JP2005068238A - Polyester film for molding and dummy container obtained from the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To obtain a polyester film for molding having excellent moldability in hot molding, elasticity and shape stability (heat shrinkage properties and thickness unevenness) in use as a molding in a normal-temperature atmosphere and excellent light resistance and a dummy container obtained from the same. <P>SOLUTION: The polyester film for molding is a polyester film comprising a copolyester constituted of an aromatic dicarboxylic acid component and a glycol component composed of ethylene glycol, a branched aliphatic glycol and/or an alicyclic glycol and having 180-1,000 MPa stress at 100% elongation in the length direction and in the width direction at 25°C and 1-100 MPa at 100°C and ≤50% light transmittance at 380 nm wavelength. The dummy container is obtained from the polyester film for molding. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention is excellent in in-mold moldability, emboss moldability, printability, transparency, etc., and excellent in heat resistance, and further suitable for use as a member for household appliances, automobile nameplates or building materials having good light resistance. The present invention relates to a polyester film and a dummy container obtained therefrom.

  Conventionally, as a sheet for processing, a polyvinyl chloride film is typical and has been preferably used in terms of workability. On the other hand, the film has problems such as generation of toxic gas when the film burns due to fire and the like, and problems such as bleed out of the plasticizer, and new materials have been demanded according to recent needs for environmental resistance.

  Conventionally, by using a copolymer polyester containing a long-chain linear aliphatic dicarboxylic acid component having 3 or more carbon atoms and / or a long-chain linear aliphatic glycol component as a film raw material, moldability is improved. There are many technical disclosures to be improved. However, the polyester resin is softened by these copolymer components, and has the disadvantages that it is poor in stability and poor in strength and elasticity not only at the time of molding but also when actually used as a molded body. If the copolymer composition ratio of the above components is decreased in order to increase the stability, the moldability is lowered, and it is difficult to achieve both moldability, strength and elasticity.

For example, a polyester film made of polyester containing neopentyl glycol as a copolymerization component is known as the copolymer polyester (see, for example, Patent Documents 1 and 2). The copolymerized polyester film described in these conventional techniques has a thickness of 50 μm or less, and is relatively easy to form.
JP-A-1-252658 Japanese Unexamined Patent Publication No. 1-445699

  However, when the thickness exceeds 50 μm, the co-polyester inherently has a tendency of insufficient control of molecular orientation from the viewpoint of stress reduction during stretching and crystallinity, and elasticity and morphology. Stability may be insufficient. Therefore, there has been a demand for a polyester film that is excellent in elasticity and shape stability (heat shrinkage characteristics, thickness unevenness) when using a molded body in a room temperature atmosphere while maintaining moldability.

On the other hand, in a vending machine for beverages in bottles and cans, dummy containers are displayed instead of actual containers as sample products. Conventionally, a plastic container that faithfully copies the actual product has been used. As these dummy container films, a heat-shrinkable polyester film intended for surface decoration of a container having a complicated shape is disclosed (for example, see Patent Document 3).
JP-A-4-199397

  However, in recent years, in response to demands for space saving and the like of vending machines, the dummy container is also being switched from a fully imitated type to a partially imitated type. That is, in the case of the dummy container, it is only necessary to understand the contents of the product when viewed from substantially the front. The partially-shaped dummy container is produced by, for example, molding a printed polyester film into a substantially half shape by press molding or the like. Accordingly, the display subspace can be reduced by the correspondence, and the economic efficiency is greatly improved. However, in recent years, beverage containers have become more sophisticated, the container shape has become more complex, and the printing on the surface layer has become more demanding for complicated and fine prints. With conventional polyester films, moldability and printability have increased. In this respect, it has become impossible to meet market demands sufficiently.

  Furthermore, when used as a member of a dummy container displayed in a vending machine, for example, conventional products are exposed to fluorescent lamps or sunlight for a long time, so that the printing ink is decomposed by ultraviolet rays contained in these lights. Occur. As a result, there is a problem that the printed body is faded and the display effect is lowered. This problem is not limited to the dummy container member, but is common to household appliances, automobile nameplates and building material members, and improvement of light resistance has been strongly desired.

