than or equal to 3% in both the longitudinal and transverse directions, on one side or both sides An application layer is formed.
  • the polyester resin such as iodine, may be derived by polymerizing an ester exchange reaction between the diol component and the dicarboxylic acid component.
  • the diol component is 90 mol 0/0 over lead i 1,4-cyclohexanedimethanol and Pohang a constituent unit derived from methanol (CHDM), preferably CHDM to 98 mole 0/0, more preferably at least 99 mole It comprises 0/0 above.
  • CHDM methanol
  • the diol component may further include a diol component other than CHDM.
  • diol components that may be further included include ethylene glycol, 1,3-propanediol, 1,2-octanediol, 1,3-octanediol, 2,3-butanediol, 1,3-butanediol, 1,4—butanediol, 1,5-pentanediol, 2,2-dimethyl-1,3-propanediol (neopennylglycol), 2-buty-2-eryl-1,3-propanediol, 2, 2-diethyl—1,5-pentanediol, 2,4-diethyl-1,5-pentanediol, 3-methyl-1,5—pentanediol, 1,1-dimeryl-1,5-pentane Diols and mixtures thereof.
  • the dicarboxylic acid component comprise the terephthalic acid to 80% or more by mole, preferably 80 mole 0/0 or more and less than 100 mole 0/0, more preferably 90 mol 0/0 100 mol is less than 0/0 Can be.
  • the polyester resin may include isophthalic acid in addition to terephthalic acid as the dicarboxylic acid component in order to lower the crystallization rate.
  • the isophthalic acid When the isophthalic acid is included, it is possible to lower the crystallization rate, which is too high as CHDM is included, and to increase the polymer agility by lowering the melting temperature (Tm) of the polymer.
  • Tm melting temperature
  • the Tg may be lowered to lower thermal characteristics such as heat resistance.
  • dicarboxylic acid component is less than the isophthaloyl ralsan 10 mol%, preferably 0 mole 0/0 larger than 7 mole 0/0 or less, more preferably 0 mole 0/0 is more than 5 mole 0/0 May include.
  • dicarboxylic acid component aromatic dicarboxylic acid, such as dimethyl terephthalic acid, naphthalenedicarboxylic acid, orthophthalic acid; Aliphatic dicarboxylic acids such as adipic acid, azelaic acid, sebacic acid, and decanedicarboxylic acid; Alicyclic dicarboxylic acid; And it may further include one or more selected from the group consisting of these esterified products. Accordingly, the polyester resin used may include 1,4-cyclohexane dimethylene terephthalate as the main repeating unit.
  • the polyester film is 0.6 ⁇ 1.2 £
  • the polyester film may have a coating layer formed on one side or both sides. The coating layer may be formed on one or both sides of the polyester film, it is possible to improve the post-processing and blocking properties of the film.
  • the coating layer may include one or more resins selected from the group consisting of polyester resins, acral resins, polyurethane resins, delamine resins and oxazoline resins, wherein the coating liquid composition comprising the resin is It may be formed by coating on one or both sides of the polyester film and then curing.
  • the coating liquid composition may include a photoinitiator, a solvent, and the like, and the kind thereof is not particularly limited.
  • the polyester resin used in the coating layer may be a polyester resin having an ester bond in the main chain black side chain.
  • the glass transition temperature (Tg) of the polyester resin may be 50 ⁇ 170 ° C, preferably 50 ⁇ 150 ° C. When the Tg is 50 ° C or more, it is possible to exert an appropriate moisture-resistant adhesive strength, and when the Tg is 17CTC or less, the resin is excellent in coatability and the resin may be uniformly applied.
  • the polyester resin may contain a component having a naphthalene and / or fluorene skeleton, or may contain an aromatic dicarboxylic acid component.
  • the replicon ester resin may be a full coating liquid based on a range of 0.1 to 50 parts by weight 0/0 on the solids content of the composition, preferably 1 to 30 parts by weight 0/0, more preferably 5 to 20% by weight.
  • the acral resin used in the coating layer may be a colloidal acrylic-ester copolymer resin.
  • the coating layer includes an acrylic resin, it may further include an isocyanate, epoxy or delamine-based curing agent for improving durability and solvent resistance.
  • the acrylic resin is based on the solid content of the entire coating liquid composition As may be ⁇ to 60 parts by weight 0/0, preferably from 1 to 50 parts by weight 0/0, and more preferably 10 to 40 parts by weight 0/0.
  • the polyurethane resin used in the coating layer may be prepared by copolymerizing dicarboxylic acid and glycol component.
  • dicarboxylic acid component include aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, 1,4-naphthalene dicarboxylic acid, 2.5-naphthalene dicarboxylic acid, 2,5-merylcarboxylic acid, and dimerylisophthalic acid.
  • Carboxylic acid Alicyclic dicarboxylic acids such as 1,3-cyclopentane dicarboxylic acid, 1,2-cyclonucleic acid dicarboxylic acid, 1,3-cyclonucleic acid dicarboxylic acid, and 1,4—cyclohexane dicarboxylic acid mountain; And aliphatic dicarboxylic acids such as adipic acid, sebacic acid, and the like, with aromatic dicarboxylic acids being particularly preferred.
  • the glycol component is preferably aliphatic glycols having 2 to 8 carbon atoms and cycloaliphatic glycols having 6 to 12 carbon atoms, for example, ylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4 -Butanediol, neopentyl glycol, 1,6-hexanediol, 1,2-cyclonucleic acid methanol, 1,3-cyclonucleic acid dimethanol, 1,4-cyclohexanedimethanol, ⁇ -xyllian glycol, dierylene Glycols, triethylene glycol, polyether glycols, polyylene glycols, and polytetramethylene glycols, and the like, of which ethylene glycol is preferred.
  • the polyurethane resin is the premise of the coating liquid composition based on the solids content of 0.1 to 50 parts by weight 0/0, preferably from 1 to 40 parts by weight to 0/0, and more preferably may be used in 5 to 30% by weight.
  • the melamine-based resin used in the coating layer may be a melamine-based crosslinking agent, but is not particularly limited, for example, methylolhotel melamine inducer obtained by condensation of queramine, delamingo ⁇ formaldehyde, and melylated delamin.
  • the partial alcohol is reacted with a lower alcohol to a partially etherified compound, or a mixture thereof.
  • the condensate which consists of a monomer, a dimer or more multimer, black, a mixture thereof, etc. can be used as a delamine type crosslinking agent.
