TWI297706B - Polyester film for molding - Google Patents

Abstract

A polyester film for forming which has excellent formability especially at a low temperature and low pressure, is excellent in solvent resistance and heat resistance, and is reduced in the burden to be imposed on the environment. The film comprises a biaxially oriented polyester film and is characterized by containing a copolyester and satisfying the following: (1) the stresses at 100% elongation in the machine direction and the transverse direction each is 10 to 1,000 MPa as measured at 25°C and is 1 to 100 MPa as measured at 100°C, (2) the storage moduli (E') in the machine direction and the transverse direction each is 10 to 1,000 MPa as measured at 100°C and is 5 to 40 MPa as measured at 180°C, and (3) the degree of heat distortion (initial load, 49 mN) in the machine direction as measured at 175°C is from -3% to +3%.

Description

1297706 IX. Description of the Invention [Technical Fields of the Invention] v The present invention relates to a polyester film for forming which has excellent formability, particularly in low temperature and low pressure, and has excellent properties. It is resistant to melting! It has low load resistance to the environment and is suitable for use as a component for household appliances, automobiles, or building materials. [Prior Art] Conventionally, the sheet for molding has been represented by a polyvinyl chloride film, and has been widely used from the viewpoint of workability and the like. On the other hand, the film has a problem that a toxic gas is generated when the film is burned due to a fire or the like, and a plasticizer is oozing out. Therefore, it is required to be exposed to environmental resistance in recent years. New materials with less environmental impact. In order to meet the above requirements, an unstretched sheet composed of a polyester, a polycarbonate, and an acrylic resin which are non-chlorinated materials has been used in a wide range of fields. In particular, the unstretched sheet composed of a polyester resin is attracting attention because of its excellent mechanical properties, transparency, and superior economy. For example, it has been disclosed that a mixture of about 30 mol% of ethylene glycol in polyethylene terephthalate is substituted with 1,4-cyclohexanedimethanol, and substantially a non-crystalline polyester resin. The non-stretched polyester film of the composition is disclosed in Japanese Laid-Open Patent Publication No. Hei 9-156267, Japanese Patent Laid-Open No. 2001-7, No. 1,669, and Japanese Patent Laid-Open No. 2001-8〇251 Japanese Laid-Open Patent Publication No. 2001-12995, No. 2002-249652. Regarding the formability or lamination suitability, the unstretched polyester sheet satisfies the market requirement of 1297706, but since it is an unstretched sheet, heat resistance or solvent resistance is insufficient, so that the height of the market cannot be met. - In order to solve the problem as described above, a method of using a biaxially-extending polyethylene terephthalate film has been disclosed, for example, Japanese Patent Laid-Open No. Hei 9-187903, Japanese Patent Laid-Open No. 10 Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. However, although the method as described above can improve heat resistance or solvent resistance, the formability becomes insufficient, so that from the viewpoint of the balance of comprehensive quality, the point that the market demand can be satisfied is still not achieved. In order to solve the problem as described above, a method of specifying a stress at a temperature of 100% elongation has been disclosed, for example, as disclosed in Japanese Laid-Open Patent Publication No. 2001-347565. This method, although improved in formability compared to the method described above, does not reach a high level sufficient to meet market requirements for formability. In particular, it is suitable for the formability which is suitable for the lowering of the forming temperature or the finishing property of the obtained molded article. The inventors of the present invention have reviewed the above-mentioned problems and proposed a specific composition of a copolymerized polyester resin as a raw material, and specificizes the stress of the film at 100% elongation, thereby improving the above-mentioned problems. The method is disclosed in, for example, Japanese Patent Application No. 2002-233694 and Japanese Patent Application No. 2003-309894. According to these methods, in the mold forming method which requires a high molding pressure at the time of molding, the moldability which is suitable for meeting the market demand and the temperature of 1297706 can be greatly improved, and the finished product can be finished. However, in the case of a forming method in which the forming pressure is low, such as a pneumatic forming method or a vacuum forming method, which is required to be more intense in the recent + field, it is urgent to further improve the finish of the molded article. SUMMARY OF THE INVENTION The object of the present invention is to provide a polyester film for forming which solves the problems of the prior art as described above and which has excellent formability, particularly at low temperatures and low pressures. It has good formability, and has excellent solvent resistance or heat resistance, and has a small environmental load. Solution to Problem The polyester film for molding of the present invention which solves the above-mentioned problems is constituted by the following structure. That is, the first invention of the present invention is a polyester film for forming, which is characterized in that it is composed of a biaxially oriented polyester film, and the film is composed of a copolymerized polyester, and (1) The stress in the longitudinal direction and the width direction of the film at 100% elongation is 10 to 1,000:\1?3 at 25 ° C, and 1 to 100 MPa at 100 ° ;; and (2) film The storage viscoelastic modulus (E') in both the length direction and the width direction is 10 to 1,000 MPa at 10 °C and 5 to 40 MPa at 18 °C; and (3) film The thermal deformation rate in the longitudinal direction (initial load 49 mN) is -3 % to + 3 % at 175 °C. The invention of claim 1, wherein the copolymerized polyester is an aromatic dicarboxylic acid component, and comprises ethylene glycol and a branched aliphatic diol and/or an alicyclic group. The diol component of the diol is a constituent component. The polyester film for forming according to the second aspect of the invention, wherein the polyester constituting the biaxially oriented polyester film further contains 1,3-propanediol or 1,4-butanediol as a diol component. . According to a fourth aspect of the invention, there is provided a polyester film for molding according to the first aspect of the invention, wherein the polyester film for molding has a system orientation of 0.095 or less. According to a fifth aspect of the invention, the polyester film for molding of the first aspect of the invention has a heat shrinkage ratio of 6.0% or less in the longitudinal direction and the transverse direction at 150 °C. According to a sixth aspect of the invention, the polyester film for molding of the first aspect of the invention has a melting point of 200 to 45 ° C. According to a seventh aspect of the invention, the polyester film for molding according to the first aspect of the invention has a ratio 値(H/d) of a haze (%) of a film thickness d (micrometer) of less than 0.010. . The polyester film for forming according to the first aspect of the invention, wherein the polyester film for molding is used as a base film, and the surface layer of the base film has a thickness of 0.01 to 5 μm, and The base film does not substantially contain particles, and only contains particles in the surface layer. According to a ninth aspect of the invention, in the polyester film for forming of the eighth aspect, the surface layer is mainly composed of an adhesive modified resin and particles. [Effect of the Invention] The polyester film for molding of the present invention can be applied to a wide range of molding methods because of its excellent moldability at 1297706 during press molding, particularly at low temperatures and low pressures. When used as a molded article in a normal temperature atmosphere, it has excellent elasticity and form stability (heat shrinkage characteristics, thickness unevenness), plus superior solvent resistance or heat resistance, and has environmental load. It is small, so it has the advantages of being suitable for use in home appliances, automobile brand names, or building materials. BEST MODE FOR CARRYING OUT THE INVENTION In the polyester film for molding of the present invention, it is important that the stress (F 1 0 025 ) is 10 to 1,000 MPa when the film is elongated at 100 ° C in the longitudinal direction and the width direction, and The stress (F1001G〇) of the film in the longitudinal direction and the width direction at 100 ° C elongation of 100% is 1 to 100 MPa. ? When 10 025 or F100100 is larger than the upper limit of the range, the formability is lowered, so it is not preferable. On the other hand, when it is less than the lower limit of the range, the elasticity or the form stability at the time of using the molded article is lowered, which is not preferable. The Fl 〇〇 25 system in the longitudinal direction and the transverse direction of the film is preferably from 1 Torr to 500 MPa, more preferably from 10 to 200 MPa, and most preferably from 10 to 150 MPa. Further, the upper limit ′ of F1 〇〇 1 Q〇 in the longitudinal direction and the transverse direction of the film is preferably 90 MPa from the viewpoint of the formability, more preferably 80 MPa, and most preferably 70 MPa. The lower limit of the relative F1 00 i , is preferably 2 MPa, more preferably 3 MPa, and most preferably 5 MPa, from the viewpoint of elasticity or form stability when using a shaped article. In the polyester film for forming of the present invention, it is important that the storage viscoelastic modulus (E') in the longitudinal direction and the width direction of the film is 1 〇 to 1, 〇〇〇 MPa, and 1 80 at 100 ° C. It is 5 to 40 MPa at °C. By controlling the storage viscoelastic modulus (1297706 E_') within this range, the formability can be ensured, especially at low temperatures and low pressures, even if an air pressure molding method using only unstretched sheets is used. In the molding method of a low molding pressure of less than 1 Torr, such as a vacuum forming method, it is also possible to obtain a molded article having excellent finishability and a good dimensional stability. * The inventors have found that the storage viscoelastic modulus (E') at 100 ° C and 180 ° C as described above affects the formability at low temperature and low pressure, and the dimensional stability and the like. It was also found that the storage viscoelastic modulus (E') especially at 100 ° C is related to the formability at low temperature and low pressure, and the storage viscoelastic modulus (E') at 180 ° C is stable with dimensional stability. Sexuality has new insights. Regarding the reason why the storage viscoelastic modulus (E') at this specific temperature can be an important index for exhibiting the characteristics of the