The object of the present invention is to solve the problems of the prior art, have excellent moldability at the time of heat molding, and elasticity and shape stability (heat shrinkage characteristics, thickness unevenness) when used in a room temperature atmosphere as a molded body. Another object of the present invention is to provide a molding polyester film excellent in light resistance and light resistance, and a dummy container obtained therefrom.
Furthermore, in addition to moldability and light resistance, the polyester film for molding that is excellent in paper feeding stability, ink adhesion, dampening water suitability, etc. in a high-speed UV offset printing press for multicolor printing and capable of high-quality printing is obtained from the same. It is to provide a dummy container.

  That is, the present invention is a polyester film comprising a copolymer polyester composed of an aromatic dicarboxylic acid component, ethylene glycol, and a glycol component containing a branched aliphatic glycol and / or an alicyclic glycol, The film has a 100% elongation stress in the longitudinal and width directions of 180 to 1000 MPa at 25 ° C. and 1 to 100 MPa at 100 ° C., and a light transmittance at a wavelength of 380 nm is 50% or less. For polyester film. Moreover, this invention is a multi-dummy container obtained from the said polyester film for shaping | molding.

  In the molding polyester film of the present invention, the stress at 100% elongation in the longitudinal direction and the width direction of the film is independently controlled at 25 ° C. and 100 ° C., and the light transmittance at a wavelength of 380 nm is 50% or less. It excels in moldability during heating, elasticity and shape stability (thickness unevenness, heat shrinkage characteristics) when used in a room temperature atmosphere as a molded body, and is excellent in light resistance.

  Furthermore, easy molding, which is a feature of the base material, is made by stacking the easy-printing coating layer A on one side of the base material and the easy-sliding coating layer B on the other side. In addition to the properties and light resistance, it is excellent in sheet feeding stability, ink adhesion, dampening water suitability, etc. in a high-speed UV offset printing machine for multicolor printing, and can perform high-quality printing at high speed.

(Function)
The molding polyester film of the present invention includes a copolyester composed of an aromatic dicarboxylic acid component and a glycol component containing ethylene glycol and a branched aliphatic glycol and / or alicyclic glycol. The branched aliphatic glycol and / or alicyclic glycol has a side chain or cyclic structure that suppresses mobility such as free rotation of the molecule, and glass is obtained by copolymerizing such monomers. The melting point (Tm) can be lowered and the elongation at break can be increased without lowering the transition temperature (Tg).

  The molding polyester film of the present invention using such a copolyester as a film raw material has excellent moldability in a high temperature atmosphere during molding, and elasticity and shape stability in a normal temperature atmosphere used as a molded body ( It has the feature of being excellent in heat shrink characteristics and thickness unevenness, and is a polyester film suitable for molding applications.

  The above-mentioned features can be expressed by physical properties of stress at 100% elongation in the longitudinal direction and width direction of 180 to 1000 MPa at 25 ° C. and 1 to 100 MPa at 100 ° C.

  The stress at 100% elongation in the longitudinal direction and the width direction of the film under an atmosphere of 25 ° C. is 180 to 1000 MPa from the viewpoint of achieving both elasticity and shape stability (thickness variation, thermal shrinkage at 150 ° C.) and moldability. It is important that

  The lower limit value of the stress at 100% elongation at 25 ° C. is preferably 210 MPa, particularly preferably 220 MPa, from the viewpoints of elasticity and thickness unevenness in a normal temperature atmosphere when using a molded body.

  On the other hand, in the case of a highly elastic film having a stress at 100% elongation in the 25 ° C. atmosphere exceeding 1000 MPa, the moldability during heat molding tends to deteriorate.

  It is important that the stress at 100% elongation in an atmosphere of 100 ° C. in the longitudinal direction and the width direction of the film is 1 to 100 MPa from the viewpoint of moldability.

  The lower limit value of the stress at 100% elongation in the 100 ° C. atmosphere is preferably 5 MPa, particularly preferably 10 MPa. In a field where high deformability is required, a small stress at 100% elongation in an atmosphere of 100 ° C. is a desirable direction from the viewpoint of moldability. However, when the stress at 100% elongation in a 100 ° C. atmosphere decreases, the stress at 100% elongation at 25 ° C. also decreases, and the elasticity and thickness unevenness in a normal temperature atmosphere tend to deteriorate.

  On the other hand, the stress at 100% elongation at 100 ° C. is preferably 90 MPa, particularly preferably 80 MPa, from the viewpoint of moldability during heat molding.

