WO2008029666A1 - Film de polyester pour moulage - Google Patents

Film de polyester pour moulage Download PDF

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Publication number
WO2008029666A1
WO2008029666A1 PCT/JP2007/066606 JP2007066606W WO2008029666A1 WO 2008029666 A1 WO2008029666 A1 WO 2008029666A1 JP 2007066606 W JP2007066606 W JP 2007066606W WO 2008029666 A1 WO2008029666 A1 WO 2008029666A1
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WO
WIPO (PCT)
Prior art keywords
film
molding
polyester film
polyester
particles
Prior art date
Application number
PCT/JP2007/066606
Other languages
English (en)
Japanese (ja)
Inventor
Katsufumi Kumano
Yuki Haraguchi
Yasushi Sasaki
Masatoshi Tanabe
Katsuya Ito
Kenichi Mori
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
Publication date
Application filed by Toyo Boseki Kabushiki Kaisha filed Critical Toyo Boseki Kabushiki Kaisha
Priority to KR1020097006909A priority Critical patent/KR101111040B1/ko
Priority to JP2008533105A priority patent/JP4609580B2/ja
Priority to CN2007800332397A priority patent/CN101511920B/zh
Publication of WO2008029666A1 publication Critical patent/WO2008029666A1/fr

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Classifications

    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C55/00—Shaping by stretching, e.g. drawing through a die; Apparatus therefor
    • B29C55/02—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets
    • B29C55/10—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets multiaxial
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C55/00—Shaping by stretching, e.g. drawing through a die; Apparatus therefor
    • B29C55/02—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets
    • B29C55/10—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets multiaxial
    • B29C55/12—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets multiaxial biaxial
    • B29C55/14—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets multiaxial biaxial successively
    • B29C55/143—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets multiaxial biaxial successively firstly parallel to the direction of feed and then transversely thereto
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C55/00—Shaping by stretching, e.g. drawing through a die; Apparatus therefor
    • B29C55/02—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets
    • B29C55/10—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets multiaxial
    • B29C55/12—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets multiaxial biaxial
    • B29C55/14—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets multiaxial biaxial successively
    • B29C55/146—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets multiaxial biaxial successively firstly transversely to the direction of feed and then parallel thereto
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C55/00—Shaping by stretching, e.g. drawing through a die; Apparatus therefor
    • B29C55/02—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets
    • B29C55/10—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets multiaxial
    • B29C55/12—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets multiaxial biaxial
    • B29C55/16—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets multiaxial biaxial simultaneously
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • 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
    • 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