film, the inventors of the present invention have not clearly explained the reason, but presumably It is involved in the molecular structure of the copolymerized component contained in the polyester used to form the film. The storage viscoelastic modulus (E') in the longitudinal direction and the width direction of the film is in the direction of the film, preferably 20 to 900 MPa at 100 ° C, more preferably 30 to 800 MPa, 40 to 700 MPa is particularly preferred. Further, the storage viscoelastic modulus (E') at 180 ° C is preferably 7 to 38 MPa, more preferably 9 to 35 MPa, and particularly preferably 10 to 30 MPa. Further, the polyester film for molding of the present invention is important in the heat deformation rate (initial load 49 mN) in the longitudinal direction and the width direction of the film, and is -3 % to + 3 % at 175 °C. The heat deformation rate (initial load 49 mN) in the longitudinal direction of the film is preferably -3 % to + 3 % at 180 ° C, and particularly preferably -3 % to + 3 % at 185 ° C. -11 - 1297706 The thermal deformation rate of the film is determined by the temperature dependence of the film deformation rate at an initial load of 49 mN, measured by a 4 thermomechanical analyzer (TMA) at a heating rate of 5 ° C / min. . The solvent resistance of the molded article can be resold as long as the characteristics can be met. For example, a molded article having a low forming pressure of less than 10 stupid pressures, such as a pneumatic forming method or a vacuum forming method, can be used to produce a molded article having a good finish. However, the heat-deformation rate of the unstretched sheet obtained through the polyester, polycarbonate, and acrylic resin at the film length of 175 °C is not within this range. The thermal deformation rate and the solvent resistance under the slight tension of the film (initial load 49 mN), at first glance, can be considered as irrelevant characteristics. The reason why the correlation can be seen is not clear. However, the inventors of the present invention presume that the polyester film for molding of the present invention exhibits a molecular orientation due to the extension of the biaxial orientation, and the solvent resistance or heat deformation resistance is improved. It is important that (1) the stress in the longitudinal direction and the width direction of the film is increased by 1% by weight, (2) the storage viscoelastic modulus (E') in the longitudinal direction and the width direction of the film, and (3) the film length. The rate of thermal deformation of the direction under a slight tension must also meet the range as described above. As long as the film can simultaneously satisfy the above characteristics, the polyester film for molding of the present invention which has the effect of satisfying various market requirements as described above can be obtained. The formed ruthenium polyester film of the present invention is a biaxially stretched polyester film containing a constituent component of the copolymerized polyester, and its structure, melting point, molecular weight, composition, and the like are not particularly limited as long as it satisfies the above characteristics. Freely selected, but the preferred mode of implementation is as follows. -12- 1297706 The polyester film for forming of the present invention is a diol component comprising an aromatic dicarboxylic acid component and a glycol-containing aliphatic diol and/or an alicyclic diol. The copolymerized polyester is preferably used in part or all of the base film material. Copolymerized polyester as described above, wherein the aromatic dicarboxylic acid component is mainly composed of terephthalic acid, naphthalene dicarboxylic acid or an ester-forming derivative thereof, but terephthalic acid for the whole dicarboxylic acid component The amount of the naphthalene dicarboxylic acid component is greater than 70 mol%, preferably greater than 85 mol%, particularly preferably greater than 95 mol%, especially preferably 100 mol%. Further, examples of the branched aliphatic diols include neopentyl glycol, 1,2-propylene glycol, and 1,2-butanediol. The alicyclic diol is, for example, 1,4-cyclohexanediethanol or tricyclodecane dimethylol. Particularly preferred among these are neopentyl glycol or 1,4-cyclohexanedimethanol. Further, in the present invention, a more preferred mode of operation is to use 1,3-propanediol or 1,4-butanediol as a copolymerization component in addition to the diol component as described above. The use of these diols as a copolymerization component is suitable for imparting the above-mentioned characteristics, and is also suitable for imparting excellent transparency or heat resistance and improving adhesion to an adhesive modified layer. Further, if necessary, a copolymerization of the polyester as described above may be carried out by using one or a combination of two or more of the following dicarboxylic acid components and/or diol components as a copolymerization component. Other dicarboxylic acid components which can be used together with terephthalic acid or its ester-forming derivative include: (1) isophthalic acid, 2,6-naphthalene dicarboxylic acid, diphenyl-4, When 4'-dicarboxylic acid, diphenoxyethane dicarboxylic acid, and diphenylphosphonium di- 13·1297706 are used at 0.50 dl/g, the formability tends to decrease. Further, when a filter for removing foreign matter is provided on the molten process line, it is preferable to set the upper limit of the inherent viscosity to 1.0 dl/g from the viewpoint of discharge stability when the molten resin is extruded. In the polyester film for molding of the present invention, the copolymerized polyester may be used as a film raw material as it is, or a copolymerized polyester having a large copolymerization component and a homopolymerized polyester (for example, polyterephthalic acid) may be used. The ethylene glycol) is blended to adjust the amount of the copolymerization component. In particular, if the film is formed by the latter doping method, transparency and high melting point (heat resistance) can be achieved while maintaining the same flexibility as in the case of using only the copolymerized polyester. Further, with respect to the case where only a high melting point homopolymerized polyester (for example, polyethylene terephthalate) is used, the softness and the practically problem-free melting point (heat resistance) can be achieved while maintaining high transparency. Further, the copolymerized polyester is blended with at least one of a homopolyester other than the polyethylene terephthalate (for example, polytetramethylene terephthalate or polybutylene terephthalate) as The raw material of the polyester film for molding of the present invention is preferably used from the viewpoint of moldability. The melting point of the polyester film is preferably from 200 to 24 ° C from the viewpoint of heat resistance and formability. Further, if the type or composition of the polymer to be used and the film forming conditions are controlled within the above-mentioned melting point range, a balance between formability and finishability can be obtained, and a high-quality molded article can be produced economically. The melting point refers to the endothermic peak temperature at the time of melting detected by the primary temperature rise of the so-called differential scanning calorimetry (DSC). The melting point of 1297706 carboxylic acid, sodium 5-sulfoisophthalate, sodium phthalate or the like, or an aromatic dicarboxylic acid such as phthalic acid* or such an ester-forming derivative; 〇2) oxalic acid, succinic acid, adipic acid, hydrazine An aliphatic dicarboxylic acid such as a diacid, a dimer acid, a maleic acid, a fumaric acid or a glutaric acid or an ester-forming derivative thereof; (3) a cyclohexane. Alicyclic dicarboxylic acids <Or such an ester-forming derivative; (4) a hydroxycarboxylic acid such as p-hydroxybenzoic acid or hydroxycaproic acid or an ester-forming derivative thereof. On the other hand, other diol components which can be used together with ethylene glycol and branched aliphatic diols and/or cycloaliphatic diols include, for example, aliphatic diols such as pentanediol and hexanediol. An aromatic diol such as bisphenol A or bisphenol S and such ethylene oxide adducts, diethylene glycol, triethylene glycol, dimer diol, and the like. Further, if necessary, the copolymerized polyester may further copolymerize a polyfunctional compound such as trimellitic acid, trimesic acid or trimethylolpropane. As the catalyst to be used in the production of the copolymerized polyester, for example, an alkaline earth metal compound, a manganese compound, a cobalt compound, an aluminum compound, a ruthenium compound, a titanium compound, a titanium/ruthenium composite oxide, a ruthenium compound or the like can be used. From the viewpoint of catalytic activity, titanium compounds, ruthenium compounds, ruthenium compounds, and aluminum compounds are preferred among these. In the production of the copolymerized polyester, it is preferred to add a phosphorus compound as a heat stabilizer. The phosphorus compound is preferably, for example, phosphoric acid or phosphorous acid. The copolymerized polyester as described above preferably has an intrinsic viscosity of more than 0.50 dl/g, more preferably more than 0.55 dl/g, and particularly preferably more than the viewpoint of moldability, adhesion, and film stability. 0.60 dl/g. Intrinsic viscosity was small -14- 1297706 was measured using a differential scanning thermal analysis device (manufactured by DuPont, V4. OB2000) at a heating rate of 20 ° C / min. The lower limit of the melting point is 2 1 (TC is preferred, particularly preferably 230 ° C. When the melting point is lower than 200 ° C, the heat resistance tends to deteriorate. Therefore, when molding or when the molded article is exposed to the crucible When it is high i, there is a possibility that it will become a problem / the upper limit of the melting point as described above, from the viewpoint of heat resistance, although the higher the better, the case is mainly polyethylene terephthalate For a film having a melting point higher than 245 ° C, the formability tends to deteriorate. Further, the transparency tends to be deteriorated. Therefore, if high formability or transparency is desired, the upper limit of the melting point should be controlled. Further, in order to improve the workability such as lubricity or take-up property of the film, it is preferable to form irregularities on the surface of the film. The method of forming irregularities on the surface of the film is such that the ruthenium generally contains the particles in the film. The method β is as described above, and the particle system includes external particles such as internal precipitated particles having an average particle diameter of 1 to 1 μm, inorganic particles, and/or organic particles. When particles having an average particle diameter of more than 10 μm are used, It is easy to cause film defects, which may lead to In the case where the average particle diameter is less than 〇·〇1 μm, the operability of the film such as lubricity or take-up property tends to decrease. From the viewpoint of operability such as lubricity or take-up property, the