JP2017105149A - Biaxially oriented laminated polyester film for molding and molding member using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a biaxially oriented laminated polyester film for molding which has excellent light resistance and is excellent in moldability.SOLUTION: A biaxially oriented laminated polyester film for molding satisfies all of (1) to (4) conditions: the condition (1) where the film has at least an A layer and a B layer, and the B layer is a surface layer of both of the layers; the condition (2) where the film contains a benzotriazole-based or a triazine-based ultraviolet absorber in a polyester resin composition constituting the B layer, and the content of the ultraviolet absorber is 3 wt.% or more and 4 wt.% or less; the condition (3) where a thickness of the B layer is 10 μm or more and 20 μm or less; the condition (4) where a transmission color tone ΔE after the film has been left in 60°C×50%RH for 24 hours using a metal halide lamp type eye super UV tester is 6 or less.SELECTED DRAWING: None

Description

  The present invention relates to a biaxially oriented laminated polyester film for molding and a molded member using the same.

  Light resistance and moisture resistance are important in the fields of automobile parts, electronic equipment, building materials, etc., and polycarbonate resin films containing acrylic resin in a polycarbonate resin and acrylic insert films are generally used as molded parts using them. (Patent Document 1, Patent Document 2).

  Moreover, the polyester film for membrane switches which provided the light resistance to the polyester film is proposed (patent document 3).

  Moreover, a polyester film for molding in which a UV absorber is added to the surface layer of the polyester film has been proposed (Patent Document 4).

JP-A-7-137210 JP-A-9-66537 JP 2005-193643 A JP 2010-221715 A

  However, the resin molded article having excellent scratch resistance and the acrylic insert film described in Patent Document 2 made of the polycarbonate resin film described in Patent Document 1 and the acrylic insert film described in Patent Document 2 have not been sufficient as a molded member having excellent light resistance.

  Moreover, the polyester film for membrane switches described in Patent Document 3 is for a membrane switch and has a poor molding property and cannot be used as a molding film having excellent light resistance.

  Moreover, although the polyester film for a shaping | molding of patent document 4 has provided the ultraviolet absorber, it was not enough as a film for shaping | molding excellent in light resistance.

  An object of the present invention is to eliminate the above-described problems. In other words, it provides a biaxially oriented laminated polyester film for molding that is resistant to whitening and yellowing even when used outdoors, such as outdoors, and that has excellent light resistance and excellent moldability. There is to do.

In order to solve the above problems, the present invention has the following configuration. That is,
[I] A biaxially oriented laminated polyester film for molding that satisfies all of the following conditions (1) to (4).
(1) It has at least A layer and B layer, and B layer is both surface layers.
(2) The polyester resin composition constituting the B layer contains a benzotriazole-based or triazine-based ultraviolet absorber, and the content thereof is 3% by weight or more and 4% by weight or less.
(3) The thickness of the B layer is 10 μm or more and 20 μm or less.
(4) Using a metal halide lamp type eye super UV tester, the transmission color tone ΔE after being left for 24 hours in 60 ° C. × 50% RH is 6 or less.
[II] The biaxially oriented laminated polyester film for molding described in [I] that satisfies all of the following conditions (1) to (3).
(1) The transmittance at a wavelength of 300 nm to 320 nm is 0.2% or less.
(2) The transmittance at a wavelength of 320 nm to 360 nm is 0.2% or less.
(3) The transmitted color tone b ^* is −1.5 or more and +1.5 or less.
[III] The biaxially oriented laminated polyester film for molding according to any one of [I] and [II] that satisfies all of the following conditions (1) to (3).
(1) Containing 0.001% by weight or more and 0.010% by weight or less of particles having an average particle diameter of 2 μm or more and 3 μm or less with respect to the entire polyester resin composition constituting the B layer.
(2) The root mean square roughness curve height (Rq) is 10 nm or more.
(3) The film haze is 2.0% or less.
[IV] A molded member using the biaxially oriented laminated polyester film for molding described in [I] to [III].
[V] The biaxially oriented laminated polyester film for molding according to any one of [I] to [IV] that satisfies the following conditions (1) and (2).
(1) The product (P) of the sum of the thicknesses of the B layer and the amount of the ultraviolet absorber contained in the polyester resin composition constituting the B layer is 1.08 or more and 1.20 or less.
P = sum of B layer thickness [μm] × UV absorber amount [wt%]
(2) The transmission color tone ΔE after being left for 1000 hours is 3 or less in a sunshine carbon arc lamp type light resistance tester stipulated in JIS B7753.

  According to the present invention, a biaxially oriented laminated polyester film for molding that does not easily cause whitening or yellowing even when used in an environment such as outdoors exposed to ultraviolet rays for a long time, has excellent light resistance, and is excellent in moldability. Can be obtained.

The biaxially oriented laminated polyester film for molding of the present invention needs to satisfy all of the following conditions (1) to (4).
(1) It has at least A layer and B layer, and B layer is both surface layers.
(2) The polyester resin composition constituting the B layer contains a benzotriazole-based or triazine-based ultraviolet absorber, and the content thereof is 3% by weight or more and 4% by weight or less.
(3) The thickness of the B layer is 10 μm or more and 20 μm or less.
(4) Using a metal halide lamp type eye super UV tester, the transmission color tone ΔE after being left for 24 hours in 60 ° C. × 50% RH is 6 or less.

  The polyester resin that constitutes each layer of the biaxially oriented laminated polyester film for molding of the present invention is a general term for polymer compounds in which main bonds in the main chain are ester bonds. The polyester resin can be usually obtained by polycondensation reaction of dicarboxylic acid or its derivative with glycol or its derivative.

In the present invention, from the viewpoints of moldability, appearance, heat resistance, dimensional stability and economy, 97 mol% or less of the glycol units constituting the polyester resin are ethylene glycol-derived structural units, and 95 mol of dicarboxylic acid units. % Or more is preferably a structural unit derived from terephthalic acid. Here, the dicarboxylic acid unit (structural unit) or the diol unit (structural unit) means a divalent organic group from which a portion to be removed by polycondensation has been removed. Represented by the general formula.
Dicarboxylic acid unit (structural unit): —CO—R—CO—
Diol unit (structural unit): —O—R′—O—
(Where R and R ′ are divalent organic groups)
The same applies to the meaning of units (structural units) of trivalent or higher carboxylic acids such as trimellitic acid units and glycerin units, and alcohols and derivatives thereof.

  Examples of glycols or derivatives thereof that give the polyester resin used in the present invention include 1,2-propanediol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, and ethylene glycol. , 5-pentanediol, 1,6-hexanediol, aliphatic dihydroxy compounds such as neopentyl glycol, polyoxyalkylene glycols such as diethylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, 1,4-cyclohexanedimethanol, Examples thereof include alicyclic dihydroxy compounds such as spiroglycol, aromatic dihydroxy compounds such as bisphenol A and bisphenol S, and derivatives thereof. Among these, 1,3-propanediol, 1,4-butanediol, neopentyl glycol, and 1,4-cyclohexanedimethanol are preferably used in terms of moldability and handleability. In particular, from the viewpoint of moldability and handleability, it is preferable to use 1,4-cyclohexanedimethanol.

  The biaxially oriented laminated polyester film for molding of the present invention preferably has a 100% elongation stress (F100 value) in the longitudinal direction and width direction at 150 ° C. of 5 MPa or more and 60 MPa or less from the viewpoint of moldability. In addition, the biaxially oriented laminated polyester film for molding of the present invention may have a elongation at break of 100% or more and 500% or less at 150 ° C. in the film longitudinal direction and width direction in order to be molded into a more complicated shape. preferable.

  As a method of setting the above range, it is important that the polyester used contains a structural unit derived from 1,4-cyclohexanedimethanol. Such a structural unit suppresses orientational crystallization of the film at the time of molding, so that the stress at 100% elongation (F100 value) of the film at 150 ° C. can be kept low, and the elongation at break can also be improved. . As a preferable concentration, the content of the 1,4-cyclohexanedimethanol component with respect to the glycol component in the film is preferably 5 mol% or more and 15 mol% or less.