  • the tie lamin-based resin may be used based on the assumption applied in the range of 0.1 to 50 parts by weight 0/0 on the solids content of the liquid composition, preferably 1 to 30 parts by weight 0/0, more preferably 5 to 20% by weight.
  • the oxazoline-based resin used in the coating layer may be an oxazoline group-containing polymer, and the oxazoline group-containing polymer may include at least one monomer having an oxazoline group, and may be copolymerized with at least one other monomer. It may be obtained.
  • cures by heating functional group addition reactions, such as a hydroxyl group and a carboxyl group, by heat.
  • the oxazoline-based resin of the whole coating liquid composition Based on the solids content of 0.1 to 70 parts by weight 0/0, preferably from 1 to 60 parts by weight 0/0, and more preferably may be used in 10 to 50 parts by weight 0 / o.
  • the coating layer may have a thickness of 0.01 to 2 ⁇ ( ⁇ , preferably 0.01 to 1.5 ⁇ . When the thickness is in the range of 0.01 ⁇ ) to 2 ⁇ , a sufficient coating layer may function.
  • the coating layer may be formed by an in-line coating method or an offline coating method, and coating with a coating liquid for forming the coating layer may include a reverse coater, a gravure coater, a rod coater, an air doctor coater, or the like. Either can be done by wrapping paper.
  • the polyester film may include a hard coating layer formed on one side of the film to improve brittleness.
  • the hard coating layer may be made of a resin such as a thermoplastic resin, a thermosetting resin, an ionizing radiation (ultraviolet ray or an electron ray) curable resin, preferably (a) a bifunctional or higher acrylate monomer having an ethylene glycol (EO), And (b) a hard coating composition including at least one of a polyfunctional urethane acrylate oligomer and a polyfunctional acrylate monomer having no ethylene glycol.
  • the bifunctional or higher functional acrylate monomer having an ethylene glycol is characterized in that when the number of functional groups thereof is n, the number of ethyl lylene glycol included is n to 2 n, and the number average molecular weight is 100 to 200 ⁇ . do.
  • bifunctional acrylate monomer in the case of a bifunctional acrylate monomer, it may include two to four ethylene glycol, and may have a horizontal equivalent molecular weight of 200 to 400.
  • trifunctional I acrylate-based monomer when it may include 3 to 6 ethylene glycol, the number average molecular weight may be 300 to 600.
  • the bifunctional or higher I acrylate monomer include the compounds of Table 1 or mixtures thereof, but are not limited thereto.
  • the content of the bifunctional or more acrylate-based monomer having a tolylene glycol in the are, and when based on the solids content of the de-coating composition, 50 to 85 parts by weight 0 /. Is preferred, and 60 to 80 parts by weight 0/0, more preferably Do.
  • the polyfunctional acrylate monomer is a general agent for bifunctional or higher polyfunctional monomers having no ethylene glycol.
  • polyfunctional acrylate monomers examples include 1,6-hexanediol diacrylate, 1,6-nucleic acid diol dimethacrylate, butanediol diacrylate, butanediol dimethacrylate, tricyclodecane diacrylate , Cyclonucleic acid diacrylate, tris (2-hydroxyaryl) isocyanurate diacrylate, hydroxyl pivalaldehyde modified triarylolpropane diacrylate, 1,4-butanediol diacrylate, merallic Diacrylates, Modified Metallic Dicrates, Acrylate Esters, Cyclohexanedi-Methanol Dimethacrylate, 1,4-Butanedi-Dimethacrylate, Metallic Dimethacrylate, Trimethylolpropane Triacryl Latex, trimerylolpropane trimethacrylate, pentaerythritol triacrylate, tris (2-hydroxyeryryl) isocyanurate tri
  • the polyfunctional urethane acrylate-based oligomer is a mixture of two or more polyfunctional urethane acrylate oligomers, and includes, for example, both aliphatic or aromatic urethane acrylate oligomers, preferably at least trifunctional and tetrafunctional. The above is more preferable.
  • polyfunctional urethane acrylate-based oligomer examples include bifunctional urethane acrylate oligomers having a number average molecular weight of 1,400 to 25,000, trifunctional urethane acrylate oligomers having a number average molecular weight of 1,700 to 16,000, and a number average molecular weight of 1,000 I 4-functional urethane acrylate.
  • Oligomers 6 functional urethane acrylate oligomers having a number average molecular weight of 818 to 2,600, 9 functional urethane acrylate oligomers having a number average molecular weight of 3,500 to 5,500, 10 functional urethane acrylate oligomers having a number average molecular weight of 3,200 to 3,900, number average molecular weight 2,300 to 20,000 15 functional urethane acrylate oligomer and the like can be used.
  • the polyfunctional arc barrels rate-based monomer and / or polyfunctional urethane content of bots hitting the acrylate-based is, and this would of 9 to 50 parts by weight 0/0 based on the solids content of the hard coating composition preferably, 15 to 40 parts by weight 0 / It is more preferable that it is zero .
  • the hard coating composition may include a photoinitiator, a solvent and the like, the type is not particularly limited.
  • the hard coating layer may have a thickness of 0.1 to 5, preferably 0.5 to 3, and more preferably 1 to 2 /.
  • the thickness of the hard coat layer is within the preferred rain I, it is advantageous to prevent cracks in the hard coat layer material while preventing cracks or chipping points of the film.
  • the hardness of the hard coating layer may be H to 5H.
  • the polyester film may be one containing fine particles in a polyester resin. When foaming the fine particles, the running and blocking resistance of the polyester film can be improved.
  • the fine particles may be, for example, inorganic particles such as colloidal silica, titanium oxide, alumina oxide, zirconium oxide or calcium carbonate, or organic particles such as crosslinked polyester particles, crosslinked polystyrene particles, or crosslinked polymer particles.
  • the polyester film may be prepared by a conventional method of biaxially stretching and heat setting the unstretched sheet in the longitudinal and transverse directions after the sheet is prepared by melt extruding and engraving the polyester resin of the specific composition. Can be. Melt extrusion is preferably performed at a temperature of I Tm + 30 o C to Tm + 60 o C with a polyester resin.
  • the temperature of the extruder during the melt extrusion is less than Tm + 30 ° C, the smooth melt does not occur, the viscosity of the extrudate is high, productivity is reduced, on the contrary, if the temperature exceeds Tm + 60 o C, depolymerization by thermal decomposition of the resin
  • the molecular weight may drop and problems with oligomers may occur.
  • the incidence is preferably made at a temperature of 30 ° C or less, more preferably at 15 0 C to 30 ° C.
