JP2009226745A - Weather resistant polyester film for forming, laminated sheet for forming using the same, and formed member - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a polyester film suited to a weather resistant polyester film for forming, having adequate weatherability and excellent formability. <P>SOLUTION: The weatherability film is formed by laminating a weather resistant coat layer on at least one side of the polyester film, and has average transmissivity in a wavelength range of 350-360 nm of 45% or less. The stress (F100 value) of the film at 100% elongation in lengthwise and widthwise directions at 190°C is 1-60 MPa, and the average transmissivity in the wavelength range of 350-360 nm after 100% elongation treatment at 25°C is 45% or less. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a polyester film and can be suitably used for molding because it is resistant to whitening and yellowing even when used in an environment exposed to ultraviolet rays for a long period of time, exhibits weather resistance, and has low molding stress. The invention relates to a weather-resistant polyester film for molding.

At present, in the field of automobile members, electronic devices, and building materials, a molded member in which an acrylic sheet or a sheet containing a weathering agent in polycarbonate resin is laminated from the viewpoint of weather resistance and moisture resistance (for example, Patent Document 1). See Patent Document 2).
However, in recent years, development of a weather-resistant polyester film for molding excellent in heat resistance, dimensional stability, mechanical properties, chemical resistance, and the like is required for the application.
Moreover, the polyester film which provided the weather resistance to the polyester film is proposed (refer patent document 3). However, the film described in Patent Document 3 is a film for a membrane switch, has poor moldability, has low weather resistance, and cannot be used as a weather-resistant film for molding.
JP-A-9-66537 JP-A-7-137210 JP 2005-193643 A

  An object of the present invention is to eliminate the above-described problems. In other words, it is a polyester film that is suitable for a weathering film for molding that is resistant to whitening and yellowing even when used in an environment such as outdoors exposed to ultraviolet rays for a long time, exhibits excellent weather resistance, and has excellent moldability. The purpose is to provide.

The present invention has the following configuration. That is,
(1) A weather resistant film in which a weather resistant coat layer is laminated on at least one side of a polyester film, and an average transmittance in a wavelength range of 350 to 360 nm is 45% or less,
100% elongation stress (F100 value) in the film longitudinal direction and width direction at 190 ° C. is 1 MPa or more and 60 MPa or less,
And the weather-resistant polyester film for shaping | molding whose average transmittance | permeability of wavelength range 350-360nm after performing 100% expansion | extension processing in 25 degreeC is 45% or less.
(2) initial color tone E1 after 100% elongation treatment at 25 ° C .;
The weatherable polyester film for molding according to (1), wherein the difference (E1-E2) from the color tone E2 after 100% elongation treatment at 25 ° C. and further a weather resistance test is 1.2 or less.
(3) The stress at 100% elongation (F100 value) in the longitudinal direction and the width direction at 190 ° C. after performing the weather resistance test without performing the elongation treatment is 1 to 60 MPa as described in (1) or (2) Weather-resistant polyester film for molding.
(4) The molding according to any one of (1) to (3), wherein the elongation at break in the longitudinal direction and the width direction at 190 ° C. is 150 to 700% after performing a weather resistance test without performing an elongation treatment. Weather-resistant polyester film.
(5) The weatherable polyester film for molding according to any one of (1) to (4), which is used for automobile members, electronic devices, and building materials.
(6) A laminated sheet for molding formed by laminating the weatherable polyester film for molding according to any one of (1) to (5) and a base material for a molded member.
(7) A molded member formed by molding the laminated sheet for molding according to (6).

  The weathering-resistant polyester film for molding of the present invention can be used as a molding film to produce a molded member having excellent weather resistance.

  The molding weather-resistant polyester film of the present invention is required to have an average transmittance of not more than 45% at a wavelength of 350 to 360 nm. If the average transmittance exceeds 45%, yellowing, whitening, and cracks may occur during long-term use. Preferably, it is 40% or less, and most preferably 35% or less. The lower limit is not particularly limited, but 0% is a substantial lower limit.

  In addition, the weather-resistant polyester film for molding of the present invention needs to have a weather-resistant coating layer laminated on at least one surface of the polyester film in order to exhibit excellent weather resistance and moldability. The thickness of the coat layer is not particularly limited, but the thickness of the weather-resistant coat layer is preferably 0.5 to 15 μm. If the thickness of the coat layer is less than 0.5 μm, excellent weather resistance may not be exhibited, and if it exceeds 15 μm, whitening or cracks may occur during molding or the moldability may be reduced. More preferably, the thickness is set to 1 to 10 μm, and more preferably 2 to 8 μm, in terms of flexibility, curling resistance, crack resistance, transparency, mechanical strength, moldability, etc. as a weathering film for molding. Most preferred.

  The term “weather resistance” as used herein means that it absorbs light energy with a wavelength of 350 to 360 nm or less and emits harmless heat energy, phosphorescence and fluorescence through extremely fast energy conversion, and suppresses photoexcitation and photochemical reaction of impurities in the polymer. And having a function of preventing whitening, embrittlement, cracking, yellowing and the like. Weather resistance can be expressed by incorporating a weather resistance agent having a known UV (ultraviolet light) absorption ability into the weather resistance coating layer.

  In the present invention, the method for laminating the weather-resistant coating layer is not particularly limited, but an extrusion laminating method or a melt coating method may be used. However, for example, gravure coating, reverse coating, spraying can be performed at a high-speed thin film coating. A method of laminating by coating, kiss coating, die coating, or metal ring bar coating is preferably used. In addition, as a method of providing the weather-resistant coating layer in-line in the film manufacturing process, a coating containing a weathering agent is uniformly applied using a metalling bar or the like on at least a uniaxially stretched polyester film, and stretched. A method of drying the coating while performing is preferable, and it is preferable to perform a corona treatment before coating.

  The weather-resistant polyester film for molding of the present invention may be a single-layer film or a laminated film of two or more layers of A layer / B layer, or a three-layer laminated film of A layer / B layer / C layer as a base film. It may be. In the case of a three-layer configuration of A layer / B layer / C layer, the polyester constituting the C layer is preferably the same as the polyester constituting the A layer from the viewpoint of economy and productivity. Furthermore, in order to improve economy and productivity, it is preferable to make the laminated thickness of the A layer and the C layer equal.

In the case of a two-layer configuration of A layer / B layer, both sides may be coated with a weathering agent, or may be coated only on one side of either A layer or B layer. It is economically preferable in terms of equipment to coat only one of the weathering agents. Moreover, since it can coat more economically by controlling the coating thickness, this is a preferred embodiment.
The weather-resistant polyester film for molding of the present invention needs to have an average transmittance of 45% or less in a wavelength range of 350 to 360 nm after 100% elongation treatment at 25 ° C. If the average transmittance exceeds 45%, it may cause whitening, yellowing and cracking in an environment where the material is exposed to UV for a long time after molding. More preferably, it is 40% or less, and most preferably 35% or less.