  From the viewpoint of moldability, the breaking elongation at 100 ° C. is preferably 150% or more, more preferably 170% or more, and particularly preferably 200% or more.

  From the viewpoint of shape stability, the elongation at break at 25 ° C. is preferably 130% or more, more preferably 150% or more, and particularly preferably 170% or more.

  Furthermore, from the point of balance of moldability in the vertical direction and the horizontal direction, the stress ratio at 100% elongation in the longitudinal direction and the width direction at 100 ° C. (the higher numerical value / the lower numerical value) is 1.05-1. .60 is preferred. The upper limit is particularly preferably 1.40. When the upper limit value exceeds 1.60, dimensional stability at the time of molding, printing deviation, and the like are likely to deteriorate.

  In the present invention, the change rate of the stress at 100% elongation in the longitudinal direction and the width direction at 100 ° C. as the temporal stability of workability ((after 1 month of film formation-immediately after film formation) × 100 / immediately after film formation) However, it is preferable that both are ± 20% or less. More preferably, it is ± 10% or less, and particularly preferably ± 5% or less.

  The thickness of the polyester film for molding of the present invention is more than 50 μm and 500 μm or less from the viewpoints of moldability, covering properties when a printed layer is provided to enhance the design of the film, film surface protection, and design properties. It is preferable. The lower limit of the film thickness is preferably 60 μm, particularly preferably 70 μm. On the other hand, the upper limit value of the film thickness is preferably 300 μm, particularly preferably 200 μm.

  The film thickness unevenness is preferably 5.5% or less. If the thickness unevenness exceeds 5.5%, the printability and dimensional stability tend to deteriorate.

  Furthermore, the fact that the thermal shrinkage rate in the longitudinal direction and the width direction at 150 ° C. of the film is 3.0% or less reduces printing deviation after providing a printing layer on the molding polyester film in order to enhance the design. To preferred.

  In addition, the molding film preferably has a haze H (%) ratio (H / d) of 0.030 or less to a thickness d (μm) from the viewpoint of transparency and print sharpness. The H / d is more than 0 and preferably 0.025 or less, particularly preferably 0.015 or less.

  The lower limit of the H / d is preferably closer to zero from the viewpoint of transparency and print sharpness, but if the necessary minimum unevenness is not formed on the film surface, handling properties such as slipperiness and rollability deteriorate, Since the film surface may be scratched or productivity may deteriorate, the lower limit value of H / d is preferably set to 0.001, particularly preferably 0.005. In the case of a translucent nameplate using a backlight or the like, a high degree of transparency is required. Therefore, the H / d is preferably closer to zero.

  Since the polyester film for molding of the present invention has a light transmittance at a wavelength of 380 nm of 50% or less, for example, the light resistance of a printing layer applied to the molding polyester film of the present invention for decoration can be improved. .

  Hereinafter, preferred embodiments of the present invention will be described in detail.

  The polyester in the present invention means a general term for high molecular weight substances constituted by ester bonds.

  In the polyester film of the present invention, a copolymer polyester composed of an aromatic dicarboxylic acid component, ethylene glycol, and a glycol component containing a branched aliphatic glycol and / or an alicyclic glycol as a part of the film raw material, Or use 100%.

  In the copolymerized polyester, the aromatic dicarboxylic acid component is mainly composed of terephthalic acid or an ester-forming derivative thereof. The amount of the terephthalic acid component with respect to the total dicarboxylic acid component is 70 mol% or more, preferably 85 mol% or more, particularly preferably. Is 95 mol% or more, and particularly preferably 100 mol%.

  Examples of the branched aliphatic glycol include neopentyl glycol, 1,2-propanediol, and 1,2-butanediol. Examples of the alicyclic glycol include 1,4-cyclohexanedimethanol and tricyclodecane dimethylol.

  Among these, neopentyl glycol and 1,4-cyclohexanedimethanol are particularly preferable, and the stress at 100% elongation in the longitudinal direction and the width direction of the film defined in the present invention is 180 to 1000 MPa at 25 ° C. and 100 ° C. It is effective for satisfying 1 to 100 MPa. Furthermore, it is not only excellent in moldability and transparency, but also excellent in heat resistance, and is preferable from the viewpoint of improving adhesion with a coating layer such as a printing layer.

  Furthermore, you may use together the following dicarboxylic acid component and / or glycol component as a copolymerization component in the said copolyester as needed, if necessary.