  • the present invention unwinds a long film wound in a roll shape that is excellent in moldability, transparency, solvent resistance, and heat resistance under low! /, Temperature and low! / Pressure.
  • blocking relates to a molding polyester film suitable for use as a casing for various portable devices or a component thereof, a member for a nameplate or a member of a building material of a home appliance or an automobile, in which the finale is not broken and the environmental load is small.
  • the present invention relates to a polyester film for molding which is excellent in light resistance suitable for use outdoors (car exterior parts or building material parts).
  • a polychlorinated bull film is representative, and has been preferably used in terms of workability.
  • the film has problems such as generation of toxic gas when the film burns due to fire and the like, bleed-out of plasticizer, etc. Due to recent environmental needs, the environmental load is small and new. Re, material is required!
  • unstretched sheets made of polyester, polycarbonate and acrylic resin as non-chlorine materials are widely used in the field! /.
  • unstretched sheets made of a polyester resin are attracting attention because they have good mechanical properties and transparency and are excellent in economic efficiency.
  • about 30 mol 0/0 E Ji glycol component in polyethylene terephthalate 1, 4 Shikuro was replaced by Cyclohexanedicarboxylic methanol to unstretched polyester sheet which substantially constituents polyester resin amorphous Are disclosed! (See, for example, patent documents;! To 5).
  • Patent Document 1 Japanese Patent Laid-Open No. 9 156267
  • Patent Document 2 Japanese Patent Laid-Open No. 2001-71669
  • Patent Document 3 Japanese Patent Publication No. 2001-80251
  • Patent Document 4 Japanese Patent Laid-Open No. 2001-129951
  • Patent Document 5 Japanese Patent Laid-Open No. 2002-249652
  • the above-mentioned unstretched polyester sheet is a strength that does not satisfy market requirements with respect to moldability and laminate suitability, and is an unstretched sheet. It ’s a regret to satisfy you.
  • Patent Document 6 JP-A-9 187903
  • Patent Document 7 JP-A-10-296937
  • Patent Document 8 Japanese Patent Laid-Open No. 1 10816
  • Patent Document 9 Japanese Patent Laid-Open No. 1 268215
  • Patent Document 10 JP-A-2-204020
  • Patent Document 11 Japanese Patent Laid-Open No. 2001-347565
  • Patent Document 12 Japanese Patent Application Laid-Open No. 2004-075713
  • a polyester film for molding that can be applied to a pressure forming method or a vacuum forming method, which is a molding method with a low molding pressure at the time of molding, it is composed of a biaxially stretched polyester film containing a copolymerized polyester
  • the present inventors have developed a polyester film for molding having a specific range of stress at 100% elongation at C and 100 ° C, storage elastic modulus ( ⁇ ⁇ ') at 100 ° C and 180 ° C, and thermal deformation rate at 175 ° C. Proposed (see, for example, Patent Document 13).
  • Patent Document 13 Japanese Patent Laid-Open No. 2005-290354 Gazette
  • the object of the present invention is to solve the above-mentioned conventional problems, and is excellent in moldability, transparency, solvent resistance, and heat resistance at low temperature and low pressure, and wound in a roll shape. Suitable for casings of various portable devices or parts, nameplates or building materials for home appliances or automobiles, with no blocking or tearing when unrolling a long film taken. It is providing the polyester film for shaping
  • the molding polyester film of the present invention capable of solving the above-described problems has the following configuration.
  • a first invention in the present invention is a polyester film for molding made of a biaxially oriented polyester film containing a copolymerized polyester, and (1) 100% elongation stress force in the longitudinal direction and the width direction of the film. S, both at 40 ° C to 300MPa at 25 ° C and 100 ° C;! To 100MPa, (2) The heat shrinkage in the longitudinal and width directions at 150 ° C of the film is 0 ⁇ 01–5.0 %, (3) Haze is 0 ⁇ ;!
  • the surface roughness (Ra) of at least one side of the film is 0 ⁇ 005—0.030 m, (5) The degree of plane orientation is 0 ⁇ 095 or less It is the polyester film for shaping
  • the second invention is the molding composition according to the first invention, characterized in that the biaxially oriented polyester film contains an ultraviolet absorber and the light transmittance at a wavelength of 370 nm is 50% or less. It is a polyester film.
  • the third invention is a copolymer composed of a copolymer polyester strength S, (a) an aromatic dicarboxylic acid component, ethylene glycol, and a darlicol component containing a branched aliphatic alicyclic or alicyclic darlicol. Polyester, there is! /, (B) A first or second invention characterized in that it is a copolyester composed of an aromatic dicarboxylic acid component containing terephthalic acid and isophthalic acid and a darlicol component containing ethylene glycol. A polyester film for molding as described in 1.
  • the fourth invention is characterized in that the polyester force constituting the biaxially oriented polyester film further includes a 1,3-propanediol unit or a 1,4 butanediol unit as a darcol component. It is the polyester film for a description of description.
  • a fifth invention is the polyester film for molding according to any one of the first to fourth inventions, wherein the biaxially oriented polyester film has a melting point of 200 to 245 ° C.
  • a sixth invention is a polyester film for molding comprising a biaxially oriented polyester film as a base film, and a surface layer having a thickness of 0.01 to 5 m is laminated on one side or both sides of the base film.
  • a seventh invention is the molding polyester film according to the sixth invention, characterized in that the surface layer is mainly composed of an adhesion modifying resin and particles.
  • An eighth invention is a molding polyester film in which a hard coat layer is provided on at least one side of the molding polyester film of any one of the first to seventh inventions.
  • a ninth invention is a polyester molded product obtained by molding the molding polyester film of any one of the first to eighth inventions by vacuum molding, pressure molding and mold molding! .
  • a hard copy on at least one side of the polyester molded product of the ninth aspect is provided.
  • This is a polyester molded product provided with a single layer.
  • the molding polyester film of the present invention is excellent in moldability at the time of heat molding at a low temperature or low pressure, and therefore can be applied to a wide variety of molding methods and used as a molded product in a room temperature atmosphere.
  • it has excellent elasticity and morphological stability (heat shrinkage characteristics, thickness unevenness), and has low solvent resistance, heat resistance, and environmental impact.
  • heat shrinkage characteristics thickness unevenness
  • solvent resistance heat resistance
  • environmental impact when unwinding a long film wound up in a roll during post-processing, blocking and tearing are unlikely to occur, resulting in excellent productivity.
  • the smoothness and transparency are highly excellent, it is excellent in design when a deposition layer, a sputtering layer, or a printing layer is provided during post-processing. Therefore, it is suitable as a casing for various types of portable devices! /, A member thereof, a member for a nameplate or a member for building material of home appliances and automobiles.
  • an ultraviolet absorber in the film and reducing the transmittance in the ultraviolet region, light resistance can be imparted, particularly for outdoor use (for automobile exteriors or building materials). It is suitable as a molding material for the member.
  • the stress at 100% elongation is a measure closely related to the moldability of the film.
  • the reason why F100 is closely related to the moldability of the film is, for example, when forming a biaxially oriented polyester film using the vacuum forming method, the film is locally more than 100% near the mold corner. May be stretched. In a film with a high F100 force S, extremely high stresses are partially generated in such locally stretched portions, and this stress concentration is considered to cause the film to break and formability to deteriorate. On the other hand, if the film is too small, the moldability is good, but in the part that is stretched uniformly, such as the flat part of the mold, a very weak tensile force is not generated.
  • the film before molding lightly follows those molds in advance.
  • the polyester film for molding in the present invention has a stress at 100% elongation (F100) at 25 ° C of 30 to 300 MPa in the longitudinal direction and the width direction of the film.
  • F100 in the longitudinal direction and the width direction of the film is 40 to 300 MPa, the lower limit.
  • the upper limit is preferably 250 MPa, more preferably 200 MPa, and even more preferably 180 MPa.
  • the film before molding may be followed by lightly following those molds in advance.
  • the mold of the film may be attached, and the finished product may have poor design properties.
  • the molding polyester film of 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.
  • MPa is preferred 80 MPa is more preferred 70 MPa is particularly preferred.
  • F100 is preferred
  • the lower limit of 100 is particularly preferably 20 MPa, more preferably 10 MPa, more preferably 10 MPa from the viewpoint of elasticity and shape stability when using a molded product.
  • the thermal shrinkage in the longitudinal direction and the width direction at 150 ° C is 0.01 to 5.0%.
  • the lower limit value of the heat shrinkage rate at 150 ° C. is preferably 0.1%, more preferably 0.5%.
  • the upper limit of the heat shrinkage rate at 150 ° C. is preferably 4.5%, more preferably 4.1%, and further preferably 3.2%.
  • Production of biaxially stretched polyester film for molding with a thermal shrinkage of less than 0.01% in the longitudinal and width directions at 150 ° C produced no noticeable difference in practical effects. Very low Therefore, the thermal shrinkage at 150 ° C is not necessarily less than 0.01%.
  • the thermal shrinkage rate of the film in the longitudinal direction and the width direction at 150 ° C exceeds 5.0%, the heat power such as vapor deposition, sputtering or printing, and the post-treatment process! The film is likely to be deformed, and the appearance and design properties of the post-processed film are poor.
  • the haze of the film is 0.;! To 3.0%.
  • the lower limit of haze is preferably 0.3%, more preferably 0.5%.
  • the upper limit of ⁇ is 2.5%, more preferably 2.0%.
  • -Films with a thickness of less than 0.1% are difficult to manufacture on an industrial scale with normal productivity due to poor sliding properties.
  • the metal or printing surface force S appears dull when the vapor deposition or sputtering surface of metal or the printed surface is viewed from the back side of the film, resulting in poor design. .
  • the film with a ⁇ of less than 2.0% It is difficult to get.
  • the surface roughness (Ra) of at least one film is 0.005-0.030 ⁇ m.
  • the lower limit of Ra is preferably 0.006 ⁇ 111 force S, more preferably 0.007 ⁇ m.
  • the upper limit of Ra is (directly 0.025 ⁇ m force ⁇ preferably, more preferably (0.015 ⁇ m.)
  • the Ra of a single-sided film becomes smaller, the film can be wound up.
  • the frequency of blocking and film tearing increases, and when Ra exceeds 0.03 m, vapor deposition, sputtering or printing is performed. In the post-processing steps such as the above, the projection becomes a defect and the design property is lowered.
  • the degree of plane orientation ( ⁇ ) of the film is also a physical property related to moldability, and the higher the degree of plane orientation, the more the molecular chains are arranged in the plane direction and the moldability is lowered.
  • the degree of plane orientation of the film is 0.095 or less.
  • the upper limit of the degree of plane orientation is preferably 0.090. Further, the smaller the degree of plane orientation, the better the moldability.
  • the strength of the film decreases, and the flatness such as thickness unevenness tends to deteriorate. Therefore, the lower limit of the degree of plane orientation is preferably 0.001, more preferably 0.01, and particularly preferably 0.04! /.