  • the polyester film may be biaxially stretched in the longitudinal and transverse directions.
  • the draw ratio may be 2 to 5 times, preferably 2.5 to 5 times, more preferably 2.5 to 4.0 times in the longitudinal direction, 2.5 to 5 times in the transverse direction, preferably 3 to 4.5 times, more preferably.
  • the heat setting temperature range is preferably 200 ⁇ 260 ° C.
  • the polyester film thus prepared may have a thickness of 12jum to 400 ⁇ .
  • the polyester film may include various additives such as a conventional electrostatic agent, an antistatic agent, a sunscreen, an antiblocking agent, and other inorganic lubricants within a range that does not impair the above effects.
  • a polyester film may have a static friction coefficient and a dynamic friction coefficient of 0.8 or less, respectively, preferably 0.1 to 0.7.
  • the polyester film may be easily wound in a * state because the static friction coefficient and the equivalence coefficient are each 8 or less.
  • the polyester film is maintained at 150 ° C. for 30 minutes, the heat shrinkage is less than or equal to 3% in both the longitudinal (length or machine direction, MD) and transverse (width, TD), and also 30 minutes at 150 o C
  • the haze change after holding is 1% or less, preferably 0.6% or less, and the total light transmission may be 90% or more.
  • the polyester film is transparent and excellent in heat resistance, and exhibits excellent hydrolysis resistance such as being able to maintain inherent excellent film properties even when exposed to long periods of time and even at high temperature and high humidity. Since there is no deterioration of the cryogenicity and less oligomer elution, it can be usefully used as an optical film for display.
  • the coating layer is formed on at least one surface of the polyester film, it has an excellent post workability due to excellent cohesion with functional layers that can be further laminated to the film.
  • reaction mixture was transferred to a second reactor equipped with a vacuum equipment, and then polymerized at 300 ° C. for 180 minutes to give a poly (1,4-cyclohexane) having an IV (high viscosity) of 075 and a weight average molecular weight of 35,000.
  • Dimerylene terephthalate) (PCT) resin was obtained.
  • the prepared PCT resin was dried at 150 ° C. for 4 hours, melt-extruded through an extruder equipped with a screw at 280-290 ° C., and then contacted with the angle of angle of 20 ° C. to obtain an unstretched sheet.
  • the sheet thus obtained was immediately preheated to 60 ° C. and then stretched three times in the longitudinal and transverse directions at 110 ° C., respectively, with longitudinal and transverse stretching speeds of 29 m / min and 30 m / min, respectively. Subsequently, the stretched sheet was heat-set at 230 ° C. to prepare a PCT biaxially stretched film having a thickness of 50 1.
  • the additive coating liquid composition was applied on the PCT biaxially stretched film prepared by the die coating method, and the solvent was dried for about 1 minute by passing through a 70 ° C. drying chamber, followed by ultraviolet lamps such as a high pressure mercury lamp and a xenon lamp. Ultraviolet rays radiated from the surface were cured by irradiating with 1,000 mJ / cm 2 light quantity, thereby completing a polyester film in which a coating layer having a thickness of 2 ⁇ was formed.
  • Example C2 and C3 As the diol component, 100 mol parts of 1,4-cyclonucleic acid dimethanol (CHDM), 97 mol parts of terephthalic acid, and 3 mol parts of isophthalic acid were used, and the coating liquid composition was shown in Table 4, respectively.
  • a PCT biaxially oriented film was prepared in the same manner as in Example C1, except that the coating layer was formed by using a composition and a content thereof.
  • Comparative Example 100 mol parts of CI ethylene glycol and 100 mol parts of terephthalic acid were added to an autoclave equipped with a stirrer-operation distillation column, and manganese acetate was added in an amount of 0.01% by weight of terephthalic acid as a transesterification catalyst, followed by 28CTC.
  • the transesterification reaction was carried out. After the transesterification reaction was completed, the tin oxide is 0.01 0/0-to-mouth as a polymerization catalyst, and the mixture was stirred for 10 minutes.
  • a polyaryl lenterephthalate (PET) resin with an IV of 0.61 and a weight average molecular weight of 34,000 was obtained.
  • the prepared PET resin was dried at 150 ° C.
  • the coated liquid composition was applied by a die coating method on the PET biaxially stretched film obtained by the method described in Comparative Example C1, and passed through a drying chamber at 70 ° C. for about 1 minute to dry the solvent, followed by a high pressure mercury lamp and xenon Irradiate ultraviolet rays emitted from ultraviolet lamps such as lamps at 1,000 mJ / cm 2 I light quantity and stabilize them.
  • the polyester film in which the coating layer of thickness was formed was completed.
  • Example C1 As in Example C1, except that 75 mol parts of CHDM and 25 mol parts of diethyl lynchol were used, and the coating liquid composition was prepared in the composition and content as shown in Table 4 below to form a coating layer.
  • PCT biaxially oriented film was prepared by performing the process of.
  • Heat shrinkage of the films prepared in Examples C1 to C3 and Comparative Examples C1 to C3 was measured together with haze, coefficient of friction, and adhesion after 30 minutes of holding at initial haze and 15 CTC.
  • the films of Examples C1 to C3 not only have excellent thermal contraction rate and permeability, but also have very low number of cases of haze.
  • the substrate for heat-resistant optics or the heat-resistant material film is advantageous for post-processing and is optically transparent as long as the oligomer is not eluted like the films of Examples C1 to C3.
  • the oligomer is eluted at the time of post-processing, since it acts as a foreign material in and and a film reduces production efficiency, the film which has little oligomer elution (hazard defense) is desired.
  • Comparative Example 2 the coating of the coating layer reduced the haze change due to reduced oligomer elution, but was still unusable due to the large amount of oligomer elution.
  • Comparative Example 3 lowered the Tg because of the CHDM content affects the crystallization with CHDM content is less than 80 mole 0/0, weakened immunity, yeolsuchukreul this was found greater, as well as changes in the haze degree relative is great due to heat .
  • the polyester film comprises (i) constituents derived from a diol component comprising at least 90 mol% of 1,4-cyclohexanedimethanol, and (ii) 10 mol of isophthalic acid .
  • a polyester resin comprising a structural unit derived from a dicarboxylic acid component containing 0 or less, having a haze of 2% or less, and after 30 minutes of holding at 150 ° C., the heat shrinkage is in the longitudinal and transverse directions. All may be 3% or less and the haze change may be less than 1%.
  • Such a polyester resin may be induced by polymerization after the ester exchange reaction between the diol component and the dicarboxylic acid component.