In order that the average transmittance in the wavelength range of 350 to 360 nm after the 100% elongation treatment at 25 ° C. of the weatherable polyester film for molding of the present invention is 45% or less, the weather resistance contained in the weather resistant coat layer It is preferable that the elongation at break in a 25 ° C. environment of the agent is 250% or more. Therefore, the weathering agent is preferably a urethane type. The ionicity of the weathering agent is preferably anionic.
The weatherable polyester film for molding of the present invention has a stress at 100% elongation (F100 value) of 1 MPa or more and 60 MPa or less in the film longitudinal direction and width direction at 190 ° C. from the viewpoint of moldability required at the time of molding the molded member. It is preferable that

  The processing step of the weatherable polyester film for molding includes a step of heat forming such as vacuum forming, pressure forming, plug assist forming after the preheating step using an infrared heater or the like.

  In many cases, the weather-resistant polyester film for molding is laminated and molded on a molding member, and examples of the molding member include thermoplastic resin sheets, metal plates, paper, and wood. Among these, since a thermoplastic resin sheet is preferably used in terms of moldability, it is often molded at about 190 ° C., which is a temperature at which the substrate is easy to mold. For this reason, even as a weather-resistant polyester film for molding, by reducing the molding stress at 190 ° C. to the above-described range, uniform molding becomes possible, and an excellent appearance can be maintained even after molding.

  If the stress at 100% elongation at 190 ° C. (F100 value) is less than 1 MPa, it cannot withstand the tension for film transfer in the preheating step in the molding process, and the film will be deformed and possibly broken. There are cases where it cannot be used as a weather-resistant polyester film for molding. On the other hand, if it exceeds 60 MPa, deformation during thermoforming is insufficient, and it cannot be used as a weatherable polyester film for molding. From the viewpoint of handleability and molding followability, the 100% elongation stress (F100 value) in the film longitudinal direction and width direction at 190 ° C. is preferably 3 to 50 MPa, and most preferably 5 to 30 MPa.

  In addition, since the weatherable polyester film for molding has a complicated shape and can be molded to a high molding magnification, the elongation in the film longitudinal direction and the width direction at 190 ° C. is preferably 150 to 700%. .

  When the elongation is less than 150%, the film may break when molding a molded member having a high molding magnification, and may not be used as a weatherable polyester film for molding. Moreover, the design of a film exceeding 700% is not preferable because it is not economical and may have poor heat resistance. In terms of moldability, heat resistance, and economy, the elongation in the film longitudinal direction and the width direction is preferably 175 to 650%, and most preferably 200 to 600%.

  Here, the stress at 100% elongation (F100 value) and elongation of the film at 190 ° C. in the present invention will be described. The value of the stress at 100% elongation when a film sample cut into a rectangular shape with a test length of 50 mm was preheated for 90 seconds in a thermostatic layer set at 190 ° C. and subjected to a tensile test at a strain rate of 300 mm / min. The elongation at 100% elongation (F100 value) and the elongation of the film when the film broke were taken as the elongation.

  In the weatherable polyester film for molding according to the present invention, the stress and elongation at 100% elongation of the film at 190 ° C. are within the above ranges as follows. It is a condition of 2.5 to 3.5 times at a temperature of ˜130 ° C., and the surface magnification (longitudinal direction draw ratio × width direction draw ratio) is preferably 7 to 11 times. The stretching temperature can be appropriately changed depending on the raw material used, but the higher the stretching temperature, the more preferable the orientation is suppressed. Furthermore, it is preferable to set the heat treatment temperature before stretching to be equal to or higher than the stretching temperature because the orientation is further suppressed. Moreover, in the heat setting process after extending | stretching, it is preferable at the point which relaxes the orientation by extending | stretching by making heat processing temperature high. The preferred temperature range is 200-250 ° C, more preferably 210-245 ° C, most preferably 220-240 ° C. Furthermore, the polyester used preferably comprises a polyethylene terephthalate resin (A) and a polyester resin (B) selected from polybutylene terephthalate resin and / or polytrimethylene terephthalate resin.

  Here, the polyethylene terephthalate resin (A) is a resin having 100 mol% polyethylene terephthalate as a constituent component, or a copolymer component of less than 30 mol%, preferably less than 20 mol%, copolymerized with polyethylene terephthalate. This resin is composed of polyethylene terephthalate (however, diethylene glycol by-product is excluded as a copolymer component). As the copolymerization component to polyethylene terephthalate, 1,2-propanediol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexane Aliphatic dihydroxy compounds such as diol and neopentyl glycol, polyoxyalkylene glycols such as polyethylene glycol, polypropylene glycol and polytetramethylene glycol, alicyclic dihydroxy compounds such as 1,4-cyclohexanedimethanol, bisphenol A, bisphenol S and the like Aromatic dihydroxy compounds, etc., but 1,3-propanediol, 1,4-butanediol, neopentyl glycol, and 1,4-cyclohexanedimethanol are preferably used in terms of moldability and handleability. It is. Preferred dicarboxylic acid components include aromatic dicarboxylic acids such as 2,6-naphthalenedicarboxylic acid, isophthalic acid, diphenyldicarboxylic acid, diphenylsulfonedicarboxylic acid, diphenoxyethanedicarboxylic acid, 5-sodiumsulfonedicarboxylic acid, and phthalic acid. , Oxalic acid, succinic acid, adipic acid, sebacic acid, dimer acid, maleic acid, fumaric acid and other aliphatic dicarboxylic acids, 1,4-cyclohexanedicarboxylic acid and other alicyclic dicarboxylic acids, paraoxybenzoic acid and other oxycarbons An acid etc. can be mentioned. Examples of dicarboxylic acid ester derivatives include esterified products of the above dicarboxylic acid compounds such as dimethyl terephthalate, diethyl terephthalate, 2-hydroxyethyl methyl terephthalate, dimethyl 2,6-naphthalenedicarboxylate, dimethyl isophthalate, and dimethyl adipate. In addition, diethyl maleate, dimethyl dimer, and the like can be mentioned, but 2,6-naphthalenedicarboxylic acid and isophthalic acid are preferably used in terms of moldability and handleability. The polyethylene terephthalate resin (A) includes a resin (a1) made of 100 mol% polyethylene terephthalate not containing a copolymer component and a polyethylene terephthalate resin (a2) containing less than 20 mol% of a copolymer component. Further, it may be composed of two or more types of polyethylene terephthalate resins. Further, the polyethylene terephthalate resin (a1) may contain less than 30 mol of a copolymer component, and the polyethylene terephthalate resin (A) may be blended with three or more kinds of polyethylene terephthalate resins.

