WO2008001932A1 - Film stratifié de polyester pour formage et son procédé de fabrication - Google Patents

Film stratifié de polyester pour formage et son procédé de fabrication Download PDF

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Publication number
WO2008001932A1
WO2008001932A1 PCT/JP2007/063223 JP2007063223W WO2008001932A1 WO 2008001932 A1 WO2008001932 A1 WO 2008001932A1 JP 2007063223 W JP2007063223 W JP 2007063223W WO 2008001932 A1 WO2008001932 A1 WO 2008001932A1
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WIPO (PCT)
Prior art keywords
film
layer
polyester film
laminated
molding
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PCT/JP2007/063223
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English (en)
Japanese (ja)
Inventor
Katsufumi Kumano
Yuki Haraguchi
Yasushi Sasaki
Masatoshi Tanabe
Katsuya Ito
Original Assignee
Toyo Boseki Kabushiki Kaisha
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
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Application filed by Toyo Boseki Kabushiki Kaisha filed Critical Toyo Boseki Kabushiki Kaisha
Priority to KR1020097001848A priority Critical patent/KR101086093B1/ko
Priority to CN2007800248359A priority patent/CN101484317B/zh
Publication of WO2008001932A1 publication Critical patent/WO2008001932A1/fr

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C55/00—Shaping by stretching, e.g. drawing through a die; Apparatus therefor
    • B29C55/02—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2067/00—Use of polyesters or derivatives thereof, as moulding material