  In the biaxially oriented laminated polyester film for molding of the present invention, as a method for setting the stress at 100% elongation and the elongation at break of the film at 150 ° C. within the above ranges, a structure derived from 1,4-cyclohexanedimethanol is used for the polyester used. It is important to include units. Such a structural unit suppresses orientational crystallization of the film at the time of molding, so that the stress at 100% elongation (F100 value) of the film at 150 ° C. can be kept low, and the elongation at break can also be improved. . As a preferable concentration, the content of the 1,4-cyclohexanedimethanol component with respect to the glycol component in the film is preferably 5 mol% or more and 15 mol% or less.

  In addition to terephthalic acid, the dicarboxylic acid or derivative thereof that provides the polyester resin used in the present invention includes isophthalic acid, phthalic acid, 2,6-naphthalenedicarboxylic acid, diphenyldicarboxylic acid, diphenylsulfone dicarboxylic acid, diphenoxyethane. Aromatic dicarboxylic acids such as dicarboxylic acid and 5-sodiumsulfone dicarboxylic acid, oxalic acid, succinic acid, adipic acid, sebacic acid, dimer acid, maleic acid, fumaric acid and other aliphatic dicarboxylic acids, 1,4-cyclohexanedicarboxylic acid Examples thereof include alicyclic dicarboxylic acids such as oxycarboxylic acids such as paraoxybenzoic acid, and derivatives thereof. Examples of dicarboxylic acid derivatives include dimethyl terephthalate, diethyl terephthalate, 2-hydroxyethyl methyl terephthalate, dimethyl 2,6-naphthalenedicarboxylate, dimethyl isophthalate, dimethyl adipate, diethyl maleate, and dimethyl dimer. An esterified product can be mentioned. Among these, isophthalic acid, 2,6-naphthalenedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, and esterified products thereof are preferably used from the viewpoint of moldability and handleability.

  The biaxially oriented laminated polyester film for molding of the present invention has at least an A layer and a B layer, and the B layer is a surface layer of both, and the benzotriazole-based or triazine-based polyester resin composition constituting the B layer It is important that the ultraviolet absorber is contained and the content thereof is 3% by weight or more and 4% by weight or less.

  Since the photodecomposition of polyester is supposed to proceed within 2 μm of the surface layer, the photodecomposition can be efficiently suppressed by including an ultraviolet absorber in the outermost layer. When the layer containing the ultraviolet absorber is used as the film inner layer, photodecomposition of the outermost layer is not suppressed and whitening due to yellowing or choking may occur. In the case of a single film configuration, the transmittance in the ultraviolet wavelength region can be suppressed, but since the ultraviolet absorber is dispersed in the film thickness direction, the effect of suppressing the photodecomposition in the surface layer portion may be reduced. In the case of a two-layer configuration of B layer / A layer, the film may be front and back, and the front and back may be mistaken when the film is processed.

  Said laminated thickness can be achieved by adjusting the discharge amount when extruding the polyester which comprises A layer, and the polyester which comprises B layer. The discharge amount can be appropriately adjusted depending on the number of rotations of the screw of the extruder, the number of rotations of the gear pump, the extrusion temperature, the viscosity of the polyester raw material, etc. when a gear pump is used. The film lamination ratio is determined by measuring the thickness of each layer by observing the cross section of the film with a scanning electron microscope, transmission electron microscope, optical microscope or the like at a magnification of 500 to 10,000 times. be able to.

  The biaxially oriented laminated polyester film for molding of the present invention has a film thickness of preferably 25 μm or more and 500 μm or less, more preferably 50 μm or more and 300 μm or less, from the viewpoint of the depth and shape retention of the molded member, and more preferably 75 μm. It is most preferable if it is 250 μm or more.

  In the biaxially oriented laminated polyester film for molding of the present invention, the thickness of the B layer needs to be 10 μm or more and 20 μm or less.

  When the thickness of the B layer containing the ultraviolet absorber is less than 10 μm, the transmittance in the ultraviolet wavelength region of 300 to 360 nm exceeds 0.2%, and the effect of suppressing photolysis may be reduced.

  When the thickness of the B layer containing the ultraviolet absorber exceeds 20 μm, the color tone of the b * value of the film exceeds 1.5 due to the decrease in the color tone of the ultraviolet absorber itself and / or the transmittance in the visible light wavelength region. From the viewpoint of later appearance, the appearance may be impaired. More preferably, the thickness of the B layer containing the ultraviolet absorber is 12 μm or more and 18 μm or less.

  In the present invention, it is important that the content (W) of the ultraviolet absorber in the B layer is 3% by weight or more and 4% by weight or less in the polyester resin component of the B layer.

  When the content of the ultraviolet absorber is less than 3% by weight, the transmittance in the ultraviolet wavelength region of 300 to 360 nm exceeds 0.2%, and the effect of suppressing photolysis may be reduced. When the content of the UV absorber exceeds 4% by weight, the color tone of the UV absorber itself and / or the transmittance in the visible light wavelength region is lowered, and the color tone of the b * value of the film exceeds 1.5. From the viewpoint of appearance, the appearance may be impaired. More preferably, the content of the UV absorber in the B layer is 3.2% by weight or more and 3.8% by weight or less.

  In the present invention, the product (P) of the sum of the thicknesses of the B layer and the amount of the ultraviolet absorber contained in the polyester resin composition constituting the B layer is preferably 1.08 or more and 1.20 or less.

  Here, the amount of the ultraviolet absorber means [% by weight] based on the B layer.

When the product (P) is less than 1.08, the transmitted color tone ΔE after being left for 1000 hours is more than 3 and exposed to ultraviolet rays such as outdoors for a long time in a sunshine carbon arc lamp type light resistance tester stipulated in JIS B7753. When used in an environment, it may cause whitening and yellowing.
When the product (P) exceeds 1.20, the color tone of the b * value of the film exceeds 1.5, and the appearance may be impaired from the viewpoint of the appearance after molding.
More preferably, the product (P) is 1.09 or more and 1.10 or less.

  It is important that the ultraviolet absorber contained in the B layer in the present invention is benzotriazole or triazine.

  The benzotriazole type is preferable because it has a melting point of 150 ° C. or higher and a molecular weight of 600 or higher. When the melting point of the ultraviolet absorber is less than 150 degrees, when it is melted together with the polyester resin by an extruder, thermal decomposition may occur, and the performance of the ultraviolet absorber may be deteriorated. When the molecular weight of the ultraviolet absorbent is less than 600, the ultraviolet absorbent may be degassed from the vent when the polyester resin is melt-extruded with a vent type twin screw extruder, and the amount added may be reduced.

Examples of the benzotriazole-based compound in the present invention include 2-2H-benzotriazol-2-yl) -4,6-bis (1-methyl-1-phenylethyl) phenol and 2- (2H-benzotriazole-2). -Yl) -4- (1,1,3,3-tetramethylbutyl) phenol, 2- (2H-benzotriazol-2-yl) -4-methylphenol, 2- (2H-benzotriazol-2-yl) ) -4,6-di-t-butylphenol, 2- (2H-benzotriazol-2-yl) -4,6-di-t-amylphenol, 2- (2H-benzotriazol-2-yl) -4 -T-butylphenol, 2- (2'-hydroxy-3'-t-butyl-5'-methylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-3) , Can be exemplified 5'-di -t- butyl-phenyl) -5-chloro-benzotriazole, or the like.
Examples of the triazine compound in the present invention include 4-bis [2-hydroxy-4-butoxyphenyl] -6- (2,4-dibutoxyphenyl) -1,3,5-triazine and 6,6 ′, 6 ″-(1,3,5-triazine-2,4,6-triyl) tris (3-hexyloxy-2-methylphenol) and the like can be exemplified.

  It is important that the biaxially oriented laminated polyester film for molding of the present invention has a transmission color tone ΔE of 6 or less after being left for 24 hours in a 60 ° C. × 50% RH using a metal halide lamp type eye super UV tester.