lower limit is preferably set to 〇·10 μm, particularly preferably 0.50 μm. On the other hand, the average particle diameter of the particles is reduced from transparency. From the viewpoint of the film defects caused by the sexual or coarse protrusions, the upper limit is preferably set to 5 μm, particularly preferably 2 μm. In addition, the average particle diameter of the particles is at least 200 or more particles. - 1297706 Several photographs were taken by submicroscopy, and the particle contour was drawn on a Ο Η P (composite projector) film, and then the image was analyzed by an image analysis device to calculate the diameter corresponding to the circle. External particles can be used, for example: wet and dry cerium oxide, colloidal cerium oxide / aluminum sulphate, titanium oxide, calcium carbonate, calcium phosphate, barium sulfate, alumina, mica, kaolin, clay, hydroxyapatite Wait Inorganic particles and organic particles having styrene, polyfluorene oxide, acrylic acid, etc., among which inorganic particles such as dry, wet and dry colloidal cerium oxide, lead oxide, etc., and styrene are preferably used. Organic particles such as polyoxymethylene, acrylic acid, methacrylic acid, polyester, divinylbenzene, etc., such internal particles, inorganic particles and/or organic particles may also be used without damaging the present application. Two or more kinds are used in the range of characteristics specified by the invention, and the content of the particles in the film is preferably in the range of 0.001 to 10% by mass. When the amount is less than 0.001% by mass, the lubricity of the film is deteriorated. The operability is likely to be lowered, such as difficulty in winding up. Conversely, when it is more than 10% by mass, it is likely to cause formation of coarse protrusions, deterioration of film formability, and transparency. Further, the particles contained in the film generally have a refractive index which is different from that of the polyester, which causes a decrease in transparency of the film. In order to improve the new style, most of the formed articles are printed on the surface of the film before forming. Most of such a printing layer is applied to the back side of the film for forming. Therefore, from the viewpoint of printing clarity, it is required that the transparency of the film must be high, so that it is highly transparent while maintaining the handleability of the film. For example, -17 to 1297706 is effective in such a manner that the particles are not substantially contained in the substrate film, and the particles are contained only in the surface layer having a thickness of 〇1 to 5 μm. Further, as described above, "the particle is not substantially contained in the base film" means that, for example, in the case of inorganic particles, when the amount of the inorganic element is determined by X-ray fluorescence analysis, k is the detection limit. Content outside the range. This is because even if it is not intended to add particles to the base film, contamination components such as foreign matter may be mixed. The formation of a thin surface layer can be achieved by coating or co-extrusion. In the case where the coating method is employed, if a composition composed of an adhesive-modified resin containing particles is used as the coating layer, the adhesion to the printing layer can be improved, which is also a preferable method. The adhesive modified resin preferably uses a resin comprising at least one selected from the group consisting of polyesters, polyurethanes, acrylic polymers, and/or copolymers thereof. Further, in order to further improve the adhesion between the main layer polyester film and the adhesive modified layer, the surface of the base film may be surface-treated in advance, and then the adhesive modified layer may be provided on the surface treated surface. For the surface treatment method, (1) a method of irradiating active energy rays such as corona discharge treatment, plasma discharge treatment, ultraviolet (UV) irradiation treatment, radiation (EB) irradiation treatment, (2) flame treatment, and (3) PVD (physical vapor deposition), vapor deposition methods such as CVD (chemical vapor deposition), and the like. With the laminated structure as described above, the ratio 値(H/d) of the haze (%) to the film thickness d (micrometer) can be made smaller than 0·01 while maintaining the workability of the film. When the polyester film for forming as described above is used for the use of transparency - 1897706 which is particularly required for transparency, from the viewpoint of transparency and print clarity, the haze for film * thickness d (micrometer) should be made Η (%) "H/d" becomes less than 0.010. More preferably, the H/d is greater than 0 and less than 0.010, particularly preferably greater than 〇 and less than 0.009. Further, in the present invention, the H/ Although the number of d is only described as the third decimal place, /1, the fourth or lower is not rounded off. For example, even if it is 0.0099, it is 0.009. From the viewpoint of transparency and print clarity. It is considered that the lower limit of the H/d is closer to zero. However, when an important minimum unevenness is not formed on the surface of the film, the workability such as lubricity or take-up property is about to deteriorate, so that It may cause damage to the surface of the film or deterioration of productivity. Therefore, the lower limit of H/d should be set to 0.001, especially preferably 0.005. In addition, in the case of using a light-transparent brand of backlight, it is required to be more highly Transparency, so the H/d should be closer to zero Preferably, the particles which are contained in the surface layer as described above may be the same as those described above, but in the particles, due to cerium oxide particles, glass cerium filler, cerium oxide-alumina composite Since the refractive index of the oxide particles is relatively close to that of the polyester, the effect is particularly excellent from the viewpoint of transparency. Further, when particles having an average particle diameter of more than 10 μm are contained in the surface layer, coarse protrusions are formed. At the frequency of the surface of the film, there is a tendency to cause deterioration of the new form. In contrast, particles having an average particle diameter of less than 0.01 μm tend to have a decrease in workability such as lubricity or take-up property of the film. The average particle diameter is preferably in the same range as when the particles are contained in the substrate film. Further, the content of the particles in the surface layer is in the range of from 1 to 25 mass% -19 to 1297706. When the amount is less than 0.01% by mass, the lubricity of the film is likely to be deteriorated, or the workability such as difficulty in winding is lowered. Conversely, when the amount is '25% by mass, the transparency or the coating property is likely to be deteriorated. The polyester film may be a polyester having a different kind of function and may be a laminated structure by a conventional method. The form of the laminated film may be, for example, A/B, although not particularly limited. Two-layer structure, two kinds of three-layer structure of B/A/B structure, and three layers of three-layer structure of C/A/B. The polyester film for forming of the present invention is important to be a biaxially stretched film. The present invention utilizes the molecular orientation of biaxial stretching to control the thermal deformation rate of the film under a slight tension (initial load 49 mN) within the scope of the present invention to improve the solvent resistance of the disadvantages of the unstretched sheet. Or dimensional stability. In other words, the solvent resistance or dimensional stability which improves the disadvantages of the unstretched sheet can be one of the features of the present invention while maintaining the formability of the unstretched sheet. The method for producing the biaxially oriented polyester film as described above is not particularly limited, but may be exemplified by drying the polyester resin as needed, and then supplying it to a conventional melt extruder, which is extruded by a slit die. After being formed into a sheet shape, and then being adhered to the casting tube by applying static electricity or the like, and solidified by cooling to obtain an unstretched sheet, the biaxially extending method of the unstretched sheet may be biaxially extended. A method of applying a heat treatment to extend the unstretched sheet in the longitudinal direction (MD) and the width direction (.TD) to produce a biaxially stretched film having a target in-plane orientation is employed. In the above-mentioned manner, from the viewpoint of the film quality of -20 to 1297706, it is preferable to adopt an MD/TD method in which the warp direction is extended in the longitudinal direction and then extend in the width direction, or to extend in the width direction, and then to The sequential biaxial stretching method such as the TD/MD method in which the length direction extends is a biaxial stretching method in which the longitudinal direction and the width direction are extended substantially simultaneously. In addition, in the case of the simultaneous biaxial stretching method, a tenter driven by a linear motor can also be used. Further, if necessary, it is also possible to use a multi-stage extension method in which the extension of the same direction is divided into multiple stages. The film stretching magnification at the time of biaxial stretching is preferably 1.6 to 4.2 times in the longitudinal direction and the width direction, particularly preferably 1.7 to 4.0 times. In this case, the extension magnification in the longitudinal direction and the width direction may be set to be either large or the same magnification. The elongation in the longitudinal direction is 2.8 to 4.0 times, and the extension in the width direction is preferably 3.0 to 4.5 times. The stretching conditions in the production of the polyester film for forming of the present invention are not particularly limited, but in order to attain the above-described characteristics as defined in the present invention, it is preferred to select the following conditions. In the longitudinal extension, the extension temperature should be 50 to 11 (TC, and the extension magnification is more preferably 16 to 4.0 times, so that the subsequent lateral extension can proceed smoothly. Usually when extending polyethylene terephthalate When the elongation temperature is lower than the appropriate condition, the stress tends to rise sharply at the initial stage of the lateral stretching, so that the elongation cannot be extended, and even if it is stretched, the thickness or the extension magnification tends to become uneven, which is not preferable. Further, when the elongation temperature is higher than the appropriate condition, the initial stress is low, but the stress does not increase even if the elongation amplification factor is increased. Therefore, the stress of -21,297,706 at 100 ° C elongation at 100 ° C is small. Membrane. Therefore, as long as the most suitable extension temperature is adopted, a highly oriented film can be obtained while ensuring the elongation. However, in the case where the copolymerized polyester contains 1 to 40 mol% of the copolymerization component, in order to eliminate the occurrence of the fall. When the stress increases the elongation temperature, the extension stress is about to drop sharply. In particular, the stress is not high in the second half of the extension, so the orientation does not become high, and the elongation is 100% at 25 °C. The stress is about to decrease. This phenomenon is likely to occur when the film thickness is 60 to 500 μm, especially the film having a thickness of 100 to 300 μm. Therefore, when the film of the copolymerized polyester of the present invention is used, the transverse direction The extension temperature is preferably as follows. First, the preheating temperature should be set to 50 to 150 ° C. Then, the extension temperature is in the first half of the lateral extension, and the preheating temperature is -20 to + 25 °. C is preferably, particularly preferably -15 to +25° (:. As for the second half of the lateral extension, the extension temperature is preferably set to -40 to -40 ° C for the extension temperature of the first half, particularly preferably -10 To -40 ° C. With the above conditions, in the first half of the lateral extension, the stress is small due to the small stress, easy to extend, and easy to align in the second half. In addition, the lateral magnification should be 2. 