  The polyester-based resin (B) selected from polybutylene terephthalate resin and polytrimethylene terephthalate resin is a resin and / or 100 mol% polytrimethylene terephthalate containing 100 mol% polybutylene terephthalate as a constituent component. Or a polyester obtained by copolymerizing a polybutylene terephthalate and / or polytrimethylene terephthalate with a copolymer component of less than 20 mol%, preferably less than 10 mol%. Alternatively, a polybutylene terephthalate resin and a polytrimethylene terephthalate resin may be mixed and used. Examples of the copolymer component to the polyester resin (B) include ethylene glycol, 1,2-propanediol, 1,3-butanediol, 1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, and the like. Aliphatic dihydroxy compounds, polyoxyalkylene glycols such as polyethylene glycol, polypropylene glycol and polytetramethylene glycol, alicyclic dihydroxy compounds such as 1,4-cyclohexanedimethanol, aromatic dihydroxy compounds such as bisphenol A and bisphenol S, etc. Is mentioned. Preferred dicarboxylic acid components include aromatic dicarboxylic acids such as 2,6-naphthalenedicarboxylic acid, isophthalic acid, diphenyldicarboxylic acid, diphenylsulfonedicarboxylic acid, diphenoxyethanedicarboxylic acid, 5-sodiumsulfonedicarboxylic acid, and phthalic acid. , Oxalic acid, succinic acid, adipic acid, sebacic acid, dimer acid, maleic acid, fumaric acid and other aliphatic dicarboxylic acids, 1,4-cyclohexanedicarboxylic acid and other alicyclic dicarboxylic acids, paraoxybenzoic acid and other oxycarbons An acid etc. can be mentioned. The dicarboxylic acid ester derivatives include esterified products of the above dicarboxylic acid compounds, such as dimethyl terephthalate, diethyl terephthalate, 2-hydroxyethyl methyl terephthalate, dimethyl 2,6-naphthalenedicarboxylate, dimethyl isophthalate, and dimethyl adipate. , Diethyl maleate, dimethyl dimer, and the like.

  From the viewpoints of handleability, moldability, and appearance after molding, the weatherable polyester film for molding of the present invention is composed of 10 to 90 mol% of ethylene glycol residues and 10 to 90 mol% of glycol residue components. It is preferable that 1,4-butanediol residue and / or 0 to 10 mol% is other glycol residue component. From the viewpoint of moldability and transparency, 1,4-cyclohexanedimethanol residue is preferably used as the other glycol component. From the viewpoint of moldability, the 1,4-butanediol residue component and / or the 1,3-propanediol residue component is more preferably 10 to 60 mol%, and particularly preferably 10 to 40 mol%. . The other glycol residue components may be a plurality of glycol residue components, and diethylene glycol residues by-produced in the production stage of polyethylene terephthalate are also included in the other glycol residue components. In order to comprise such a glycol residue component, a polyethylene terephthalate resin (A) and a polybutylene terephthalate resin and / or a polyester resin (B) selected from polytrimethylene terephthalate resin are used. A film made of a polyester resin composition in which 10 to 90% by mass of the resin (A) and 90 to 10% by mass of the resin (B) are mixed based on the whole film is preferable. When the resin (A) exceeds 90% by mass, the effect of improving moldability that is manifested by mixing with the resin (B) is not recognized. Conversely, when the resin (B) exceeds 90% by mass, the crystallization rate of the resin Becomes too fast, the film-forming property, particularly the stretchability is deteriorated, and whitening due to crystallization becomes remarkable. As a mixing ratio of the resin (A) and the resin (B), film formation stability is obtained if the resin (A) is 40 to 90% by mass and the resin (B) is 60 to 10% by mass, based on the entire film. It is more preferable in terms of heat resistance and moldability, and it is particularly preferable if the resin (A) is 60 to 90% by mass and the resin (B) is 40 to 10% by mass.

  Further, the resin (B) is composed of a mixture containing a polybutylene terephthalate resin (b1) and a polytrimethylene terephthalate resin (b2), and is composed of the resin (A), the resin (b1), and the resin (b2). Since orientation and crystallization during stretching are suppressed, molding followability with a molded sheet is improved, which is very preferable. Here, the mixing ratio of the polybutylene terephthalate resin (b1) and the polytrimethylene terephthalate resin (b2) is 10 to 90 mass of the resin (b1) based on the total amount of the resin (b1) and the resin (b2). % And the resin (b2) are preferably mixed at 90 to 10% by mass. More preferably, the resin (b1) is mixed at 30 to 70% by mass and the resin (b2) at 70 to 30% by mass, the resin (b1) is 40 to 60% by mass and the resin (b2) is 60 to 40% by mass. It is particularly preferable if it is mixed in%.

  The molding weather-resistant polyester film of the present invention preferably has a melting point of 210 to 270 ° C. from the viewpoint of heat resistance, dimensional stability and the like. When the melting point is less than 210 ° C., the heat resistance is inferior, and when the thermoforming or the like is performed, the film surface becomes rough due to heat loss, and the appearance may be deteriorated. On the other hand, if the melting point exceeds 270 ° C., the melting point becomes too high and the thermoformability may be inferior. From the viewpoints of both heat resistance and moldability, the melting point is preferably 220 to 265 ° C, and more preferably 246 to 255 ° C. Here, the melting point of the polyester film is an endothermic peak temperature that is manifested by a melting phenomenon when measured with a differential scanning calorimeter (DSC) at a heating rate of 20 ° C./min. When a polyester resin having a different composition is blended and used as a film, a plurality of endothermic peaks due to melting may appear.In this case, the endothermic peak temperature appearing at the highest temperature is the melting point of the polyester film of the present invention. And

  As a method of setting the temperature range to apply the melting point of the polyester film, it is preferable to set the melting point in the range of 210 to 270 ° C. in the polyester resin stage used at the time of film formation, and even when a polyester resin having a different composition is used. In order to suppress a melting point drop due to a transesterification reaction between resins during melt kneading even when using a polyester resin having a melting point of 210 ° C. or higher and blending a polyester resin having a low melting point In order to deactivate the catalyst remaining in the resin in advance or to reduce the catalytic ability, a phosphorus compound is added. Moreover, melting | fusing point can be made into the range of 210-270 degreeC by preparing the polyester resin with a low residual catalyst amount.

  Regarding the polyester resin used in the present invention, commercially available polyethylene terephthalate resin and polybutylene terephthalate resin and copolymers thereof can be purchased and used. For example, in the case of polyethylene terephthalate resin, as follows: Can be polymerized.

  To a mixture of 100 parts by weight of dimethyl terephthalate and 70 parts by weight of ethylene glycol, 0.09 parts by weight of magnesium acetate and 0.03 parts by weight of antimony trioxide are added, the temperature is gradually raised, and finally Performs transesterification while distilling methanol at 220 ° C. Next, 0.020 parts by mass of an 85% aqueous solution of phosphoric acid is added to the transesterification reaction product, and then the mixture is transferred to a polycondensation reaction kettle. The reaction system is gradually depressurized while heating in the polymerization kettle, and a polycondensation reaction is performed at 290 ° C. under a reduced pressure of 1 hPa to obtain a polyethylene terephthalate resin having a desired intrinsic viscosity, for example, an intrinsic viscosity of 0.65. it can.

  Polybutylene terephthalate and polytrimethylene terephthalate can be similarly polymerized. For example, in the case of polybutylene terephthalate, a mixture of 100 parts by mass of terephthalic acid and 110 parts by mass of 1,4-butanediol is added in a nitrogen atmosphere. Then, the mixture is heated to 140 ° C. to obtain a homogeneous solution, and 0.054 parts by mass of tetra-n-butyl orthotitanate and 0.054 parts by mass of monohydroxybutyltin oxide are added to carry out an esterification reaction. Subsequently, 0.066 parts by mass of tetra-n-butyl orthotitanate is added and a polycondensation reaction is performed under reduced pressure to obtain a polybutylene terephthalate resin having a desired intrinsic viscosity, for example, an intrinsic viscosity of 0.9. it can.