  Here, using a metal halide lamp type eye super UV tester and leaving for 24 hours in 60 ° C. × 50% RH means (7) light resistance test described later in Examples.

  When the transmission color tone ΔE of the film after the light resistance test exceeds 6, the color may change due to long-term outdoor use. More preferably, the transmission color tone ΔE is 4 or less, and particularly preferably 3 or less.

The biaxially oriented laminated polyester film for molding of the present invention preferably satisfies all the following conditions (1) to (3).
(1) The transmittance at a wavelength of 300 nm to 320 nm is 0.2% or less.
(2) The transmittance at a wavelength of 320 nm to 360 nm is 0.2% or less.
(3) The transmitted color tone b ^* is −1.5 or more and +1.5 or less.

  The biaxially oriented laminated polyester film for molding of the present invention preferably has a transmittance at a wavelength of 300 nm to 320 nm of 0.2% or less.

  In general, polyester resins, especially polyethylene terephthalate, are known to undergo photodegradation when irradiated with a wavelength of 310 nm. Therefore, by setting the transmittance at a wavelength of 300 nm to 320 nm to 0.2% or less, light is emitted. Decomposition can be suppressed. When it exceeds 0.2%, photodegradation proceeds due to exposure to ultraviolet rays for a long time, and whitening and / or yellowing due to choking may occur.

  The biaxially oriented laminated polyester film for molding of the present invention preferably has a transmittance of wavelengths of 320 nm to 360 nm of 0.2% or less.

  Generally, a polyester resin, especially polyethylene terephthalate, is said to be purified by irradiating a wavelength of 330 nm to 360 nm, whereby the chemical bond of the polyester is dissociated and a yellowing substance is purified. By setting the transmittance to 0.2% or less, yellowing of the film can be suppressed. If it exceeds 0.2%, the film may be yellowed by being exposed to ultraviolet rays for a long time.

  The biaxially oriented laminated polyester film for molding of the present invention preferably has a transmission color tone b * value of −1.5 or more and 1.5 or less from the viewpoint of appearance after molding. When the transmission color tone b * value is less than −1.5, the appearance of the molded body using the biaxially oriented laminated polyester film for molding of the present invention may become bluish and the appearance may be impaired. When the transmission color tone b * value exceeds 1.5, the appearance may be yellowish and the appearance may be deteriorated. More preferably, the transmitted color tone b * value is 0 or more and 1.5 or less, and particularly preferably 0 or more and 1.2 or less.

The biaxially oriented laminated polyester film for molding of the present invention preferably satisfies all the following conditions (1) to (3).
(1) Containing 0.001% by weight or more and 0.010% by weight or less of particles having an average particle diameter of 2 μm or more and 3 μm or less with respect to the entire polyester resin composition constituting the B layer.
(2) The root mean square roughness curve height (Rq) is 10 nm or more.
(3) The film haze is 2.0% or less.

  The biaxially oriented laminated polyester film for molding of the present invention contains 0.001 wt% or more and 0.010 wt% or less of particles having an average particle diameter of 2 μm or more and 3 μm or less with respect to the entire polyester resin composition constituting the B layer. It is preferable to do. When the average particle diameter is less than 2 μm, the contribution to the surface root mean square roughness curve Rq is low, so the content must be increased and the haze may exceed 2.0%. When the average particle diameter exceeds 3 μm, the content of particles increases by a power of size in order to secure the number of particles per area. When the content of the particles is less than 0.001% by weight of the polyester resin component of the B layer, the surface root mean square roughness curve Rq is less than 10 nm, and the scratch resistance may be lowered. When content of particle | grains exceeds 0.010 weight% among the polyester resin components of B layer, a haze may exceed 2.0%.

  The biaxially oriented laminated polyester film for molding of the present invention preferably has a root mean square roughness curve height (Rq) of 10 nm or more. When the thickness is less than 10 nm, the outermost layer B layer containing an ultraviolet absorber may be easily damaged by the ultraviolet absorber due to the ultraviolet absorber. Regarding the scratch resistance, the upper limit of the surface root-mean-square roughness curve Rq is preferably 13 nm or less with a film haze of 2.0% or less from the viewpoint of appearance after molding.

  The biaxially oriented laminated polyester film for molding of the present invention preferably has a film haze of 2.0% or less. When it exceeds 2.0%, the external appearance after molding may become cloudy and the design may be inferior. The lower limit of haze is preferably 1.3% or more from the viewpoint of scratch resistance.

  Examples of the method of setting the haze to 2.0% or less include a method of reducing the concentration of particles to be contained in order to improve the film transportability. The biaxially oriented laminated polyester film for molding of the present invention can contain particles in the film in order to improve the transportability of the film. Here, the particles to be used are not particularly limited, but externally added particles are preferably used in terms of transportability and appearance. Examples of the external additive particles include wet and dry silica, colloidal silica, aluminum silicate, titanium oxide, calcium carbonate, calcium phosphate, barium sulfate, and aluminum oxide, and organic particles include styrene, silicone, acrylic acids, methacrylic acids, Particles containing polyesters, divinyl compounds and the like as constituent components can be used. Among them, it is preferable to use inorganic particles such as wet and dry silica and alumina, and particles containing styrene, silicone, acrylic acid, methacrylic acid, polyester, divinylbenzene and the like as constituent components. Further, these externally added particles may be used in combination of two or more.

  The biaxially oriented laminated polyester film for molding of the present invention preferably has a 100% elongation stress (F100 value) in the longitudinal direction and width direction at 150 ° C. of 5 MPa or more and 60 MPa or less from the viewpoint of moldability. Examples of the molding method of the molded member include heat molding methods such as vacuum molding, pressure molding, vacuum pressure molding, press molding, plug assist molding, and any of these molding methods increases the temperature of the film by a preheating process using an infrared heater or the like. It has the process shape | molded after making it into a state. For this reason, it becomes possible to shape | mold into a complicated shape by reducing the molding stress at high temperature. For this reason, it is preferable that the stress at 100% elongation at 150 ° C. (F100 value) is 5 MPa or more and 60 MPa or less. If the F100 value is less than 5 MPa, it may not be able to withstand the tension for film transfer in the preheating step in the molding process, and the film may be deformed or broken in some cases. It becomes an unbearable film. On the other hand, when it exceeds 60 MPa, deformation during thermoforming is insufficient, and it becomes difficult to mold into a complicated shape. In terms of handleability and moldability, the 100% elongation stress (F100 value) in the film longitudinal direction and width direction at 150 ° C. is preferably 10 MPa or more and 50 MPa or less, and most preferably 15 MPa or more and 45 MPa or less.

  In addition, the biaxially oriented laminated polyester film for molding of the present invention may have a elongation at break of 100% or more and 500% or less at 150 ° C. in the film longitudinal direction and width direction in order to be molded into a more complicated shape. preferable. Even when it is molded into a complicated shape, it can follow a high molding processing magnification, and can be excellent in economic efficiency and heat resistance. In terms of moldability, heat resistance, and economy, the elongation in the longitudinal direction and the width direction is preferably 100% or more and 400% or less, and most preferably 120% or more and 300% or less. In particular, when used in applications that require dimensional stability, the elongation in the longitudinal direction or width direction of the film is preferably 120% or more and 200% or less.

  In the present invention, as a method for setting the stress at 100% elongation and the elongation at break of the film at 150 ° C. within the above ranges, it is important that the polyester to be used contains a structural unit derived from 1,4-cyclohexanedimethanol. . Such a structural unit suppresses orientational crystallization of the film at the time of molding, so that the stress at 100% elongation (F100 value) of the film at 150 ° C. can be kept low, and the elongation at break can also be improved. . As a preferable concentration, the content of the 1,4-cyclohexanedimethanol component with respect to the glycol component in the film is 5 mol% or more and 15 mol% or less.

  The biaxially oriented laminated polyester film for molding of the present invention preferably has a storage elastic modulus at 80 ° C. of from 2001 MPa to 4000 MPa from the viewpoint of dimensional stability during processing. More preferably, it is 2400 MPa or more and 3000 MPa or less. If the storage elastic modulus at 80 ° C. is less than 2001 MPa, the dimensional stability in processing steps such as printing, vapor deposition, coating, and laminating decreases. Conversely, when the storage elastic modulus is greater than 4000 MPa, the dimensional stability is excellent, but the moldability may be deteriorated, which is not preferable.