Definitions

  • the present invention relates to moldability, particularly moldability at low temperature and low pressure, particularly moldability at low temperature and low pressure, transparency, solvent resistance, and form stability (heat shrinkage characteristics, thickness).
  • the present invention relates to a laminated polyester film for molding, which is excellent in non-uniformity and further excellent in impact resistance, and suitable for use as an interior material, exterior material, or building material for home appliances, mobile phones, and automobiles, and a method for producing the same.
  • a polysalt-bulb film is representative and has been preferably used in terms of workability.
  • problems in terms of environmental suitability such as generation of toxic gases during film burning and bleed out plasticizers.
  • unstretched sheets made of polyester, polycarbonate, or acrylate resin have been used in a wide range of fields as materials excellent in environmental suitability.
  • an unstretched sheet made of polyester resin is excellent in moldability and laminate suitability.
  • heat resistance is inferior in solvent resistance.
  • the unstretched sheet has insufficient impact resistance and form stability (heat shrinkage characteristics). Therefore, (a) If the speed during printing or molding is increased to improve productivity, breaks or holes will occur during processing. (B) Printing misalignment will occur due to heating during molding, or ( c) When the molded product is exposed to a temperature higher than room temperature, there is a problem that the molded product is distorted.
  • Patent Document 1 Japanese Patent Laid-Open No. 2-204020
  • Patent Document 2 Japanese Patent Laid-Open No. 2001-347565
  • the present inventor has a copolymer polyester resin as a constituent component, a film 100% elongation stress (25 ° C, 100 ° C), storage elastic modulus (100 ° C, 180 ° C), longitudinal Proposed a method for improving the above-mentioned problems by using a biaxially oriented polyester film having a thermal deformation rate (175 ° C) in a specific range under a small tension in the direction (for example, Patent Document 3). See).
  • Patent Document 3 Japanese Patent Laid-Open No. 2005-290354
  • each layer is assigned functions so that the film has a laminated structure, the skin layer has chemical resistance, and the core layer has sufficient moldability, aiming to achieve both chemical resistance and moldability.
  • Inventions have also been proposed (see, for example, Patent Document 4).
  • Patent Document 4 Japanese Patent Laid-Open No. 2005-335276
  • the heat treatment temperature is increased until the core layer has a substantially non-oriented structure.
  • Extremely low elongation at room temperature (2) Whitening when heated, narrow range of processing temperature, (3) Non-uniform thickness, appearance quality, processing There is a problem that time stability and reproducibility deteriorate.
  • An object of the present invention is to solve the above-mentioned conventional problems, and the moldability, in particular, the moldability at low temperature and low pressure, transparency, solvent resistance, and shape stability (heat shrinkage).
  • An object of the present invention is to provide a laminated polyester film for molding, which is excellent in properties and unevenness in thickness, and has excellent impact resistance, and a method for producing the same.
  • the laminated polyester film for molding and the method for producing the same of the present invention that can solve the above-described problems also have the following constitutional power.
  • the first invention in the present invention is a biaxially oriented laminated polyester film obtained by laminating a polyester B layer on one side or both sides of a polyester A layer,
  • Both layer A and layer B consist of copolymer polyester, or copolymer polyester and homopolyester, and the melting point of layer A (TmA: ° C) and the melting point of layer B (TmB: ° C) are as follows: Satisfying the equations (1) and (2) simultaneously,
  • the laminated polyester film has an orientation structure in both the A layer and the B layer, the thermal shrinkage rate at 150 ° C is 6.0% or less in both the longitudinal direction and the width direction, and the thickness fluctuation rate in the width direction is 10%. It is the laminated polyester film for molding characterized by being the following.
  • the second invention is a copolyester force (a) a copolymer polyester comprising an aromatic dicarboxylic acid component, ethylene glycol, and a darlicol component containing a branched aliphatic glycol or alicyclic glycol, Or (b) A laminated polyester film for molding according to the first invention, characterized in that it is composed of an aromatic dicarboxylic acid component containing terephthalic acid and isophthalic acid, and a Daricol component containing ethylene glycol.
  • the third invention is a homopolyester strength polyethylene terephthalate, polytetramethylene
  • the laminated polyester film for molding according to the first invention characterized in that it is at least one selected from the group force consisting of terephthalate and polybutylene terephthalate.
  • the fourth invention is characterized in that the total thickness of the laminated polyester film is 10 to 500 ⁇ m, and the thickness of the B layer is 1 to 30% of the whole. It is a laminated polyester film for molding.
  • the 100% stretching stress in the longitudinal and width directions of the laminated polyester film is 40 to 300 MPa at 25 ° C and 1 to LOOM Pa at 100 ° C.
  • the laminated polyester film for molding according to the first invention characterized by the above.
  • a sixth invention is the laminated polyester film for molding according to the first invention, characterized in that the haze of the laminated polyester film is 2.0% or less.
  • the laminated polyester film according to the first aspect is used as a base material, and a coating layer (C layer) having a thickness of 0.01 to 5 m is further provided on one or both sides of the base material.
  • a coating layer (C layer) having a thickness of 0.01 to 5 m is further provided on one or both sides of the base material.
  • It is a laminated polyester film for molding formed by laminating, and the coating layer has polyester, polyurethane, acrylic polymer, or a copolymer force thereof, and a composition force containing at least one selected resin and particles.
  • the substrate is a laminated polyester film for molding characterized by containing substantially no particles.
  • the eighth invention is a process for producing an unstretched sheet in which a polyester B layer is laminated on one or both sides of a polyester A layer using a coextrusion method, A process for biaxially stretching in the width direction, a process power for heat treatment while holding a biaxially stretched film with a clip, and a method for producing a laminated polyester film for molding,
  • the heat treatment process has two or more heat treatment sections, and in the heat treatment section, the maximum heating rate is 10 to 30 ° CZ seconds and the maximum heat treatment temperature is (the melting point of layer A—10 ° C) to (the layer A
  • the method for producing a laminated polyester film for molding according to the first invention wherein the melting point is controlled to + 20 ° C.
  • the melting point is controlled to + 20 ° C.
  • at least one of the following methods (i) to (V) is performed in the vicinity of the clip.
  • the method for producing a laminated polyester film for molding according to the eighth invention characterized in that the film is cooled using, and then the clip force film is opened at the tenter outlet.
  • the laminated polyester film for molding of the present invention has a skin layer (B layer) on one or both sides of the core layer (A layer), and the skin layer has a melting point higher than that of the core layer.
  • the core layer (A) can be given sufficient flexibility to further improve the moldability.
  • the thickness unevenness is improved, and the function of improving heat resistance and chemical resistance by orientation crystallization is expressed.
  • productivity and quality can be improved during continuous production of films, during post-processing of films (printing, laminating metal films and metal oxide films, etc.), molding processes, and when using molded products. The stability of the can be further increased.
  • the laminated polyester film for molding of the present invention By using the laminated polyester film for molding of the present invention, it was difficult to mold with the conventional biaxially oriented polyester film, and the molding pressure during molding was under a low pressure of 10 atm or less. Even molding methods such as vacuum molding and pressure molding can provide molded products with good finish. In addition, these molding methods are advantageous in terms of economics in the production of molded products because the molding costs are low. Therefore, the characteristics of the laminated polyester film for molding of the present invention are most effectively exhibited by applying to these molding methods. Togashi.