  Other dicarboxylic acid components that can be used in combination with terephthalic acid or its ester-forming derivatives include (1) isophthalic acid, 2,6-naphthalenedicarboxylic acid, diphenyl-4,4′-dicarboxylic acid, diphenoxyethanedicarboxylic acid Aromatic dicarboxylic acids such as acid, diphenylsulfone dicarboxylic acid, 5-sodium sulfoisophthalic acid, phthalic acid or their ester-forming derivatives, (2) oxalic acid, succinic acid, adipic acid, sebacic acid, dimer acid, maleic acid Aliphatic dicarboxylic acids such as fumaric acid and glutaric acid or ester-forming derivatives thereof; (3) alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid or ester-forming derivatives thereof; (4) p-oxybenzoic acid; Oxycarboxylic acids such as oxycaproic acid or their esthetics Forming derivatives, and the like.

  On the other hand, examples of other glycol components that can be used together with ethylene glycol and branched aliphatic glycol and / or alicyclic glycol include 1,3-propanediol, 1,4-butanediol, pentanediol, and hexane. Examples include aliphatic glycols such as diols, aromatic glycols such as bisphenol A and bisphenol S, and ethylene oxide adducts thereof, diethylene glycol, and triethylene glycol.

  Furthermore, a polyfunctional compound such as trimellitic acid, trimesic acid, and trimethylolpropane can be further copolymerized with the copolymerized polyester as necessary.

  Examples of the catalyst used for producing the copolymer polyester include alkaline earth metal compounds, manganese compounds, cobalt compounds, aluminum compounds, antimony compounds, titanium compounds, titanium / silicon composite oxides, and germanium compounds. . Among these, titanium compounds, antimony compounds, and germanium compounds are preferable from the viewpoint of catalytic activity.

  When producing the copolymer polyester, it is preferable to add a phosphorus compound as a heat stabilizer. As said phosphorus compound, phosphoric acid, phosphorous acid, etc. are preferable, for example.

  The copolyester preferably has an intrinsic viscosity of 0.50 dl / g or more, more preferably 0.55 dl / g or more, and particularly preferably 0.00 from the viewpoint of moldability, adhesiveness, and film formation stability. 60 dl / g or more. If the intrinsic viscosity is less than 0.50 dl / g, the moldability tends to decrease.

  In the polyester film of the present invention, the copolymer polyester may be used as a film raw material as it is, or a copolymer polyester having a large composition of copolymer components may be blended with a homopolyester to adjust the amount of copolymer components. Absent.

  Moreover, it is preferable from the point of a moldability to blend 2 or more types of the said copolyester and to use as a raw material of the polyester film of this invention. Among these, a mixed polymer obtained by blending polyneopentene terephthalate and / or polycyclohexanedimethylene terephthalate with polyethylene terephthalate is particularly preferable from the viewpoint of flexibility and moldability.

  The melting point of the polyester film in the present invention is preferably 230 to 270 ° C. from the viewpoint of heat resistance and moldability. The lower limit of the melting point is more preferably 235 ° C, particularly preferably 240 ° C. If the melting point is less than 230 ° C, the heat resistance tends to deteriorate. Therefore, it may become a problem when exposed to high temperatures during molding or use of the molded body. Here, the melting point of the polyester film is an endothermic peak temperature at the time of melting detected at the time of primary temperature rise in so-called differential scanning calorimetry (DSC).

  Further, it is preferable to form irregularities on the film surface in order to improve handling properties such as slipperiness and winding property of the film. As a method for forming irregularities on the film surface, a method of incorporating particles in the film is generally used.

  Examples of the particles include known externally precipitated particles having an average particle diameter of 0.01 to 10 μm, externally added particles such as inorganic particles and / or organic particles. When particles having an average particle diameter exceeding 10 μm are used, defects in the film are liable to occur and the design properties tend to deteriorate. On the other hand, in the case of particles having an average particle diameter of less than 0.01 μm, handling properties such as film slipperiness and winding property tend to be lowered.