  In the present invention, as a method of setting the storage elastic modulus at 80 ° C. in the above range, for example, a method of setting the peak temperature of loss tangent to 100 ° C. or more and 120 ° C. or less is preferably used. By setting the loss tangent peak temperature within the above range, it is possible to control the storage elastic modulus at 80 ° C. to be 2001 MPa or more and 3500 MPa or less while maintaining the moldability. The loss tangent peak is based on the glass transition of the polymer. If the loss tangent peak temperature is less than 100 ° C., the storage elastic modulus at 80 ° C. may be less than 2001 MPa, and the dimensional stability decreases. End up. On the other hand, if the peak temperature of the loss tangent is to be made higher than 120 ° C., the 100% elongation stress (F100 value) in the film longitudinal direction and the width direction at 150 ° C. may be larger than 60 MPa, and the moldability is lowered. End up. A more preferable range of the loss tangent is 100 ° C. or higher and 115 ° C. or lower.

  In addition, the biaxially oriented laminated polyester film for molding of the present invention has a storage elastic modulus in the film longitudinal direction and width direction at 100 ° C. of 1001 MPa or more and 3000 MPa or less in order to further improve dimensional stability during processing. It is preferable. More preferably, it is 1050 MPa or more and 2500 MPa or less, and most preferably 1100 MPa or more and 2000 MPa or less. By setting the storage elastic modulus in the film longitudinal direction and width direction at 100 ° C. within the above ranges, the dimensional stability during processing can be further improved, and the processing temperature region is widened, which is very preferable.

  In the present invention, the method for setting the storage elastic modulus at 100 ° C. in the above range is not particularly limited, but, for example, a method of setting the loss tangent peak temperature to 105 ° C. or higher and 120 ° C. or lower is preferably used, and more preferably. It is 105 degreeC or more and 110 degrees C or less.

  As a method for controlling the peak temperature of loss tangent, it is preferable to increase the draw ratio. The stretching ratio is preferably 10 times or more in terms of surface magnification, more preferably 11 times or more, and most preferably 12 times or more. Further, it is preferable to lower the stretching temperature to such an extent that uneven stretching does not occur. In particular, in sequential biaxial stretching in which stretching in the width direction is performed after stretching in the longitudinal direction, a method of lowering the stretching temperature in the longitudinal direction, specifically, a method of 80 ° C. to 90 ° C. is preferable, and the stretching temperature in the width direction is preferred. Is preferably 90 ° C to 100 ° C, which is higher than the stretching temperature in the longitudinal direction.

  In the present invention, the plane orientation coefficient of the B layer is 0.14 or more and 0.17 or less, and the difference (TmB−TmA) between the melting point (TmB) of the B layer and the melting point (TmA) of the A layer is 7 ° C. or more and 15 ° C. or less. The method is also preferable. By setting the plane orientation coefficient of the B layer to 0.14 or more and 0.17 or less, dimensional stability can be secured, and by forming the melting point of the A layer with a lower melting point than that of the B layer, moldability is achieved. be able to. At this time, from the viewpoint of moldability, dimensional stability, and interlayer adhesion between the B layer and the A layer, the difference (TmB−TmA) between the melting point of the B layer (TmB) and the melting point of the A layer (TmA) is 7 It is preferable to set it as 15 to 15 degreeC.

  From the viewpoint of moldability and dimensional stability, the plane orientation coefficient of the B layer is more preferably from 0.145 to 0.165, and most preferably from 0.149 to 0.165.

  The B layer in the present invention has a melting point (TmB) of 250 ° C. or more and 255 ° C. or less and a density of 1.380 g / cm 3 or more and 1.400 g / cm 3 or less from the viewpoint of heat resistance and dimensional stability. preferable. In order to make the melting point and density of the B layer within such ranges, the B layer contains an ethylene glycol component of 90 mol% or more and less than 99 mol% and a 1,4-cyclohexanedimethanol component of 1 mol% or more and less than 10 mol% It is preferable to do.

  From the viewpoint of moldability, the A layer in the present invention preferably has a melting point (TmA) of 235 ° C. or more and 245 ° C. or less and a density of 1.350 g / cm 3 or more and 1.365 g / cm 3 or less. In order to make the melting point and density of the A layer within such ranges, the A layer contains an ethylene glycol component of 85 to 95 mol% and a 1,4-cyclohexanedimethanol component of 5 to 15 mol%. It is preferable to do.

  By adopting such a configuration, it is excellent in moldability, dimensional stability, and heat resistance, and also in the interlaminar adhesion between the B layer and the A layer after high-magnification molding.

  In addition, the biaxially oriented laminated polyester film for molding of the present invention preferably has a storage elastic modulus in the film longitudinal direction and width direction at 180 ° C. of 41 MPa or more and 400 MPa or less from the viewpoint of heat resistance. If the storage elastic modulus at 180 ° C. is less than 41 MPa, the heat resistance is lowered, and the quality such as roughening of the film surface may be deteriorated during molding. Conversely, if the storage elastic modulus is greater than 400 MPa, the moldability may be deteriorated, which is not preferable. From the viewpoint of heat resistance and moldability, the storage elastic modulus in the film longitudinal direction and the width direction at 180 ° C. is more preferably from 100 MPa to 300 MPa, and most preferably from 130 MPa to 250 MPa.

  As a method for setting the storage elastic modulus in the film longitudinal direction and the width direction at 180 ° C. to 41 MPa or more and 400 MPa or less, for example, the melting point of the polyester film is preferably 220 ° C. or more. From the viewpoint of heat resistance and moldability, the melting point of the polyester film is preferably 230 ° C. or higher and 255 ° C. or lower, and most preferably 235 ° C. or higher and 245 ° C. or lower. Moreover, when setting it as a laminated structure, it is preferable that melting | fusing point (TmB) of B layer shall be 250 degreeC or more and 255 degrees C or less.

  In the present invention, in order to satisfy moldability, dimensional stability, and heat resistance, the B layer contains 1,4-cyclohexanedimethanol component in an amount of 1 mol% to less than 5 mol%, and the A layer contains 1,4-cyclohexane. A configuration in which the dimethanol component is contained in an amount of 5 mol% to 15 mol% and the film melting point is 235 ° C. to 245 ° C. is a very preferable embodiment. In order to make the film melting point 235 ° C. or more and 245 ° C. or less with such a configuration, a method of mixing the polyethylene terephthalate resin and the 1,4-cyclohexanedimethanol copolymerized polyethylene terephthalate resin in the extruder as the A layer is preferable. Used. At that time, the copolymerization amount of 1,4-cyclohexanedimethanol in the 1,4-cyclohexanedimethanol copolymerized polyethylene terephthalate resin is preferably 25 mol% or more and 35 mol% or less. By using the amount of copolymerization with a resin in the above range, an appropriate transesterification reaction proceeds, and the film melting point can be adjusted to 235 ° C. or higher and 245 ° C. or lower. Furthermore, the residence time in the extruder of the polyester resin of the A layer is preferably 5 minutes or more and 15 minutes or less.

  Here, the melting point of the polyester film is an endothermic peak temperature expressed by a melting phenomenon when measured at a heating rate of 20 ° C./min using a differential scanning calorimeter (DSC) (details will be described later). . When a polyester resin having a different composition is blended and used as a film, an endothermic peak due to multiple melting may appear. In that case, the endothermic peak temperature appearing at the highest temperature is set to the temperature of the polyester film of the present invention. The melting point.

  In order to improve the dimensional stability after molding, the biaxially oriented laminated polyester film for molding of the present invention preferably has a heat shrinkage rate of 150% at 1 ° C. in the longitudinal direction and the width direction. Here, the heat shrinkage rate in the longitudinal direction and the width direction at 150 ° C. means that a film is cut into a rectangle 150 mm long × 10 mm wide in the longitudinal direction and the width direction, and marked lines are drawn on the sample at intervals of 100 mm. Is the rate of change in the distance between the marked lines before and after the heat treatment is performed by installing in a hot air oven heated to 150 ° C. for 30 minutes.