  • the laminated polyester film for molding of the present invention is excellent in moldability at the time of heat molding, particularly moldability at low temperature and low pressure, so a wide range of molding such as mold molding, pressure molding, and vacuum molding.
  • the method can be applied.
  • a molded product formed by such a method is used in a normal temperature atmosphere, it is excellent in elasticity and form stability (heat shrinkage characteristics, thickness unevenness), and also in transparency, solvent resistance and heat resistance. Since it is excellent in impact resistance, it is suitable for interior materials for home appliances, mobile phones, automobiles, exterior materials, or building material members.
  • the laminated polyester film for molding of the present invention is molded using a molding method such as press molding, laminate molding, in-mold molding, drawing molding, bending molding, etc. in addition to the above-described molding method. It is also suitable as a material for use.
  • the heat shrinkage (HS150) at 150 ° C. is preferably 6.0% or less in both the longitudinal direction and the width direction.
  • the upper limit value of HS150 is more preferably 5.0%, further preferably 4.0%, and particularly preferably 3.0%.
  • the lower limit value of HS150 is preferably 0.01%, more preferably 0.1%, and particularly preferably 0.5%, from a practical point of view.
  • HS 150 is preferably small, but appropriate management standards are established from the viewpoint of practical effect and productivity according to the heat treatment temperature during post-processing of the molding film and the temperature atmosphere in which the molded product is used. Just do it. H S150 strength. Even if a film of less than 01% is produced, there is no significant difference in practical effect. Rather, productivity is greatly reduced, so HS150 is not necessarily less than 0.01%.
  • the thickness variation rate of the film is used as a characteristic value related to macroscopic impact resistance.
  • Film thickness fluctuation rate is generally used as one of the characteristic values indicating the quality of film appearance.
  • a large film thickness fluctuation rate means that the physical properties that affect the film thickness fluctuate.
  • the thickness variation rate of the film increases, the impact resistance decreases at the thin part. For this reason, when manufacturing a film continuously for a long time, during post-processing of the film (printing, laminating metal film or metal oxide film, etc.), molding process, or using molded products, Film tearing is likely to occur.
  • the film is molded, the deformation of the film becomes non-uniform and the formability becomes non-uniform.
  • the film thickness variation rate By setting the film thickness variation rate to 10% or less in the width direction, impact resistance can be improved. Therefore, it is possible to reduce the frequency of film breakage during continuous production, post-processing, molding, or use of molded products.
  • the thickness variation rate in the longitudinal direction is equally important, but since it is linked with the width direction, the thickness variation rate in the width direction is used as a representative in the present invention.
  • the stress at 100% elongation is a measure closely related to the moldability of the film.
  • F100 is closely related to film formability
  • the film may locally extend to 100% or more near the corner of the mold.
  • the stress required for deformation is too high, resulting in insufficient deformation and reduced formability.
  • films with F100 that are too small can be deformed with low stress.
  • a very weak tension is not generated. For this reason, it is presumed that the film cannot be uniformly stretched in the portion, and the molding is distorted.
  • 100% elongation stress (F100) at 100 ° C. is used as a physical property related to the moldability corresponding to the molding temperature. Also, the mold for molding is
  • the polyester film for molding in the present invention has a 100% elongation stress (F100) at 25 ° C in the longitudinal and width directions of the film of 40 to 300 MPa.
  • F100 in the longitudinal direction and the width direction of the film is preferably a lower limit force, more preferably 50
  • MPa is particularly preferred.
  • the upper limit is preferably 25 OMPa force, more preferably 200 MPa, and particularly preferably 180 MPa.
  • the polyester film for molding in the present invention has a 100% elongation stress (F100) force at 100 ° C in the longitudinal direction and the width direction of the film.
  • the upper limit of F100 in the longitudinal and width directions of the film is 90% from the viewpoint of moldability.
  • the lower limit of F10 0 is more preferably 5 MPa from the viewpoint of elasticity and shape stability when using molded products.
  • More preferred lOMPa is more preferred 20MPa.
  • the laminated polyester film for molding of the present invention preferably has a haze of 2% or less.
  • various decorations such as printing, metal vapor deposition, sputtered layer, and transfer layer are enhanced in clarity and luxury, and the product value can be greatly increased.
  • the haze is more preferably 1.8% or less, and particularly preferably 1.6% or less.
  • the elongation at break at 25 ° C is a characteristic value related to the handleability of the film near room temperature. For example, by managing the elongation at break at 25 ° C, it is possible to maintain the passability of post-processing such as printing and slitting in a good state.
  • the laminated polyester film for molding of the present invention is a biaxially oriented laminated polyester film in which a polyester B layer (skin layer) is laminated on one side or both sides of a polyester A layer (core layer).
  • the laminated structure of the laminated polyester film of the present invention is basically composed of two types and three layers of BZAZB or two types and two layers of BZA.
  • a coating layer may be provided on at least one side of the base material to provide quality improvement or other functions on one side or both sides of the film of the present invention. it can.
  • each of the A layer and the B layer is composed of a copolyester, or a copolyester and a homopolyester, and has a melting point (TmA: ° C) of the A layer.
  • TmA melting point
  • TmB ° C
  • a polyester layer having a higher melting point than polyester A of the core layer (A layer) and a skin layer (B layer) having a B force is laminated on one or both sides of the core layer, and the core layer is also oriented. It is characterized by having a structure. The reason for leaving the oriented structure in the core layer (A) will be described in detail later.
  • the melting point (° C) of layer A is TmA, B
  • the melting point (° C) of the layer is TmB
  • the melting point means the endothermic peak temperature at the time of melting, which is detected at the first temperature rise in differential scanning calorimetry (DSC).
  • TmA and TmB are preferably less than 260 ° C.
  • TmB and TmA be higher than 200 ° C in order to maintain the heat resistance of the entire film and to reduce thermal deformation at high temperatures.
  • TmB and TmA are preferably higher than 205 ° C, particularly preferably higher than 210 ° C.
  • the melting point (TmB) of the skin layer (B layer) is set larger than the melting point (TmA) of the core layer (A layer), so that flexibility, slipperiness, and chemical resistance are increased. It is important from the viewpoint of highly balancing heat resistance.
  • the laminated polyester film for molding of the present invention satisfies the following relational expression (2) when the melting point (° C) of layer A is TmA and the melting point (° C) of layer B is TmB. This is very important.
  • TmB—TMA When “TmB—TMA” is 50 ° C or higher, the difference in melting point between layer A and layer B is too large, so heat shrinkage, flexibility, impact strength, stability over time, and processing stability You will not be able to fully satisfy “TmB—TMA” is preferably less than 40 ° C., more preferably less than 35 ° C. Also, when “TmB-TMA” is 5 ° C or less, the difference in melting point is too small, making it difficult to achieve a high balance between flexibility, slipperiness, chemical resistance, and heat resistance. “TmB—TMA” is preferably higher than 10 ° C., particularly preferably higher than 15 ° C.
  • a polyester film obtained by using a copolymerized polyester containing 5 to 50 mol% of a copolymerization component as a raw material as in the present invention has a lower crystallization rate and crystallinity than a polyethylene terephthalate film or the like. Low.