  • the diol component comprises structural units derived from 90 mole 0/0 or more 1,4-cyclohexanedimethanol (CHDM), preferably CHDM to 98 mol%, more preferably at least 99 mole 0/0 or more Pohang.
  • the diol component may further include a diol component other than CHDM.
  • diol component which may be further included as such are ethylene glycol, 1,3-propanediol, 1,2-octanediol, 1,3-octanediol, 2,3-butanediol, 1,3-butanediol , 1,4-butanediol, 1,5-pentanediol, 2,2-dimeryl-1,3-propanediol (neopennylglycol), 2-buryl-2-eryl-1,3-propanediol, 2,2-diethane—1,5-pentanediol, 2,4-diethal-1,5-pentanediol, 3-meryl-1,5-pentanediol, 1,1-dimeryl-1,5 —Pentanediol and mixtures thereof.
  • the polyester resin may include isopral acid as the dicarboxylic acid component in order to lower the crystallization rate.
  • the crystallization rate which is excessively high as CHDM is included, may be lowered, and the handleability of the polymerizer may be increased by lowering the melting temperature (Tm) of the polymerizing agent.
  • Tm melting temperature
  • dicarboxylic acid component is less than the isophthaloyl ralsan 10 rule 0/0, preferably at most 0 mole 0/0 larger than 7 mol%, more preferably 0 mole 0/0 is more than 5 mole 0/0 include can do.
  • the dicarboxylic acid component is the isophthalic acid in addition to 80 mole 0/0 or more, preferably 80 mol 0/0 or more and less than 100 mole 0/0, more preferably less than than 90 mole 0/0 100 mole 0/0 May include terephthalic acid.
  • Aromatic dicarboxylic acid such as dimetal terephthalic acid, naphthalenedicarboxylic acid, orthophthalic acid; Aliphatic dicarboxylic acids such as adipic acid, azelaic acid, sebacic acid, and degandicarboxylic acid; Alicyclic dicarboxylic acid; And it may further include one or more selected from the group consisting of these esterified products.
  • the polyester resin may include 1,4-cyclohexanedimethylene terephthalate as the main repeating unit.
  • the polyester film has an intrinsic viscosity (at 25 0 C) of 0.7 to 1.2 for filming, and preferably has a weight average molecular weight of 30,000 to 50,000 g / mol, especially 30,000 to 40,000 g / m. .
  • the polyester film may include a hard coating layer formed on one side of the film to improve brittleness.
  • the hard coating layer may be made of a resin such as a thermoplastic resin, a thermosetting resin, an ionizing radiation (ultraviolet or electron radiation) curable resin, preferably (a) a bifunctional or higher acrylate monomer having ethylene glycol (EO), And (b) a hard coating composition comprising at least one of a polyfunctional urethane acrylate oligomer and a polyfunctional acrylate monomer having no ethylene glycol.
  • the bifunctional or higher functional acrylate monomer having ethylene glycol is characterized in that when the number of functional groups thereof is n, the number of ethylene glycol contained is n to 2n, and the number average molecular weight is 100? To 200 ?. .
  • a bifunctional acrylate-based monomer it may include 2 to 4 ethyl lian glycol, and may have a horizontal homogeneous molecular weight of 200 to 400.
  • a trifunctional acrylate monomer it may include 3 to 6 ethylene glycol, the number average molecular weight may be 300 to 600.
  • the bifunctional or higher I acrylate monomer include the compounds of Table 1 or mixtures thereof, but are not limited thereto.
  • the content of the bifunctional or higher acrylate monomer having an ethylene glycol is preferably from 50 to 85% by weight, more preferably from 60 to 80% by weight, based on the solid content of the hard coating composition.
  • the polyfunctional acrylate monomer is a total of two or more polyfunctional acrylate monomers having no ethylene glycol, preferably trifunctional or more.
  • polyfunctional acrylate monomers include 1,6-hexanediol diacrylate, 1,6-hexanoic dimethacrylate, butanediol diacrylate, butanediol dimethacrylate, tricyclodecane diac Lylate, cyclonucleic acid diacrylate, tris (2-hydroxyethyl) isocyanurate diacrylate, hydroxyl pivalaldehyde modified trimerylolpropane diacrylate, 1,4-butanedi diacrylate, Merallic diacrylate, modified metallic diacrylate, acrylate ester, cyclohexane dimethane dimethacrylate, 1,4-butanediol dimethacrylate, metallic dimethacrylate, trimethylolpropane tri Acrylate, Trimethylolpropane trimethacrylate, Pentaerythritol triacrylate, Tris (2-hydroxyethyl) isocyanurate triacryllay
  • the polyfunctional urethane acrylate-based oligomer is a bifunctional or more than one polyfunctional urethane acrylate oligomer.
  • all aliphatic or aromatic urethane acrylate oligomers are contained, and trifunctional or more than four functional groups are preferred. More preferred.
  • Examples of the polyfunctional urethane acrylate oligomer include bifunctional urethane acrylate oligomers having a number average molecular weight of 1,400 to 25,000, trifunctional urethane acrylate oligomers having a number average molecular weight of 1,700 to 16,000, and a number average molecular weight of 1,000 tetrafunctional urethane.
  • Acrylate oligomer 6 functional urethane acrylate oligomer of number average molecular weight 818 to 2,600, 9 functional urethane acrylate oligomer of number average molecular weight 3,500 to 5,500, 10 functional urethane acrylate oligomer of number average molecular weight 3,200 to 3,900, number 15 functional urethane acrylate oligomer and the like with an average molecular weight of 2,300 to 20,000 can be used.
  • the polyfunctional acrylate-based monomer and / or polyfunctional urethane arc barrels rate-based all-hitting meoeu I content and the like a hard coating based on solids with 9 to 50% by weight of the composition preferably 15 to 40 parts by weight 0/0, More preferred.
  • the hard coating composition may include a photoinitiator, a solvent and the like, the type is not particularly limited.
  • the hard coating layer may have a thickness of 0,1 to 5 ⁇ , preferably 0.5 to 3 ⁇ , and more preferably 1 to 2 ⁇ m. When the thickness of the hard coating layer is within the preferred range, it is advantageous to prevent cracks in the hard coating layer itself while preventing cracks or chipping points of the film.
  • the hardness of the hard coating layer may be H to 5H.
  • the polyester film may be prepared by a conventional method of biaxially stretching and heat setting the unstretched sheet in the longitudinal and transverse directions after the sheet is manufactured by melt extruding and engraving the polyester resin of the specific composition. . Melt-extrusion is preferably be done at a temperature of polyester resin + 30 ° C to Tm Tm + 60 o C.