5 to 5.0 times. As a result, a film conforming to the F1 0025 or F100Oio specified in the present invention can be obtained. Next, the heat treatment of the film is carried out after biaxial stretching, which can be carried out in a heat treatment oven or on a heated drum. According to the conventional method Further, the heat treatment temperature and the heat treatment time may be arbitrarily set according to the degree of heat shrinkage. The heat treatment temperature is preferably from 120 to 245 ° C, particularly from -22 to 1297706, preferably from 150 to 240 ° C. The heat treatment time is carried out by 1 Further, the heat treatment may be carried out while the film is relaxed in the longitudinal direction and/or the width direction thereof. Further, the heat treatment temperature of the present invention is within the range of the above heat treatment temperature, Since the composition of the membrane material used is different from the appropriate range, <The heat treatment temperature in which the degree of surface orientation of the film is set to 0.095 or less is important. The reason is as follows. In order to reduce the heat shrinkage ratio of the film in the longitudinal direction and the transverse direction at 150 °C, it is preferred to carry out the method of increasing the heat treatment temperature, extending the heat treatment time, and performing the relaxation treatment. Specifically, if the heat shrinkage ratio of the film in the longitudinal direction and the transverse direction at 150 ° C is 6.0% or less, the heat treatment temperature should be 200 to 220 ° C, and the relaxation rate is 1 to 8 %. It is better to implement the slow side. Further, it may be extended more than once in each direction, or may be subjected to heat treatment thereafter. In order to reduce the heat shrinkage rate of the film in the longitudinal direction and the transverse direction at 150 ° C and to extend the production line to prolong the heat treatment time, it is difficult to limit the equipment. In addition, slowing down the rate of film transport will soon lead to a decrease in productivity. Thus, in the extension section, the section temperature must be maintained at a relatively low temperature of, e.g., 1 〇〇 °C, whereas in the case of heat fixation, it must be rapidly warmed to a high temperature of about 200 °C. Therefore, in order to solve the problem, it is considered that a far-infrared heater is provided in the heat treatment section to reinforce the heating. Further, it is possible to adopt a method of further providing an adiabatic section of more than 1 m between the extending section and the heat fixing section in order to improve the heating efficiency after the adiabatic section. Specifically, by enhancing the distinguishing function between each segment to reduce the flow of heat -23- 1297706, the heating efficiency can be improved. Further, it is also possible to use a method of adjusting the air balance and the strength to adjust the pressure in the heat treatment oven while ensuring the air volume to suppress the heat flow leakage. In addition, for the heating which is still limited by the hot air heating method, it is also preferable to adopt the method of adding an infrared heater in the strong heating section. In addition to this, it is also effective to increase the amount of heating by increasing the length of the heat-fixing section and the number of sections. The polyester film for molding of the present invention has a storage viscoelastic modulus (E') in the longitudinal direction and the width direction of the film of 10 to 1, 〇〇〇MPa, and 180 ° C at 100 ° C. It is 5 to 40 MPa. In order to achieve such a storage viscoelastic modulus (E'), it is important to control the surface orientation of the film to a specific range when a biaxially stretched film containing the copolymerized polyester is produced as a substrate. In other words, it is preferred to suppress the degree of orientation of the film to less than 0.095, particularly preferably from 0.001 to 0.090. Thus, the degree of orientation of the face is suppressed, whereby the storage viscoelastic modulus (E') of the film can be suppressed. However, simply by lowering the orientation of the film, the storage viscoelastic modulus (E') of the film at 180 °C will become too small. However, a copolymerized polyester having a branched aliphatic diol and/or an alicyclic diol as a copolymerization component in a preferred embodiment of the present invention is used as a film raw material, whereby the diol can be used. Molecular structure bulkiness to inhibit molecular motility at high temperatures, and can be controlled as described above at 18 (TC film) by using a synergistic effect produced by a specific extension condition capable of suppressing the degree of orientation of the film. The storage viscoelastic modulus (E') is in the range as described above. Further, the effect of 1,3-propanediol or 1,4-butanediol exemplified as a preferred embodiment may be due to introduction of the component. , such that the microcrystals are formed in the copolymerized polyester molecule to exhibit an effect of suppressing -24,297,706 which the storage viscoelastic modulus (E') at 180 ° C becomes too small. " It is one of the preferred embodiments to set the plane orientation of the biaxially oriented polyester film to a low level as described above. However, the method for attaching the characteristic is not particularly limited and can be arbitrarily employed. In general, Although the method of reducing the plane orientation is known to have a reduced delay The method of magnification and the method of increasing the heat setting temperature, but it is not preferable because the former method causes the thickness of the film to deteriorate. Therefore, the latter method is preferable. Although the latter method causes the above problem, it can be implemented as The method exemplified in the mode is avoided. In addition, in the present invention, the biaxially oriented polyester film system must use a copolymerized polyester, because the melting point is lower than that of the homopolymer, and the film is raised at a heat setting temperature. It will be easily melted and attached to the jig for holding the film in the lateral stretching process. Therefore, it is important to sufficiently cool the vicinity of the jig when the tenter exit jig is about to open the film. Specifically, to prevent melting of the film and the jig Adhesion, the preferred countermeasure is to use the following methods: (1) a method of providing a heat shielding wall in the clamp portion to make the fixture not easily heated; (2) a method of adding a fixture cooling device to the tenter; (3) In order to enhance the cooling capacity, the cooling section after heat setting is lengthened to fully implement the method of cooling the entire membrane; (4) increasing the length and division of the cooling section a method for increasing the cooling efficiency; and (5) a method of using a clamp return portion to walk outside the oven to enhance the cooling of the jig, etc. Further, in the present invention, it is preferred that the substrate film has a wavelength of 350 The light transmittance below nanometer is preferably less than 1%, more preferably 0.8% or less, and particularly preferably 0.6% or less. By imparting this property, the polyester film for forming can be improved - 25-1297706' The light resistance of the printed layer at the time of printing is applied to the film. The light transmittance of the wavelength of 35 〇 ' 米 or less is not particularly limited, and may be arbitrarily selected, but it is recommended for molding. A method of mixing the ultraviolet absorber with any one of the polyester film structural layers. The purple wire absorbent which can be used in the method is not particularly limited as long as it can impart the characteristics as described above, and may be appropriately selected. Any of inorganic or organic systems can be used. The organic ultraviolet absorber includes a benzotriazole system, a benzophenone system, a cyclic imido ester system, and the like, and combinations thereof. From the viewpoint of heat resistance, a benzotriazole-based or cyclic imido ester system is preferred.