  • the heat treatment is suddenly performed at a high temperature after stretching. For this reason, the mobility of molecules constituting the material having low crystallinity is increased in the heat treatment section. Therefore, the surface protrusions formed by the bulging of the particles (the particles in the biaxially oriented film!
  • a manufacturing method is used in which the heat treatment process is divided into multi-stage heat treatment sections and the temperature increase rate in the heat treatment section is set to a specific range so as to promote crystallization of the film and relax the orientation.
  • Tm melting point
  • the melting point is obtained when the transesterification is completely random, and in the blend, the operating conditions of the extruder, the residence time in the melt line, the raw material composition, the molecular weight, the raw material moisture content, the catalyst, etc.
  • the transesterification rate is determined by the additive, acid value and the like. If all these factors are fixed, a constant melting point can be obtained with good reproducibility, and if only one factor is changed, a transesterification rate corresponding to that can be obtained, and the melting point with good reproducibility under these conditions. Is obtained.
  • the polyester used in B) is a copolyester or a blend of copolyester and homopolyester.
  • the copolyester includes (a) an aromatic dicarboxylic acid component, ethylene glycol,
  • a copolymer polyester composed of a rubonic acid component and a Dalicol component containing ethylene glycol is preferred.
  • the copolymerization component of the copolyester is a branched aliphatic glycol or alicyclic glycol
  • molecular mobility at high temperatures can be suppressed due to the bulkiness of the molecular structure of the glycol. Therefore, a film using a copolymerized polyester containing a branched aliphatic glycol or alicyclic glycol as a copolymerization component has improved heat resistance.
  • the carboxylic acid component of the copolymer component consists only of an aromatic dicarboxylic acid component, the heat resistance is improved.
  • the polyester power constituting the biaxially oriented polyester film further includes 1,3 propanediol units or 1,4 butanediol units as glycol components to further improve the moldability. Further, by introducing these units into the copolyester, microcrystals are formed in the molecule, and for example, a decrease in elastic modulus at 180 ° C. can be suppressed. These units may be introduced as a copolymerization component of the copolymer polyester, or a method of blending a homopolyester such as polytrimethylene terephthalate (PTT) or polybutylene terephthalate (PBT) may be used. .
  • PTT polytrimethylene terephthalate
  • PBT polybutylene terephthalate
  • the film raw material is a copolymerized polyester alone, a blend of two or more types of copolymerized polyesters, or a blend of at least one type of homopolyester and at least one type of copolymerized polyester. Either method is possible. Among these, the blending force of homopolyester and copolymerized polyester is preferable from the viewpoint of suppressing a decrease in melting point.
  • the aromatic dicarboxylic acid is used.
  • terephthalic acid isophthalic acid, 2, 6 naphthalenedicarboxylic acid or an ester-forming derivative thereof is suitable.
  • the molar ratio of terephthalic acid units to 2,6 naphthalene dicarboxylic acid units is 100ZO-50Z50 [0060]
  • Examples of branched aliphatic glycols include neopentyldaricol, 1,2-propanediol, 1,3 propanediol, 1,4 butanediol, and the like.
  • Examples of the alicyclic glycol include 1,4 cyclohexane dimethanol and tricyclodecane dimethylol.
  • neopentyl glycol and 1,4-cyclohexanedimethanol are particularly preferred.
  • Use of these glycols as a copolymerization component is suitable for imparting the above properties, and is excellent in transparency and heat resistance, and has good adhesion to the coating layer when the coating layer is provided.
  • the point power to improve is also preferable.
  • the amount of ethylene glycol is as follows. It is 70 mol% or more, preferably 85 mol% or more, particularly preferably 95 mol% or more, particularly preferably 100 mol%, based on all glycol components.
  • the glycol component other than ethylene glycol the above-mentioned branched aliphatic glycol, alicyclic glycol, or diethylene glycol is preferable.
  • the molar ratio of the terephthalic acid unit to the isophthalic acid unit is preferably in the range of 100ZO to 50Z50.
  • Examples of the catalyst used in the production of the copolyester include alkaline earth metal compounds, manganese compounds, cobalt compounds, aluminum compounds, antimony compounds, titanium compounds, and titanium alloys. Complex oxides and germanium compounds can be used. Among these, titanium compounds, antimony compounds, germanium compounds
  • Aluminum compounds are preferred from the viewpoint of catalytic activity.
  • a phosphorus compound as a heat stabilizer.
  • phosphorus compound phosphoric acid, phosphorous acid, etc. are preferable, for example.
  • the copolyester has an intrinsic viscosity of 0 from the viewpoint of moldability and film-forming stability.
  • the intrinsic viscosity of the film is 0.6.OdlZg or more. By doing so, the impact strength of the film is improved, and the frequency of breakage during film formation or in the caulking can be reduced.
  • the upper limit of the intrinsic viscosity is preferably 1. Od lZg from the viewpoint of ejection stability during extrusion of the molten resin.
  • At least one type of homopolyester and at least one type of copolymerized polyester are used as film raw materials, and these are blended to form a film, whereby only the copolymerized polyester is used.
  • Transparency and high melting point (heat resistance) can be achieved while maintaining the same flexibility.
  • a high-melting homopolyester for example, polyethylene terephthalate
  • the copolyester and at least one homopolyester other than polyethylene terephthalate are blended to obtain the laminated polyester film for molding of the present invention.
  • Use as a raw material is more preferable in terms of moldability.
  • the copolymer polyester may be used in combination with one or more dicarboxylic acid components as described below and Z or Daricol components as copolymer components.
  • dicarboxylic acid components that can be used in combination with terephthalic acid or an ester-forming derivative thereof include (1) isophthalic acid, 2,6-naphthalenedicarboxylic acid, diphenyl 4,4'-dicarboxylic acid, Aromatic dicarboxylic acids such as diphenoxyethanedicarboxylic acid, diphenylsulfone dicarboxylic acid, 5-sodium sulfoisophthalic acid, phthalic acid or ester-forming derivatives thereof, (2) oxalic acid, succinic acid, adipic acid, sebacine Aliphatic dicarboxylic acids such as acid, dimer acid, maleic acid, fumaric acid and dartaric acid or their ester-forming derivatives, (3) Alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid or their ester-forming derivatives (4) Derivation of oxycarboxylic acids such as p-oxybenzoic acid and
  • ethylene glycol, branched aliphatic glycols and other darlicol components that can be used together with Z or alicyclic glycols include, for example, aliphatic glycols such as pentanediol and hexanediol, Bisphenol A, Bisphenol S Aromatic glycols such as these and ethylene oxide adducts thereof, diethylene glycol, triethylene glycol and the like.
  • the copolymerized polyester may be further copolymerized with a polyfunctional compound such as trimellitic acid, trimesic acid, trimethylolpropane and the like.
  • the particles contained in the film generally have a refractive index different from that of polyester, it causes a decrease in the transparency of the film. Molded products are often printed on the surface of the film before it is molded in order to enhance the design. Since such a printing layer is often applied to the back side of a film for molding, it is desired that the transparency of the film is high from the viewpoint of print clarity.
  • the thickness of the skin layer (B layer) of the laminated polyester film is 1 to 5 ⁇ m, and only the skin layer (B layer) contains particles, and the core layer (A layer) contains particles. It is a structure that does not contain substantially.
  • a laminated polyester film is used as a base material, and a coating layer (C layer) having a thickness of 0.01 to 5 ⁇ m is further laminated on one side or both sides of the base material.
  • Polyurethane, acrylic polymer, or copolymer thereof is a composition containing at least one selected resin and particles, and the substrate is substantially free of particles. It is.
  • the upper limit of the thickness of the surface layer containing the particles is preferably 3 ⁇ m, particularly preferably 1 ⁇ m.
  • the method using the coating layer (C layer) has the advantage of being excellent in adhesion to the printing layer in addition to providing transparency and slipperiness.