  A preferred method for producing the polyester film of the present invention using these resins will be specifically described.

  First, the polyethylene terephthalate-based resin (A) and polybutylene terephthalate-based resin (b1) and / or polytrimethylene terephthalate-based resin (b2) to be used and the pearl pigment master pellet are used at a predetermined ratio, if necessary. Weigh and dry in a nitrogen or vacuum atmosphere before or after mixing. It is preferable that the moisture content in the resin after drying is 50 ppm or less. Then, the mixed polyester resin is supplied to a single screw or twin screw extruder and melt extruded. Next, foreign matter is removed and the amount of extrusion is leveled through a filter and a gear pump, respectively, and discharged from the T die onto a cooling drum in a sheet form. At that time, an electrostatic application method in which the cooling drum and the resin are brought into close contact with each other using an electrode applied with a high voltage, a casting method in which a water film is provided between the casting drum and the extruded polymer sheet, and the casting drum temperature is set to a value of the polyester resin. The sheet-like polymer is brought into close contact with the casting drum, cooled and solidified by a method of adhering the extruded polymer at a glass transition point to (glass transition point−20 ° C.) or a combination of these methods, and unstretched. Get a film. Among these casting methods, when using polyester, a method of applying an electrostatic force is preferably used from the viewpoint of productivity and flatness.

  The polyester film of the present invention exhibits excellent moldability and appearance even when used as unstretched, but by making it a biaxially oriented film, the preheating process during molding, the heat resistance in the molding process, Is preferable because heat resistance and aging resistance after forming a molded member are improved. The biaxially oriented film is obtained by stretching an unstretched film in the longitudinal direction and then stretching in the width direction, or by stretching in the width direction and then stretching in the longitudinal direction, or by the longitudinal direction of the film. It can be obtained by stretching by a simultaneous biaxial stretching method in which the width direction is stretched almost simultaneously.

As a draw ratio in such a drawing method, preferably 2.5 to 3.5 times, more preferably 2.8 to 3.5 times, and particularly preferably 3 to 3.4 times are employed in each direction. The The stretching speed is preferably 1,000 to 200,000% / min. The stretching temperature is preferably 90 to 130 ° C, more preferably 100 to 120 ° C in the longitudinal direction and 90 to 110 ° C in the width direction. Further, the stretching may be performed a plurality of times in each direction.
Moreover, about the method of providing a coating layer, after extending | stretching uniaxially, a coating layer is laminated | stacked in-line. In addition, a method of performing simultaneous biaxial stretching after coating before stretching, or a method of coating after stretching uniaxially in the longitudinal direction and stretching in the width direction can also be used.

  Furthermore, the film is heat-treated after biaxial stretching. The heat treatment can be performed by any conventionally known method such as in an oven or on a heated roll. This heat treatment is performed at a temperature of 120 ° C. or higher and below the melting point of the polyester, but is preferably 200 to 250 ° C. The heat treatment time can be arbitrarily set within a range not deteriorating the characteristics, and is preferably 1 to 60 seconds, more preferably 1 to 30 seconds. Further, the heat treatment may be performed by relaxing the film in the longitudinal direction and / or the width direction. Furthermore, in order to improve the adhesive force with the ink print layer, the adhesive, and the vapor deposition layer, at least one surface can be subjected to corona treatment or a coating layer can be provided.

The weatherable polyester film for molding according to the present invention has an initial color tone E1 after 100% elongation treatment at 25 ° C. and a color tone E2 after 100% elongation treatment at 25 ° C. and further subjected to a weather resistance test. Elongation with a difference (E1-E2) of 1.2 or less is preferable from the viewpoint of flexibility, curl resistance, crack resistance, transparency, mechanical strength, moldability, etc. as a weather-resistant polyester film for molding. .
When the difference between the initial color tone and the color tone after the weather resistance test (E1-E2 value) exceeds 1.2, the film is whitened and yellowed, so it can be used as a weather-resistant polyester film for molding. Is not. More preferably, it is 1.1 or less, and most preferably 1.0 or less. The lower limit is not particularly limited, but since a significant change in color tone is not welcomed, it is preferably −2.0 or more, more preferably −1.0 or more, and even more preferably 0.0 or more. is there.

In order to make E1-E2 value into the said range, it is preferable to laminate | stack the weather resistance coating layer containing the weathering agent mentioned above.
The weatherable polyester film for molding according to the present invention is 100% in the longitudinal direction and the width direction at 190 ° C. after performing a weather resistance test without performing an elongation treatment from the viewpoint of moldability required at the time of molding of the molded member. The stress at elongation (F100 value) is preferably 1 to 60 MPa.

The processing step of the weatherable polyester film for molding includes a step of heat forming such as vacuum forming, pressure forming, plug assist forming after the preheating step using an infrared heater or the like.

  In many cases, the weather-resistant polyester film for molding is laminated and molded on a molding member, and examples of the molding member include thermoplastic resin sheets, metal plates, paper, and wood. Among these, since a thermoplastic resin sheet is preferably used in terms of moldability, it is often molded at about 190 ° C., which is a temperature at which the substrate is easy to mold. For this reason, even as a weather-resistant polyester film for molding, by reducing the molding stress at 190 ° C., uniform molding becomes possible, and an excellent appearance can be maintained even after molding.

  If the stress at 100% elongation at 190 ° C. (F100 value) is less than 1 MPa, it cannot withstand the tension for film transfer in the preheating step in the molding process, and the film will be deformed and possibly broken. In some cases, it may not be used as a weather-resistant polyester film for molding. On the other hand, if it exceeds 60 MPa, deformation during thermoforming is insufficient, and it cannot be used as a weatherable polyester film for molding. From the viewpoint of handleability and molding followability, the 100% elongation stress (F100 value) in the film longitudinal direction and width direction at 190 ° C. is preferably 3 to 50 MPa, and most preferably 5 to 30 MPa.

  Moreover, although the film of this invention may be extended | stretched in a shaping | molding process, the stress distortion at the time of an elongation process may remain in a film after a shaping | molding process. If the film does not have sufficient weather resistance, the film deteriorates and the mechanical strength of the film decreases in an environment where the film is exposed to ultraviolet light for a long time such as outdoors. Then, the film is destroyed from the inside due to the residual stress in the film. In order to prevent such a phenomenon, it is effective to reduce the stress remaining in the film. Specifically, the longitudinal direction and width at 190 ° C. after the weather resistance test is performed without performing the elongation treatment. This can be achieved by setting the stress at 100% elongation in the direction (F100 value) to 1 to 60 MPa.

  In addition, the stress-resistant polyester film for molding of the present invention is subjected to a weather resistance test without being subjected to an elongation treatment, and a stress at 100% elongation in the longitudinal direction and width direction at 190 ° C. (F100 value) is 1 to 60 MPa. For this purpose, it can be achieved by laminating the above-mentioned weather-resistant coat layer on at least one side of the film using the above-described polyester resin.

  The weather-resistant polyester film for molding of the present invention preferably has a breaking elongation of 150 to 700% in the longitudinal direction and the width direction at 190 ° C. after being subjected to a weather resistance test without being subjected to elongation treatment. In terms of moldability, heat resistance, and economy, the elongation in the film longitudinal direction and the width direction is preferably 175 to 650%, and most preferably 200 to 600%.