倂 When two or more types of UV absorbers are used, the UV absorption effect can be further improved by absorbing ultraviolet rays of various wavelengths at the same time. The benzotriazole-based ultraviolet absorber includes, for example, 2-[ 2'-hydroxy-5'-(methacryloxymethyl)phenyl]-2H-benzotriazole, 2-[2,- Hydroxy-5,-(methacryloxyethyl)phenyl]-2H-benzotriazole, 2-[ 2'-hydroxy-5'-(methacryloxypropyl)phenyl] -2H-benzotriazole, 2-[2,-hydroxy-5,-(methacryloxylhexyl)phenyl]-2H-benzotriazole, 2-[2,-hydroxy-3,- Third butyl-5,-(methacryloxyethyl)phenyl]-2H-benzotriazole, 2-[2,-hydroxy-5-t-butyl-3'-(methyl Acetone oxyethyl)phenyl]-2H-benzotriazole, 2-[2,-hydroxy-5,-(methacryloxyethyl)phenyl]-5-chloro-2H- Benzotriazole, 2-[2,-hydroxy-5,-(methacryloxyethyl)phenyl]-5-methoxy-2H-benzotriazole, 2-[2,-hydroxyl - 5,-(methacryloxyethyl)phenyl]-5-cyano-2H-benzotriazole, 2-[2,-hydroxy-5'-(methacryloxyethyl) Phenyl] tert-butyl-21 benzene-26 - 1297706 and triazole, 2, [ 2 '-hydroxy-5'-(methyl propyl Acyl oxy ethyl) -5-nitro-phenyl] -2H- benzotriazole and the like, but " is not limited to such. The cyclic imine-based ultraviolet absorber includes, for example, 2, 2'-(1,4-phenylene)bis(4H-3,1-benzoxanthone-4-one), 2-methyl group. -3, 1-benzoxanthene-4-one 4,2-butyl-3, 1-benzoxanthene-4-one, 2-phenyl-3,1-benzoxanthene-4-one , 2-(1- or 2-naphthyl)-3, 1-benzoxanthene-4-one, 2-(4-biphenyl)-3,1-benzoxanthene-4-one, 2 -p-Nitrophenyl-3,1-benzoxanthene-4-one, 2-m-nitrophenyl-3, 1-benzoxanth-4-one, 2-p-benzonitrile Phenyl-3,1-benzoxanthene-4-one, 2-p-methoxyphenyl-3,1-benzoxanth-4-one, 2-o-methoxyphenyl- 3, 1-benzoxanth-4-one, 2-cyclohexyl-3, 1-benzoxanthene-4-one, 2-p-(or m-)phthalic acid imide phenyl- 3,1-benzoxanthene-4-one, 2, 2'-(1,4-phenylene) bis(4H-3, benzoxanthone-4-one) 2,2'-double (3,1-benzoxanth-4-one), 2,2'-extended ethyl bis(3,1-benzoxanthene-4-one), 2,2'-tetramethylene double ( 3,1-benzoxanthene-4-one), 2,2'-decamethylenebis(3,1-benzoxanthene-4-one), 2,2'-p-phenylene (3, 1-Benzene Esophage-4-ke), 2, 2'-m-phenylphenyl (3,1-benzoxanth-4-one), 2,2'-(4,4, diphenyl) (3,1-benzoxanthene-4-one), 2, 2, (2,6- or 1,5-naphthalene)bis(3,1-benzoxanthene-4-one), 2, 2 '- (2-Methyl-p-phenylene) bis(3,1-benzoxanthene-4-one), 2,2,-(2-nitro-p-phenylene) bis (3) , 1-benzoxanthene-4-one), 2,2,-(2-chloro-p-phenylene)bis(3,1-benzoxanthene-4-one), 2,2'- (1,4-cyclohexyl) bis(3,1-benzoxanthene-4-one) 1,3,5,-tris(3,1-benzoxanthone-4-one-2-yl Benzene, 1,3,5,-tris(3,1-benzoxanthene-4-one-2-yl)naphthalene-27- 1297706, and 2,4,6-tris(3,1-benzo) Odoza-4-keto-2-yl)naphthalene, 2,8-dimethyl*yl-4H,6H-benzo(1,2-d; 5,4-d,)* bis-(1,3) - oxalic acid-4,6-dione, 2,7-dimethyl-4H,9H-benzo(1,2-d; 5,4-d') bis-(1,3)-caca-trap 4,9-dione, 2,8-diphenyl-4H, 8H-benzo (1,2-d; 5, « * 4-d,) bis-(1,3)-oxo 4, 6-diketone, 2, 7-diphenyl-4H, 9H-benzo (1, 2-d; 5 4-d') bis-(1,3)-caustic-4,6-dione, 6,6, bis(2-methyl-4H,3,1-benzoxanthene-4-one), 6,6'·-bis(2-ethyl-4H,3,1-benzoxanthene-4-one), 6,6'-bis(2-phenyl-4H,3,1-benzaldehyde Till-4-keto), 6,6'-methylenebis(2-methyl-4H,3,1-benzoxanthene-4-one), 6,6'-methylenebis(2- Phenyl-4H,3,1-benzoxanthene-4-one), 6,6, extended ethyl bis(2-methyl-4H,3,1-benzoxanthene-4-one), 6 , 6'-extended ethyl bis(2-phenyl-4H,3,1-benzoxanthene-4-one), 6,6'-extended* butylbis(2-methyl-4H, 3, 1-benzoxanthene-4-one), 6,6'-butylbutyl bis(2-phenyl-4H, 3,1-benzoxanthene-4-one), 6,6'-oxyl Bis(2-methyl-4H,3,1-benzoxanthene-4-one), 6,6'-oxybis(2-phenyl-4H, 3,1-benzoxanthene-4-嗣), 6,6'-extended bis(2-methyl-4H,3,1-benzoaceto-4-one), 6,6'-sulfonyl bis(2-phenyl-4H) , 3,1-benzo-b-oxan-4-one), 6,6'-carbonylbis(2-methyl-4H,3,1-benzo-b-butan-4-one), 6,6 -Carbohydrazide bis(2-phenyl-4H, 3, benzoxanthene-4-one), 7,7-methylenebis(2-methyl-411,3,:1-benzoxanth-4-one), 7,7'- Methylene bis(2-phenyl-4H,3,1-benzoxanthene-4-one), 7,7'-bis(2-methyl-4H,3,1-benzoindole-4 -ketone), 7,7'-extended ethyl bis(2-methyl-411,3,1-benzoaceto-4-one), 7,7'-oxybis(2-methyl-411 , 3, benzoxanthone-4-one), 7,7'-sulfonyl bis(2-methyl-4H,3,1-benzo-28- 1297706 oxaso-4-ketone), 7 , 7'-carbonyl bis(2-methyl-4H,3,1-benzoxanthine-cardinone), 46,7, bis(2-methyl-4H,3,1-benzoxanthine D# -4 -keto), 6,7'-bis(2-phenyl-4H,3,1-benzoxanth-4-one), 6,7'-methylenebis(2-methyl-4H, 3 , 1-benzoxanthene-4-one) and 6,7'-methylenebis(2-benzene 4*yl-4H,3,1-benzoxanthene-4-one). When the organic ultraviolet absorber is mixed into the film as described above, since the extrusion process is exposed to a high temperature, the ultraviolet absorber should use ultraviolet rays having a decomposition start temperature of 290 ° C or more in reducing process contamination at the time of film formation. Absorbent. When a UV absorber having a decomposition start temperature of 290 ° C or less is used, the decomposition product of the ultraviolet absorber adheres to the roller group or the like during film formation, and is attached to the film to cause damage to the optical defect, so that it cannot be used. . The inorganic ultraviolet absorber is an ultrafine particle of a metal oxide such as cerium oxide, zinc oxide or titanium oxide. Another method for suppressing the light transmittance of the wavelength of 350 nm or less to be 1% or less is to use a compound for forming a polyester such as naphthalene dicarboxylic acid having absorption in the wavelength region as a polyester. The method of polymerizing components. As described above, as long as the polyester film for molding of the present invention is used, a molding method such as vacuum forming or air pressure molding which is difficult to form by orienting the polyester film in the prior biaxial direction can be obtained. These molding methods are those in which the molding pressure at the time of molding requires a pressure of 10 or less. Moreover, since these forming methods are inexpensive to form, they are in an advantageous position in the economics of manufacturing a molded article. Therefore, the characteristics of the polyester film for molding of the present invention can be most effectively exerted by applying these molding methods. -29- 1297706 On the other hand, the mold forming method, although its metal mold or forming device is expensive, is economically disadvantageous, but it can be formed with high precision, for example, the forming method described above is a complicated shape. Molded product. Therefore, when the molding polyester film which is used in the present invention is used for mold forming, it is possible to exhibit a comparatively biaxially oriented polyester film which can be formed at a lower temperature and It can improve the remarkable effect of the finished product of the molded article. Further, when the molded article thus formed is used in a normal temperature atmosphere, it has excellent elasticity and form stability (heat shrinkage characteristics, uneven thickness), plus superior solvent resistance or heat resistance, and environmental resistance. Since the load is also small, it can be suitably used as a molded member such as a brand name for home appliances, a brand name for automobiles, a fake can, a building material, a decorative panel, a decorative steel plate, and a transfer sheet. Further, the polyester film for molding of the present invention is suitable for molding which is formed by a molding method such as press molding, lamination molding, in-mold molding, deep drawing, or bending molding, in addition to the above-described molding method. material. [Embodiment] The present invention will be described in detail by way of examples. Further, the properties of the film obtained in each of the examples were measured and evaluated by the following methods. (1) Intrinsic viscosity A pellet of 〇·1 gram is accurately weighed and then dissolved in a mixture of 25 ml of phenol/tetrachloroethane = 60/40 (mass ratio), and then an Oswald viscometer is used. Measured at 30 °C. The assay was performed 3 times and the average enthalpy was determined. (2) Thickness unevenness is obtained by taking a continuous strip sample of -30 to 1297706 degrees in the direction of 3 mm in the lateral direction and 5 cm in the longitudinal direction, and then measuring the film thickness continuously (manufactured by Anritz Co., Ltd.) The film thickness was measured and recorded on a recorder, and then the maximum thickness T (Tmax ), the minimum 値 (Tmin ), and the average 値 (Tav ) were determined from the graph, and then the thickness unevenness (%) was determined by the following formula. In addition, the measurement was performed three times and the average enthalpy was determined. In addition, when the length in the lateral direction is less than 3 meters, it is carried out in succession, but the measurement data in the succeeding part is deleted. 〇 Thickness unevenness (%) = [(Tmax - Tmin) / Tav]X 100. (3) Haze According to JIS K7 136, it was measured by a haze meter (made by Nippon Denshoku Industries Co., Ltd., 300 A). The measurement was performed twice and the average enthalpy was determined. (4) Film thickness Using Millitron, three pieces were measured, each of which was 5 points, totaling 15 points, and the average enthalpy was determined. (5) Stress and elongation at break at 100% elongation For the longitudinal direction and the transverse direction of the biaxially stretched film, the sample was cut into a length of 180 mm and a width of 10 mm by a razor. Then, a tensile tester (manufactured by Toyo Seiki Co., Ltd.) was used to stretch the long poetry shape, and the stress (MP) and elongation at break when the elongation was 1% in each direction were obtained from the obtained load-strain curve. ( % ) ° In addition, the measurement was carried out in an atmosphere of 25 ° C with an initial length of 40 mm, a jig pitch of 100 mm, a crosshead speed of 100 mm/min, a -31 to 1297706 recording speed of 200 mm/min, and a load sense. The test was carried out under the conditions of 25 kgf. The assay was performed 1 time and the average enthalpy was used. Further, a tensile test of the same conditions as described above was also carried out under an atmosphere of 100 °C. At this time, the sample was held in an atmosphere of 100 ° C for 30 seconds, and then measured by sinus. The assay was performed 10 times and the average enthalpy was used. (6) Heat shrinkage at 150 °C For the length direction and the transverse direction of the film, strips of lengths of 250 mm and widths of 20 mm were cut out respectively. The two marks are marked at intervals of 200 mm in the longitudinal direction of each sample, and the interval A of the two marks is measured at a tension of 5 gf (tension in the longitudinal direction). Next, one side of each sample of the long test piece was hung in a basket with a load-free clamp, and then placed in a Geer's oven under a 150 ° C atmosphere, and timing was started. After 30 minutes, the basket was taken out from the Gil incubator and left at room temperature for 30 minutes. Next, for each sample, the interval B of the two marks was measured by a vernier gauge at a constant tension of 5 gf in units of 0.25 mm. From the measured intervals A and B, the heat shrinkage rate of each sample at 15 (TC: heat shrinkage rate (%) = [(AB) / A] x 100 was calculated by the following formula. (7) Storage viscoelasticity Modulus (E') Using a dynamic viscoelasticity measuring device (manufactured by IT Measurement and Control Co., Ltd., DVA 225), the length direction of the film was determined to be -32 - 1297706 (MD) and the transverse direction (Ding). Storage at 100 ° C and 180 ° C • Viscoelastic modulus (E'): r (a) Sample width: 5 mm (b) Measurement temperature range: -5 〇 to 2 50 °C ' (c Frequency: 1 〇 Hz * - (d) Heating rate · 5 ° C / min (8) The thermal deformation rate of the film at 175 ° C is measured using a thermomechanical analyzer (TMA SS/100, manufactured by Seiko Instruments Inc.). The dimensional change in the longitudinal direction of the film as a function of temperature was continuously measured under the following conditions to determine the dimensional change of the film in the longitudinal direction at 175 ° C. (a) Sample width mm (b) Measurement temperature range: 30 to 250 ° C (c ) initial load: 49 mN ( 5 gf) (d) heating rate: 5 ° C / min (9) surface orientation (△ P) with sodium D-ray (wavelength 589 nm) as the light source, and Use Abbe folding The refractive index (Nz) in the longitudinal direction, the refractive index (Ny) in the width direction, and the refractive index (Nz) in the thickness direction of the film were measured by the following formula: Δ P = [(Nx + Ny ) / 2 ] - Nz (10) Light transmittance at a wavelength of 350 nm using a spectrophotometer (UV-1200, manufactured by Shimadzu Corporation), measuring the light transmittance in the ultraviolet region of 350 nm. -33- 1297706 (11) Lightfastness The printed sample of the offset printing was placed in the dark box so that the printing surface of the printed sample was placed on the back side and placed in the fluorescent lamp (U-shaped fluorescent lamp FUL9EX, manufactured by Matsushita Electric Co., Ltd.) 3 cm. Then, the light was irradiated continuously for 2,000 hours, and then the color difference (ΔE値) was measured in accordance with JIS Z 8730 according to the color (a*, b*, L*) before and after the light irradiation on the printing surface side. The smaller the color difference (Δ E値), the smaller the color change before and after light irradiation, that is, it means superior light resistance. The light level of the light resistance is less than the color difference (.