  • substantially no particles are contained in the base film means, for example, in the case of inorganic particles, when the inorganic element is quantified by key X-ray analysis and below the detection limit. Means the content of This is because contaminants derived from foreign substances may be mixed without intentionally adding particles to the base film.
  • the particles have an average particle size (number average particle size based on SEM) of 0.01 to: LO Examples include known internal particles of ⁇ m, inorganic particles, and external particles such as Z or organic particles. When particles having an average particle diameter exceeding 10 m are used, defects in the film are liable to occur and the design properties tend to be poor. On the other hand, when the average particle size is less than 0.01 m, the handling properties such as film slipping and winding properties tend to be lowered.
  • the average particle diameter of the particles is such that at least 200 particles are photographed by electron microscopy, the particle outline is traced on an OHP film, and the trace image is circled by an image analyzer. Calculated in terms of equivalent diameter.
  • Examples of the external particles include wet and dry silica, colloidal silica, aluminum silicate, titanium oxide, calcium carbonate, calcium phosphate, barium sulfate, alumina, my strength, strength, clay, hydroxyapatite, and other inorganic particles and styrene.
  • Organic particles containing silicone, acrylic acid, or the like as constituent components can be used.
  • inorganic particles such as dry, wet and dry colloidal silica and alumina, and organic particles containing styrene, silicone, acrylic acid, methacrylic acid, polyester, divinylbenzene and the like are preferably used.
  • silica particles, glass fillers, and silica-alumina composite oxide particles are particularly suitable from the viewpoint of transparency because the refractive index is relatively close to that of polyester.
  • Two or more of these internal particles, inorganic particles, and Z or organic particles may be used in combination as long as the properties are not impaired.
  • the content of the particles in the layer containing the particles is within a range in which the haze of the laminated film is 2.0% or less and the slipperiness of the film is not a problem. It is preferable to adjust within the range of 001-1 0% by mass.
  • the laminated polyester film for molding of the present invention is a biaxially stretched film.
  • solvent resistance and dimensional stability, which are disadvantages of an unstretched sheet are improved by molecular orientation by biaxial stretching. That is, one of the features of the present invention is that the solvent resistance and heat resistance, which are disadvantages of the unstretched sheet, are improved while maintaining the good formability of the unstretched sheet.
  • the following method is used. After drying the polyester used for the polyester A layer and the polyester B layer, separately supply them to two or more melt extruders, and in the molten state by the coextrusion method, Is laminated on BZAZB. These are extruded into a sheet shape from a slit-shaped die, and brought into close contact with a casting drum by a method such as electrostatic application, and then cooled and solidified to obtain an unstretched sheet. Next, a method of biaxially stretching this unstretched sheet is exemplified. When using a vent type extruder, it is not always necessary to dry the film raw material chips.
  • the melt extrusion conditions are appropriately adjusted according to the raw materials used, and the progress of hydrolysis and thermal deterioration is suppressed, and the melting point of the film is in an appropriate range. Select the condition to be adjusted.
  • the extrusion temperature is set to (melting point + 100 ° C) or lower, preferably (melting point + 90 ° C) or lower, more preferably (melting point + 80 ° C) or lower.
  • the residence time to the die outlet is also set to 20 minutes or less, preferably 18 minutes, and more preferably 16 minutes or less to suppress decomposition and melting point drop.
  • melt extruder used for the A layer and the B layer for example, an extruder having a feed part, a compression part, a metering part, and a melt line part is used.
  • the temperature of the resin is gradually raised, and the upper limit of the temperature of the resin is controlled within the above range to completely melt the resin.
  • the resin temperature is preferably less than 280 ° C.
  • the temperature is preferably 275 ° C. or less, more preferably 270 ° C. or less.
  • the biaxial stretching method a method is employed in which an unstretched sheet is stretched in the longitudinal direction (MD) and the width direction (TD) and heat-treated to obtain a biaxially stretched film having desired physical properties.
  • sequential biaxial stretching such as the MDZTD method in which the film is stretched in the longitudinal direction and then stretched in the width direction, or the TDZ MD method in which the film is stretched in the width direction and then stretched in the longitudinal direction.
  • a simultaneous biaxial stretching method in which the method, the longitudinal direction and the width direction are stretched almost simultaneously is desirable.
  • a tenter driven by a linear motor may be used.
  • a multi-stage stretching method in which stretching in the same direction is performed in multiple stages may be used.
  • the film stretching ratio in biaxial stretching is 1.6 to 4.2 times in the longitudinal direction and the width direction. It is particularly preferable that the ratio is 1.7 to 4.0 times. In this case, the stretching ratio in the longitudinal direction and the width direction may be either larger or the same ratio. More preferably, the stretching ratio in the longitudinal direction is 2.8 to 4.0 times, and the stretching ratio in the width direction is 3.0 to 4.5 times.
  • the stretching temperature is 50 to 110 ° C and the stretching ratio is 1.5 to 4.0 times so that the subsequent stretching in the width direction can be performed smoothly.
  • the preheating temperature is preferably 90 to 140 ° C.
  • the stretching temperature is preferably ⁇ 10 to 25 ° C., particularly preferably ⁇ 10 to 20 ° C. with respect to the preheating temperature.
  • the stretching temperature is preferably 0 to + 20 ° C., particularly preferably +5 to + 20 ° C. with respect to the stretching temperature of the first half.
  • the film is heat-treated after biaxial stretching.
  • This heat treatment can be performed by a conventionally known method such as in a tenter or on a heated roll. Further, the heat treatment temperature and heat treatment time can be arbitrarily set according to the level of heat shrinkage required.
  • the heat treatment process is performed in two or more heat treatment sections, and in the heat treatment section, the maximum heating rate is 10 to 30 ° CZ seconds, and the maximum heat treatment temperature is (the melting point of layer A is 10 ° C). It is preferable to control to (melting point of layer A + 20 ° C). Further, it is more preferable that the heat treatment section is 3 sections or more, and 4 sections or more are particularly preferable.
  • the heat treatment time is determined in an appropriate range depending on the film feed speed and the length of the heat treatment process, but it is preferably performed for 1 to 6.0 seconds, for example.
  • the heat treatment may be performed while relaxing the film in the longitudinal direction and the Z or width direction.
  • the thermal shrinkage at 150 ° C in the longitudinal and transverse directions of the film It is preferable to increase the heat treatment temperature, increase the heat treatment time, and perform relaxation treatment. Specifically, in order to reduce the heat shrinkage rate at 150 ° C in the longitudinal and width directions of the film to 6.0% or less, the maximum heat treatment temperature in the heat treatment step (the melting point of layer A is 10 ° C) ) To (melting point of layer A + 20 ° C.), and it is preferable to carry out relaxation while relaxing at 1 to 8%. Further, re-stretching may be performed one or more times in each direction, and then heat treatment may be performed.
  • the upper limit of the maximum heat treatment temperature in the heat treatment step is preferably (the melting point of the A layer + 15 ° C), more preferably (the melting point of the A layer + 10 ° C), particularly preferably (the melting point of layer A + 5 ° C).
  • This heat treatment temperature is the set temperature, not the actual film temperature.
  • a heat insulation section of lm or more is provided between the stretching section and the heat treatment section and the heating efficiency thereafter is increased.
  • the heating efficiency is increased by strengthening the partition for each section to reduce the leakage of heat flow.
  • By adjusting the balance and strength of the air volume it is possible to adjust the pressure in the tenter and suppress the leakage of heat flow while ensuring the air volume.