  • a polyester film obtained using a copolymerized polyester containing 5 to 50 mol% of a copolymer component as a raw material as in the present invention has a slower crystallization rate and lower crystallinity than a polyethylene terephthalate film.
  • the heat treatment is suddenly performed at a high temperature after completion of stretching. Therefore, the mobility of molecules constituting the low crystalline material in the heat treatment zone is increased.
  • the above-mentioned problems can be achieved by using a suitable method in which the heat treatment zone is formed in two stages (or more) and the first stage heat treatment temperature TS1 and the second stage heat treatment temperature TS2 are controlled within a specific range.
  • the point was solved. This mechanism is considered as follows.
  • the crystallization of the film is promoted to some extent, and even if the temperature is sufficiently increased in the second-stage heat treatment zone, The mobility of the molecule is sufficiently lowered, and the film having a low thermal shrinkage rate can be obtained by further promoting the crystallinity while forming the protrusions on the surface. Moreover, it is not necessary to contain particles more than necessary from the viewpoint of transparency.
  • the polyester film for molding of the present invention uses a copolymerized polyester as a raw material.
  • the copolyester include (a) a copolyester composed of an aromatic dicarboxylic acid component, ethylene glycol, and a daricol component containing a branched aliphatic glycol or alicyclic glycol, or (b) terephthalic acid and isophthalic acid.
  • a copolymer polyester composed of an aromatic dicarboxylic acid component containing an acid and a dallicol component containing ethylene glycol is preferred.
  • the polyester force constituting the biaxially oriented polyester film further contains 1,3-propanediol units or 1,4 butanediol units as glycol components.
  • the polyester force constituting the biaxially oriented polyester film further contains 1,3-propanediol units or 1,4 butanediol units as glycol components.
  • the film raw material any of a copolymer polyester alone, a blend of one or more homopolyesters or copolymer polyesters, or a combination of homopolyester and copolymer polyester is used. Is also possible. Among these, the blend method is preferable from the viewpoint of suppressing the lowering of the melting point.
  • the copolymer polyester composed of an aromatic dicarboxylic acid component, ethylene glycol, and a darlicol component containing a branched aliphatic darlicol or alicyclic darlicol
  • the aromatic dicarboxylic acid As the component, terephthalic acid, isophthalic acid, naphthalene dicarboxylic acid or ester-forming derivatives thereof are suitable, and the amount of terephthalic acid and / or naphthalene dicarboxylic acid component relative to the total dicarboxylic acid component is 70 mol% or more, preferably 85 mol% or more, particularly preferably 95 molar% or more, especially preferably 100 mol 0/0.
  • examples of the branched aliphatic glycol include neopentyldaricol, 1,2-propanediol, 1,3-propanediol, and 1,4 butanediol.
  • examples of the alicyclic glycol include 1,4-cyclohexanedimethanol and tricyclodecane dimethylol.
  • neopentyl glycol and 1,4-cyclohexanedimethanol are particularly preferable.
  • 1,3 propanediol or 1,4 butanediol is used as a copolymer component, which is a more preferable embodiment.
  • Use of these glycols as a copolymerization component is suitable for imparting the above-mentioned properties, and further, is excellent in transparency and heat resistance, and improves the adhesion with the adhesion modified layer. Is also preferable.
  • the amount of ethylene glycol is ingredients to 7 0 mole 0/0 or more, preferably 85 mole 0/0 or more, particularly preferably 95 mol 0/0 or more, especially good Mashiku 100 mole 0/0.
  • the glycol component other than ethylene glycol the above-mentioned branched aliphatic dalico-aliphatic alicyclic dallicol or diethylene dallicol is preferable.
  • 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, titanium / silicon composite oxides, and germanium compounds. Etc. can be used. Of these, titanium compounds, antimony compounds, germanium compounds, and 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 preferably has an intrinsic viscosity of 0.50 dl / g or more, more preferably 0.55 dl / g or more, particularly from the viewpoint of moldability, adhesion, and film formation stability. Preferably it is 0.60 dl / g or more. If the intrinsic viscosity is less than 0.50 dl / g, the moldability tends to decrease. In addition, when a filter for removing foreign substances is provided in the melt line, the upper limit of the intrinsic viscosity is preferably 1. Odl / g from the viewpoint of ejection stability during extrusion of the molten resin.
  • one or more types of homopolyesters or copolymer polyesters are used as film raw materials, and these are blended to form a film, which is equivalent to the case of using only copolymer polyesters. It is possible to achieve transparency and high melting point (heat resistance) while maintaining flexibility. In addition, when only a high melting point homopolyester (for example, polyethylene terephthalate) is used, flexibility and no practical problem are achieved while maintaining high transparency. Power S can be.
  • a high melting point homopolyester for example, polyethylene terephthalate
  • the melting point of the polyester film is preferably 200 to 245 ° C from the viewpoint of heat resistance and moldability.
  • the moldability and finish can be balanced, and a high-quality molded product can be produced economically.
  • the melting point is the endothermic peak temperature at the time of melting, which is detected at the first temperature rise in so-called differential scanning calorimetry (DSC).
  • DSC differential scanning calorimetry
  • the fusion The point was determined by measuring with a differential scanning calorimeter (manufactured by Mac Science, DSC3100S) at a heating rate of 20 ° C / min.
  • the lower limit of the melting point is particularly preferably 210 ° C, particularly preferably 230 ° C. If the melting point is less than 200 ° C, the heat resistance tends to deteriorate. This may cause problems when exposed to high temperatures during molding or use of molded products.
  • the molding polyester film of the present invention preferably has a light transmittance at a wavelength of 370 nm of S50% or less, more preferably 40% or less, and particularly preferably 30% or less.
  • a light transmittance at a wavelength of 370 nm of S50% or less more preferably 40% or less, and particularly preferably 30% or less.
  • a method for controlling the light transmittance at a wavelength of 370 nm to 50% or less a method of blending an ultraviolet absorber in any of the constituent layers of the molding polyester film is used.
  • the ultraviolet absorber may be either inorganic or organic as long as it can impart the above-mentioned characteristics.
  • organic ultraviolet absorbers include benzotozole, benzophenone, cyclic imino ester, and combinations thereof. From the viewpoint of heat resistance, benzotozole and cyclic iminoesters are preferred.
  • ultraviolet rays having different wavelengths can be absorbed simultaneously, so that the effect of absorbing ultraviolet rays can be improved.
  • Examples of the benzotriazole-based ultraviolet absorber include 2- [2'-hydroxy-5 '-(methacryloyloxymethinole) phenyl] 2H-benzotriazole, 2- [2'-hydroxy 5' ( Methacryloyloxychettinole) phenyl] 2H Benzotriazole, 2- [2'-Hydroxy-5 '(methacryloyloxypropynole) phenyl] 2H Benzotriazole, 2 -— [2'Hydroxy-5' (methacryloyloxyhexyl) ) Phenyl] 2H-benzotriazole, 2- [2'-hydroxyl 3'- tert butyl 5 '-(methacryloyloxychettinole) phenyl] 2H benzotriazole, 2- [2'-hydroxy 5'-ter t-butyl-3' (Methacryloyloxychettinole) phenyl
  • cyclic iminoester UV absorbers examples include 2, 2 ′-(1,4-phenylene) bis (4H 3,1-benzoxazine mono 4-one), 2-methyl 3,1-benzoxazine mono 4- ON, 2 Butyl 3, 1-Benzoxazine 1-ON, 2 Phenylol 3, 1-Benzoxazine 1- 4-ON, 2— (1- or 2-Naphtyl) 3, 1-Benzoxazine 1-ON, 2— ( 4-biphenyl) 1, 3, 1-benzoxazine 1-on, 2-p 12 tropeninole 3, 1-benzoxazine 4-on, 2-m 2-tlofenenole 3, 1-benzoxazine 4-on, 2-p benzoylf Enyl 1,3-benzoxazine-4-one, 2-p methoxyphenenoyl 3,1-benzoxazine-4-one, 2-o methoxyphenyl 3,1-benzoxazine 4-one, 2 cyclohexyl 3, 1
  • the above-mentioned organic ultraviolet absorber When the above-mentioned organic ultraviolet absorber is blended into a film, it is exposed to a high temperature in the extrusion process. Therefore, it is preferable to use an ultraviolet absorber having a decomposition start temperature of 290 ° C or higher as the ultraviolet absorber. This is preferable in order to reduce the process contamination at the time.
  • an ultraviolet absorber with a decomposition start temperature of 290 ° C or lower is used, the decomposed product of the ultraviolet absorber adheres to the rolls of the production equipment during film formation, and may reattach to the film or be damaged. This is not preferable because it causes optical defects.
  • Examples of inorganic ultraviolet absorbers include ultrafine particles of metal oxides such as cerium oxide, zinc oxide, and titanium oxide.
  • the upper limit of the melting point is preferably higher from the viewpoint of heat resistance, but when a polyethylene terephthalate unit is the main component, a film having a melting point exceeding 250 ° C tends to deteriorate moldability. is there. In addition, transparency tends to deteriorate. Furthermore, in order to obtain high moldability and transparency, it is preferable to control the upper limit of the melting point to 245 ° C.
  • Examples of the particles include internal particles having an average particle diameter of 0.01 to 10 m, and external particles such as inorganic particles and / or organic particles.
  • particles having an average particle diameter exceeding 10 m are used, defects in the film tend to occur, and the design and transparency tend to deteriorate.
  • particles having an average particle diameter of less than 0.01 tend to decrease the handling properties such as the slipperiness and winding property of the film.
  • the lower limit of the average particle diameter of the particles is more preferably from 0.10 in, particularly preferably from 0.50 111, from the viewpoint of handling properties such as slipping and winding properties.
  • the average particle diameter of the particles is more preferably 2 m, and the upper limit is more preferably 2 ⁇ in view of transparency and reduction of film defects due to coarse protrusions.
  • the average particle size 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 inorganic particles such as wet and dry silica, colloidal silica, aluminum silicate, titanium oxide, calcium carbonate, calcium phosphate, barium sulfate, alumina, mica, kaolin, clay, and hydroxyapatite.
  • Organic particles containing styrene, silicone, acrylic acid, etc. 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, dibutenebenzene and the like as constituent components are preferably used. Two or more kinds of these internal particles, inorganic particles and / or organic particles may be used in combination as long as the characteristics defined in the present invention are not impaired.
  • the content in a film of said particles 0.00 is preferably in the range of 1-10 mass 0/0!.
  • the handling properties are liable to deteriorate, for example, the slipperiness of the film deteriorates or the winding becomes difficult.
  • it exceeds 10% by mass it tends to cause formation of coarse protrusions, deterioration of film forming properties and transparency.
  • the particles contained in the film generally have a refractive index different from that of polyester, it becomes a factor of lowering the transparency of the film.
  • Molded products are often printed on the surface of the film before it is molded to enhance the design. Since such a printing layer is often applied to the back side of a molding film, it is desired that the transparency of the film is high from the viewpoint of printing clarity.
  • the surface of the base layer film containing substantially no particles and having a thickness of 0.01 to 5 111 It is effective to use a laminated film having a laminated structure in which particles are contained only in the layer.