  Although the film of the present invention may be stretched in the molding process, stress strain (mainly shrinkage stress) during the stretching process may remain in the film even after the molding process. If the film does not have sufficient weather resistance, the film deteriorates and the mechanical strength of the film decreases in an environment where the film is exposed to ultraviolet light for a long time such as outdoors. Then, the film is destroyed from the inside due to the residual stress in the film. In order to prevent such a phenomenon, it is preferable to use a film that can maintain high molding performance (elongation performance) even when exposed to ultraviolet light of the film. Specifically, a weather resistance test is performed without performing an elongation treatment. This can be achieved by setting the elongation at break in the longitudinal direction and the width direction at 190 ° C. to 150 to 700%.

  Moreover, in order to set the elongation at break in the longitudinal direction and the width direction at 190 ° C. after performing the weather resistance test without performing the elongation treatment to 150 to 700%, at least one side of the film using the polyester resin described above This can be achieved by laminating the above-mentioned weather-resistant coat layer. The molding weather-resistant polyester film of the present invention has excellent molding processability, and can easily produce a molded part that follows the mold in thermoforming such as vacuum and pressure molding. Moreover, since it has the outstanding weather resistance, it is preferably used as a use of components, such as building materials, a motor vehicle member, an electronic device, and an electrical product. The molding member used is not particularly limited, but for building materials, for example, wallpaper skin materials, signboards, and automobile members, for example, exterior members such as bumpers and door mirrors, interior members such as center panels and door panels, electronic devices and electrical equipment In products, for example, it is preferably used for mobile phones, personal computers, portable game machines and the like.

  Moreover, although the weather-resistant polyester film for molding of the present invention is preferably used for molding, it is preferably used for insert molding, for example. Insert molding generally refers to a molding method in which a plastic material such as a film is previously set in a mold, and a resin is injected and filled therein. The film itself may be placed in the mold and formed into a desired shape with resin pressure. However, in order to obtain a more complicated shape, the film placed in the mold is vacuum-molded, vacuum-compressed, or plug-assist. A method of pre-molding into a desired shape by molding or the like and filling the shape with resin is preferably used.

  When used for insert molding, an easy-adhesion layer may be provided on the resin-side surface in order to enhance adhesion to the resin to be injection-molded. As the resin for injection molding, polycarbonate, ABS (acrylonitrile-butadiene-styrene), AS (acrylonitrile-styrene), polypropylene, polymethyl methacrylate, TPO (Thermo Plastic Olefin elastomer) or a mixed resin thereof is preferably used. It is preferable that the adhesiveness with the resin is high. Although it does not specifically limit as an easily bonding layer, Polyester type, urethane type, an acrylic type, a chlorinated polypropylene type etc. are mentioned.

When the weather-resistant polyester film for molding of the present invention is used for insert molding, the thickness is preferably 75 to 500 μm, preferably 100 to 300 μm in terms of depth and shape retention of the molded body after molding. If it is more preferable, it is most preferable if it is 100-250 micrometers.
The weathering-resistant polyester film for molding of the present invention is preferably used for molding. For example, it can be used by being bonded to a molding substrate. By bonding to the molding substrate, a molding weather-resistant sheet composed of the molding substrate / molding weather-resistant polyester film is obtained.

  Although it does not specifically limit as a base material for shaping | molding, A resin sheet, a metal plate, paper, wood, etc. are mentioned. Among these, a resin sheet is preferably used in terms of moldability, and a thermoplastic resin sheet is preferably used in terms of high moldability.

  Here, the thermoplastic resin sheet is not particularly limited as long as it is a polymer sheet that can be thermoformed. However, an acrylic sheet, an ABS (acrylonitrile-butadiene-styrene) sheet, a polystyrene sheet, and an AS (acrylonitrile-styrene) sheet. , TPO (Thermo Plastic Olefin elastomer) sheet, TPU (Thermo Plastic Urethane elastomer), etc. are preferably used. The thickness of the sheet is 50 μm to 2000 μm, more preferably 100 μm to 1800 μm, and still more preferably 250 to 1500 μm.

  Moreover, in order to improve the adhesiveness with the shaping | molding base material, it is preferable to provide an adhesive layer in the weathering-resistant polyester film for shaping | molding of this invention. Although it does not specifically limit as an adhesive layer, A polyester type, a urethane type, an acrylic type, a chlorinated polypropylene type etc. are used preferably.

  Although the molding method of the decorative sheet for molding having the above configuration will be specifically described, the molding method is not limited to this.

  The weathering sheet for molding is heated to 150-400 ° C using a far-infrared heater so that the surface temperature becomes 30-200 ° C, the mold is pushed up, and the mold is evacuated to form the desired shape. To do. In the case of molding with a large molding magnification, deeper molding becomes possible by further applying pressure to the sheet and molding. The molded decorative sheet thus formed is trimmed to form a molded member. The molded member may be used as it is. However, in order to give strength as a molded product, TPO, polycarbonate, ABS resin, or the like may be injected into a depressed portion by pressing a mold. In this way, the molded member is completed.

(1) It measured using melting | fusing point differential scanning calorimeter (Seiko Denshi Kogyo make, RDC220). When 5 mg of film is used as a sample and there are multiple endothermic peaks with the endothermic peak temperature at 25 ° C. up to 300 ° C. at 20 ° C./min, the peak temperature of the endothermic peak on the highest temperature side is the melting point. It was.

(2) Intrinsic viscosity of polyester The intrinsic viscosity of the polyester resin and the film was measured at 25 ° C. using an Ostwald viscometer after dissolving the polyester in orthochlorophenol.

(3) Composition of polyester The polyester resin and film were dissolved in hexafluoroisopropanol (HFIP), and the content of each monomer residue and by-product diethylene glycol was quantified using ¹ H-NMR and ¹³ C-NMR.

(4) Average transmittance in the wavelength range of 350 to 360 nm
The film was cut into a square having a length of 30 mm and a width of 30 mm in the longitudinal direction and the width direction to obtain a sample. Measurement was performed using a self-recording spectrophotometer (Hitachi, Ltd. U-3410 type) to obtain a transmittance curve in the wavelength range of 350 to 360 nm, and the average transmittance was obtained. The measurement was performed 5 times for each sample, and the average value was evaluated.

(5) The stress film at 100% elongation at 190 ° C. was cut into a rectangle 150 mm long × 10 mm wide in the longitudinal direction and the width direction, and used as a sample. Using a tensile tester (Orientec Tensilon UCT-100), the tensile test was performed in the longitudinal direction and the width direction of the film at an initial tensile chuck distance of 50 mm and a tensile speed of 300 mm / min. For the measurement, a film sample was set in a constant temperature layer set at 190 ° C. in advance, and a tensile test was performed after preheating for 90 seconds. Read the load applied to the film when the sample is stretched 100% (when the distance between chucks is 100 mm), and divide by the cross-sectional area (film thickness x 10 mm) of the sample before the test. F100 value). The measurement was performed 5 times in each direction, and the average value was evaluated.

(6) Tensile tests were conducted in the longitudinal direction and width direction of the film in the same manner as in elongation (5), and the elongation when the film was broken was defined as the respective elongation. In addition, the measurement was performed 5 times for each sample and each direction, and the average value was evaluated.