△ E値). 0.5. In addition, the color difference (Δ E値) is calculated by the following formula: Δ E = /" ( Δ a2 + Δ b2 + Δ L2 ) (12) Formability (a) Vacuum formability After the film is applied with a 5 mm square pattern printing, the infrared heater heated to 5 ° C will be used. After the film was heated for 10 to 15 seconds, vacuum forming was carried out at a mold temperature of 30 to 100 °C. Heating conditions The optimum conditions were selected within this range for each film. The mold was used in the shape of a cup, the opening was 50 mm in diameter, the bottom portion was 40 mm, the depth was 50 mm, and a bend of 0.5 mm in diameter was formed at all corners. The five molded articles vacuum-formed under the optimum conditions were evaluated for formability and finish, and were classified according to the following criteria. Among them, ◎ and 〇 represent the passing, and X represents the failure. -34- 1297706 ◎ · (i) The molded article has no crack, (the radius of curvature of the corner is less than 1 mm, and the printing deviation is less than 0.1 mm' (iii) plus there is no appearance defect equivalent to X ( i) The molded article is not cracked, (ϋ) The radius of curvature of the corner is greater than 1 mm and less than 1.5 mm, and the printing deviation is greater than 〇·1 mm and less than 0.2 mm, (iii) plus no appearance equivalent to X Defective, and belong to the no-problem level of the guest. X: The molded article has a crack, or although it does not break, but meets any of the following items (i) to (iv), (the radius of curvature of the corner Those who are larger than 1.5 mm, (ii) have large wrinkles, have poor appearance, (iii) the film is whitened, and the transparency is lowered, (iv) the printing deviation is greater than 0.2 mm. (b) The air pressure forming property is applied 5 mm to the film. After the square check pattern is printed, the film is heated by an infrared heater heated to 500 ° C for 10 to 15 seconds, and then the air pressure is formed at a mold temperature of 30 to 10 ° C under a pressure of 4 atmospheres. The heating conditions are selected for each film within the range of optimum conditions. The shape is cup type, the opening diameter is 60 mm, the bottom portion is 55 mm, the depth is 50 mm, and a bend of 0.5 mm in diameter is formed at all corners. -35 - 1297706 For the pressure under optimal conditions The formed five molded articles were evaluated for formability and finishability, and were classified according to the following criteria. Among them, ◎ and 〇 represent the pass, and X represents the fail. ® : ( i ) the molded article is not broken, (ii) The radius of curvature of the corner A is less than 1 mm, and the printing deviation is less than 〇.1 mm, (iii) plus the appearance defect which is not equivalent to X. (i) The molded article is not broken, (ϋ) The radius of curvature is greater than 1 mm and less than 1.5 mm, or the printing deviation is greater than 0.1 mm and less than 0.2 mm, (Ui) _ plus there is no appearance defect equivalent to X, and it is a practically problem-free grade. X : Molded article If there is a cracker, or if it is not broken, but it meets any of the following items (i) to (iv), (i) if the radius of curvature of the corner is greater than 1.5 mm, (ϋ) has a large crepe pattern and has a poor appearance. (Hi) The film is whitened, the transparency is reduced, (iv) printed (c) Mold formability After the film is applied for printing, it is heated by contact with a hot plate heated to 100 to 140 ° C for 4 seconds, at a mold temperature of 30 to 70 ° C, and a dwell time. The press forming was carried out for 5 seconds. The heating conditions were selected for each film within the range. The mold was used in the shape of -36 - 1297706 cup, the opening diameter was 50 mm, and the bottom portion was 40 mm. The depth is 30 mm, and a bend of 〇·5 mm in diameter is formed at all corners. The five molded articles molded under the optimum conditions were evaluated for formability and finish, and were classified according to the following criteria. Among them, ◎ and 〇 represent the passing, and X represents the failure. ◎ : ( i) The molded article is not broken, (the radius of curvature of the i〇隅 corner is less than 1 mm, and the printing deviation is less than 0.1 mm, (iii) plus the appearance defect that does not correspond to X〇(i) The molded article has no crack, and the radius of curvature of the (隅) corner is less than 1 mm and greater than 1.5 mm, and the printing deviation is less than 〇.;! mm and greater than 0.2 mm, (iii) plus no appearance equivalent to X Defective X: If the molded product has a crack, or if it does not break, it meets any of the following items (i) to (iv). (i) If the radius of curvature of the corner is greater than 1.5 mm, (ϋ) is large The crepe pattern, the appearance is poor, (iii) the film is whitened, the transparency is decreased, (iv) the printing deviation is greater than 0.2 mm. Solvent resistance The sample is immersed in toluene adjusted to 25 ° C for 30 minutes. The change in appearance before and after immersion was determined by the following criteria using -37-(13) 1297706, and the 〇 is represented by 〇. The haze is measured by the method described above. 〇: The appearance is almost unchanged, and the haze is changed to Less than 1%, X : There is a change in appearance, or the haze is changed to more than 1%. (li) Printing quality 4 will be printed The front film was heat-treated at 90 ° C for 30 minutes, and then 4-color screen printing was carried out. Then, the film on which the printing layer was set was dried at 80 ° C for 30 minutes. The evaluation of the printing quality was not from printing. On the other hand, the film is visually judged from the back surface through the film to visually determine the following print appearance such as clearness, printability, and print deviation. The criterion is that all the points are not problematic, and at least one problem is attached with X. a) Clearness: The printed pattern will not be obscured by the substrate film or the coating layer, b) The printing suitability will not cause poor printing ink transfer: the color unevenness or shedding , c) The printing deviation cannot be judged visually by the printing deviation. Example 1 A terephthalic acid unit having an aromatic dicarboxylic acid component of 100 mol%, an ethylene glycol unit having a diol component of 40 mol%, and a neopentyl glycol unit of 60 mol%. The pellet (A) of the copolymerized polyester having an intrinsic viscosity of 〇·69 dl/g, and an intrinsic viscosity of 〇·69 dl/g, and an average particle diameter of 0.04% by mass (SEM method; scanning) Electron microscopy) was a pellet of the amorphous cerium oxide (B) of -38 to 1297706 1 · 5 μm and dried separately. The granules are then mixed with the diced (B) to form a mass ratio of 25.4. Next, the pelletized mixture was melt extruded from the slit of the T-die at 270 ° C using an extruder, and quenched and cured on a chill roll having a surface temperature of 40 ° C while using The electrostatic application method is such that it is attached to the edge of the chill roll to obtain an amorphous unstretched sheet. The obtained unstretched sheet was extended 3.3 times in the longitudinal direction at 90 ° C between the heating roll and the cooling roll. Next, the uniaxially stretched film is introduced into a tenter, preheated at 120 ° C for 1 〇 second, and then the front half is extended at 110 ° C, and the second half is extended at 10 ° C. 3.9 times. Further, a heat-fixing treatment was applied at 235 ° C while applying a 7% relaxation treatment side to the lateral direction to obtain a biaxially stretched polyester film having a thickness of 100 μm. In addition, in the heat-fixing treatment section, an intermediate section of 2 meters is provided between the extension section, and a far-infrared heater is disposed in the heating section of the heat-fixing section, and each section is The shielding plate is arranged to expand to an extreme position that does not come into contact with the film. The cooling section after heating also strengthens the shielding between the sections, and the clamp return method adopts an external return mode, and a fixture cooling device is provided, and then forced cooling is performed by cold air of 20 ° C to implement the temperature of the tenter exit clamp. It is recommended to prevent the sticking of the fixture below 40 °C. Comparative 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. Comparative example 2

The evaluation of the characteristics of a commercially available A-PET unstretched sheet (made by Toyobo Co., Ltd., PETMAX-39-1297706 (R) A560GE0R, thickness: 200 μm) was carried out. Comparative Example 3 " τ The commercially available polycarbonate unstretched sheet (manufactured by Teijin Chemical Co., Ltd., Panlight Sheet (R) pc 2151, thickness: 200 μm) was evaluated for its performance. Comparative Example 4 The implementation of the acrylic system was not extended. Evaluation of the characteristics of a sheet (Acryplain (R) HBS 006, thickness: 125 μm manufactured by Mitsubishi Chemical Corporation) Example 2 A terephthalic acid unit having an aromatic dicarboxylic acid component of 100 mol%, 70 mol% The ethylene glycol unit as a diol component and the neopentyl glycol unit of 3 〇 mol% are granules (C) of a copolymerized polyester having an intrinsic viscosity of 〇·77 dl/g, and intrinsic viscosity It is 63 dl/g, and contains 0. 04% by mass of an average particle diameter (SEM method) of 1⁄4 μm of amorphous cerium oxide pellet (D), and an intrinsic viscosity of 0.75 dl/g, And containing 0.04% by mass of an amorphous ceria polytrimethylene terephthalate pellet (E) having an average particle diameter (SEM method) of 1.5 μm, and dried separately. Then, the pellet (C) was cut. The pellet (D) and the pellet (E) are mixed to form a mass ratio of 50:1〇:40. Then, the cut is The mixture was melt extruded from a slit of a T-die at 270 ° C using an extruder, and quenched and solidified on a chill roll having a surface temperature of 40 ° C while being adhered to it by electrostatic application. The chilled roll has an amorphous unstretched sheet. The unstretched sheet obtained is extended by 3 to 5 times in the longitudinal direction between the heating roll and the chill roll at 83 ° C. Then, the uniaxially stretched film is introduced into the pull. The web was preheated at 120 -40 - 1297706 °0 for 10 seconds, then the front half was extended at 80 °c, the second half was extended at 750 °C at 75 °c, and the lateral direction was applied 7%. The heat-treated treatment was applied at 200 ° C to obtain a biaxially stretched polyester film having a thickness of 100 μm.