  • the upper limit of the thickness of the surface layer is preferably 3 m, particularly preferably 1 m. In this case, the particles exemplified above can be used.
  • the above-mentioned base film does not substantially contain particles, and the thickness is 0.01 to 5 It is preferable to form a laminated structure in which a surface layer 111 is formed and particles are contained only in the surface layer. Handling It is difficult to obtain a film with a particle size of 2.0% or less just by adding particles to the film while maintaining the properties.
  • substantially no particles are contained in the base film means that, for example, in the case of inorganic particles, when the inorganic element is quantified by key X-ray analysis, it is below the detection limit. Means content. This is because contaminants derived from foreign substances may be mixed without intentionally adding particles to the base film.
  • the substrate film does not substantially contain particles, but if it is 30 ppm or less, particles may be added to the substrate film. Absent.
  • the formation of the thin surface layer can be performed by a coating method or a coextrusion method.
  • a coating method the use of a composition comprising an adhesion modifying resin containing particles as the coating layer is preferable because the adhesion with the printing layer can be improved.
  • the adhesion modifying resin is preferably a resin comprising at least one selected from polyesters, polyurethanes, acrylic polymers and / or copolymers thereof.
  • the particles to be contained in the surface layer it is possible to use the same particles as those described above.
  • 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.
  • the particle content in the surface layer is preferably in the range of 0.0;! To 25% by mass.
  • the content is less than 01% by mass, the handling property is liable to deteriorate, for example, the slipperiness of the film deteriorates or the winding becomes difficult.
  • it exceeds 25% by mass transparency and coatability tend to deteriorate.
  • the polyester film of the present invention can be made into a laminated structure by a known method using different types of polyester.
  • the shape of the laminated film is not particularly limited, but for example, A / B, 2 types, 2 layers, B / A / B, 2 types, 3 layers, C / A / B, 3 types, 3 layers Examples of layered configurations
  • the molding polyester film of the present invention is a biaxially stretched film.
  • the molecular orientation by biaxial stretching makes it possible to control the thermal deformation rate of the film under the micro tension (initial load 49 mN) within the range of the present invention, which is a disadvantage of the unstretched sheet.
  • Solvent resistance and dimensional stability are improved. That is, it is one of the features of the present invention that the solvent resistance and heat resistance, which are defects of the unstretched sheet, are improved while maintaining the good formability of the unstretched sheet.
  • the method for producing the biaxially oriented polyester film is not particularly limited.
  • the polyester resin is supplied to a known melt extruder and extruded from a slit-shaped die into a sheet.
  • An example is a method in which a non-stretched sheet (original fabric) is obtained by bringing it into close contact with a casting drum by a method such as electrostatic application, cooling and solidifying, and then biaxially stretching the unstretched sheet.
  • the biaxial stretching method there is a method 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 a desired in-plane orientation degree.
  • MD longitudinal direction
  • TD width direction
  • the MD / TD method in which the film is stretched in the longitudinal direction and then stretched in the width direction
  • the TD / MD method in which the film is stretched in the width direction and then stretched in the longitudinal direction.
  • An axial stretching method and a simultaneous biaxial stretching method in which the longitudinal direction and the width direction are stretched almost simultaneously are desirable.
  • a tenter driven by a linear motor may be used.
  • a multi-stage stretching method in which stretching in the same direction is divided into multi-stages may be used.
  • the film stretch ratio in biaxial stretching is preferably a force S of 1.6 to 4.2 times in the longitudinal direction and the width direction, and more preferably 1.7 to 4.0 times.
  • 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 more preferably 50 to 110 ° C and the stretching ratio is 1.6 to 4.0 times so that the subsequent lateral stretching can be performed smoothly.
  • the stretching temperature when the stretching temperature is higher than appropriate conditions, the initial stress is reduced. The stress does not increase even if the stretching ratio is increased. Therefore, the film has a low stress at 100% elongation at 25 ° C. Therefore, by taking the optimum stretching temperature, it is possible to obtain a highly oriented film while ensuring stretchability.
  • the stretching stress rapidly decreases as the stretching temperature is increased so as to eliminate the yield stress.
  • the orientation does not increase and the stress at 100% elongation at 25 ° C decreases.
  • the transverse stretching temperature is preferably set to the following conditions.
  • the preheating temperature is within the range of + 10 ° C + 50 ° C of the glass transition temperature when the mixture (raw material) after extruding the film material with an extruder is DSC! Do.
  • the stretching temperature is preferably -20 ° C + 15 ° C relative to the preheating temperature.
  • the stretching temperature should be 0 ° C and 30 ° C with respect to the stretching temperature of the first half.S is preferred, and particularly preferably within the range of 10 ° C and 20 ° C with respect to the stretching temperature of the first half. It is.
  • the film is easily stretched and is easily oriented in the second half.
  • the stretching ratio in the transverse direction is preferably 2.5.5.0.
  • the film is subjected to heat treatment (heat setting treatment).
  • heat treatment heat setting treatment
  • the first stage heat treatment temperature (TS1) is in the range of -5 ° C to -30 ° C of the second stage heat treatment temperature (TS2), and the lower limit is preferably TS2-10 ° C.
  • the limit value is preferably TS2-25 ° C.
  • the second stage heat treatment temperature (TS2) is within the range of -5 ° C to 35 ° C of the melting point when the mixture (raw material) after extruding the film material with an extruder is measured by DSC described later.
  • the lower limit of TS2 is preferably melting point—10 ° C.
  • the upper limit of TS2 is preferably melting point—30 ° C.
  • An intermediate heat treatment zone can be provided between TS1 and TS2, and a heat treatment zone can be provided after TS2. In these cases, TS2 shows the highest heat treatment temperature. By taking these conditions, a film having low haze and good slipperiness can be obtained.
  • the heat treatment may be either a tension heat treatment or a relaxation heat treatment.
  • relaxation heat treatment of 3 to 10% is preferable.
  • a polyester film containing about 5 to 50 mol% of a copolymer component as in the present invention has a slower crystallization rate and lower crystallinity than a polyethylene terephthalate film. Therefore, if heat treatment is rapidly performed at a high temperature after stretching, the crystallinity in the heat treatment zone is low, and the mobility of molecules constituting the material is increased. Therefore, the surface protrusion force formed by the bulging of the particles (particles in the film and / or coating layer particles) in the stretching process is buried again in the heat treatment zone, so that the surface roughness is sufficient. Can't get.
  • the content of the particles is increased beyond the necessary amount of polyethylene terephthalate film, which causes haze deterioration.
  • the temperature of TS2 is lower than the predetermined temperature, a finoleum having a sufficiently low heat shrinkage at 150 ° C cannot be obtained.
  • the method of the present invention in which the heat treatment zone has two stages (or more) is that the crystallization of the film is promoted to some extent before the particles are embedded in the film in TS1. Furthermore, even if the temperature is raised sufficiently in the TS2 zone, the mobility of the molecules is sufficiently reduced compared to the state in the previous section, and while the protrusions on the surface are formed, the crystallinity is further promoted and a film with a low thermal shrinkage rate can get. Moreover, it is possible to prevent the addition of unnecessary particles.
  • a method of providing a heat shielding wall in the clip part so that the clip is difficult to be heated (2) a tip cooling mechanism is added to the tenter (3) A method to sufficiently cool the entire film by setting a long cooling section after heat setting to enhance cooling capacity, (4) By increasing the length of the cooling section and the number of sections, It is preferable to adopt a method of increasing the cooling efficiency, or (5) a method of enhancing the cooling of the clip by using a type in which the return portion of the clip travels outside the furnace.
  • the molding polyester film of the present invention As explained above, by using the molding polyester film of the present invention, it was difficult to mold with the conventional biaxially oriented polyester film, and the molding pressure force S at the time of molding was as low as 10 atm or less. Even in the molding methods such as vacuum molding and pressure molding below, it is possible to obtain molded products with good finishing power. In addition, these molding methods are advantageous in terms of economics in the production of molded products because the molding costs are low. Therefore, application to these molding methods can be achieved with the force S that exerts the effect of the molding polyester film of the present invention most effectively.
  • mold molding is expensive in terms of mold and molding equipment, and is disadvantageous in terms of economy, but it is characterized in that a molded product having a more complicated shape than the above molding method is molded with high accuracy. There is. Therefore, when molding using the molding polyester film of the present invention, it can be molded at a lower molding temperature than the conventional biaxially oriented polyester film and the finishing power of the molded product ⁇ The remarkable effect that sex is improved is expressed.
  • the molded product molded in this way has elasticity and elasticity when used in a room temperature atmosphere. Excellent shape stability (heat-shrinkage characteristics, thickness unevenness), solvent resistance and heat resistance, and environmental impact is small, so it can be used for home appliance nameplates, automotive nameplates, dummy cans, building materials, decorative plates, cosmetics. It can be suitably used as a molded member such as a steel sheet or transfer sheet.
  • the molding polyester film of the present invention can be used as a molding material to be molded using a molding method such as press molding, laminate molding, in-mold molding, drawing molding, or bending molding, in addition to the molding method described above. Is also suitable.
  • Another embodiment of the present invention is a polyester film for molding in which a hard coat layer is provided directly on at least one side of the polyester film for molding or through a surface layer made of an adhesion improving resin.
  • the hard coat layer refers to a layer having a coating film having a hardness higher than that of the base material which supplements the surface hardness of the base material made of the polyester film for molding and improves the scratch resistance.
  • the layer having a hard coat property that can be used in the present invention is not particularly limited in that a melamine-based, acrylic-based, or silicon-based hard coat can be used.
  • An acrylic hard coat layer is preferred.
  • acrylic hard coat layer in the present invention after applying a coating agent containing a polyfunctional (meth) acrylate compound having two or more (meth) attalyloyl groups in one molecule, polymerization, and A film made of a resin by reacting is preferably used.