  Examples of the externally added particles include, for example, wet and dry silica, colloidal silica, aluminum silicate, titanium oxide, calcium carbonate, calcium phosphate, barium sulfate, alumina, mica, kaolin, clay, hydroxyapatite, and other inorganic particles such as styrene, silicone, Organic particles containing acrylic acid as a constituent can be used. Among these, inorganic particles such as dry, wet and dry colloidal silica and alumina, and organic particles containing styrene, silicone, acrylic acid, methacrylic acid, polyester, divinylbenzene and the like as constituent components are preferably used. Two or more of these internal particles, inorganic particles and / or organic particles may be used in combination as long as the properties are not impaired.

  Furthermore, the content of the particles in the film is preferably in the range of 0.001 to 10% by mass. When the amount is less than 0.001% by mass, the handling property is likely to be deteriorated, for example, the slipperiness of the film is deteriorated or winding becomes difficult. . On the other hand, if it exceeds 10% by mass, it tends to cause coarse protrusions and deterioration of film forming properties.

  The polyester film of the present invention is preferably an unstretched film for applications that require severe moldability. From the viewpoint of heat resistance and dimensional stability, a biaxially stretched polyester film is preferred. Such a biaxial stretching method may be either simultaneous biaxial stretching or sequential biaxial stretching.

  The polyester film of the present invention can be made into a laminated structure by a known method using different types of polyester. The form of such a laminated film is not particularly limited. For example, a laminated form of a two-layer structure of A / B, a three-layer structure of B / A / B, and a three-layer structure of C / A / B. Is mentioned.

  Although it does not specifically limit as a manufacturing method of the polyester film of this invention, For example, after drying polyester as needed, it supplies to a well-known melt extruder, it extrudes in a sheet form from a slit-shaped die, an electrostatic application etc. The method of sticking to a casting drum by this method, cooling and solidifying to obtain an unstretched sheet, and then biaxially stretching the unstretched sheet is exemplified.

  Such a stretching method may be either simultaneous biaxial stretching or sequential biaxial stretching. In short, the unstretched sheet is stretched and heat-treated in the longitudinal direction (MD) and the width direction (TD) of the film, and the intended surface. A method of obtaining a biaxially stretched film having an internal orientation degree is employed. Among these methods, in terms of film quality, the MD / TD method in which the film is stretched in the longitudinal direction and then stretched in the width direction, or the TD / MD method in which the film is stretched in the width direction and then stretched in the longitudinal direction. An axial stretching method and a simultaneous biaxial stretching method in which the longitudinal direction and the width direction are stretched almost simultaneously are desirable. Furthermore, if necessary, a multistage stretching method in which stretching in the same direction is performed in multiple stages may be used.

  The film stretching ratio when biaxially stretching is preferably 1.6 to 4.2 times in the longitudinal direction and the width direction, particularly preferably 1.7 to 4.0 times. In this case, the stretching ratio in the longitudinal direction and the width direction may be either larger or the same ratio.

  In the polyester film of the present invention, (1) a copolymer polyester comprising terephthalic acid and ethylene glycol or neopentyl glycol, or (2) a copolymer polyester comprising terephthalic acid, ethylene glycol or 1,4-cyclohexanedimethanol is used. In this case, in order for the stress at 100% elongation in the longitudinal direction and the width direction to be 180 to 1000 MPa at 25 ° C. and 1 to 100 MPa at 100 ° C., the stretching ratio in the longitudinal direction is 2.8 to 4.0 times, the width The stretching ratio in the direction is preferably 3.0 to 4.5 times.

  The stretching conditions for producing the polyester film of the present invention are not particularly limited. However, in order to satisfy the range of stress at 100% elongation at 25 ° C. and 100 ° C. defined in the present invention, it is preferable to adopt the following conditions, for example.

  In the longitudinal stretching, the stretching temperature is preferably 50 to 110 ° C. and the stretching ratio is preferably 1.5 to 4.0 times so that the subsequent lateral stretching can be performed smoothly.

  In transverse stretching, stress at 100% elongation in the longitudinal direction and the width direction is particularly important because the stress at 25 ° C. is 180 to 1000 MPa and 100 ° C. is 1 to 100 MPa.

  Usually, when stretching the polyethylene terephthalate, if the stretching temperature is lower than the appropriate conditions, the yield stress increases rapidly at the beginning of the lateral stretching, and therefore stretching cannot be performed. Moreover, even if it can extend | stretch, since thickness and a draw ratio become easy to become nonuniform, it is unpreferable.