  • the nyaenggak is 30 o C or less is preferably formed at a temperature of, and takes place in more bar preferably from 15 ° C to 30 o C.
  • the polyester film may be biaxially stretched in the longitudinal and transverse directions.
  • the defect is mostly due to the decomposition of the polyester chains due to hydrolysis, and especially at the minimum chain length, the brittleness of the film produced using the same can no longer withstand mechanical deformation such as elongation or bending. . Therefore, as a method for slowing down the decomposition rate, the resistance to the decomposition rate can be greatly increased by providing the orientation to the molecular procedure by adjusting the stretching conditions, that is, the stretching rate and the stretching ratio.
  • the stretching conditions biaxial stretching in both the longitudinal and transverse directions is carried out, the stretching temperature being in the range of glass transition temperature (Tg) + 5 0 C to Tg + 50 ° C of the polyester resin, preferably Preferably Tg + 10 ° C.
  • the lower the Tg the better the ductility, but breakage may occur.
  • the draw ratio may be 2 to 5, preferably 2.5 to 5, more preferably 2.5 to 4.0 in the longitudinal direction, 2.5 to 5 in the transverse direction, preferably 3 to 4.5, more preferably 3.2 to May be 4.2.
  • the polyester film manufactured as Io I ⁇ may have a thickness of 12 ⁇ to 400 / ⁇ .
  • the polyester film may include various additives such as a conventional electrostatic agent, an antistatic agent, a sunscreen, an antiblocking agent, and other inorganic lubricants within a range that does not impair the above effects.
  • the polyester film has a haze of 2% or less, and after heat retention at 150 ° C. for 30 minutes, and further 3 hours, thermal shrinkage is performed in the longitudinal direction (length direction or machine direction, MD) and in the transverse direction (width direction, TD). All are 3% or less, and the haze change is less than 1% after holding for 30 minutes at 150 ° C. and further for 3 hours.
  • the polyester film has a wavelength of 400 to 700 nm
  • the permeate may be at least 90%.
  • the polyester film such as iodine, is transparent and excellent in heat resistance, and exhibits excellent hydrolysis resistance, such as being able to maintain inherent excellent film properties even when exposed to high temperatures and humidity for a long time, and crystallization in silver Since there is no degradation in physical properties, it can be usefully used as an optical film for display.
  • the reaction product was transferred to a second reactor equipped with a vacuum equipment, and then polymerized at 300 ° C. for 180 minutes to give poly (1,4-cyclohexane) having an IV (intrinsic viscosity) of 0.7501 and a weight average molecular weight of 35,000.
  • Dimethylene terephthalate) (PCT) resin was obtained.
  • the prepared PCT resin was dried at 150 ° C. for 4 hours and melt-extruded through an extruder equipped with a screw at 280-290 ° C., followed by contact with the angle of angle of 20 ° C. to obtain an unstretched sheet.
  • the sheet thus obtained was immediately preheated to 60 ° C., and then stretched 2.9 times and 3.4 times in the longitudinal and transverse directions at 110 ° C., respectively, with longitudinal and transverse stretching speeds of 29 m / min and 30 m /, respectively. It was minutes. Subsequently, the stretched sheet was heat-set at 230 ° C. to prepare a polyester film having a thickness of 50.
  • PCT biaxially by performing the same procedure as in Example D1, except that the contents of 1,4-cyclohexanedimethanol (CH DM), isophthalic acid and terephthalic acid were each changed as shown in Table 5 below.
  • CH DM 1,4-cyclohexanedimethanol
  • isophthalic acid 1,4-cyclohexanedimethanol
  • terephthalic acid 1,4-cyclohexanedimethanol
  • Table 5 1,4-cyclohexanedimethanol
  • Comparative Example D2 tolylene In the glycidyl cool to 100 molar parts, and terephthalic acid 100 mol parts of a stirrer O The autoclave was attached a distillation column in, and as a transesterification catalyst added manganese acetate with 0.01 0 / 0. I the amount of Te Lev ralsan After, the transesterification was carried out at 280 ° C. After the completion of the transesterification reaction, 0.01 wt% of tin oxide was added as a polymerization catalyst and stirred for 10 minutes. Polyether lenterephthalate (PET) resin with an IV of 0.61 and a weight average molecular weight of 34,000 was obtained.
  • PET Polyether lenterephthalate
  • reaction product was transferred to a second reactor equipped with a vacuum equipment, and then polymerized at 260 ° C. for 180 minutes to obtain a polyylene terephthalate (PET) resin having an IV of 0.75 and a weight average molecular weight of 45,300. Obtained.
  • PET polyylene terephthalate
  • polyester film was prepared by the same method as Comparative Example D1 using the polyetherene terephthalate (PET) resin.
  • a PCT resin was obtained through the same method as in Example D1, except that 75 mol parts of CHDM was used, and a polyester film was prepared in the same manner as in Example using the PCT resin.
  • Comparative Example D4 Except that no isophthalic acid was used, a PCT resin was obtained by the same method as Example D1, and then a polyester film was prepared by the same method as Example D1 using the PCT resin. .
  • Comparative Example D5 A PCT resin was obtained through the same method as described above except that 15 mol parts of isophthalic acid was used, and then the same composition as in Example D1 was performed using the PCT resin. A polyester film was prepared through the method.
  • Example D6 Triylene glycol diacrylate (SR272, manufactured by Satomer), polyfunctional urethane acrylate oligomer (MU9500, Miwon Specialty Chemical Co., Ltd.), and photoinitiator (1-184, BASF ⁇ ) based on solid content respectively, the hard coating composition was prepared by adding to 15 parts by weight of the composition Merrill 100 parts by weight of the hair Kerron and stirred comprising 74 parts by weight 0/0, 18 weight 0/0, and 8% by weight. After applying the hard coating composition to one surface of the polyester film obtained in Example D1 by a die coating method, the solvent is dried for about 1 minute through a 70 ° C. drying chamber, a high-pressure mercury lamp, xenon lamp, etc. Ultraviolet rays radiated from the UV lamps were cured by irradiating with 1,000 mJ / cm 2 light quantity, thereby preparing a polyester film having a hard coating layer having a thickness of 1 ⁇ ⁇ .
  • Examples D7 to D10 Using the polyester films prepared in Examples D2 to D5, the same method as in Example D6 was performed except that the thicknesses of the hard coat layers were formed as shown in Table 6 below, respectively. To prepare a polyester film formed with a hard coating layer.