  • a coating agent containing a polyfunctional (meth) acrylate compound having two or more (meth) attalyloyl groups in one molecule polymerization, and A film made of a resin by reacting is preferably used.
  • One or more polyfunctional (meth) acrylate compounds may be used in combination.
  • (meth) atallyloyl group is an abbreviation of “atallyloyl group” or “meta-atallyloyl group”).
  • a compound in which the hydroxyl group of the polyhydric alcohol having a functional hydroxyl group is an esterified product of two or more (meth) acrylic acids can be used.
  • it contains a polyfunctional (meth) atalylate monomer compound having two (meth) attalyloyl groups in one molecule and a monomer compound having three or more (meth) attalyloyl groups in one molecule.
  • a polyfunctional (meth) acrylate compound having two (meth) attalyloyl groups in one molecule includes (a) (meth) acrylic of alkylene glycol having 2 to 12 carbon atoms; Acid diesters: ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, 1, 4 butanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 1, 6— (B) Polyoxyalkylene glycol (meth) acrylate diesters such as hexanediol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene Glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, polyethylene Glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, polyprop
  • Specific examples of the monomer compound having three or more (meth) attalyloyl groups in one molecule include pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, Dipentaerythritol tri (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, trimethylol propane tri (meth) Atallate and the like.
  • the proportion of the monomer having three or more (meth) attalyloyl groups in one molecule is desirably 30 to 90% by mass with respect to the total solid content.
  • the proportion of the monomer used is less than 30% by mass, it is difficult to obtain a cured film having sufficient scratch resistance, and when the amount exceeds 0% by mass, the flexibility of the film decreases. This is not preferred because cracks occur in the hard coat layer during molding.
  • Examples of a method for polymerizing and / or reacting the compound composition of the hard coat layer include a method of irradiating an electron beam, radiation, and ultraviolet rays. In the case of irradiating with ultraviolet rays, the composition is subjected to photopolymerization. It is desirable to add an initiator.
  • photopolymerization initiator examples include acetophenone, 2, 2 jetoxyacetophenone, p dimethylacetophenone, p dimethylaminopropiophenone, benzophenone, 2-clobenbenzophenone, 4 , 4 '-Diclonal Benzophenone, 4, 4' Bisjetinoreamino benzophenone, Michler's ketone, benzyl, benzoin, benzoin methyl ether, benzoin ethinoreethenole, benzoin isopropinoreethenole, methinolebenzoinoreformate , P isopropylinole ⁇ -hydroxyisobutylphenone, ⁇ -hydroxyisobutynole phenone, 2, 2-dimethoxy-2-phenylacetophenone, 1-hydroxycyclohexyl phenyl ketone, and other carbonyl compounds, tetramethylthiuram mono Sulfide,
  • photopolymerization initiators examples include peroxide compounds such as butyl peroxide. These photopolymerization initiators may be used alone or in combination of two or more.
  • the addition amount of the photopolymerization initiator is suitably 0.01 to 10% by mass in the solid content. When the amount used is small, the reaction is slow and the productivity becomes poor. Sufficient hard coat properties cannot be obtained. Conversely, if the amount added is large, the photoinitiator causes a problem that the hard coat layer turns yellow.
  • the compound composition forming the hard coat layer used in the present invention includes hydroquinone and hydroquinone monomethyl ether in order to prevent thermal polymerization during production and wrinkle reaction during storage. It is desirable to add known thermal polymerization inhibitors such as tellurium and 2,5-t-butylhydroquinone. The addition amount of the thermal polymerization inhibitor is preferably 0.005-0.05% by mass in the solid content.
  • the compound composition forming the hard coat layer used in the present invention has the purpose of improving the workability during coating and controlling the coating film thickness, within a range that does not impair the purpose of the present invention.
  • An organic solvent can be blended.
  • the organic solvent has a boiling point of 50 to 150 ° C because the drying temperature after coating needs to be adjusted to 150 ° C or less due to the heat resistance problem of the molding polyester film as the base material.
  • Those are preferred. Specific examples include alcohol solvents such as methanol, ethanol, and isopropyl alcohol, ester solvents such as methyl acetate, ethyl acetate, and butyl acetate, ketone solvents such as acetone and methyl ethyl ketone, and toluene. And aromatic ether solvents, and cyclic ether solvents such as dioxane. These solvents can be used alone or in admixture of two or more.
  • additives may be blended in the hard coat layer of the present invention as required.
  • fillers for surface irregularities and relaxation of internal stress for example, fluorine and silicon compounds for imparting water repellency, leveling agents and antifoaming agents for improving coatability and appearance, And dyes and pigments for coloring.
  • the hard coat layer may be applied after molding, but is preferably laminated on a film before molding that can be continuously processed in a roll form.
  • force including known methods, specifically, spray method, dipping method, roll coating method, die coating method, gravure coating method and the like can be mentioned.
  • the thickness of the hard coat layer is preferably 0.5 m or more and 10 m or less.
  • a particularly preferred thickness is 1 m or more and 6 m or less.
  • the film for molding provided with the hard coat layer of the present invention can be easily obtained a molded product having good moldability and good finish, and excellent surface scratch resistance, It can be suitably used as a molded member for home appliance nameplates, automobile nameplates, dummy cans, building materials, decorative plates, decorative steel plates, and the like.
  • 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.
  • a continuous tape-like sample of 3m in length in the transverse direction and 5cm in width in the longitudinal direction is taken up, and the film thickness is measured with a continuous film thickness measuring machine (manufactured by Anritsu Corporation) and recorded on a recorder. To do. From the chart, the maximum value (Tmax), minimum value (Tmin), and average value (Tav) of the thickness were obtained, and the thickness unevenness (%) was calculated by the following formula. The measurement was performed three times and the average value was obtained. If the length in the transverse direction is less than 3m, it will be joined. In addition, the measurement data in the connection part was deleted.
  • Thickness variation (%) ((Tmax-Tmin) / Tav) X 100
  • the haze of the film was measured using a ⁇ 1 meter (manufactured by Nippon Denshoku Industries Co., Ltd., 300A). The measurement was performed twice and the average value was obtained.
  • 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 tester manufactured by Toyo Seiki Co., Ltd.
  • pull the strip-shaped sample and from the obtained load-strain curve, calculate 100% elongation stress (MPa) and breaking elongation (%) in each direction. Asked.
  • the measurement was performed in an atmosphere of 25 ° C, initial length (distance between marked lines) 40mm, distance between chucks 100mm, crosshead speed 100mm / min, chart speed of recorder 200mm / min, load cell 25kgf Performed under conditions. This measurement was performed 10 times and the average value was used. It was.
  • Ra of the film was measured with Surfcom 304B (manufactured by Tokyo Seimitsu Co., Ltd.). The measurement conditions were cut-off 0.08 H m, stylus radius 2 ⁇ m, measurement length 0.8 mm, and measurement speed 0.03 mm / sec.
  • the refractive index (Nz) in the longitudinal direction, refractive index (Ny) in the width direction, and refractive index (Nz) in the thickness direction were measured as follows.
  • the degree of plane orientation ( ⁇ P) was calculated from the equation.
  • the formed film is wrapped around a 3-inch paper tube 300mm wide x 200m long and left for 72 hours in a 23 ° C 65R H% atmosphere. Then place the film in the vacuum deposition machine, 1 X 1 In an atmosphere of 0_ 4 torr, when unrolled at 50m / min, it was evaluated as follows in until after winding. Judgment criteria are ⁇ for those that have no problem from all points of view, and X when there is at least one problem.
  • Tpm melting peak temperature
  • ⁇ ⁇ ( ⁇ & 2 + A b 2 + AL 2 )
  • Mold shape Is a cup type, the opening has a diameter of 50 mm, the bottom part has a diameter of 40 mm, the depth is 50 mm, and all corners are curved with a diameter of 0.5 mm.
  • corner radius of curvature is lmm or less and printing deviation is 0.1mm or less
  • Corner radius of curvature exceeds lmm, 1.5mm or less, or print misalignment is 0.1
  • 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 0.1 lmm or less, (iii) Further, there is no appearance defect corresponding to X
  • Corner radius of curvature exceeds lmm, 1.5mm or less, or print misalignment is 0.1
  • Molded product is torn or even if it is not torn, it falls under any of the following items (i) to (iv)
  • the heating conditions were selected within the above range for each film.
  • the shape of the mold is a cup shape, the opening is 50 mm in diameter, the bottom is 40 mm in diameter, 30 mm in depth, and all corners are curved with a diameter of 0.5 mm. Was used.
  • 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
  • the sample was immersed in toluene adjusted to 25 ° C for 30 minutes, and the appearance change before and after immersion was judged based on the following criteria.
  • the haze value was measured by the method described above.
  • the film before printing was heat-treated at 90 ° C for 30 minutes, and then four-color screen printing was performed. Further, the film provided with the printing layer was dried at 80 ° C. for 30 minutes.
  • the print quality was evaluated by visually examining the appearance of printing such as clear feeling, printing suitability, and printing misalignment, as described below, from the backside of the printing surface and from the film. Judgment criteria were ⁇ for those that had no problems from all points of view, ⁇ for those that had problems with at least one point, and X for those that had problems with two or more points.
  • Printing suitability Color unevenness or missing due to poor transfer of printing ink does not occur.
  • Printing misalignment Printing misalignment cannot be visually recognized!
  • the surface was reciprocated 20 times with # 0000 steel wool with a load of lkgf, and evaluated by visual observation after being left for 24 hours.
  • the obtained unstretched sheet was stretched 3.3 times at 90 ° C in the longitudinal direction between the heating roll and the cooling roll.
  • the uniaxially stretched film was guided to a tenter and preheated at 120 ° C for 10 seconds, and the first half of the transverse stretching was 110 ° C and the latter half was stretched 3.9 times at 100 ° C.
  • the first heat treatment (TS 1) is 205 ° C
  • the second heat treatment (TS2) is 7% relaxation treatment in the horizontal direction! /
  • the heat fixation treatment is performed at 235 ° C.
  • an intermediate section of 2 m is provided between the stretching section, a far infrared heater is installed in the heating section of the heat setting zone, and a shielding plate for each section is used as a film. It was expanded and installed to the limit position where it did not touch. Even in the cooling section after heating, the section shielding is strengthened, an external return method is used as a clip return method, a clip cooling device is installed, and forced cooling is performed with cold air of 20 ° C, and the clip temperature at the tenter outlet is increased. Measures were taken to prevent clip fusion at 40 ° C or lower.
  • Example 1 a biaxially stretched polyester film was obtained in the same manner as in Example 1, except that the heat setting temperature was changed to 235 ° C. for both TS1 and TS2.
  • Example 1 a biaxially stretched polyester film was obtained in the same manner as in Example 1, except that the heat setting temperature was changed to 205 ° C. for both TS1 and TS2.