  In addition, when the stretching temperature is higher than appropriate conditions, the initial stress is low, but the stress does not increase even when the stretch ratio is high. Therefore, the film has a small stress at 100% elongation at 25 ° C. Therefore, by taking the optimum stretching temperature, a highly oriented film can be obtained while ensuring stretchability.

  However, when the copolymerized polyester contains 1 to 40 mol% of a copolymer component, the stretching stress rapidly decreases as the stretching temperature is increased so as to eliminate the yield stress. In particular, since the stress does not increase even in the latter half of the stretching, the orientation does not increase and the stress at 100% elongation at 25 ° C. decreases.

  Such a phenomenon is likely to occur when the thickness of the film is 60 to 500 μm, and is particularly noticeable in a film having a thickness of 100 to 300 μm. Therefore, for example, in the case of a film using polyester copolymerized with neopentyl glycol or 1,4-cyclohexanedimethanol, the stretching temperature in the transverse direction is preferably set as follows.

  First, the preheating temperature is 90 to 120 ° C., and the preheating temperature is preferably +5 to 25 ° C. in the first half of the transverse stretching, and the first half is preferably −15 to −40 ° C. in the second half of the transverse stretching. By adopting such conditions, the first half of the transverse stretching is easy to stretch because the yield stress is small, and the second half is easily oriented. In addition, it is preferable that the draw ratio of a horizontal direction shall be 22.5-5.0 times. As a result, it is possible to obtain a film in which the stress at 100% elongation in the longitudinal direction and the width direction satisfies 180 to 1000 MPa at 25 ° C. and 1 to 100 MPa at 100 ° C.

  Further, the film is subjected to heat treatment after biaxial stretching, and this heat treatment can be performed by a conventionally known method such as in an oven or on a heated roll. Further, the heat treatment temperature and the heat treatment time can be arbitrarily set according to the required level of heat shrinkage. The heat treatment temperature is preferably in the range of 120 to 245 ° C, particularly preferably 150 to 230 ° C. The heat treatment time is preferably 1 to 60 seconds. In addition, you may perform this heat processing, relaxing a film to the longitudinal direction and / or the width direction. In order to reduce the thermal shrinkage in the longitudinal direction and the lateral direction at 150 ° C., it is preferable to increase the heat treatment temperature, lengthen the heat treatment time, and perform relaxation treatment. It is difficult to lengthen the line and increase the heat treatment time due to equipment limitations. Further, when the film feeding speed is slowed, productivity is lowered.

  In order to set the thermal shrinkage rate in the longitudinal direction and the width direction at 150 ° C. to 3.0% or less, the heat treatment temperature is preferably 200 to 220 ° C. and relaxed at a relaxation rate of 1 to 8%. Furthermore, re-stretching may be performed once or more in each direction, and then heat treatment may be performed.

  The molding polyester film of the present invention needs to have a light transmittance at a wavelength of 380 nm of 50% or less, preferably 65% or less, particularly preferably 80% or less. When the light transmittance is less than 50%, when the polyester film for molding, particularly the film, is printed, the light resistance of the printed layer is deteriorated.

  A method of setting the light transmittance at a wavelength of 380 nm to 50% or less is arbitrary without limitation, but a method of blending an ultraviolet absorber in any of the constituent layers of the molding polyester film is recommended. The constituent layer may be the above-described base material, a coating layer described later, or both.

  The ultraviolet absorber used in the above method may be appropriately selected without limitation as long as it can impart the above-mentioned characteristics. Any of inorganic, organic, and polymer systems may be used. Examples of organic ultraviolet absorbers include benzotoazole, benzophenone, cyclic imino ester, and combinations thereof. From the viewpoint of durability, benzotoazole and cyclic imino ester are particularly preferable. When two or more kinds of ultraviolet absorbers are used in combination, ultraviolet rays having different wavelengths can be absorbed simultaneously, so that the ultraviolet absorption effect can be further improved.