  • an infrared heater it is preferable to add an infrared heater to the strong heating section. It is also effective to increase the amount of heat by increasing the length of the heat-fixed section and the number of sections.
  • the maximum heat treatment temperature in the heat treatment section from the low temperature around 100 ° C after the stretching is finished is 10 ° C or more (A
  • the following problems occur when the temperature is rapidly raised to a temperature below the melting point of the layer + 20 ° C).
  • the laminated film of the present invention uses a copolyester, the degree of crystallization is low. Therefore, in the heat treatment section, the thickness unevenness of the film is not impact strength. During film formation only by lowering, the film may have holes in the heat treatment zone, and continuous film formation may not be possible.
  • the total thickness of the laminated polyester film of the present invention may be appropriately set in the range of 10 to 500 ⁇ m depending on the application. In general, the film thickness is often used in the range of 20 to 188 / zm. Further, it is preferable that the thickness of the layer B is in the range of 1 to 30% of the total thickness, more preferably 2 to 27%, and further preferably 3 to 25%. When the thickness of the B layer is 1% or more of the total thickness, it is possible to prevent a decrease in chemical resistance and heat resistance due to the B layer. Moreover, it is excellent also in film forming stability. On the other hand, when the thickness of the B layer is 30% or less of the total thickness, deterioration of moldability and heat shrinkage rate can be suppressed.
  • a method of reducing the degree of plane orientation is generally used.
  • a method for reducing the draw ratio is known as a means for reducing the degree of plane orientation.
  • this method deteriorates the uneven thickness of the film.
  • the present invention uses a method in which orientation relaxation is performed while growing the crystal of the film by setting the heat treatment temperature higher than usual and controlling the temperature rising rate in the heat treatment section to a certain range.
  • the non-oriented portion may turn white due to heating, resulting in a poor appearance. This limits the temperature range during use or care.
  • an appropriate heat treatment temperature should not be selected to leave the core layer in an unoriented state.
  • the copolyester used as a raw material for the film has a lower melting point than that of the homopolymer. Therefore, when the heat treatment temperature is increased, the film adheres to the clip that holds the film in the tenter, There is a problem that it becomes difficult to peel off. Therefore, when the clip releases the film at the tenter outlet, it is important for the vicinity of the clip to be sufficiently cooled during continuous film formation.
  • Example [0106] Hereinafter, the present invention will be described in detail by way of examples.
  • the film characteristics obtained in each example were measured and evaluated by the following methods.
  • the sample amount was about 0.001 g
  • the measurement temperature range was from room temperature to 300 ° C
  • the temperature increase rate was 20 ° CZ.
  • To determine the melting point of layer A and layer B cut the film into A4 size, adhere and fix it to a flat plate, scrape the surface with a single-blade force razor, and measure the melting point of layer B by DSC measurement. .
  • the melting point of the entire film was determined by DSC measurement, and the melting peak of the A layer was determined by removing the melting peak information relating to the melting point of the B layer.
  • the sample for judgment is made using a microtome, and a thin section (thickness: 10 m) is created parallel to the MD direction of the film for transmission observation of the cross section in the thickness direction.
  • a transmission type polarizing microscope the brightness of the image in the A layer when the polarizing plate is rotated is visually determined according to the following criteria. The magnification was 200 times.
  • a sample was cut into a strip shape having a length of 180 mm and a width of 10 mm, respectively, with a single-blade force razor.
  • a tensile testing machine Toyo Using a Seiki Co., Ltd., a strip-shaped sample was stretched, and 100% elongation stress (MPa) and elongation at break (%) in each direction were determined from the obtained load-strain curve.
  • the measurement was performed in an atmosphere of 25 ° C, with an initial length of 40 mm, a chuck-to-chuck distance of 100 mm, a crosshead speed of 100 mmZmin, a recorder chart speed of 200 mmZmin, and a load cell of 25 kgf. This measurement was performed 10 times and the average value was used.
  • the sample was held for 30 seconds in an atmosphere of 100 ° C, and then measured. The measurement was performed 10 times and the average value was used.
  • the distance B between two marks (the distance between the two marks after heat treatment) is read with a gold finger in units of 0.25 mm under a constant tension of 5 gf (tension in the length direction).
  • the thermal shrinkage rate of each sample at 150 ° C was calculated according to the following formula and judged according to the following criteria. The measurement was performed three times, and the average value was obtained. Numbers are rounded to the first decimal place by rounding to the first decimal place.
  • Thickness variation rate (%) ((dmax-dmin) / d) X 100
  • the film for measurement was pressed with a clamp, pierced with a 1Z2 inch diameter hemispherical impact head, and the impact strength of the sample was measured. .
  • the sample was lOOmmX 100 mm or more, and the ring for fixing the sample had an inner diameter of 30 mm.
  • the measurement was performed 10 times and the average value was obtained.
  • the average value was converted per lmm thickness and determined as the impact strength (jZmm) of the film, and judged according to the following criteria.
  • the film was heated for 10 to 15 seconds with an infrared heater heated to 500 ° C., and then vacuum molded at a mold temperature of 30 to 100 ° C.
  • the optimum heating condition was selected within the above range for each film.
  • the shape of the mold is a cup shape, the opening is 50mm in diameter, the bottom is 40mm in diameter, the depth is 50mm, and all corners are curved with a diameter of 0.5mm. It was.
  • Corner radius of curvature is lmm or less and printing deviation is 0.1 lmm or less
  • Corner radius of curvature exceeds lmm, 1.5mm or less, or print misalignment is 0.1 greater than 0.2 mm and less than 0.2 mm
  • Molded product is torn or even if it is not torn, it falls under any of the following items (i) to (iv)
  • corner radius of curvature is lmm or less and printing deviation is 0.1mm or less
  • Molded product is torn or even if it is not torn, it falls under any of the following items (i) to (iv)
  • contact heating was performed with a hot plate heated to 100 to 140 ° C for 4 seconds, and then press molding was performed at a mold temperature of 30 to 70 ° C and a holding time of 5 seconds.
  • the heating conditions were selected within the above range for each film.
  • the mold is cup-shaped, the opening is 50mm in diameter, the bottom is diametric force Omm, the depth is 30mm, and all corners are curved with a diameter of 0.5mm. Was used.
  • corner radius of curvature is lmm or less and printing deviation is 0.1mm or less
  • Molded product is torn or even if it is not torn, it falls under any of the following items (i) to (iv)
  • the sample was immersed in toluene adjusted to 25 ° C for 30 minutes, and the appearance change before and after immersion was judged according to the following criteria.
  • the haze value was measured by the method described above.
  • Specimen for flat plate width 130mm, length 250mm, non-printing side used
  • ⁇ is a pass.
  • Mixing was performed to prepare coating solution A.
  • the resin having the composition shown in Table 1 was dried and used as a raw material for the core layer (A layer) and skin layer (B layer).
  • the raw material for layer B was coextruded under the conditions for extruding B layer in Table 2, and the raw material for layer A was similarly coextruded under the conditions for extruding layer A in Table 2.
  • the residence time of the skin layer (B layer) was 18 minutes, the residence time of the core layer (A) was 8 minutes, and solidified rapidly on a cast drum with a surface temperature of 40 ° C to obtain an amorphous sheet.
  • the obtained sheet was stretched 3.3 times at 83 ° C in the longitudinal direction between the preheating roll and the cooling roll due to the difference in rotational speed. Apply the above coating solution a to one side of the obtained uniaxially stretched film The coating solution b was applied to the surface by a reverse coating method. In addition, each coating liquid is between the roll gaps.