In addition, in the heat-fixing treatment section, an intermediate section of 2 meters is provided between the extension section, and a far-infrared heater is provided in the heating section of the heat-fixing section, and each section is provided. The shielding plate is arranged to expand to an extreme position that does not come into contact with the film. The cooling section after heating also strengthens the shielding between the sections, and the clamp return method adopts an external return mode, and a fixture cooling device is provided, and then forced cooling is performed by cold air of 20 ° C to implement the temperature of the tenter exit clamp. It is recommended to prevent the sticking of the fixture below 40 °C. Example 3 A terephthalic acid unit having an aromatic dicarboxylic acid component of 100 mol%, an ethylene glycol unit having a diol component of 70 mol%, and an I,4-ring of 3 mol%. The hexane dimethanol unit is a granule (F) of a copolymerized polyester having an intrinsic viscosity of 0.71 dl/g, and is mixed with polytrimethylene terephthalate pellet (B) to a mass of 50:50. Than and dry. Then, the pelletized mixture was melt extruded from the slit of the T-die at 270 ° C using an extruder and quenched and solidified on a chill roll having a surface temperature of 40 ° C while using static electricity application. The edge is attached to the edge of the chill roll to obtain an amorphous unstretched sheet. The obtained unstretched sheet was stretched by 3.5 times in the longitudinal direction between the heating roll and the cooling roll. Then, the uniaxially stretched film was introduced into the tenter, and preheated at 10 ° C for 10 seconds. The clock is then extended to the front half at 105 °c, -41 - 1297706 I* to extend the rear half at 3.9 times at 100 °c, and the laterally applied 7% of the flaring treatment edge to 22 (TC applied heat fixation) Treating < to obtain a biaxially stretched polyester film having a thickness of 1 μm. / In addition, in the heat-fixing treatment section, an intermediate section of 2 #m is disposed between the extending section and The Vcr thermal section of the heat-fixing section is provided with a far-infrared heater, and the shielding plate of each section is arranged to be enlarged so as not to contact the extreme position of the film. The cooling section after heating also strengthens the section. Inter-shielding, and the clamp return method is to use external return mode, and set the fixture cooling device, and then use 20 ° C cold air for forced cooling to implement the clamp welding of the tenter exit clamp temperature to less than 40 ° C. Prevent countermeasures. 廿, hinge example 5 In the third embodiment, except for changing the heat setting temperature A biaxially stretched polyester film having a thickness of 185 μm was obtained in the same manner as in Example 3 except for 205 ° C. Example 4 Phenylenediene having an aromatic dicarboxylic acid component of 100 mol% was used. The formic acid unit, 40 mol% of the ethylene glycol unit as the diol component, and 60 mol% of the neopentyl glycol unit are the granules of the copolymerized polyester having an intrinsic viscosity of 0.69 dl/g (A) The polybutylene terephthalate pellet (G) having an intrinsic viscosity of 0.69 dl/g and containing 0.04% by mass of an amorphous ceria having an average particle diameter (SEM method) of 1.5 μm is dried. The pellet (A), the pellet (G), and the benzotriazole-based ultraviolet absorber (I) (manufactured by Ciba Specialty Chemicals Co., Ltd., Chinubin 326) were mixed to have a mass ratio of 25.0 : 74.5 : 0.5. Next, The pelletized mixture was melt extruded from a slit of a τ-type die at 265 ° C using a -42- 1297706 extruder and allowed to rapidly solidify on a chill roll having a surface temperature of 20 ° C while making f An amorphous unstretched sheet is obtained by electrostatic application while being adhered to the edge of the chill roll. The unstretched sheet obtained is added. The heat roller and the cooling roller are extended in the longitudinal direction at 80 ° C. 3 times. Then, the uniaxially stretched film is introduced into the puller 1 'preheating at 95 ° C for 1 〇 second' to make the lateral extension The front half extends 3.8 times at 80 ° C in the rear half of 85 ° C. And the side is applied with a 7% slow processing side to apply a heat setting treatment at 200 ° C to obtain a double shaft with a thickness of 1 μm. Further extending the polyester film. Further, in the heat-fixing treatment section, an intermediate section of 2 meters is provided between the extension section, and a far-infrared heater is provided in the heating section of the heat-fixing section, and The shield plates of each segment are arranged to expand to an extreme position that does not contact the film. The cooling section after heating also strengthens the shielding between the sections, and the clamp return method adopts an external return mode, and a fixture cooling device is provided, and then forced cooling is performed by cold air of 20 ° C to implement the temperature of the tenter exit clamp. It is recommended to prevent the sticking of the fixture from being lower than .40 °C. Comparative Example 6 A biaxially stretched polyester film having a thickness of 100 μm was obtained in the same manner as in Example 4 except that the heat setting temperature was changed to 185 °C. Example 5 (Adjustment of coating liquid) A coating liquid was prepared in an aqueous solution of 40% by mass of isopropyl alcohol so as to contain the following components: a copolymerized polyester having a solid content of 3-15% by mass. -43- 1297706 Resin (Baironarl MD-1250, manufactured by Toyobo Co., Ltd.), 5.85 mass% in terms of solid content - water-soluble urethane resin in which a terminal isocyanate group is polymerized by a hydrophilic group (No.) Erastron 3·3), 0.8% by mass of cerium oxide particles having an average particle diameter of 1.0 μm, and 10·〇 for 10% by mass of the whole resin. 5 micron cerium oxide particles. The prepared coating liquid was then adjusted to pH 6.5 using a 5% by mass sodium hydrogen carbonate solution. Subsequently, it was filtered with a bag filter (manufactured by Sumitomo 3M Co., Ltd., liquid filter bag), and then stirred at 15 ° C for 2 hours in a coating liquid circulation system storage tank. (Production of laminated film) In Example 1, except that the pellet (H) of polyethylene terephthalate was used instead of the pellet (B) of polyethylene terephthalate, the rest was carried out. Example 1 Similarly, an amorphous unstretched sheet was obtained. However, the amount of molten resin extruded was adjusted so that the final film thickness became 188 μm. Then, the obtained unstretched sheet was longitudinally extended 3.3 times between the heating roll and the cooling roll at 90 °C. Then, the coating liquid was applied to one surface of the uniaxially stretched film so that the thickness of the solid portion of the resin before stretching was 〇·9 μm by a reverse roll 舐 method. Then, the laminated film having the coating layer is introduced into the tenter by a dry edge, preheated at 120 ° C for 1 〇 second, and then the lateral half is extended at 85 ° C, and the second half is at 1 〇〇. It extends 3.9 times at °C. Further, a heat-fixing treatment was applied at 235 ° C while applying a 7% relaxation treatment to the lateral direction to obtain a biaxially stretched polyester film having a thickness of 100 μm. In addition, in the heat-fixing treatment section, an intermediate section of 2 meters is provided between the extension section, and in the heating section of the heat-fixing section, a far-red-44-1297706 external heater is set and The shield of each segment is arranged to expand to an extreme position that does not contact the film. The cooling section after heating also strengthens the shielding between the sections, and the clamp return method adopts an external return mode, and a fixture cooling device is provided, and then 201: cold air is used for forced cooling to implement temperature suppression of the tenter exit jig. It is a measure to prevent sticking of the fixture below 40 °C. In addition to the hinge example 7, dimethyl terephthalate and ethylene glycol were added, and manganese acetate (M) and antimony trioxide as catalysts, phosphoric acid (P) as an additive, and average particle diameter (SEM method) were added. For the wet cerium oxide (0·08 mass%) of 1.5 μm, polyethylene terephthalate was polymerized by a predetermined method to obtain a pellet of polyethylene terephthalate (PET). ). The pelletized (J) of the obtained PET had an intrinsic viscosity of 0.65 dl/g, a carboxyl end group concentration of 25 eq/ton, and a Μ/P molar ratio of 2.5 〇. The pellet (1) of the above PET was subjected to 180 ° C. After drying for 4 hours, it was supplied to a melt extruder, extruded in a crack-like die, adhered to a mirror cooling drum by electrostatic application (3.0 kV), and solidified by cooling to form an unstretched sheet. The unstretched sheet was first stretched 3.0 times in the longitudinal direction at a roll heated at 10 ° C, and then extended at a temperature of 125 ° C for 3.2 times in the width direction, and then 6% relaxation in the width direction of 195 t, 6 The heat treatment was performed for a second time to obtain a biaxially stretched polyester film having a thickness of 100 μm and a face orientation of 0.138. Further, Comparative Example 7 is an additional experiment of Example 1 of JP-A-2001-347565, and an experiment compared with the prior art was carried out. With respect to Examples 1 to 5 and Comparative Examples 1, 5, 6, and 7, the raw material composition and polymer characteristics of the polymer used are shown in Table 1, and the conditions and characteristics of the film production - 45 - 1297706 are shown in the table. 2 to 5. Further, the film characteristics of Comparative Examples 2 to 4 are shown in Table 6. "The biaxially oriented polyester film obtained in the first to fifth embodiments can be molded by a vacuum forming method or a pneumatic forming method having a low molding pressure at the time of molding, and a molded article having excellent finishability can be obtained. The obtained molded article was also excellent in solvent resistance or dimensional stability. On the other hand, the film obtained in Example 4 had a light transmittance of ultraviolet rays in a wavelength of 350 nm due to the inclusion of an ultraviolet absorber. 0.6%, and the chromatic aberration on the side of the printing surface before and after the irradiation of light for 2,000 hours was less than 0.5, so the color difference was smaller than that of the film obtained by the Examples 1 to 3, and the light resistance was excellent. The film ratio was superior to that of the film obtained in Example 1 containing cerium oxide particles in the base film. In contrast, the films obtained by Comparative Examples 1, 5, 6 and 7 were vacuum-formed. The formability in the engraving method or the air pressure molding method is inferior and the finishing property of the molded article is not good. Moreover, the film obtained by the above Comparative Examples is formed in the mold shape in the form of the film obtained in Examples 1 to 4. Fine addition In addition, the unstretched sheets of Comparative Examples 2 to 4 have poor formability, but are inferior in solvent resistance or dimensional stability. [Industrial Applicability] Since the ester film has excellent moldability at the time of press molding, and particularly moldability at a low temperature and a low pressure, it can be applied to a wide-flow molding method, and when used as a molded article in a normal temperature atmosphere. It has excellent elasticity and shape stability (heat shrinkage characteristics, thickness unevenness), plus superior solvent resistance or heat resistance, and has the advantage of -46-1297706 for less environmental load. In the print-improving layer of the above film, various printing and decoration methods such as relief printing, gravure printing, lithographic printing, screen printing, offset printing, gravure printing, inkjet printing, flexographic printing, and the like are used. , transfer, painting, plating, evaporation, sputtering, cvb, lamination, etc., applying new patterns such as printing layers, pattern layers, etc., by mold forming, air pressure forming, true Various molding methods such as forming are suitable for the three-dimensional decorative method of molding, and are excellent in the in-mold forming method or the embossing forming method. They are suitable for use as appliances for household appliances and automobiles, and members for building materials. Concentration of the boundary. -47- 1297706 Intrinsic viscosity of polymer properties (dl/g) 0.69 0.69 QJT 0.63 0.75 0.71 0.69 0.69 0.65 1 Particle 1 Si02 content (ppm) 1 400 * 1 oo 400 1 oo 1 og Composition of polyester (Mole%) diol component 〇1 1 1 1 ! 1 o rH 1 1 〇1 1 1 1 o 1—i 1 1 馨1 CHDM 1 1 1 1 I 1 1 1 NPG 1 1 1 1 1 1 1 〇 〇rH oo fH 1 o 1 oo 100 acid component TPA 〇Ο rH oo 〇o 100 100 oooo 100 copolymerized PEs (1) PET (1) copolymerized PEs (2) PET (2) PTT copolymerized PEs (3) PBT PET (3) PET (4) < 〇Q w CD K Η-»' 1297706