(7) The weathering test film was cut into A4 size and used as a sample. Using a weather resistance tester (Iwasaki Electric Co., Ltd. metal halide lamp type eye super UV tester, SUV-W151), a weather resistance test was performed at 60 ° C. × 50% RH for 24 hours.

(8) Color difference (E2-E1)
The film before the weather resistance test and the film after 100% elongation and after the weather resistance test were cut into a rectangle of 150 mm length × 30 mm width in the longitudinal direction and the width direction, and used as samples. The color tone difference of the film was measured using a spectroscopic colorimeter (SE-2000 manufactured by Nippon Denshoku Industries Co., Ltd.). In addition, the measurement was performed 5 times for each sample, and the average value was evaluated.

(9) Molding property To the weathering polyester film for molding according to the present invention, an adhesive mixed with an adhesive AD503 manufactured by Toyo Morton Co., Ltd., a curing agent CAT10, and ethyl acetate at 20: 1: 20 was applied as an adhesive layer. . An ABS sheet having a thickness of 1500 μm was bonded to the adhesive layer, and thermocompression bonding (80 ° C., 0.1 MPa, 3 m / min) was performed using a laminator to prepare a sheet for decorative molding. The molding decorative sheet is heated using a far-infrared heater at 400 ° C. so that the surface temperature becomes 190 ° C., and vacuum forming is performed along a mold (bottom diameter 50 mm) heated to 70 ° C. went. The state of being molded along the mold was evaluated according to the following criteria using the molding degree (drawing ratio: molding height / bottom diameter).
S: Molding was possible at a drawing ratio of 0.5 or more.
A: Molding was possible with a drawing ratio of 0.5 to 0.3.
B: Molding was possible with a drawing ratio of 0.3.
C: Low followability and could not be formed into a shape with a drawing ratio of 0.3. (10) Formability-2
The weather-resistant polyester film for molding of the present invention is heated using a far-infrared heater at 400 ° C. so that the surface temperature becomes 190 ° C., and is heated to 70 ° C. along the mold (bottom diameter 50 mm). Vacuum forming was performed. The state of being molded along the mold was evaluated according to the following criteria using the molding degree (drawing ratio: molding height / bottom diameter).
S: Molding was possible at a drawing ratio of 0.5 or more.
A: Molding was possible with a drawing ratio of 0.5 to 0.3.
B: Molding was possible with a drawing ratio of 0.3.
C: Low followability and could not be formed into a shape with a drawing ratio of 0.3.

(11) An average transmittance film having a wavelength range of 350 to 360 nm after 100% elongation treatment at 25 ° C. was cut into a rectangle having a length of 150 mm and a width of 30 mm in the longitudinal direction and the width direction as a sample. Using a tensile tester (Orientec Tensilon UCT-100), the tensile test was performed in the longitudinal direction and the width direction of the film at an initial tensile chuck distance of 50 mm and a tensile speed of 300 mm / min. For measurement, a film sample is set in a constant temperature layer set at 25 ° C. in advance, a tensile test is performed after 90 seconds of preheating, the test is stopped when the sample is 100% stretched, and 100% stretch treatment is performed at 25 ° C. A sample 1 was obtained.
A rectangular sample having a length of 30 mm and a width of 30 mm was cut out from the sample 1 and used as sample 2. Here, it is assumed that the center of gravity of sample 1 and the center of gravity of sample 2 are matched.
Using this sample 2, the average transmittance was determined in the same manner as in (4).

(12) Stress at 100% elongation (F100 value) at 190 ° C. after performing a weather resistance test without performing elongation treatment
After conducting the weather resistance test of (7), the stress at elongation (F100 value) was determined by the same method as in (5).

(13) After performing a weather resistance test of the elongation at break (7) at 190 ° C. after performing the weather resistance test without performing the elongation treatment, the stress at elongation (F100 value) was determined in the same manner as (6). Asked.

  Below, an example regarding manufacture of the weather-resistant polyester film for shaping | molding of this invention, etc. is described.

(Manufacture of polyester)
The polyester resin used for film formation was prepared as follows.

(PET)
To a mixture of 100 parts by weight of dimethyl terephthalate and 70 parts by weight of ethylene glycol, 0.09 parts by weight of magnesium acetate and 0.03 parts by weight of antimony trioxide are added, the temperature is gradually raised, and finally Conducted transesterification while distilling methanol at 220 ° C. Subsequently, 0.020 part by mass of an 85% aqueous solution of phosphoric acid was added to the transesterification reaction product, and then transferred to a polycondensation reaction kettle. Polyethylene in which the reaction system is gradually depressurized while being heated in a polymerization kettle and subjected to a polycondensation reaction at 290 ° C. under a reduced pressure of 1 hPa, and an intrinsic viscosity of 0.65 and 2 mol% of diethylene glycol as a by-product are copolymerized. A terephthalate resin was obtained.

(Particle master: written as particle M in the table)
When the polyethylene terephthalate is produced, a polycondensation reaction is performed after adding an ethylene glycol slurry of agglomerated silica particles having an average particle size of 2.4 μm after the transesterification reaction, thereby producing a particle master having a particle concentration of 2% by mass in the polymer. did.

(PBT)
A mixture of 100 parts by mass of terephthalic acid and 110 parts by mass of 1,4-butanediol was heated to 140 ° C. under a nitrogen atmosphere to obtain a homogeneous solution, and then 0.054 parts by mass of tetra-n-butyl orthotitanate. Then, 0.054 parts by mass of monohydroxybutyltin oxide was added to carry out an esterification reaction. Next, 0.066 parts by mass of tetra-n-butyl orthotitanate was added and a polycondensation reaction was performed under reduced pressure to prepare a polybutylene terephthalate resin having an intrinsic viscosity of 0.88. Thereafter, crystallization was performed at 140 ° C. in a nitrogen atmosphere, followed by solid phase polymerization at 200 ° C. for 6 hours in a nitrogen atmosphere to obtain a polybutylene terephthalate resin having an intrinsic viscosity of 1.22.

(PTT)
Using 100 parts by weight of dimethyl terephthalate and 80 parts by weight of 1,3-propanediol as a catalyst in a nitrogen atmosphere, the temperature was gradually raised from 140 ° C. to 230 ° C., and the ester exchange reaction was carried out while distilling methanol. went. Further, a polycondensation reaction was carried out for 3 hours under a constant temperature of 250 ° C. to obtain a polytrimethylene terephthalate resin having an intrinsic viscosity [η] of 0.86.

(PET-G)
To a mixture of 100 parts by weight of dimethyl terephthalate, 60 parts by weight of ethylene glycol, and 20 parts by weight of 1,4-cyclohexanedimethanol, 0.04 parts by weight of manganese acetate is added, and the temperature is gradually raised. Transesterification was carried out while distilling methanol at 0 ° C. Next, 0.045 parts by mass of 85% phosphoric acid aqueous solution and 0.01 parts by mass of germanium dioxide were added, and the temperature was gradually raised and reduced. Finally, the temperature was raised to 275 ° C. and 1 hPa, and the intrinsic viscosity was reduced. The polycondensation reaction was carried out until 0.67, and then a strand was discharged, cooled, and cut to obtain a polyethylene terephthalate resin copolymerized with 8 mol% of 1,4-cyclohexanedimethanol. The polymer was cut into cubes having a diameter of 3 mm, and solid phase polymerization was performed using a rotary vacuum polymerization apparatus under a reduced pressure of 1 hPa at 225 ° C. until the intrinsic viscosity was 0.8.