  It is very preferable that the heat shrinkage rate at 150 ° C. is 1% or less in both the longitudinal direction and the width direction because deformation or the like when the molded member after film formation is heated can be suppressed.

  Examples of a method for adjusting the heat shrinkage rate in the longitudinal direction and the width direction at 150 ° C. to 1% or less include a method of adjusting the heat treatment conditions of the film after biaxial stretching. When the treatment temperature is high, orientation relaxation occurs and the thermal shrinkage tends to be reduced, but the heat treatment temperature after biaxial stretching is 200 ° C. to 240 ° C. from the viewpoint of dimensional stability and film quality. It is preferable if it is 210 ° C to 235 ° C, more preferably 215 ° C to 230 ° C. In addition, the heat treatment temperature of the biaxially oriented laminated polyester film for molding of the present invention is shown in the DSC curve when measured with a differential scanning calorimeter (DSC) in a nitrogen atmosphere at a heating rate of 20 ° C./min. It can be determined from the resulting minute endothermic peak.

  Moreover, as preferable heat processing time, although it can set arbitrarily in 5 to 60 second, it is preferable to set it as 10 to 40 second from a viewpoint of a moldability, dimensional stability, a color tone, and productivity, and 15-30. Preferably it is seconds. Further, the heat treatment is preferably performed while relaxing in the longitudinal direction and / or the width direction, since the heat shrinkage rate can be reduced. A preferable relaxation rate (relaxation rate) at the time of heat treatment is 3% or more. From the viewpoint of dimensional stability and productivity, 3% to 10% is preferable, and 3% to 5% is most preferable. preferable.

  Also, a method of heat treatment under two or more conditions is very preferable. After the heat treatment at a high temperature of 200 ° C. to 245 ° C., the heat shrinkage can be further reduced by performing the heat treatment at a temperature lower than the heat treatment temperature while relaxing in the longitudinal direction and / or the width direction. The heat treatment temperature in the second stage at this time is preferably 120 ° C. to 180 ° C., more preferably 150 ° C. to 180 ° C.

  Further, as a method for further reducing the thermal shrinkage rate, off-annealing treatment can be mentioned. That is, it is a method in which the polyester film once wound is subjected to heat treatment again.

  The thermal contraction rate at 150 ° C. is more preferably 0.8% or less, and most preferably 0.5% or less.

  The biaxially oriented laminated polyester film for molding according to the present invention is obtained when the temperature is increased from 25 ° C. to 220 ° C. at a temperature increase rate of 5 ° C./min with a load of 19.6 mN in order to improve dimensional stability after molding. It is preferable that the thermal deformation rate of the film at 150 ° C. in at least one direction is 0 to + 3%. In order to improve the dimensional stability after molding, as described above, the off-annealing treatment is very effective, but the off-annealing treatment temperature is set to 140 ° C. or more and less than 160 ° C., and the width direction is made free. The thermal deformation rate in the width direction can be within the above range, and the longitudinal thermal deformation rate can be reduced by 0.5 to 5% lower than the unwinding rate to reduce the longitudinal thermal deformation rate. It can be a range. Furthermore, it is preferable to provide a stepwise cooling zone after the off-annealing treatment because the thermal contraction rate can be further reduced. More preferably, when the load is 19.6 mN and the temperature is increased from 25 ° C. to 220 ° C. at a rate of temperature increase of 5 ° C./min, the thermal deformation rate of the film at 150 ° C. in the longitudinal and width directions is 0 to + 3%. It is most preferable if the thermal deformation rate of the film at 150 ° C. in the longitudinal direction and the width direction is 0.5 to + 2%.

  When the biaxially oriented laminated polyester film for molding of the present invention is used for applications in which dimensional stability after molding is particularly severe, the temperature is increased from 25 ° C. to 220 ° C. at a rate of temperature increase of 5 ° C./min at a load of 19.6 mN. It is preferable that the thermal deformation rate of the film at 180 ° C. in at least one direction when heated is 0 to + 3%. More preferably, when the load is 19.6 mN and the temperature is increased from 25 ° C. to 220 ° C. at a rate of temperature increase of 5 ° C./min, the thermal deformation rate of the film at 150 ° C. in the longitudinal and width directions is 0 to + 3%. It is most preferable if the thermal deformation rate of the film at 180 ° C. in the longitudinal direction and the width direction is 0.5 to + 2%.

  In order to achieve the thermal deformation rate, it is possible to set the thermal deformation rate in the width direction to the above range by setting the off-annealing treatment temperature to 160 ° C. or more and 180 ° C. or less and making the width direction free. Moreover, the thermal deformation rate in the longitudinal direction can be set to the above range by reducing the winding speed in the longitudinal direction by 0.5 to 5% from the unwinding speed. Furthermore, it is preferable to provide a stepwise cooling zone after the off-annealing treatment because the thermal contraction rate can be further reduced. More preferably, the film has a thermal deformation rate of 0 to + 3% at 180 ° C. in the longitudinal direction and the width direction when the temperature is increased from 25 ° C. to 220 ° C. at a rate of temperature increase of 5 ° C./min with a load of 19.6 mN. It is most preferable if the thermal deformation rate of the film at 180 ° C. in the longitudinal direction and the width direction is 0.5 to + 2%.

  The biaxially oriented laminated polyester film for molding of the present invention preferably has a birefringence (Δn) of less than 20 × 10 −3 from the viewpoint of uniform moldability. Here, uniform moldability means that the anisotropy of the film is small and the difference in the degree of molding is small depending on the direction. Birefringence is a numerical value defined by the refractive index of a film measured with an Abbe refractometer or the like. When the refractive index in the longitudinal direction of the film is nMD and the refractive index in the width direction is nTD, Δn = | NMD−nTD | A birefringence of 20 × 10 −3 or more is not preferable because the orientation balance in the plane direction of the film is poor, and the moldability may deteriorate due to the influence of the high orientation direction. In order to improve the uniform moldability, it is more preferably less than 15 × 10 −3 and most preferably less than 10 × 10 −3. In order to make birefringence into said range, it can achieve by adjusting a draw ratio, for example. In the case of the biaxial stretching method, birefringence can be reduced by bringing the stretching ratios in the longitudinal direction and the width direction close to each other. For example, the stretching ratio in the longitudinal direction is 3 to 3.8 times, the stretching ratio in the width direction is 3 to 3.8 times, preferably the stretching ratio in the longitudinal direction is 3 to 3.5 times, and the stretching ratio in the width direction is It is preferably 3 to 3.5 times. In order to set the birefringence within the above range, the preheating temperature for transverse stretching is preferably 80 to 100 ° C, more preferably 85 to 95 ° C. The transverse stretching temperature is preferably 90 ° C. or higher and 120 ° C. or lower, more preferably 95 ° C. or higher and 110 ° C. or lower, and most preferably 90 ° C. or higher and 100 ° C. or lower.

  Next, although the example of the specific manufacturing method of the biaxially-oriented laminated polyester film for shaping | molding of this invention is described, this invention is limited to the example which concerns and this invention is not interpreted.

  First, as polyester A used for the polyester A layer, polyethylene terephthalate resin (a) and 1,4-cyclohexanedimethanol copolymerized polyethylene terephthalate resin (b) are weighed at a predetermined ratio. Moreover, as polyester B used for the polyester B layer, polyethylene terephthalate resin (c), 1,4-cyclohexanedimethanol copolymerized polyethylene terephthalate resin (d), and particles having an average particle diameter of 2 μm or more and 3 μm or less are predetermined. A master chip containing a ratio and a master chip containing a UV absorber at a predetermined ratio are weighed at a predetermined ratio.