  • a shear rate of 1000 (1 Z seconds) or more was applied, and the film was applied to the substrate film within 2 seconds, and dried for 2 seconds in an environment of 65 ° C., 60% RH, and wind speed of 15 mZ seconds. Furthermore, it is dried for 3 seconds in an environment of 130 ° C and wind speed of 20mZ seconds to remove moisture and lead to a tenter, preheated at 100 ° C for 3 seconds, the first half of lateral stretching is 100 ° C, and the second half is 95 ° Stretched 3.8 times at C, heated at 140 ° C for 3 seconds, 170 ° C for 3 seconds, 205 ° C for 3 seconds, heat treated at 205 ° C, 5% transverse direction
  • a laminated biaxially stretched polyester film having a thickness of 100 m having a coating layer a on one side and a coating layer b on the other side was obtained.
  • the intrinsic viscosity of the obtained film was 0.65 dlZg.
  • the clip return is an external return method
  • a clip cooling device is installed, forced cooling is performed with cold air of 20 ° C, and the clip temperature at the TD outlet is 40 ° C or less. Measures to prevent adhesion were taken. Table 3 shows the properties and evaluation results of the obtained film.
  • Example 1 a thickness of 100 m with coating layer a on one side and coating layer b on the other side was the same as in Example 1 except that the raw material shown in Table 1 and the film forming conditions shown in Table 4 were changed. A laminated biaxially stretched polyester film was obtained. The intrinsic viscosity of the obtained film was 0.66 dl Zg. Further, the final dry coating amounts of the coating layer a and the coating layer b were both 0.1 lg / m 2 . Table 6 shows the properties and evaluation results of the obtained film.
  • Example 1 a thickness of 100 m with coating layer a on one side and coating layer b on the other side was the same as in Example 1 except that the raw material shown in Table 1 and the film forming conditions shown in Table 4 were changed. A laminated biaxially stretched polyester film was obtained. The intrinsic viscosity of the obtained film was 0.66 dl Zg. Further, the final dry coating amounts of the coating layer a and the coating layer b were both 0.1 lg / m 2 . Table 6 shows the properties and evaluation results of the obtained film.
  • Example 1 a thickness of 100 m with coating layer a on one side and coating layer b on the other side was the same as in Example 1 except that the raw material shown in Table 1 and the film forming conditions shown in Table 4 were changed. of A laminated biaxially stretched polyester film was obtained. The intrinsic viscosity of the obtained film was 0.70 dl Zg. Further, the final dry coating amounts of the coating layer a and the coating layer b were both 0.1 lg / m 2 . Table 6 shows the properties and evaluation results of the obtained film.
  • Example 1 the raw material shown in Table 1 was changed, the discharge amount during melt extrusion was adjusted to change the thickness of the unstretched sheet, the film forming conditions shown in Table 4 were changed, and a coating layer was further provided.
  • a laminated biaxially stretched polyester film having a thickness of 25 m was obtained in the same manner as Example 1 except for the above.
  • the obtained film had an intrinsic viscosity of 0.65 dlZg.
  • Table 6 shows the characteristics and evaluation results of the obtained film.
  • Example 1 the same raw materials as in Example 2 were used, except that the thickness of the unstretched sheet was changed by adjusting the discharge rate during melt extrusion, and the film forming conditions shown in Table 4 were changed.
  • a laminated biaxially stretched polyester film having a thickness of 50 m having a coating layer a on one side and a coating layer b on the other side was obtained.
  • the intrinsic viscosity of the obtained film was 0.64 dlZg.
  • the final dry coating amounts of the coating layer a and the coating layer b were both 0.1 lgZm 2 .
  • Table 6 shows the properties and evaluation results of the obtained film.
  • Example 1 except that the raw material for layer B is changed to the raw material shown in Table 2, it is the same as in Example 1 with a thickness of 50 m having coating layer a on one side and coating layer b on the other side.
  • a laminated biaxially stretched polyester film was obtained.
  • the resulting film had an intrinsic viscosity of 0.70 dlZg.
  • the final dry coating amount of the coating layer a and the coating layer b were both 0. lgZm 2.
  • Table 6 shows the properties and evaluation results of the obtained film.
  • Example 1 a single layer having a thickness of 100 m was obtained in the same manner as in Example 1 except that the raw material shown in Table 2 and the film forming conditions shown in Table 5 were changed and the skin layer (B) was not provided. A biaxially stretched polyester film having a structure was obtained. Table 7 shows the properties and evaluation results of the obtained film.
  • Example 2 a single layer having a thickness of 100 m was obtained in the same manner as in Example 1 except that the raw material shown in Table 2 and the film forming conditions shown in Table 5 were changed and the skin layer (B) was not provided. A biaxially stretched polyester film having a structure was obtained. Table 7 shows the properties and evaluation results of the obtained film.
  • Example 1 except for changing to the film forming conditions shown in Table 5, a laminated biaxially stretched polyester having a thickness of 100 m and having a coating layer a on one side and a coating layer b on the other side was the same as Example 1. A tellurium film was obtained. The intrinsic viscosity of the obtained film was 0.71 dlZg. The final dry coating weight of the coated fabric layer a and the coating layer b were both 0. lgZm 2. Table 7 shows the characteristics and evaluation results of the obtained film.
  • Example 1 except that the raw material for layer B was changed to the raw material shown in Table 3 and further changed to the film forming conditions shown in Table 5, the coating layer a on one side and the other side in the same manner as Example 1.
  • the intrinsic viscosity of the obtained film was 0.71 dlZg.
  • the final dry coating fabric of the coating layer a and the coating layer b were both 0. lgZm 2.
  • the properties and evaluation results of the obtained film are shown in Table 7.
  • Example 4 except for changing to the film forming conditions described in Table 5, a laminated biaxial film having a thickness of 100 m having a coating layer a on one side and a coating layer b on the other side, as in Example 4. A stretched polyester film was obtained. The intrinsic viscosity of the obtained film was 0.71 dlZg. The final dry coating amount of the coating layer a and the coating layer b were both 0. lgZm 2. Table 7 shows the characteristics and evaluation results of the obtained film.
  • Example 1 a thickness of 100 m with coating layer a on one side and coating layer b on the other side was the same as in Example 1 except that the raw material shown in Table 3 and the film forming conditions shown in Table 5 were changed. A laminated biaxially stretched polyester film was obtained. The intrinsic viscosity of the obtained film was 0.70 dl Zg. Also, the final dry coating amount of coating layer a and coating layer b is both 0.lg / m 2 Met. Table 7 shows the properties and evaluation results of the obtained film.
  • the resin listed in Table 3 was prepared, dried, and used as a raw material for the A layer and the B layer. Next, using a co-extrudable melt extruder having a feed block and a T die, the raw material for the B layer was melted at 285 ° C. and the raw material for the A layer was melted at 285 ° C. by separate melt extruders. Next, the layer configuration was BZA / B, the thickness ratio of the B layer and the ZA layer was 0.11, and co-extruded and rapidly cooled and solidified on a cast drum to obtain an unstretched laminated sheet.
  • the obtained unstretched laminated sheet was biaxially stretched 3.0 times at 110 ° C in the longitudinal direction and 3.2 times at 120 ° C in the transverse direction, and then heat treated at 235 ° C.
  • a laminated biaxially stretched polyester film having two types and three layers was obtained. Table 7 shows the properties and evaluation results of the obtained film.
  • Example 1 a thickness of 100 m with coating layer a on one side and coating layer b on the other side was the same as in Example 1 except that the raw material shown in Table 3 and the film forming conditions shown in Table 5 were changed. A laminated biaxially stretched polyester film was obtained. The intrinsic viscosity of the obtained film was 0.70 dl Zg. Further, the final dry coating amounts of the coating layer a and the coating layer b were both 0.1 lg / m 2 . Table 7 shows the properties and evaluation results of the obtained film.
  • Example 1 a thickness of 100 m with coating layer a on one side and coating layer b on the other side was the same as in Example 1 except that the raw material shown in Table 3 and the film forming conditions shown in Table 5 were changed. Force to obtain a laminated biaxially stretched polyester film A fracture occurred in the tenter, and it was impossible to obtain a film.