(PET-I)
To a mixture of 82.5 parts by weight of dimethyl terephthalate, 8 parts by weight of dimethyl isophthalate, and 70 parts by weight of ethylene glycol, 0.09 parts by weight of magnesium acetate and 0.03 parts by weight of antimony trioxide are added, The temperature was gradually raised, and finally transesterification was carried out while distilling methanol at 220 ° C. Subsequently, 0.020 parts by mass of an 85% aqueous solution of phosphoric acid was added to the transesterification reaction product, and then transferred to a polycondensation reaction kettle. The reaction system is gradually depressurized while being heated in the polymerization kettle, and the polycondensation reaction is performed at 287 ° C. under a reduced pressure of 1 hPa, and the intrinsic viscosity is 0.7 and by-product diethylene glycol is copolymerized by 2 mol%. An acid 8 mol% copolymerized polyethylene terephthalate resin was obtained.

(Coating 1)
Weathering agent: UX-0823 (manufactured by ADEKA Corporation, urethane system, solid content concentration 32% by weight, solvent: MNP, elongation at break in an environment of 25 ° C .: 275%).

(Coating agent 2)
Weathering agent: UX-537-7 (manufactured by ADEKA Corporation, urethane system, solid content concentration 32% by weight, solvent: MNP, elongation at break in a 25 ° C. environment: 275%).

(Coating agent 3)
Weathering agent: HUX-350 (manufactured by ADEKA Corporation, urethane system, solid content concentration 32% by weight, solvent: MNP, elongation at break in an environment of 25 ° C .: 275%).

(Coating agent 4)
Alpha coat UVHA2-20-1 (manufactured by Alpha Kaken Co., Ltd., acrylic silicon type, solid content concentration 39% by weight, solvent: toluene, butyl acetate, isobutanol).

(Coating 5)
Alpha coat UVHA2-24 (manufactured by Alpha Kaken Co., Ltd., acrylic silicon type, solid content concentration 46%, solvent: xylene, isobutanol).

Example 1
A three-layer film of A / B / A was obtained. As polyester constituting the A layer, PET, PBT and particle master were mixed at a mass ratio of 69: 30: 1. As polyester which comprises B layer, PET and PBT were mixed and used by mass ratio 70:30.
Each mixed polyester resin was individually dried in a vacuum dryer at 180 ° C. for 4 hours, and after sufficiently removing moisture, supplied to separate single screw extruders, melted at 280 ° C., and filtered through separate paths. After removing the foreign matter and leveling the amount of extrusion through the gear pump, A layer / B layer / A layer (see the table for lamination thickness ratio) in the feed block installed on the top of the T die After the lamination, the sheet was discharged from a T die onto a cooling drum whose temperature was controlled at 25 ° C. At that time, a wire-like electrode having a diameter of 0.1 mm was applied electrostatically and adhered to the cooling drum to obtain an unstretched film.

Then, before stretching in the longitudinal direction, the film temperature is raised with a heating roll, the preheating temperature is 110 ° C., the stretching temperature is 105 ° C., the stretching is 3.0 times in the longitudinal direction, and the temperature is immediately controlled to 40 ° C. Cooled with a roll. The uniaxially stretched film was subjected to corona discharge treatment in air, and the treated surface was coated with coating agent 1 as a coating solution using a metal ring bar (# 4). Next, the film was stretched 3.0 times in the width direction at a preheating temperature of 95 ° C. and a stretching temperature of 120 ° C. with a tenter-type transverse stretching machine, and while being relaxed by 4% in the width direction in the tenter, the temperature was maintained at 240 ° C. for 5 seconds. Heat treatment was performed to obtain a biaxially oriented polyester film having a film thickness of 25 μm.
The film showed excellent properties as a weatherable polyester film for molding in the tests (4) to (10). The characteristics and the like are shown in the table (the same applies to other examples and comparative examples).

(Example 2)
A three-layer film of A / B / A was obtained. As polyester constituting the A layer, PET, PBT, PTT and particle master were mixed at a mass ratio of 69: 15: 15: 1. As polyester which comprises B layer, PET, PBT, and PTT were mixed and used by mass ratio 70:15:15. Thereafter, a biaxially oriented polyester film having a film thickness of 25 μm was obtained in the same manner as in Example 1 except that the lamination thickness ratio was changed. This biaxially oriented polyester film is subjected to corona discharge treatment in the air, coated with coating agent 2 using a metering bar (# 26), dried in a hot air dryer at 100 ° C. for 60 seconds, and then coated. A biaxially oriented polyester film in which the layers were laminated was obtained.
The film showed excellent properties as a weatherable polyester film for molding in the tests (4) to (10).

(Example 3)
A three-layer film of A / B / A was obtained. As polyester constituting the A layer, PET, PBT, and particle master were mixed at a mass ratio of 49: 30: 1. As polyester which comprises B layer, PET and PET-G were mixed and used by mass ratio 50:50.
Thereafter, a biaxially oriented polyester film having a film thickness of 20 μm was obtained in the same manner as in Example 1 except that the lamination thickness ratio was changed. A biaxially oriented polyester film having a coating layer laminated thereon was obtained in the same manner as in Example 2 except that this biaxially oriented polyester film was coated with the coating agent 3 as a coating agent.
The film exhibited excellent properties as a weatherable polyester film for molding.

Example 4
It was set as the single layer film. PET, PET-G and particle master were mixed at a mass ratio of 89.2: 10: 0.8.
Thereafter, a biaxially oriented polyester having a film thickness of 25 μm was prepared in the same manner as in Example 1 except that the preheating temperature in the longitudinal direction was 95 ° C., the draw ratio was 3.1 times, and the draw ratio in the width direction was 3.1 times. A film was obtained. A biaxially oriented polyester film having a coating layer laminated thereon was obtained in the same manner as in Example 2 except that this biaxially oriented polyester film was coated with the coating agent 1 as a coating agent.
Although this film had a high F100 value at 190 ° C., its moldability was slightly lowered, but it was at a level that was not a problem as a weather-resistant polyester film for molding.

(Example 5)
A / B two-layer laminated film was obtained. As polyester constituting the A layer, PET, PBT, Pearl B, and particle master were mixed at a mass ratio of 89: 10: 1. As polyester which comprises B layer, PET and PBT were mixed and used by mass ratio 80:20.
Thereafter, a biaxially oriented polyester film having a film thickness of 25 μm was obtained in the same manner as in Example 1 except that the lamination thickness ratio was changed. A biaxially oriented polyester film having a coating layer laminated thereon was obtained in the same manner as in Example 2 except that this biaxially oriented polyester film was coated with the coating agent 6 as a coating agent and used a metal ring bar (# 3). Although the film had a slightly high F100 value at 190 ° C., the moldability was slightly lowered, but the film exhibited excellent characteristics as a weather-resistant polyester film for molding.