  • Example 3 A biaxially stretched polyester film was obtained in the same manner as in Example 1 except that the chip (B) in Example 1 was changed to a polyethylene terephthalate chip (C) containing no ultraviolet absorber. [0136]
  • Example 3 A biaxially stretched polyester film was obtained in the same manner as in Example 1 except that the chip (B) in Example 1 was changed to a polyethylene terephthalate chip (C) containing no ultraviolet absorber.
  • Water-soluble urethane resin in which a copolymerized polyester resin (Toyobo Co., Ltd., Vironal MD-1250) is solid solid content 3.15% by mass and terminal isocyanate group is blocked with a hydrophilic group in a 40 % by mass aqueous solution of isopropanol (1st Elastolon H-3), manufactured by Kogyo Seiyaku Co., Ltd., in solid form, 5.85% by mass, and silica particles with an average particle size of 1.0 111 are 0.8% by mass and the average particle size is 0. 05
  • the coating solution was adjusted so that the silica particles of 111 contained 10% by mass with respect to the total resin.
  • the resulting coating solution was adjusted to pH 6.5 using a 5% by mass aqueous sodium bicarbonate solution.
  • the solution was filtered through a bag-type filter (Sumitomo 3EM Co., Ltd., liquid filter bag), and stirred at 15 ° C for 2 hours in a coating liquid circulation system stock tank.
  • the chip is composed of 100 mol% terephthalic acid unit as the aromatic dicarboxylic acid component, 70 mol% ethylene glycol unit and 30 mol% neopentylglycol unit as the diol component, and benzotriazole UV absorbing Chip of copolymer polyester containing 0.5% by mass of agent (N) (Ciba Specialty Chemicals Co., Ltd., Tinuvin 326) and having an intrinsic viscosity of 0.77 dl / g.
  • agent (N) Ciba Specialty Chemicals Co., Ltd., Tinuvin 326
  • Chip (J) contains 0.667% by mass of benzotriazole-based ultraviolet absorber (N) (Chinoku, Specialty Chemica Norez Co., Ltd., Tinuvin 326), and has an intrinsic viscosity of 0.77dl / g. This is a polyethylene terephthalate chip.
  • N benzotriazole-based ultraviolet absorber
  • Chip is a polypropylene terephthalate (PPT) containing 0.67% by mass of benzotriazole UV absorber (N) (Ciba 'Specialty' Chemicals Co., Ltd., Tinuvin 326) with an intrinsic viscosity of 0.75 dl / g. It is a chip.
  • PPT polypropylene terephthalate
  • N benzotriazole UV absorber
  • chips (D), chip (J), and chip (F) were mixed so as to have a mass ratio of 50:10:40.
  • these chip mixtures were melt-extruded from the slit of the T die at 270 ° C by an extruder, rapidly cooled and solidified on a chill roll having a surface temperature of 40 ° C, and at the same time without being in close contact with the chill roll using an electrostatic application method A regular unstretched sheet was obtained.
  • the obtained unstretched sheet was stretched 3.5 times at 83 ° C in the longitudinal direction between the heating roll and the cooling roll. Stretched.
  • the coating solution was applied to the chill roll surface side (F surface) of the uniaxially stretched film by a reverse kiss coating method so that the thickness of the resin solid before stretching was 0.9 m.
  • the laminated film having the coating layer was dried and guided to a tenter, preheated at 95 ° C for 10 seconds, and the first half of the transverse stretching was stretched 3.9 times at 80 ° C and the latter half at 75 ° C.
  • the first heat treatment (TS 1) is 190 ° C
  • the second heat treatment (TS 2) is 7% relaxed in the lateral direction! /, While heat fixing at 210 ° C
  • an intermediate section of 2 m is provided between the stretching section, a far infrared heater is installed in the heating section of the heat setting zone, and a shielding plate for each section is used as a film. It was expanded and installed to the limit position where it did not touch. Even in the cooling section after heating, the section shielding is strengthened, an external return method is used as a clip return method, a clip cooling device is installed, and forced cooling is performed with cold air of 20 ° C, and the clip temperature at the tenter outlet is increased. Measures were taken to prevent clip fusion at 40 ° C or lower.
  • Example 3 a biaxially stretched polyester film was obtained in the same manner as in Example 3 except that the heat setting temperature was changed to 205 ° C. for both TS1 and TS2.
  • a biaxially stretched polyester film was obtained in the same manner as in Example 2, except that the heat setting temperature in Example 3 was changed to 180 ° C. (TS1) and 220 ° C. (TS2).
  • Example 3 The raw material composition of Example 3 is used as a core layer, and a chip in which chips (D) and chips (J) are mixed at a mass ratio of 50:50 is introduced into another extruder as a raw material for the skin layer and melted at 280 ° C.
  • a chip in which chips (D) and chips (J) are mixed at a mass ratio of 50:50 is introduced into another extruder as a raw material for the skin layer and melted at 280 ° C.
  • the same as in Example 2, except that the raw material of the core layer and skin layer / core layer / skin layer 10/80/10 were joined by a feed block and then extruded from a T-die at 270 ° C.
  • a biaxially stretched polyester film was obtained by this method.
  • Chip ( ⁇ ) consists of 60 mol% terephthalic acid unit as an aromatic dicarboxylic acid component This is a chip of copolymerized polyester having an intrinsic viscosity of 0.71 dl / g, comprising 40 mol% of taric acid units and 100 mol% of ethylene glycol units as diol components.
  • Chip (P) has an intrinsic viscosity of 0.71 dl, comprising 60 mol% of terephthalic acid units as aromatic dicarboxylic acid components and 40 mol% of naphthalene dicarboxylic acid components, and 100 mol% of ethylene glycol units as diol components. / g copolymer polyester chip.
  • Chip (J) and the above-mentioned copolymer polyester chip (O) and polyethylene terephthalate chip (P) were mixed at a mass ratio of 50:25:25 and dried. Next, these chip mixtures were melt-extruded from the slit of the T die at 270 ° C by an extruder, rapidly cooled and solidified on a chill roll having a surface temperature of 40 ° C, and at the same time being in close contact with the chill roll using an electrostatic application method. An amorphous unstretched sheet was obtained.
  • the obtained unstretched sheet was stretched 3.5 times at 90 ° C in the longitudinal direction between the heating roll and the cooling roll.
  • the uniaxially stretched film was guided to a tenter and preheated at 120 ° C for 10 seconds, and the first half of the lateral stretch was stretched 3.9 times at 110 ° C and the latter half at 100 ° C.
  • heat treatment was performed at 23 8 ° C while the first heat treatment (TS 1) was 205 ° C and the second heat treatment (TS2) was subjected to a 7% relaxation treatment in the lateral direction, resulting in a thickness of 100 m.
  • TS 1 first heat treatment
  • TS2 second heat treatment
  • an intermediate section of 2m is provided between the stretching section, a far infrared heater is installed in the heating section of the heat setting zone, and a shielding plate for each section is used as a film. It was expanded and installed to the limit position where it did not touch. Even in the cooling section after heating, the section shielding is strengthened, an external return method is used as a clip return method, a clip cooling device is installed, and forced cooling is performed with cold air of 20 ° C, and the clip temperature at the tenter outlet is increased. Measures were taken to prevent clip fusion at 40 ° C or lower.
  • chip (A), chip (I), benzotriazole-based ultraviolet absorber (N) manufactured by Ciba 'Specialty Chemicals Co., Ltd., Tinuvin 326), 25 ⁇ 0: 74.5: 0.5 It mixed so that it might become mass ratio.
  • these mixtures were melt-extruded from the slit of the T die at 265 ° C by an extruder, rapidly cooled and solidified on a chill roll having a surface temperature of 20 ° C, and at the same time, fixed in contact with the chill roll using an electrostatic application method. An unstretched sheet was obtained.
  • the obtained unstretched sheet was stretched 3.3 times in the machine direction at 80 ° C between the heating roll and the cooling roll.
  • the uniaxially stretched film was led to a tenter, preheated at 95 ° C for 10 seconds, and the first half of the transverse stretching was stretched 3.8 times at 85 ° C and the latter half at 80 ° C.
  • the first heat treatment (TS 1) was 185 ° C and the second heat treatment (TS2) was 7% relaxed laterally!
  • TS 1 was 185 ° C
  • TS2 was 7% relaxed laterally!
  • a 100 m biaxially stretched polyester film was obtained.
  • an intermediate section of 2m is provided between the stretching section, a far infrared heater is installed in the heating section of the heat setting zone, and a shielding plate for each section is used as a film. It was expanded and installed to the limit position where it did not touch. Even in the cooling section after heating, the section shielding is strengthened, an external return method is used as a clip return method, a clip cooling device is installed, and forced cooling is performed with cold air of 20 ° C, and the clip temperature at the tenter outlet is increased. Measures were taken to prevent clip fusion at 40 ° C or lower.
  • the following hard coat coating solution was applied to the molding polyester film obtained in Example 3 by a microgravure method so that the thickness after drying would be 3 m, dried with hot air at 80 ° C, and output 160 W
  • a molding polyester film provided with a hard coat layer was obtained by passing a position 20 cm under a high-pressure mercury lamp of / cm at a speed of 30 m / min.
  • the formability (vacuum formability, pressure formability, mold formability) of the film provided with the hard coat layer was the same as that of the film of Example 3 in which no hard coat layer was laminated. Further, no crack was generated in the coating layer of the obtained molded product. In addition, as a result of evaluating scratch resistance The surface was good with no scratches.
  • coating solution A The following materials were mixed at the mass ratio shown below, stirred for 30 minutes or more, and then undissolved substances and foreign substances were removed using a filter with a nominal filtration accuracy of 1 ⁇ m to prepare coating solution A. .
  • 6-functional polyurethane-based acrylic monomer 35.00 mass 0/0
  • the molding polyester film of the present invention is excellent in moldability at the time of heat molding at a low temperature and a low pressure, so that it can be applied to a wide variety of molding methods, and when used in a room temperature atmosphere as a molded product, It has excellent morphological stability (heat shrinkage characteristics, thickness unevenness), solvent resistance, heat resistance, and environmental impact.
  • morphological stability heat shrinkage characteristics, thickness unevenness
  • solvent resistance heat resistance
  • heat resistance heat resistance
  • environmental impact when unwinding a long film that has been wound into a roll during post-processing, blocking and tearing are unlikely to occur, resulting in excellent productivity.
  • the printing quality improving layer of the film includes relief printing, intaglio printing, planographic printing, screen printing, offset printing, gravure printing, inkjet printing, flexographic printing, etc.
  • Designs such as printing layers and design layers are applied by various printing decoration methods and decoration methods such as printing, transfer, painting, painting, vapor deposition, sputtering, CVD, and lamination, followed by mold forming, pressure forming, It is suitable for 3D decoration methods that are molded by various molding methods such as vacuum molding, and has excellent in-mold and embossability. Therefore, mobile phones, audio, portable players / recorders, IC recorders, car navigation systems, PDAs, etc. It is suitable as a casing or member of portable devices and notebook PCs, as a nameplate member for home appliances and automobiles, or as a member for building materials, and contributes greatly to the industry.
  • an ultraviolet absorber in the film and reducing the transmittance in the ultraviolet region, light resistance can be imparted, particularly for applications used outdoors (members for automobile exteriors or building materials). It is suitable as a molding material.