  • Comparative Examples D6 to D10 Using the polyester films prepared in Comparative Examples D1 to D5, the same method as in Example D6 was performed except that the thicknesses of the hard coat layers were formed as shown in Table 6 below. To prepare a polyester film formed with a hard coating layer.
  • the films of Examples D1 to D5 are not only excellent in thermal contraction rate and permeateol, but also very low in number of haze.
  • the substrate for heat-resistant optics or the heat-resistant material film should not dissolve oligomers like the films of Examples D1 to D5 above, which is advantageous for post processing, optically transparent, and oligomers should not elute.
  • the oligomer is eluted at the time of post-processing, since it acts as a foreign material in and and a film reduces production efficiency, the film which has little oligomer elution (hazard defense) is desired.
  • a ⁇ substrate or an ITO protective film undergoes heat treatment during processing due to ITO crystallization, and thus oligomers are generated on the surface of a general PET film.
  • Table 6 there is a case in which a separate hard coating or inline coating may be performed by using the oligomeric blocking, but the film of the embodiment does not require such a separate coating process. From the results of Table 6, it can be seen that the films of Examples D1 to D5 are hard-coated, and there is no change in haze even without eliminating the blocking.
  • Comparative Example D1 is a general optical PET, and Comparative Example D2 solidifies the resin of 1 to increase Tg and Tm to improve heat resistance.
  • the law of the haze is relatively large, and a large amount of oligomer dissolution occurs at high temperature.
  • the oligomer elutes to the film surface after the heat resistance test in the oven, thereby raising the haze.
  • white oligomers are collected when the film surface is rubbed with a spatulator.
  • the value of the oligomer elution can be confirmed by Haze, and the SEM photographs of FIGS. (2,000 times), the oligomer shape can be reconfirmed.
  • Comparative Example D3 the CHDM content is less than 80 mol%, the Tg is lowered due to the CHDM content affecting crystallization, and the heat resistance is weakened.
  • the polyester film (D 1,4- cyclohexanedimethanol methanol configuration danwoo derived from a diol component containing 90 mol 0/0 more than
  • Polyester resin comprising a structural unit derived from a dicarboxylic acid component containing at least / 0 , and a spherical monodisperse particles of 200 to 3,000 ppm relative to the polyester resin, the polyester resin I
  • the vitrification temperature is not lower than 88 ° C., and after 30 minutes of holding at 15 CTC, the heat shrinkage may be 3% or less in both the longitudinal and the transverse directions. It can be induced by polymerization.
  • the diol component is more than 90 mole 0/0 1,4-cyclohexanedimethanol comprises the constitutional unit derived from methanol (CHDM), preferably from the CHDM 98 mole 0/0, more preferably at least 99 mole 0 / It contains 0 or more.
  • the diol component may further include a diol component other than CHDM.
  • diol component examples include ethylene glycol, 1,3-propanediol, 1,2-octanediol, 1,3-octanediol, 2,3—butanediol, 1,3-butanediol , 1,4-butanediol, 1,5-pentanediol, 2,2-dimeryl-1,3-propanediol (neopennylglycol), 2-buryl-2-eryl-1,3- Propanediol, 2,2-diaryl-1,5-pentanediol, 2,4-diaryl-1,5-pentanediol, 3-metal-1,5-pentanediol, 1,1-dimeryl- 1,5-pentanediol and these mixed wool.
  • the polyester resin is the dicarboxylic acid component as the 80 mol% or more, the wind directly from 80 mole 0 / ⁇ or more and less than 100 mole 0/0, more preferably less than 0/0 90 mol to 100 mol% of Te
  • the polyester resin may include isophthalic acid in addition to terephthalic acid as the dicarboxylic acid component in order to lower the crystallization rate.
  • the polyester resin is an isophthalic acid 10 mol 0/0 or less, preferably 0 mol% second and I ⁇ 7 mole 0/0 or less, more preferably in an amount of more than 0 mole 0/0 is more than 5 mole 0/0 It may include.
  • Aromatic dicarboxylic acid such as dimethyl terephthalic acid, naphthalene dicarboxylic acid, orthophthalic acid; Aliphatic dicarboxylic acids such as adipic acid, azelaic acid, sebacic acid, and decanedicarboxylic acid; Alicyclic dicarboxylic acid; And it may further include one or more selected from the group consisting of these esterified products.
  • the polyester resin may include 1,4-cyclonucleic acid dimethylene terephthalate as a main repeating unit.
  • the polyester film is 0.6 ⁇ 1.2 £
  • the polyester resin may comprise 200 to 3,000 ppm, preferably 400 to 1,500 ppm of spherical monodisperse particles.
  • spherical monodisperse particles By including the spherical monodisperse particles to increase the slip properties of the polyester film, it is possible to solve the difficulty of winding due to the self-adhesion of the polyester film.
  • the spherical monodisperse particles may have a flatness of 0.1 to 2.5, preferably 0.1 to 2.0 ⁇ .
  • the particle diameter ratio may be 0.5 to 1.2, preferably 0.8 to 1.2, more preferably 0.8 to 1.1.
  • the particle diameter ratio may be expressed as the ratio of the average value of the long diameter of the spherical monodisperse particles to the average value of the short diameter.
  • the friction coefficient of the film can be set to 0.8 or less while preventing the haze from increasing due to the occurrence of no stage or dispersion.
  • the spherical monodisperse particles may be inorganic particles or organic particles, but preferably inorganic particles, for example, may be at least one selected from the group consisting of spherical silica, spherical titanium oxide, and spherical zirconium.
  • the polyester film includes spherical monodisperse particles having an average particle diameter and a particle diameter ratio in the above range. I can solve it. Therefore, the spherical monodisperse particles may be added in the middle of the polymerization of the polyester resin, or may be included in the polyester film by compounding by adding to the finished polyester resin.
  • the polyester film may include a hard coating layer formed on one side of the film to improve brittleness.
  • the hard coating layer may be made of a resin such as a thermoplastic resin, a thermosetting resin, an ionizing radiation (ultraviolet ray or an electron ray) curable resin, preferably (a) a bifunctional or higher acrylate monomer having an ethylene glycol (EO), And (b) at least one of a polyfunctional urethane acrylate based oligomer and a polyfunctional acrylate monomer having no ethylene glycol.
  • the bifunctional or higher acrylate monomer having ethylene glycol is characterized in that when the number of functional groups thereof is n, the number of ethylene glycol contained I is ⁇ to 2n, and the number average molecular weight is 100 to 200 ⁇ . It is done.