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  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Laminated Bodies (AREA)
  • Shaping By String And By Release Of Stress In Plastics And The Like (AREA)
  • Blow-Moulding Or Thermoforming Of Plastics Or The Like (AREA)

Abstract

L'invention concerne un film stratifié de polyester pour formage, ledit film comprenant une couche (A) et une couche (B) superposée sur l'un ou les deux côtés de la couche (A), les couches (A) et (B) comprenant chacune un copolyester ou comprenant un copolyester et un homopolyester, et le point de fusion de la couche (A) (TmA : °C) et celui de la couche (B) (TmB : °C) satisfaisant les équations 260 > TmB > TmA > 200 et 50 > TmB-TmA >5. Les couches (A) et (B) du film stratifié de polyester ont chacune une structure orientée. Le film présente un degré de retrait thermique à 150 °C inférieur ou égal à 6,0 % et un changement d'épaisseur à 150 °C inférieur ou égal à 10 %. Il présente une excellente capacité de moulage à faible température et faible pression, une excellente transparence, une excellente résistance aux solvants, une excellente rétention de forme et une excellente résistance aux chocs.
PCT/JP2007/063223 2006-06-30 2007-07-02 Film stratifié de polyester pour formage et son procédé de fabrication WO2008001932A1 (fr)

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CN2007800248359A CN101484317B (zh) 2006-06-30 2007-07-02 成型用层叠聚酯薄膜及其制造方法

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2017043756A (ja) * 2015-08-28 2017-03-02 東レ株式会社 光学フィルム製造用ポリエステルフィルム

Families Citing this family (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR101548182B1 (ko) 2010-09-16 2015-08-31 미쓰비시 가가꾸 가부시키가이샤 신규 페놀술폰산 아릴 에스테르 유도체 및 그것을 사용한 감열 기록 재료
JP2013022887A (ja) * 2011-07-25 2013-02-04 Mitsubishi Plastics Inc インサート成形用ポリエステルフィルム
JP6058949B2 (ja) * 2011-09-01 2017-01-11 ユニチカ株式会社 インモールド成型用二軸延伸ポリエステルフィルム
KR101330259B1 (ko) * 2011-12-16 2013-11-15 도레이첨단소재 주식회사 용제 접착력이 우수한 열수축성 폴리에스테르 필름
KR101402308B1 (ko) * 2012-01-06 2014-06-03 도레이첨단소재 주식회사 용기 부착성이 우수한 열수축성 폴리에스테르 필름
JP6295664B2 (ja) * 2012-07-30 2018-03-20 東レ株式会社 液晶ディスプレイ用白色ポリエステルフィルム、その製造方法及び液晶ディスプレイ用バックライト
JP6609940B2 (ja) * 2014-03-14 2019-11-27 東レ株式会社 光学フィルム製造用ポリエステルフィルム
CN106459444B (zh) * 2014-04-11 2019-07-30 可隆工业株式会社 聚酯薄膜及其制造方法，以及使用该聚酯薄膜的聚酯模制品及其制造方法
KR20180064192A (ko) 2016-12-05 2018-06-14 도레이첨단소재 주식회사 성형용 폴리에스테르 필름
KR102221506B1 (ko) * 2018-01-24 2021-03-02 도레이첨단소재 주식회사 윈도우용 폴리에스테르 필름
US20230183434A1 (en) * 2020-04-30 2023-06-15 C.I. Takiron Corporation Polyester-based shrink film

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001260295A (ja) * 2000-03-17 2001-09-25 Toyobo Co Ltd ラミネート用ポリエステル積層フィルム、積層フィルムラミネート金属板および金属容器
JP2005290354A (ja) * 2003-09-03 2005-10-20 Toyobo Co Ltd 成型用ポリエステルフィルム
JP2005335276A (ja) * 2004-05-28 2005-12-08 Teijin Dupont Films Japan Ltd 多層フィルム
JP2006007743A (ja) * 2003-10-30 2006-01-12 Toyobo Co Ltd 金属板被覆用ポリエステルフィルム、ポリエステルフィルム被覆金属板及びポリエステルフィルム被覆金属容器

Family Cites Families (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH09164641A (ja) * 1995-12-15 1997-06-24 Toray Ind Inc 二軸配向ポリエステルフィルム
JP3262031B2 (ja) * 1996-08-06 2002-03-04 東洋製罐株式会社 積層体及びそれを用いた容器
JPH11207909A (ja) * 1998-01-26 1999-08-03 Teijin Ltd 金属板貼合せ成形加工用積層ポリエステルフィルム
JP3742550B2 (ja) * 2000-09-01 2006-02-08 帝人株式会社 熱成形用シート用樹脂組成物および熱成形用シート
JP2002240224A (ja) * 2001-02-22 2002-08-28 Teijin Ltd 金属板貼合せ成形加工用白色積層ポリエステルフィルム
JP2002337290A (ja) * 2001-05-16 2002-11-27 Toyobo Co Ltd 積層ポリエステルフィルム
JP3971386B2 (ja) * 2002-02-21 2007-09-05 帝人株式会社 多層ポリエステルフィルムおよびその製造方法
TWI281891B (en) * 2002-03-01 2007-06-01 Teijin Ltd Biaxially oriented multi-layered laminated film and method for manufacture thereof
JP4512988B2 (ja) * 2003-12-25 2010-07-28 東洋紡績株式会社 インサート成型用ポリエステルフィルム
JP2006015675A (ja) * 2004-07-05 2006-01-19 Toray Ind Inc 建築材料用積層ポリエステルフィルム
JP2006264136A (ja) * 2005-03-24 2006-10-05 Toray Ind Inc 成型加飾材用ポリエステルフィルム
KR101248299B1 (ko) * 2005-03-28 2013-03-27 도레이 카부시키가이샤 2축 배향 폴리에스테르 필름 및 금속조 적층 필름

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001260295A (ja) * 2000-03-17 2001-09-25 Toyobo Co Ltd ラミネート用ポリエステル積層フィルム、積層フィルムラミネート金属板および金属容器
JP2005290354A (ja) * 2003-09-03 2005-10-20 Toyobo Co Ltd 成型用ポリエステルフィルム
JP2006007743A (ja) * 2003-10-30 2006-01-12 Toyobo Co Ltd 金属板被覆用ポリエステルフィルム、ポリエステルフィルム被覆金属板及びポリエステルフィルム被覆金属容器
JP2005335276A (ja) * 2004-05-28 2005-12-08 Teijin Dupont Films Japan Ltd 多層フィルム

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2017043756A (ja) * 2015-08-28 2017-03-02 東レ株式会社 光学フィルム製造用ポリエステルフィルム

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CN101484317B (zh) 2012-08-29
TWI406766B (zh) 2013-09-01
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KR20090031596A (ko) 2009-03-26
JP2010208341A (ja) 2010-09-24

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