  Next, the mixed polyester resin is supplied to a vent type twin screw extruder and melt extruded. At this time, it is preferable to control the resin temperature to 275 ° C. to 295 ° C. under an atmosphere of flowing nitrogen in the extruder, with an oxygen concentration of 0.7% by volume or less. Next, foreign matter is removed and the amount of extrusion is leveled through a filter and a gear pump, and the sheet is discharged from the T die onto the cooling drum in a sheet form. At that time, an electrostatic application method in which a cooling drum and the resin are brought into close contact with each other by static electricity 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, The sheet-like polymer is brought into close contact with the casting drum, cooled and solidified by a method of sticking 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 biaxially oriented laminated polyester film for molding of the present invention needs to be a biaxially oriented film from the viewpoint of heat resistance and dimensional stability. 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.

  The stretching ratio in such a stretching method is preferably 3.0 times or more and 4.2 times, more preferably 3.0 times or more and 4.0 times or less, particularly preferably in each of the longitudinal direction and the width direction. 3 times or more and 3.8 times or less are adopted. The stretching speed is desirably 1,000% / min or more and 200,000% / min or less. The stretching temperature is preferably 70 ° C. or higher and 120 ° C. or lower in the longitudinal direction and 80 ° C. or higher and 120 ° C. or lower in the width direction. Further, the stretching may be performed a plurality of times in each direction.

  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, preferably 200 ° C. or higher and 240 ° C. or lower, more preferably 210 ° C. to 235 ° C., and even more preferably 215 ° C. to 230 ° C. Is most preferable. The heat treatment time can be arbitrarily set within a range not deteriorating the characteristics, and is preferably 5 seconds to 60 seconds, more preferably 10 seconds to 40 seconds, and most preferably 15 seconds to 30 seconds. Good. 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 various processed layers such as a printing layer, an adhesive, a vapor deposition layer, a hard coat layer, and a weathering layer, at least one surface can be subjected to corona treatment or an easy adhesion layer can be coated. As a method of providing the coating layer in-line in the film manufacturing process, at least uniaxially stretched film with a coating layer composition dispersed in water is uniformly applied using a metalling ring bar or gravure roll. Then, a method of drying the coating while stretching is preferable, and the thickness of the easy-adhesion layer is preferably 0.01 μm or more and 1 μm or less. Also, various additives such as antioxidants, heat stabilizers, ultraviolet absorbers, infrared absorbers, pigments, dyes, organic or inorganic particles, antistatic agents, nucleating agents, etc. may be added to the easy-adhesion layer. Good. The resin preferably used for the easy-adhesion layer is preferably at least one resin selected from an acrylic resin, a polyester resin, and a urethane resin from the viewpoint of adhesiveness and handleability. Of these, acrylic resins are preferred because they are excellent in light resistance, heat resistance and moisture resistance. Furthermore, in order to improve the dimensional stability after molding, it is preferable to perform off-annealing at 140 to 180 ° C.

  The biaxially oriented laminated polyester film for molding of the present invention preferably contains an antioxidant from the viewpoint of film quality. By containing the antioxidant, it is possible to suppress the oxidative decomposition in the drying step and the extrusion step of the polyester resin, and it is possible to prevent the deterioration of the quality due to the gel-like foreign matter. Although it does not specifically limit as a kind of antioxidant, For example, the antioxidant classified into hindered phenols, hydrazine, phosphites, etc. can be used conveniently. Among them, pentaerythrityl-tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 3,5-di-tert-butyl-4-hydroxy-benzylphosphonate-diethyl ester 1,3,5-trimethyl-2,4,6-tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene, tris (2,4-di-t-butylphenyl) phosphite, etc. Is preferably used.

  In addition, the biaxially oriented laminated polyester film for molding of the present invention can be laminated with a hard coat layer when used for applications with particularly severe scratch resistance. The hard coat layer only needs to have high hardness, scratch resistance, and wear resistance, and may be composed of acrylic, urethane, melamine, organic silicate compound, silicone, metal oxide, etc. it can. In particular, an acrylic, particularly active ray curable acrylic composition, or a thermosetting acrylic composition is preferably used in terms of hardness and durability, as well as curability and productivity. In the present invention, the pencil hardness of the film after laminating the hard coat layer is preferably HB or more, more preferably H or more, and most preferably 2H or more.

  When the biaxially oriented laminated polyester film for molding of the present invention is used for metallic decoration, it is preferable to use a metal compound deposited on at least one side of the film. By vapor-depositing and using a metal compound, the appearance becomes metallic, and it can be used as an alternative to a molded part using a currently plated resin. Among these, it is more preferable to use a metal compound having a melting point of 150 ° C. or higher and 400 ° C. or lower by vapor deposition. It is preferable to use a metal having a melting point range, since the polyester film can be molded in a temperature range, and the deposited metal layer can be molded, and it is easy to suppress the occurrence of a deposited layer defect due to molding. A particularly preferable melting point of the metal compound is 150 ° C. or higher and 300 ° C. or lower. Although it does not specifically limit as a metal compound whose melting | fusing point is 150 degreeC or more and 400 degrees C or less, Indium (157 degreeC) and tin (232 degreeC) are preferable, and indium is used preferably especially at the point of metallic luster and a color tone. be able to. Further, as a method for producing a vapor deposition film, a vacuum vapor deposition method, an EB vapor deposition method, a sputtering method, an ion plating method, or the like can be used. In order to further improve the adhesion between the polyester film and the vapor deposition layer, the surface of the film may be pretreated by a method such as a corona discharge treatment or an anchor coating agent. The thickness of the deposited film is preferably 1 nm or more and 500 nm or less, and more preferably 3n or more and 300 nm or less. From the viewpoint of productivity, it is preferably 3 nm or more and 200 nm or less.

  When the biaxially oriented laminated polyester film for molding of the present invention is used on the surface of a molded member by printing, the appearance and design can be imparted. The printing method is not particularly limited, but gravure printing, offset printing, screen printing, and the like are preferably used. The thickness of the printing layer is preferably 1 nm or more and 20 μm or less.

  The biaxially oriented laminated polyester film for molding of the present invention is preferably used for decorative use of molded members, and is preferably used for, for example, in-mold molding applications and insert molding applications as a molding decoration method. The in-mold molding referred to here is a molding method in which a film itself is placed in a mold and molded into a desired shape with a resin pressure to be injected to obtain a molded decorative body. In addition, insert molding is to create a film molded body to be installed in the mold by vacuum molding, pressure molding, vacuum pressure molding, press molding, plug assist molding, etc., and filling the shape with resin, This is a molding method for obtaining a molded decorative body. Since a more complicated shape can be produced, the biaxially oriented laminated polyester film for molding of the present invention is particularly preferably used for insert molding.

  Since the biaxially oriented laminated polyester film for molding of the present invention has a low molding stress in the molding temperature range, various moldings such as vacuum molding, pressure molding, vacuum pressure molding, in-mold molding molded by injection resin pressure, etc. It is possible to mold by the method, and because the storage elastic modulus in the processing temperature range is in a specific range, it has excellent dimensional stability in processing processes such as coating, laminating, printing, vapor deposition, printing, It can be decorated by vapor deposition, etc., and since it has a high storage elastic modulus in the high temperature region, it has excellent heat resistance, excellent surface properties even after molding, and has excellent color tone and appearance. As a molding member using the same, for example, it can be suitably used for molding decoration of building materials, mobile devices, electrical products, automobile parts, game machine parts and the like.

(1) Layer thickness The film was embedded in an epoxy resin, and the film cross section was cut out with a microtome. The cross section was observed with a transmission electron microscope (TEMH7100 manufactured by Hitachi, Ltd.) at a magnification of 5000 times to determine the lamination ratio of each layer. The thickness of each layer was calculated from the film thickness and the obtained lamination ratio.

(2) Composition of polyester resin The polyester resin and film can be dissolved in hexafluoroisopropanol (HFIP), and the content of each monomer residue component and by-product diethylene glycol can be quantified using 1H-NMR and 13C-NMR. . In the case of a laminated film, the components constituting each layer can be collected and evaluated by scraping off each layer of the film according to the laminated thickness. In addition, about the film, the composition was computed by calculation from the mixing ratio at the time of film manufacture.