Table 2 Example 1 Comparative Example 1 Example; Mass ratio of raw materials A copolymerized PEs (1) 25 25 - C Copolymerized PEs (2) - - 50 F Copolymerized PEs (3) - - - B PET (1) 75 75 -1 D PET (2) - - 10 Η PET t3) - - Ε PTT - - 40 G PBT - - - . Film forming conditions Longitudinal extension temperature (°C) 90 90 83 Extension ratio (-) 3.3 3.3 3.5 Pre-service in the horizontal direction 120 120 95 Warm-up time (seconds) 10 10 10 The first half of the extension temperature (.〇110 110 80 The second half of the extension temperature (.〇100 100 75 Extension ratio (1) 3.9 3.9 3.9 Relaxation rate (%) 7 7 7 Overall mmmmco 235 205 200 Membrane characteristic thickness (micron) 100 100 100 1 Haze (%) 3.6 3.6 3.7 Tm (°C) 230 230 215 Orientation degree 0.078 0.11 0.035 F100 (MPa) MD/TD (25〇C) 80 /85 110/120 70/75 MD/TD (100°C) 30/30 70/75 25/25 E, (MPa) MD/TD (100°C) 250/250 1,050/ 1,100 90/90 MD /TD (180°C) 30/30 60/60 15/15 TE (%) MD/TD (100°C) 350/330 230/240 330/330 Thermal deformation rate (%) at 175°C: MD 1 ·0 1.5 1.5 Thermal shrinkage (%) MD/TD (150°C) 1.5/0.6 2.3/1.2 1.8/0.9 Thickness not Uniform J f (%) 5.5 5.1 4.9 Light pass rate (%) at a wavelength of 350 nm 75 75 75 Vacuum formability 〇X 〇Air pressure formability 〇X ◎ Mold formability ◎ 0 ◎ Solvent resistance 〇〇. 〇Print quality XXX -49- 1297706 Table 3

Example 3 Comparative Example 5 Example 4 Comparative Example 6 Mass ratio of raw materials A copolymerized PEs (1) - - 25.0 25.0 B PET (1) 50 50 - - C Copolymerized PEs (2) - - - - D PET (2) - -- - - - E PTT • - _ - F Copolymerized PEs (3) * 50 50 - Ju G PBT - - 74.5 74.5 I uv absorber - - 0.5 0.5 Film forming conditions Longitudinal extension temperature rc) 90 90 80 80 Extension ratio (-) 3.5 3.5 3.3 3.3 Horizontal preheating temperature rc) 120 120 95 95 Preheating time (seconds) 10 10 10 10 Extension temperature first half (.〇105 105 85 85 Extension temperature second half (.C) 100 100 80 80 Extension ratio (:) 3.9 3.9 3.8 3.8 Relaxation rate (%) 7 7 7 7 Total heat treatment temperature (.C) 220 205 200 185 Membrane characteristic thickness (micron) 100 100 100 100 Haze (%) 3.9 3.9 3.2 3.2 Tm(°c) 230 230 200 200 Surface orientation. 0.082 0.11 0.085 0.12 F100 (MPa) MD/TD (25〇C) 80/80 110/110 70/80 105/110 MD/TD (100°C) 30/25 70/75 25/25 70/75 E, (MPa) MD/TD (100°C) 300/300 1,100/ 1,100 250/250 1,000/ 1,050 MD/TD (180°C) 35/35 70/ 70 30/30 60/60 TE (%) MD/TD (100° C) 330/330 250/240 330/330 250/250 175〇C thermal deformation rate (%): MD 1.0 1.0 2.0 2.0 Thermal shrinkage (%) MD/TD (150°C) 1.9/1.0 2.4/1.2 2.1/1.0 2.6/1.3 Uneven thickness jt (%) 5.7 5.3 5.7 4.6 Light transmittance at a wavelength of 350 nm (%) 75 75 0.6 0.6 Vacuum formability 〇X 〇X Air pressure formability ___ 〇X ◎ X Mold formability ◎ 〇◎ 0 Solvent resistance 〇〇〇〇 Printing quality XXXX 50- 1297706 Table 4 Implementation carving 1 Example 5 Raw material mass ratio A Copolymerized PEs (1) 25 25 B PET (1) 75 - Η PET (3) - 75 Film forming conditions Longitudinal extension temperature (°C) 90 90 Extension ratio (-) 3.3 3.3 Horizontal preheating temperature CC) 120 120 Preheating time (seconds) 10 10 Extension temperature first half α) 110 110 Extension temperature second half ( . C) 100 100 Extension ratio (1) 3.9 3.9 Relaxation rate (%) 7 7 Whole heat treatment Brewing α) 235 205 Particle content Substrate film SiO 2 (1.5 μm) 0.03% - Coating layer - Si02 (1·0 μm) 0.05% Si02 (0·05 micron) 10% Membrane characteristic thickness (micron) 100 188 Haze (%) 3.6 1.0 Haze/thickness 0.036 0.005 Tm (°C) 230 230 Orientation degree 0.078 0.078 F100 (MPa) MD/TD (25 〇C) 80/85 85/85 MD/TD (100°C) 30/30 30/30 E, (MPa) MD/TD (100°C) 250/250 250/250 MD/TD (180°C) 30/30 30/30 TE (%) MD/TD (100°C) 350/330 350/330 Thermal deformation rate (%) at 175 °C: MD 1.0 1.0 Thermal shrinkage (%) MD/TD (150° C) 1.5/0.6 1.5/0.6 Uneven thickness J 荽 (%) 5.5 5.5 Light transmittance at a wavelength of 350 nm (%) 75 75 Vacuum formability 〇〇 Air pressure formability 〇〇 Mold formability ◎ ◎ Solvent resistance 〇〇 Printing Quality X 〇-51- 1297706 Table 5

Compare the mass ratio of the 7 raw materials to J PET (4) 100 Film forming conditions The longitudinal preheating temperature (°C) 105 Preheating time (seconds) 7 Extension temperature (.C) Ϊ05 — Extension ratio (1) 3.0 Transverse surface Degree rc) 115 Warm-up time (seconds) 6 Extension temperature rc) 125 Extension ratio (1) 3.2 Relaxation rate (%) 6 Overall heat treatment filling 195 Film characteristic thickness (micron) 100 Haze (%) 13 Haze/thickness 0.13 Tm(°c) 256 face orientation 0.138 F100 (MPa) MD/TD (25°〇125/135 MD/TD (100°C) 75/75 E, (MPa) MD/TD (100°C) 1100/ 110 MD/TD (180°C) 70/70 TE (%) MD/TD (100°C) 240/230 175°C thermal deformation rate (%): MD 0.5 heat shrinkage (%) MD/TD ( 150°C) 1.5/0.3 Uneven thickness J t (%) 14 Light lapse rate (%) at a wavelength of 350 nm 78 Vacuum formability X Air pressure formability X 顚 Formability Δ Solvent resistance 〇 Print quality X -52- 1297706 Table 6 Comparative Example 2 Comparative Example 3 Comparative collar 4 Thickness (-micron) 200 200 125 F100 (MPa) MD/TD (25〇C) 55/55 70/70 - MD/TD (100 °C) 2/2 35 /35 11/11 E, (MPa) MD/TD (100°C) 20/20 1 , 800/1, 800 1,000/1,000 MD/TD (180°C) 10/10 6/6 2/2 175°C thermal deformation rate (%): MD ^ 10 ^ 10 k 10 Light transmittance at 350 nm (%) 78 0 0 Vacuum formability ◎ 〇〇Air pressure formability ◎ 〇0 Mold formability ◎ ◎ ◎ Solvent resistance XXX _J quality X 〇〇 [Simple description of the drawing]: None-53-

Claims (1)

1297706 No. 93 1 2630 No. 1 "Polyester film for forming" patent (amended on March 26, 2007) X. Patent application scope 1. A polyester film for forming characterized by copolymerizing polyester and homopolymerization A polyester film for forming comprising a biaxially oriented polyester film having a melting point of 200 to 245 ° C as a raw material, wherein the copolymerized polyester is composed of 100 mol% of an aromatic dicarboxylic acid component, and contains A glycol component of at least one of ethylene glycol and a branched aliphatic diol or an alicyclic diol, and has an intrinsic viscosity of 0.50 to 1.0 dl/g, and the polyester is selected from the group consisting of poly(pairs). At least one of ethylene phthalate, polytetramethylene terephthalate, or polybutylene terephthalate, and the length direction and width direction of the biaxially oriented polyester film system (1) The stress at 100% elongation is 10 to 1,000 MPa at 25 ° C and 1 to 100 MPa at 100 ° C, and (2 ) the storage viscoelastic modulus in the longitudinal and width directions of the film ( E' ) is 10 to 1,000 MPa at 100 ° C and 5 to 40 MPa at 180 ° C. (3) Thermal deformation rate of the film in the longitudinal direction (initial load) 49 mN ) is -3 % to + 3 % at 175 °C. 2. The polyester film for forming according to the first aspect of the invention, which is a polyester film for forming formed by laminating a coating layer having a thickness of 0.01 to 5/m on the biaxially oriented polyester film, and a) the biaxially oriented polyester film system does not substantially contain particles, and (b) the coating layer contains at least 1 selected from the group consisting of polyester, polyurethane, 1297706 acrylic polymer or copolymers thereof. The composition of the resin and the particles is composed of (C) the ratio (H/d) of the haze H (%) to the film thickness d (micrometer) of the polyester film for molding is less than 〇.〇1. 3. The polyester film for forming according to the ninth aspect of the invention, wherein the biaxially oriented polyester film is further composed of a UV absorber selected from the group consisting of benzotriene or cyclic imidate, and The light transmittance at a wavelength of 350 nm is less than 1%. 4. The polyester film for forming according to claim 1, wherein the molding polyester film has a system orientation of 0.095 or less. 5. The polyester film for forming according to the first aspect of the invention, wherein the polyester film for forming has a heat shrinkage ratio of 6.0% or less in the longitudinal direction and the transverse direction at 150 °C. 6. A method for producing a polyester film for forming, characterized in that a mixture of a copolymerized polyester and a homopolyester is used as a raw material, and the raw material is dried and supplied to a melt press, and extruded into a sheet from a slit die. a method of preparing a polyester film for forming, which is obtained by adhering to a casting drum, and cooling and solidifying the unstretched sheet by biaxial stretching and heat setting, and having a melting point of 200 to 24 ° C. The aromatic di-residual acid component of 旲% is composed of a diol component containing at least one of ethylene glycol, a branched aliphatic diol or an alicyclic diol, and has an intrinsic viscosity of 0.50 to 1 . 〇 dl / g, the homopolyester is selected from the group consisting of polyethylene terephthalate, polytetramethylene terephthalate, or polybutylene terephthalate, at least When the film is held by the jig while the film is stretched laterally and heat-fixed, (a) the heat shielding wall is provided in the clamp portion. 1297706 $ &; (b) Method of adding a fixture cooling device to the tenter (c) lengthen the cooling section after the heat-solidification to fully cool the entire membrane Method; (d) increasing the length of the cooling section, the number of segments to increase the cooling efficiency; or (e) using the type of the clamp return portion to walk outside the oven to enhance the fixture cooling method, after cooling the vicinity of the fixture, The film is separated from the jig at the exit of the tenter and a biaxially oriented polyester film is produced, and the following characteristics are satisfied by controlling the heat setting temperature (1) to (3) · (1) length direction and width direction of the film The stress at 100% elongation is 10 to 1,000 MPa at 25 ° C and 1 to 100 MPa at 10 ° C, and (2) storage viscoelasticity in the longitudinal and width directions of the film. The modulus (E') is 10 to 1,000 Å at 100 ° C and 5 to 40 MPa at 180 ° C. (3) The thermal deformation rate at a slight tension in the length direction of the film 'at 175 ° C The time is -3% to + 3 %.