  • a bifunctional acrylate monomer in the case of a bifunctional acrylate monomer, it may include two to four ethylene glycol, and may have a horizontal homogeneous molecular weight of 200 to 400. In addition, in the case of a trifunctional acrylate monomer, it may include three to six ethylene glycol, the number average molecular weight may be 300 to 600.
  • Preferred examples of the bifunctional or higher acrylate monomers include those of Table 1 above. Compounds or mixtures thereof are possible, but are not limited to these.
  • the content of the bifunctional or higher acrylate monomer having ethylene glycol is preferably 50 to 85% by weight, more preferably 60 to 80% by weight based on the solids content of the hard coating composition.
  • the polyfunctional acrylate monomer is a bifunctional or more than one polyfunctional acrylate monomer having no ethylene glycol, and is preferably trifunctional or more.
  • polyfunctional acrylate monomers examples include 1,6-hexanediol diacrylate, 1,6—nucleic acid diol dimethacrylate, butanediol diacrylate, butanediol dimethacrylate, and tricyclodecane diacrylate Latex, cyclohexane diacrylate, tris (2-hydroxyethyl) isocyanurate diacrylate, hydroxyl pivalaldehyde modified trimeryl to propane diacrylate, 1,4-butanedi diacrylate, Merallic diacrylate, modified metallic diacrylate, acrylate esters, cyclonucleic acid dimethanol dimethacrylate, 1,4-butanediol dimethacrylate, metallic dietaacrylate, triarylolpropane triacrylic Triacrylate, trimethylolpropane trimethacrylate, pentaerythritol tris, tris (2-hydroxyeryryl) isocyanurate triacrylate
  • the polyfunctional urethane acrylate oligomer is a bifunctional polyfunctional urethane acrylate oligomer, and includes, for example, both aliphatic or aromatic urethane acrylate oligomers, preferably at least trifunctional and at least tetrafunctional. More preferred.
  • Examples of the polyfunctional urethane acrylate oligomer include bifunctional urethane acrylate oligomers having a number average molecular weight of 1,400 to 25,000, trifunctional urethane acrylate oligomers having a number average molecular weight of 1,700 to 16,000, and a number average molecular weight of 1,000 tetrafunctional urethane arc.
  • Lallylate oligomers 6 functional urethane acrylate oligomers with number average molecular weights 818 to 2,600, 9 functional urethane acrylate oligomers with number average molecular weights 3,500 to 5,500, 10 functional urethane acrylates with number average molecular weights 3,200 to 3,900 Yit oligomer, 15 functional urethane acrylate oligomer of the number average molecular weight 2,300-20,000, etc. can be used.
  • the polyfunctional arc barrels rate-based monomer and / or polyfunctional urethane arc barrels hitting rate based come meoeu i content and the like a hard coating based on solids with 9 to 50% by weight of the composition preferably 15 to 40 parts by weight 0/0 More preferably.
  • the hard coating composition may include a photoinitiator, a solvent and the like, the type is not particularly limited.
  • the hard coating layer may have a thickness of 0.1 to 5 ⁇ ( ⁇ , preferably 5 to 3 ⁇ , and more preferably 1 to 2 ⁇ . When it is inside, it is advantageous to prevent cracks in the hard coat layer material while preventing cracks or chipping points of the film, and the hardness of the hard coat layer may be H to 5H.
  • the polyester film may be prepared by a conventional method of biaxially stretching and heat setting the unstretched sheet in the longitudinal and transverse directions after the sheet is manufactured by melt extruding and engraving the polyester resin of the specific composition. .
  • Melt extrusion is preferably performed at a temperature of Tm + 30 o C to Tm + 60 o C of the polyester resin. If the temperature of the extruder during the melt extrusion is less than Tm + 30 ° C, the smooth melt does not occur, the viscosity of the extrudate is high, productivity is lowered, if the temperature exceeds Tm + 60 o C, on the contrary, depolymerization by thermal decomposition ⁇ Molecular weight drops and oligomers may cause problems.
  • the nyaenggak is preferably formed at a temperature below 30 ° C, it takes place at a quite bar preferably from 15 ° C to 30 o C.
  • the polyester film may be biaxially stretched in the longitudinal and transverse directions.
  • the defect is mostly due to the decomposition of the polyester chains due to hydrolysis, and especially at the minimum chain length, the brittleness of the film produced using it is no longer able to withstand mechanical deformations such as elongation or stiffness. . Therefore, as a method for slowing down the decomposition rate, the resistance to the decomposition rate can be greatly increased by providing an orientation to the molecular chain by adjusting the stretching conditions, that is, the stretching rate and the stretching ratio.
  • the stretching temperature being in the range of glass transition temperature (Tg) + 5 ° C to Tg + 50 ° C of the polyester resin, preferably T g + 10 o C to Tg + 40 o C.
  • Tg glass transition temperature
  • the stretching temperature is in the range of Tg + 10 ° C. to Tg + 40 ° C., the brittleness of the produced film can be improved.
  • the draw ratio may be 2 to 5 times, preferably 2.5 to 5 times, more preferably 2.5 to 4.0 times in the longitudinal direction, 2.5 to 5 times in the transverse direction, preferably 3 to 4.5 times, more Preferably 3.2 to 4.2 times.
  • the film is heat fixed after stretching, the film is relaxed in the longitudinal and / or transverse direction after starting the heat fixing, the heat setting temperature range is preferably 200 ⁇ 260 ° C.
  • the polyester film prepared as Iojan may have a thickness of 12 ⁇ to 400 ⁇ .
  • the polyester film may include various additives such as a conventional electrostatic agent, an antistatic agent, a sunscreen, an antiblocking agent, and other inorganic lubricants within a range that does not impair the above effects.
  • a conventional electrostatic agent such as iodine contains spherical monodisperse particles
  • the static friction coefficient and the dynamic friction coefficient may each be 0.8 or less, and preferably may be 0.05 to 0.7. Since the polyester film has a static friction coefficient and a dynamic friction coefficient of 0.8 or less, respectively, it can be easily wound in the state of.
  • the polyester film is maintained at 150 ° C. for 30 minutes, the heat shrinkage is less than or equal to 3% in both the longitudinal (length or machine direction, MD) and transverse (width, TD), and 30 minutes at 150 o C
  • the haze change after 3 hours of further maintenance is 2% or less, preferably 0.6% or less, and the total light transmission may be 90% or more.