(3) Contained particle concentration in film It calculated by calculation from the particle concentration in the particle master produced by adding particles during polymerization and the particle master concentration in the film.
The particle concentration in the particle master was determined from the following by dissolving 10 g of the master chip in 100 g of orthochlorophenol and centrifuging the particles from the polyester.
(Particle concentration) = (particle mass) / (total film mass) × 100
(4) Average particle diameter of particle The cross section which cut | disconnected the film is observed by 10000 times using the transmission electron microscope (TEM H7100 by Hitachi, Ltd.), and the image of particle | grains is processed with an image analyzer. The number average diameter D obtained by performing the following numerical processing with the number of particles of 1000 with different observation locations was defined as the average particle size.
D = ΣDi / N (Di: equivalent circle diameter of particles, N: number of particles)
(5) Film haze Based on JIS K 7105 (1985), the film haze was measured using a haze meter (HGM-2GP manufactured by Suga Test Instruments Co., Ltd.). The measurement was performed at three arbitrary locations, and the average value was adopted. In addition, the haze in this invention shows the haze value with respect to film thickness.

(6) Transmittance in the wavelength range of 300 to 320 nm and 320 to 360 nm The film was cut into a square having a length of 50 mm and a width of 50 mm in the longitudinal direction and the width direction to obtain a sample. The transmittance was measured with a basic configuration using an integrating sphere attached to a spectrophotometer (U-4100 Spectrophotometer) manufactured by Hitachi, Ltd. (incident angle 0 °). The measurement is based on the sub-white plate of aluminum oxide attached to the apparatus, the measurement conditions are slit 2 nm (visible) / automatic control (infrared), gain 2 and scanning speed 600 nm / min. Measured with The transmittance curves in the wavelength range of 300 to 320 nm and 320 to 360 nm were obtained, and the average transmittance was obtained. The measurement was performed 5 times for each sample, and the average value was evaluated.

(7) Light resistance test 1
The film was cut into a square having a length of 50 mm and a width of 50 mm in the longitudinal direction and the width direction to obtain a sample. Using a light resistance tester (Iwasaki Electric Co., Ltd. metal halide lamp type eye super UV tester, SUV-W151), the light resistance test was performed by leaving it at 60 ° C. × 50% RH for 24 hours.
(8) Light resistance test 2
The film was cut into a square having a length of 50 mm and a width of 50 mm in the longitudinal direction and the width direction to obtain a sample. Using a sunshine carbon arc lamp type light resistance tester defined by JIS B7753 (Sunshine Weather Meter S80D, manufactured by Suga Test Instruments Co., Ltd.), the light resistance test was performed by leaving it at 60 ° C. for 1000 hours.

(9) Transmission color tone difference ΔE (E2-E1)
The color tone of the film sample before the light resistance test and the film sample after the light resistance test of (7) and (8) was measured using a Konica Minolta Co., Ltd. CM-3600d under target mask conditions with a measurement diameter of φ25.4 mm. Then, the L * value, a ^* value, and b ^* value were measured five times for each sample by the SCI method, and ΔE was calculated from the following formula based on the average value. The white calibration plate was CM-A103, and the zero calibration box was CM-A104.
ΔE = √ {( _before L * value _test−after L * value _test ) ² + ( _before a * value _test−after a * value _test ) ² + ( _before b * value _test−after b * value _test ) ² }
(10) Transmission color tone b ^*
The transmission ^{b *} values of each film, using CM-3600d manufactured by Konica Minolta Co., target mask under the conditions of measurement diameter φ25.4mm, ^{L *} values and ^{a *} values at SCI method, the ^{b *} value Each sample was performed 5 times, and ΔE was calculated from the following formula based on the average value. The white calibration plate was CM-A103, and the zero calibration box was CM-A104.

(11) Formability, whitening after molding Using a far infrared heater at 450 ° C., the film was heated to a surface temperature of 150 ° C. and heated to 60 ° C. (70 × 70 mm, high And vacuum / pressure formation (pressure: 0.2 Ma). Three types of square dies, R, 1 mm, 2 mm, and 3 mm were prepared for the edge portion, respectively, and vacuum / compression molding was performed. The state of being molded along the mold was evaluated according to the following criteria.
S: Molded with R1 mm (R1 mm could be reproduced).
A: Molding was possible at R2 mm (R2 mm could be reproduced), but molding was not possible at R1 mm.
B: R3 mm could be molded (R3 mm could be reproduced), but R2 mm could not be molded.
C: Could not be molded with R3 mm.
Moreover, the whitening state after molding was evaluated according to the following criteria.
○: Visually confirmed with three-wavelength fluorescent lamp reflection and no whitening confirmed ×: Visually confirmed with three-wavelength fluorescent lamp reflection and whitened (12) Root mean square roughness curve height (Rq)
The film was cut into a square having a length of 50 mm and a width of 50 mm in the longitudinal direction and the width direction to obtain a sample. The three-dimensional arithmetic root mean square roughness curve height (Sq) of the sample surface was measured using a trade name VertScan 2.0R5200G manufactured by Ryoka System. The measurement was performed under the following conditions.
Measurement mode: Wave mode
Field size: 640 × 480
Used filter: 530 nm white filter
Objective lens magnification: x10
Zoom lens magnification: x1
Measurement range for each measurement: 1.25 mm x 1.0 mm
Integration count: 1 time
The raw data obtained under the above conditions was subjected to only fourth-order surface correction without interpolation, and used as measurement data. It calculated and calculated | required based on the following formula | equation from this measurement data.

(13) Scratch resistance A4 size cut sample was used as the film.
A pencil hardness test was performed according to the standard of JIS K5600-5-4 (ISO / DIN 15184). The measurement was performed under the following conditions.
(13-1) Apparatus: VF2391 manufactured by Co-Tech Co., Ltd.
(13-2) Pencil: MITSU-BISHI
Push the device at a speed of 0.5-1 mm / sec from the operator at a distance of at least 7 mm.
Examine the surface with the naked eye to determine the type of trace.
The test is repeated with the hardness scale raised until a scratch mark of 3 mm or more is generated even if the number of test sites is small.
Underlay: 3mm thick glass plate (Manufacture of polyester)
The polyester resin used for film formation was prepared as follows.

(Polyester A)
Polyethylene terephthalate resin (inherent viscosity 0.65) in which the terephthalic component is 100 mol% as the dicarboxylic acid component, the ethylene glycol component is 98.8 mol%, and the diethylene glycol component is 1.2 mol% as the glycol component.

(Polyester B)
Copolyester (GN001 manufactured by Eastman Chemical Co., Ltd.) obtained by copolymerizing 33 mol% of 1,4-cyclohexanedimethanol with respect to the glycol component was used as cyclohexanedimethanol copolymerized polyethylene terephthalate (inherent viscosity 0.75).

(Particle Master C)
Polyethylene terephthalate particle master (intrinsic viscosity 0.65) containing polyester A with aggregated silica particles having an average particle size of 2.2 μm at a particle concentration of 2 mass%.

(UV absorber master D)
Polyester A prepared as described above and Adeka stab LA31 (CAS No. 103597-45-1) manufactured by ADEKA as a UV absorber were mixed at a mass ratio of 80:20, and 280 using a vent type twin screw extruder. The mixture was kneaded at 0 ° C. to prepare a UV absorber master.

Example 1
As layer A, polyester A and polyester B are mixed at a mass ratio of 60:40 and supplied to a bent twin-screw extruder having an oxygen concentration of 0.2% by volume. As layer B, polyester A, polyester B and particle master C And UV absorber master D are mixed at a mass ratio of 62.3: 20.0: 0.2: 17.5 and supplied to a bent twin-screw extruder having an oxygen concentration of 0.2% by volume. The mixture was melted at 280 ° C. with a machine and measured with a gear pump so that the discharge ratio was A layer composition / B layer composition = 7/3, and after passing through a filter, they were joined by a feed block. . The merged A layer and B layer were laminated bodies in which B layer / A layer / B layer = 15/70/15.

  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.