(Example 6)
A three-layer film of A / B / A was obtained. PET-I was used as the polyester constituting the A layer. As polyester which comprises B layer, 100 mass% of PET was used.
Thereafter, in the same manner as in Example 1, a biaxially oriented polyester film having a film thickness of 25 μm was obtained. A biaxially oriented polyester film in which a coating layer was laminated was obtained in the same manner as in Example 2 except that this biaxially oriented polyester film was coated with the coating agent 3 as a coating agent and used a metalling bar (# 30).
Since the molding stress was slightly high because the molding stress was slightly high and the melting point was low, the heat resistance of the molded product was slightly reduced, but the film exhibited excellent properties as a weather-resistant polyester film for molding.

(Example 7)
A three-layer film of A / B / A was obtained. As polyester A constituting the A layer, PET and particle master were mixed at 99: 1 and used. As polyester which comprises B layer, PET and PBT were mixed and used by 95: 5 :.
Each mixed polyester resin was individually dried in a vacuum dryer at 180 ° C. for 4 hours, and after sufficiently removing moisture, supplied to separate single screw extruders, melted at 280 ° C., and filtered through separate paths. After removing the foreign matter and leveling the amount of extrusion through the gear pump, A layer / B layer / A layer (see the table for lamination thickness ratio) in the feed block installed on the top of the T die After the lamination, the sheet was discharged from a T die onto a cooling drum whose temperature was controlled at 25 ° C. At that time, a wire-like electrode having a diameter of 0.1 mm was applied electrostatically and adhered to the cooling drum to obtain an unstretched film. An unstretched polyester film having a coating layer laminated thereon was obtained in the same manner as in Example 2 except that the unstretched polyester film was coated with coating agent 2 as a coating agent and used as a metalling bar (# 6).
Since the film was an unstretched film, although the heat resistance of the molded product was lowered, it was at a level with no problem as a weather-resistant polyester film for molding.

(Example 8)
A three-layer film of A / B / A was obtained. PET-I was used as the polyester constituting the A layer. PET was used as the polyester constituting the B layer.
Thereafter, in the same manner as in Example 1, a biaxially oriented polyester film having a film thickness of 25 μm was obtained. A biaxially oriented polyester film having a coating layer laminated thereon was obtained in the same manner as in Example 2 except that this biaxially oriented polyester film was coated with the coating agent 3 as a coating agent. Although the film had a high F100 value at 190 ° C., the moldability was lowered, but it was a level with no problem as a weatherable polyester film for molding.

(Comparative Example 1)
It was set as the single layer film. PET and particle master were mixed and used at a mass ratio of 97: 3.
Thereafter, in the same manner as in Example 1, a biaxially oriented polyester film having a film thickness of 25 μm was obtained. A biaxially oriented polyester film having a coating layer laminated thereon was obtained in the same manner as in Example 2 except that a metalling bar (# 30) was used for this biaxially oriented polyester film and coating agent 1 was coated as a coating agent.
The film had a high F100 value at 190 ° C., was inferior in moldability, and could not be used as a weatherable polyester film for molding.

(Comparative Example 2)
A / B two-layer laminated film was obtained. As polyester constituting the A layer, PET, PBT and particle master were mixed at a mass ratio of 84: 15: 1. As polyester which comprises B layer, PET and PBT were mixed and used by mass ratio 85:15.
Thereafter, an unstretched film having a film thickness of 50 μm was obtained in the same manner as in Example 7 except that the lamination thickness ratio was changed. Unstretched polyester with a coating layer laminated in the same manner as in Example 2, except that this biaxially oriented polyester film was coated with metalling bar (# 15) and the coating agent was coated with coating agent 2. A film was obtained. Since the F100 value at 190 ° C. was extremely low and the heat resistance of the molded product was inferior, the film was unusable as a weather-resistant polyester film for molding.

(Comparative Example 3)
A three-layer film of A / B / A was obtained. As polyester constituting the A layer, PET and a particle master were mixed and used at a mass ratio of 99: 1. As polyester which comprises B layer, PET and PBT were mixed and used by mass ratio 80:20.
Thereafter, in the same manner as in Example 1, a biaxially oriented polyester film having a film thickness of 25 μm was obtained. A biaxially oriented polyester film having a coating layer laminated thereon was obtained in the same manner as in Example 2 except that a metalling bar (# 4) was used on this biaxially oriented polyester film and coating agent 4 was coated as a coating agent. The film was unusable as a weatherable polyester film for molding because the coating layer was cracked during molding. Moreover, the E2-E1 value was large, resulting in poor appearance characteristics.

(Comparative Example 4)
A / B two-layer laminated film was obtained. As polyester constituting the A layer, PET, PBT and particle master were mixed at a mass ratio of 69: 30: 1. As polyester which comprises B layer, PET and PBT were mixed and used by mass ratio 70:30.
Thereafter, a biaxially oriented polyester film having a film thickness of 25 μm was obtained in the same manner as in Example 1 except that the lamination thickness ratio was changed. A biaxially oriented polyester film having a coating layer laminated thereon was obtained in the same manner as in Example 2 except that a metalling bar (# 10) was used on this biaxially oriented polyester film and the coating agent 5 was coated as a coating agent. Since the coating layer had a too low solid content concentration, yellowing occurred after the weather resistance test, and the film was unusable as a weather-resistant polyester film for molding. Moreover, the E2-E1 value was large, resulting in poor appearance characteristics.

  The present invention relates to a polyester film and exhibits excellent weather resistance, and can be suitably used for molding because of low molding stress. In particular, it is preferably used as a decoration application for parts such as building materials, automobile parts, mobile phones and electrical products.

Claims (7)

A weather resistance film having a wavelength range of 350 to 360 nm and an average transmittance of 45% or less, in which a weather resistance coat layer is laminated on at least one side of a polyester film,
100% elongation stress (F100 value) in the film longitudinal direction and width direction at 190 ° C. is 1 MPa or more and 60 MPa or less,
And the weather-resistant polyester film for shaping | molding whose average transmittance | permeability of wavelength range 350-360nm after performing 100% expansion | extension processing in 25 degreeC is 45% or less. An initial color tone E1 after 100% elongation at 25 ° C .;
The weatherable polyester film for molding according to claim 1, wherein the difference (E1-E2) from the color tone E2 after 100% elongation treatment at 25 ° C and further a weather resistance test is 1.2 or less. The weatherable polyester for molding according to claim 1 or 2, wherein a stress at 100% elongation (F100 value) in the longitudinal direction and the width direction at 190 ° C after performing a weathering test without performing an elongation treatment is 1 to 60 MPa. the film. The weather-resistant polyester film for molding according to any one of claims 1 to 3, wherein the elongation at break in the longitudinal direction and the width direction at 190 ° C after conducting a weather resistance test without performing an elongation treatment is 150 to 700%. The weather-resistant polyester film for molding according to any one of claims 1 to 4, which is used for automobile members, electronic devices, and building materials. The laminated sheet for shaping | molding formed by bonding together the weather-resistant polyester film for shaping | molding in any one of Claims 1-5, and the base material for shaping | molding members. The molding member formed by shape | molding the lamination sheet for shaping | molding of Claim 6.