  • the polyester film is transparent and excellent in heat resistance, and exhibits excellent hydrolysis resistance such as being able to maintain inherent excellent film properties even when exposed to high temperature and humidity for a long time. Since there is no degradation of properties and less oligomer dissolution, it can be usefully used as an optical film for display.
  • the polyester resin preparation according to the above embodiment are described.
  • silica particles (sylisia SKM-407, fuji sylysia) (.) Having an average particle diameter of 0.5 ⁇ and a particle size ratio of 0.8 were added to the PCT resin in an amount of 600 ppm relative to the PCT resin, Compounding a PCT resin containing silica particles by compounding using an extruder, PCT resin containing silica particles was dried for 4 hours at 150 ° C and equipped with a screw at 280 ⁇ 290 ° C After melt extruding through an extruder, an unstretched sheet was obtained by bringing the corner angle angled at 20 ° C.
  • a polyester film was prepared by performing the same process as in Example E1 except that Examples ⁇ 2 to ⁇ 4, and Comparative Examples E1 to ⁇ 5 spherical monodisperse particles were of the kind, particle size, and content as shown in Table 7 below. It was.
  • the films prepared in Examples El to E4 and Comparative Examples E1 to E5 are shown in Table 7 below.
  • the polyester film of Examples E1 to ⁇ 4 has a low shrinkage and haze value, there is no change over time, it can be confirmed that the excellent stretchability and total light transmission. It can be seen that in Comparative Example E1, the particle content was insufficient and the coefficient of friction was high due to high friction coefficient. In addition, Comparative Example ⁇ 2 did not contain particles, so the coefficient of friction was too high to determine the exact coefficient of friction.
  • a 10 cm ⁇ 10 cm square film sample was used with the film cut so that one edge was parallel to the machine direction (longitudinal) and the other edge was perpendicular to the machine direction (lateral). After holding the film for 30 minutes in an oven at 150 ° C. air is circulated, the sample was taken out to measure the length change in the longitudinal and transverse directions at the salon to calculate the longitudinal and transverse thermal shrinkage according to the following formula.
  • Specimens were fabricated using a 10 cm ⁇ 10 cm square film sample, with one edge cut parallel to the machine direction (vertical) and the other edge perpendicular to the machine direction (lateral). Measure the haze (%) by using a haze meter (model name: NDH-5000W, manufactured by Nippon Denshoku Kogyo Co., Ltd.) for the specimen, and then place the film in an oven at 150 ° C. for 30 minutes for air circulation. After holding, the sample was taken out, and the haze (%) was again calculated using the haze meter, and then the haze change value was calculated through Equation 2 below. In addition, the haze value after heat treatment (aging) at 150 ° C. for 3 hours was also measured in the same manner to calculate the haze change value.
  • a haze meter model name: NDH-5000W, manufactured by Nippon Denshoku Kogyo Co., Ltd.
  • the film loading state after 24 hours was classified and evaluated as follows.
  • Adhesiveness of each film prepared in the adhesive example and the comparative example was determined by the following method:

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Laminated Bodies (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)
  • Shaping By String And By Release Of Stress In Plastics And The Like (AREA)

Abstract

Cette invention concerne un film polyester comprenant une résine polyester comprenant (i) une unité constitutive dérivée d'un composant diol contenant 90 % en moles ou plus de 1,4-cyclohexanediméthanol et (ii) une unité constitutive dérivée d'un composant acide dicarboxylique contenant de 3 à 25 % en moles d'acide isophtalique, ledit film polyester étant caractérisé par un voile de 2 % ou moins, un retrait thermique de 3 % ou moins à la fois dans les sens longitudinal et transversal après maintien à 150°C pendant une heure, et une variation dans la valeur de voile inférieure à 1 %. Le film polyester selon l'invention est transparent, fait preuve d'une remarquable résistance à la chaleur, et manifeste, quand il est exposé à une température et à une humidité élevées, une excellente résistance à l'hydrolyse telle qu'une propriété capable de conserver les remarquables propriétés intrinsèques du film pendant longtemps sans détérioration des propriétés physiques provoquée par la cristallisation à une température élevée, ledit film polyester pouvant par conséquent être utile à titre de film optique pour affichage.
PCT/KR2014/012975 2013-12-30 2014-12-29 Film polyester ayant une résistance élevée à la chaleur WO2015102339A1 (fr)

Applications Claiming Priority (10)

Application Number Priority Date Filing Date Title
KR10-2013-0167005 2013-12-30
KR1020130167005A KR101594542B1 (ko) 2013-12-30 2013-12-30 투명 이축연신 폴리에스테르 필름 및 이의 제조방법
KR1020140004741A KR101647470B1 (ko) 2014-01-14 2014-01-14 고내열성을 가지는 폴리에스테르 필름
KR10-2014-0004741 2014-01-14
KR1020140015977A KR101605413B1 (ko) 2014-02-12 2014-02-12 고내열성을 가지는 폴리에스테르 필름
KR10-2014-0015977 2014-02-12
KR10-2014-0020456 2014-02-21
KR1020140020456A KR101605411B1 (ko) 2014-02-21 2014-02-21 고내열성을 가지는 폴리에스테르 필름
KR10-2014-0191073 2014-12-26
KR1020140191073A KR101647475B1 (ko) 2014-12-26 2014-12-26 고내열성을 가지는 폴리에스테르 필름

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Cited By (2)

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CN109679303A (zh) * 2018-12-19 2019-04-26 长园长通新材料股份有限公司 一种耐高温高湿型pet热缩套管材料及其制备方法
US10767041B2 (en) 2015-11-24 2020-09-08 Eastman Chemical Company Polymer compositions and substrates for high temperature transparent conductive film applications

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KR102369349B1 (ko) * 2019-10-02 2022-03-02 에스케이씨 주식회사 전자기판용 필름 및 적층체, 및 이를 포함하는 전자기판
TWI727664B (zh) * 2020-02-18 2021-05-11 南亞塑膠工業股份有限公司 低寡聚物易延伸改性聚酯膜及其製造方法

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* Cited by examiner, † Cited by third party
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US10767041B2 (en) 2015-11-24 2020-09-08 Eastman Chemical Company Polymer compositions and substrates for high temperature transparent conductive film applications
CN109679303A (zh) * 2018-12-19 2019-04-26 长园长通新材料股份有限公司 一种耐高温高湿型pet热缩套管材料及其制备方法
CN109679303B (zh) * 2018-12-19 2021-02-09 长园长通新材料股份有限公司 一种耐高温高湿型pet热缩套管材料及其制备方法

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