  Next, before stretching in the longitudinal direction, the film temperature is raised with a heated roll, the preheating temperature is 85 ° C., the stretching temperature is 90 ° C., and the film is stretched 3 times in the longitudinal direction, and immediately controlled at 40 ° C. Cooled down.

  Next, the film was stretched 3.3 times in the width direction at a preheating temperature of 95 ° C. and a stretching temperature of 100 ° C. with a tenter-type transverse stretching machine, and the temperature was maintained at 230 ° C. for 5 seconds while relaxing 4% in the width direction. Heat treatment was performed to obtain a biaxially oriented laminated polyester film having a film thickness of 100 μm.

(Example 2)
As layer B, polyester A, polyester B, particle master C and UV absorber master D were mixed in a mass ratio of 64.8: 20.0: 0.2: 15.0 in the same manner as in Example 1. Thus, a biaxially oriented laminated polyester film was obtained. The results are shown in Table 1.

(Example 3)
As layer B, polyester A, polyester B, particle master C, and UV absorber master D were mixed in a mass ratio of 59.8: 20.0: 0.2: 20.0 in the same manner as in Example 1. Thus, a biaxially oriented laminated polyester film was obtained. The results are shown in Table 1.

Example 4
While metering with a gear pump so that the discharge ratio was A layer composition / B layer composition = 6/4, the mixture was passed through a filter and then merged with a feed block. A biaxially oriented laminated polyester film was obtained in the same manner as in Example 1 except that the joined A layer and B layer were laminated layers of B layer / A layer / B layer = 20/60/20. . The results are shown in Table 1.

(Example 5)
While metering with a gear pump so that the discharge ratio was A layer composition / B layer composition = 8/2, the mixture was passed through a filter and then merged with a feed block. A biaxially oriented laminated polyester film was obtained in the same manner as in Example 1 except that the joined A layer and B layer were laminated layers of B layer / A layer / B layer = 10/80/10. . The results are shown in Table 1.

(Example 6)
As layer B, polyester A, polyester B, particle master C and UV absorber master D were mixed in a mass ratio of 62.0: 20.0: 0.5: 17.5 in the same manner as in Example 1. Thus, a biaxially oriented laminated polyester film was obtained. The results are shown in Table 1.

(Example 7)
As layer B, polyester A, polyester B, particle master C and UV absorber master D were mixed in a mass ratio of 62.45: 20.0: 0.05: 17.5 in the same manner as in Example 1. Thus, a biaxially oriented laminated polyester film was obtained. The results are shown in Table 1.

(Example 8)
As layer B, polyester A, polyester B, particle master C and UV absorber master D were mixed in a mass ratio of 61.5: 20.0: 1.0: 17.5 in the same manner as in Example 1. Thus, a biaxially oriented laminated polyester film was obtained. The results are shown in Table 1.

Example 9
As layer B, polyester A, polyester B, particle master C and UV absorber master D were mixed in a mass ratio of 62.5: 20.0: 0.0: 17.5 in the same manner as in Example 1. Thus, a biaxially oriented laminated polyester film was obtained. The results are shown in Table 1.

(Example 10)
While metering with a gear pump so that the discharge ratio was A layer composition / B layer composition = 6/4, the mixture was passed through a filter and then merged with a feed block. A biaxially oriented laminated polyester film was obtained in the same manner as in Example 2 except that the joined A layer and B layer were laminated layers of B layer / A layer / B layer = 20/60/20. . The results are shown in Table 1.

(Example 11)
While metering with a gear pump so that the discharge ratio was A layer composition / B layer composition = 6.4 / 3.6, the mixture was passed through a filter and then merged in a feed block. A biaxially oriented laminated polyester film was obtained in the same manner as in Example 2 except that the merged A layer and B layer were a laminate laminated with B layer / A layer / B layer = 18/64/18. . The results are shown in Table 1.

(Example 12)
While measuring with a gear pump so that the discharge ratio was A layer composition / B layer composition = 3.8 / 6.2, the mixture was passed through a filter and then merged in a feed block. A biaxially oriented laminated polyester film was obtained in the same manner as in Example 2 except that the joined A layer and B layer were laminated layers of B layer / A layer / B layer = 19/62/19. . The results are shown in Table 1.

(Comparative Example 1)
As layer B, polyester A, polyester B, particle master C, and UV absorber master D were mixed in a mass ratio of 79.8: 20.0: 0.2: 0.0 as in Example 1. Thus, a biaxially oriented laminated polyester film was obtained. The results are shown in Table 1.

(Comparative Example 2)
As layer B, polyester A, polyester B, particle master C and UV absorber master D were mixed in a mass ratio of 54.8: 20.0: 0.2: 25.0 in the same manner as in Example 1. Thus, a biaxially oriented laminated polyester film was obtained. The results are shown in Table 1.

(Comparative Example 3)
As layer B, polyester A, polyester B, particle master C and UV absorber master D were mixed in a mass ratio of 72.3: 20.0: 0.2: 7.5 in the same manner as in Example 1. Thus, a biaxially oriented laminated polyester film was obtained. The results are shown in Table 1.

(Comparative Example 4)
While metering with a gear pump such that the discharge ratio was A layer composition / B layer composition = 10/90, the mixture was passed through a filter and then merged in a feed block. A biaxially oriented laminated polyester film was obtained in the same manner as in Example 1 except that the joined A layer and B layer were laminated layers of B layer / A layer / B layer = 5/90/5. . The results are shown in Table 1.

(Comparative Example 5)
While metering with a gear pump such that the discharge ratio was A layer composition / B layer composition = 5/5, the mixture was passed through a filter and then merged with a feed block. A biaxially oriented laminated polyester film was obtained in the same manner as in Example 1 except that the joined A layer and B layer were laminated layers of B layer / A layer / B layer = 25/50/25. . The results are shown in Table 1.

Since the biaxially oriented laminated polyester film for molding of the present invention has excellent light resistance and moldability, molding materials such as building materials, mobile devices, electrical products, automobile parts, and gaming machine parts are used as molding members using the film. It can be suitably used for decoration.

Claims (5)

A biaxially oriented laminated polyester film for molding that satisfies all of the following conditions (1) to (4).
(1) It has at least A layer and B layer, and B layer is both surface layers.
(2) The polyester resin composition constituting the B layer contains a benzotriazole-based or triazine-based ultraviolet absorber, and the content thereof is 3% by weight or more and 4% by weight or less.
(3) The thickness of the B layer is 10 μm or more and 20 μm or less.
(4) Using a metal halide lamp type eye super UV tester, the transmission color tone ΔE after being left for 24 hours in 60 ° C. × 50% RH is 6 or less. The biaxially oriented laminated polyester film for molding according to claim 1, which satisfies all of the following conditions (1) to (3).
(1) The transmittance at a wavelength of 300 nm to 320 nm is 0.2% or less.
(2) The transmittance at a wavelength of 320 nm to 360 nm is 0.2% or less.
(3) The transmitted color tone b ^* is −1.5 or more and +1.5 or less. The biaxially oriented laminated polyester film for molding according to any one of claims 1 and 2, which satisfies all of the following conditions (1) to (3).
(1) Containing 0.001% by weight or more and 0.010% by weight or less of particles having an average particle diameter of 2 μm or more and 3 μm or less with respect to the entire polyester resin composition constituting the B layer.
(2) The root mean square roughness curve height (Rq) is 10 nm or more.
(3) The film haze is 2.0% or less.   The shaping | molding member using the biaxially-oriented laminated polyester film for shaping | molding in any one of Claims 1-3. The biaxially oriented laminated polyester film for molding according to any one of claims 1 to 4, which satisfies the following conditions (1) and (2).
(1) The product P of the sum of the thicknesses of the B layer and the amount of the ultraviolet absorber contained in the polyester resin composition constituting the B layer is 1.08 or more and 1.20 or less.
P = B layer thickness [μm] × 2 [layer] × UV absorber amount [wt%]
(2) The transmission color tone ΔE after being left for 1000 hours is 3 or less in a sunshine carbon arc lamp type light resistance tester stipulated in JIS B7753.