Abstract

L'objet de l'invention est un film polyester pour le moulage qui présente une excellente aptitude au moulage à basse température et basse pression, une excellente transparence, une excellente résistance au solvant, ainsi qu'une excellente résistance thermique, et qui n'entraîne pas de blocage ni ne se déchire lors du déroulement d'un rouleau du film en une longueur continue. De plus, ledit film polyester a une charge environnementale inférieure et est adapté pour les plaques signalétiques des appareils électriques, des automobiles ou des éléments pour matériaux de construction. Le film polyester pour le moulage selon l'invention est constitué par un film polyester orienté selon deux axes contenant un copolyester, caractérisé en ce que : (1) les contraintes dans la direction de la longueur et dans la direction de la largeur du film à un allongement de 100 % à 25°C sont de 40 à 300 MPa et celles à 100°C sont de 1 à 100 MPa, (2) les facteurs de rétraction thermique dans la direction de la longueur et dans la direction de la largeur du film à 150°C sont de 0,01 à 5,0 %, (3) le trouble est de 0,1 à 3,0 %, (4) la rugosité de surface (Ra) d'au moins un côté du film est de 0,005 à 0,030 µm, et (5) le degré d'orientation planaire est inférieur ou égal à 0,095.
PCT/JP2007/066606 2006-09-06 2007-08-28 Film de polyester pour moulage WO2008029666A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
KR1020097006909A KR101111040B1 (ko) 2006-09-06 2007-08-28 성형용 폴리에스테르 필름
JP2008533105A JP4609580B2 (ja) 2006-09-06 2007-08-28 成型用ポリエステルフィルムの製造方法
CN2007800332397A CN101511920B (zh) 2006-09-06 2007-08-28 成型用聚酯薄膜

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2006-241629 2006-09-06
JP2006241629 2006-09-06

Publications (1)

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WO2008029666A1 true WO2008029666A1 (fr) 2008-03-13

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PCT/JP2007/066606 WO2008029666A1 (fr) 2006-09-06 2007-08-28 Film de polyester pour moulage

Country Status (5)

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JP (3) JP4609580B2 (fr)
KR (1) KR101111040B1 (fr)
CN (1) CN101511920B (fr)
TW (1) TWI418578B (fr)
WO (1) WO2008029666A1 (fr)

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JP2010052334A (ja) * 2008-08-29 2010-03-11 Tomoegawa Paper Co Ltd インモールド成形用ハードコートフィルム、インモールドラベルおよび樹脂成形品
WO2010092847A1 (fr) * 2009-02-12 2010-08-19 東洋紡績株式会社 Film de couche dure pour formage
JP2010248519A (ja) * 2006-09-06 2010-11-04 Toyobo Co Ltd 積層成型用ポリエステルフィルム
JP2011011364A (ja) * 2009-06-30 2011-01-20 Toyobo Co Ltd 成型用ポリエステルフィルムおよび成型用ハードコートフィルム
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JP2011131410A (ja) * 2009-12-22 2011-07-07 Toyobo Co Ltd 保護フィルム付成型用ハードコートフィルム
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JP2012040713A (ja) * 2010-08-17 2012-03-01 Toyobo Co Ltd 成型用積層体
JP2012140499A (ja) * 2010-12-28 2012-07-26 Mitsubishi Plastics Inc 貼り合せ化粧材用ポリエステルフィルム
KR20130030195A (ko) * 2011-09-16 2013-03-26 후지필름 가부시키가이샤 2 축 연신 열가소성 수지 필름 및 그 제조 방법, 태양 전지용 백시트, 그리고 태양 전지 모듈
JP2013189583A (ja) * 2012-03-15 2013-09-26 Mitsubishi Plastics Inc 二軸配向ポリエステルフィルム
JP2014040104A (ja) * 2013-10-29 2014-03-06 Toyobo Co Ltd 保護フィルム付成型用ハードコートフィルム
JP2014058161A (ja) * 2013-10-29 2014-04-03 Toyobo Co Ltd 保護フィルム付成型用ハードコートフィルム
CN104793826A (zh) * 2015-05-01 2015-07-22 张家港康得新光电材料有限公司 双面硬化膜与包括该双面硬化膜的电容式触摸屏
WO2019188337A1 (fr) * 2018-03-30 2019-10-03 東洋紡株式会社 Film thermorétractable à base de polyester
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KR101355324B1 (ko) * 2008-06-18 2014-01-23 도요보 가부시키가이샤 성형용 하드코트 필름
JP2010024450A (ja) * 2008-06-18 2010-02-04 Toyobo Co Ltd 成型用ハードコート用樹脂組成物
TWI400284B (zh) * 2008-06-18 2013-07-01 Toyo Boseki 成型用硬被覆膜
WO2009154042A1 (fr) * 2008-06-18 2009-12-23 東洋紡績株式会社 Film de revêtement dur pour le moulage
JP2010052334A (ja) * 2008-08-29 2010-03-11 Tomoegawa Paper Co Ltd インモールド成形用ハードコートフィルム、インモールドラベルおよび樹脂成形品
WO2010092847A1 (fr) * 2009-02-12 2010-08-19 東洋紡績株式会社 Film de couche dure pour formage
JP2010185000A (ja) * 2009-02-12 2010-08-26 Toyobo Co Ltd 成型用ハードコートフィルム
JP2011011364A (ja) * 2009-06-30 2011-01-20 Toyobo Co Ltd 成型用ポリエステルフィルムおよび成型用ハードコートフィルム
JP2011011363A (ja) * 2009-06-30 2011-01-20 Toyobo Co Ltd 成型用ポリエステルフィルムおよび成型用ハードコートフィルム
JP2011057850A (ja) * 2009-09-10 2011-03-24 Toyobo Co Ltd 成型用ポリエステルフィルム
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JP2011126162A (ja) * 2009-12-18 2011-06-30 Toyobo Co Ltd 成型用ポリエステルフィルムおよび成型用ハードコートフィルム
JP2011126157A (ja) * 2009-12-18 2011-06-30 Toyobo Co Ltd 成型用ハードコートフィルム
JP2011126159A (ja) * 2009-12-18 2011-06-30 Toyobo Co Ltd 成型用ポリエステルフィルムおよび成型用ハードコートフィルム
JP2011126160A (ja) * 2009-12-18 2011-06-30 Toyobo Co Ltd 成型用ハードコートフィルム
JP2011126163A (ja) * 2009-12-18 2011-06-30 Toyobo Co Ltd 成型用ハードコートフィルム
JP2011131409A (ja) * 2009-12-22 2011-07-07 Toyobo Co Ltd 成型用ポリエステルフィルムおよび成型用ハードコートフィルム
JP2011131410A (ja) * 2009-12-22 2011-07-07 Toyobo Co Ltd 保護フィルム付成型用ハードコートフィルム
JP2012040713A (ja) * 2010-08-17 2012-03-01 Toyobo Co Ltd 成型用積層体
JP2012140499A (ja) * 2010-12-28 2012-07-26 Mitsubishi Plastics Inc 貼り合せ化粧材用ポリエステルフィルム
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EP2570252A3 (fr) * 2011-09-16 2013-07-24 FUJIFILM Corporation Film de résine thermoplastique étiré biaxialement, son procédé de fabrication, feuille support pour cellule solaire et module de cellule solaire
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CN104793826A (zh) * 2015-05-01 2015-07-22 张家港康得新光电材料有限公司 双面硬化膜与包括该双面硬化膜的电容式触摸屏
WO2019188337A1 (fr) * 2018-03-30 2019-10-03 東洋紡株式会社 Film thermorétractable à base de polyester
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JP2019178194A (ja) * 2018-03-30 2019-10-17 東洋紡株式会社 熱収縮性ポリエステル系フィルム
JPWO2019188922A1 (ja) * 2018-03-30 2020-04-30 東洋紡株式会社 熱収縮性ポリエステル系フィルム
JP2021080463A (ja) * 2018-03-30 2021-05-27 東洋紡株式会社 熱収縮性ポリエステル系フィルム
JP7070727B2 (ja) 2018-03-30 2022-05-18 東洋紡株式会社 熱収縮性ポリエステル系フィルム

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TWI418578B (zh) 2013-12-11
JP5170160B2 (ja) 2013-03-27
JP4609580B2 (ja) 2011-01-12
CN101511920B (zh) 2012-05-09
KR101111040B1 (ko) 2012-03-13
JP2010248519A (ja) 2010-11-04
JP5287793B2 (ja) 2013-09-11
JPWO2008029666A1 (ja) 2010-01-21
JP2010221715A (ja) 2010-10-07
CN101511920A (zh) 2009-08-19
KR20090051264A (ko) 2009-05-21
TW200831572A (en) 2008-08-01

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