  Examples of the benzotriazole ultraviolet absorber include 2- [2′-hydroxy-5 ′-(methacryloyloxymethyl) phenyl] -2H-benzotriazole, 2- [2′-hydroxy-5 ′-(methacryloyloxyethyl). ) Phenyl] -2H-benzotriazole, 2- [2'-hydroxy-5 '-(methacryloyloxypropyl) phenyl] -2H-benzotriazole, 2- [2'-hydroxy-5'-(methacryloyloxyhexyl) phenyl ] -2H-benzotriazole, 2- [2'-hydroxy-3'-tert-butyl-5 '-(methacryloyloxyethyl) phenyl] -2H-benzotriazole, 2- [2'-hydroxy-5'-tert -Butyl-3 '-(methacryloyloxyethyl) phenyl] -2 -Benzotriazole, 2- [2'-hydroxy-5 '-(methacryloyloxyethyl) phenyl] -5-chloro-2H-benzotriazole, 2- [2'-hydroxy-5'-(methacryloyloxyethyl) phenyl] -5-methoxy-2H-benzotriazole, 2- [2'-hydroxy-5 '-(methacryloyloxyethyl) phenyl] -5-cyano-2H-benzotriazole, 2- [2'-hydroxy-5'-( Methacryloyloxyethyl) phenyl] -5-tert-butyl-2H-benzotriazole, 2- [2'-hydroxy-5 '-(methacryloyloxyethyl) phenyl] -5-nitro-2H-benzotriazole, and the like. However, it is not particularly limited to these.

  Examples of the cyclic imino ester ultraviolet absorber include 2,2 ′-(1,4-phenylene) bis (4H-3,1-benzoxazinon-4-one), 2-methyl-3,1-benzo. Oxazin-4-one, 2-butyl-3,1-benzoxazin-4-one, 2-phenyl-3,1-benzoxazin-4-one, 2- (1- or 2-naphthyl) -3,1 -Benzoxazin-4-one, 2- (4-biphenyl) -3,1-benzoxazin-4-one, 2-p-nitrophenyl-3,1-benzoxazin-4-one, 2-m-nitro Phenyl-3,1-benzoxazin-4-one, 2-p-benzoylphenyl-3,1-benzoxazin-4-one, 2-p-methoxyphenyl-3,1-benzoxazin-4-one, 2 -O-metoki Phenyl-3,1-benzoxazin-4-one, 2-cyclohexyl-3,1-benzoxazin-4-one, 2-p- (or m-) phthalimidophenyl-3,1-benzoxazin-4-one 2,2 '-(1,4-phenylene) bis (4H-3,1-benzoxazinon-4-one) 2,2'-bis (3,1-benzoxazin-4-one), 2, 2'-ethylenebis (3,1-benzoxazin-4-one), 2,2'-tetramethylenebis (3,1-benzoxazin-4-one), 2,2'-decamethylenebis (3 1-benzoxazin-4-one), 2,2′-p-phenylenebis (3,1-benzoxazin-4-one), 2,2′-m-phenylenebis (3,1-benzoxazine-4 -On), 2,2 '-(4 4'-diphenylene) bis (3,1-benzoxazin-4-one), 2,2 '-(2,6- or 1,5-naphthalene) bis (3,1-benzoxazin-4-one), 2,2 '-(2-methyl-p-phenylene) bis (3,1-benzoxazin-4-one), 2,2'-(2-nitro-p-phenylene) bis (3,1-benzoxazine -4-one), 2,2 '-(2-chloro-p-phenylene) bis (3,1-benzoxazin-4-one), 2,2'-(1,4-cyclohexylene) bis (3 , 1-Benzoxazin-4-one) 1,3,5-tri (3,1-benzoxazin-4-one-2-yl) benzene, 1,3,5-tri (3,1-benzoxazine- 4-On-2-yl) naphthalene and 2,4,6-tri (3,1- Nzookisajin-4-one-2-yl) naphthalene. 2,8-dimethyl-4H, 6H-benzo (1,2-d; 5,4-d ') bis- (1,3) -oxazine-4,6-dione, 2,7-dimethyl-4H, 9H -Benzo (1,2-d; 5,4-d ') bis- (1,3) -oxazine-4,9-dione, 2,8-diphenyl-4H, 8H-benzo (1,2-d; 5,4-d ') bis- (1,3) -oxazine-4,6-dione, 2,7-diphenyl-4H, 9H-benzo (1,2-d; 5,4-d') bis- (1,3) -Oxazine-4,6-dione, 6,6'-bis (2-methyl-4H, 3,1-benzoxazin-4-one), 6,6'-bis (2-ethyl- 4H, 3,1-benzoxazin-4-one), 6,6′-bis (2-phenyl-4H, 3,1-benzoxazin-4-one), 6, '-Methylenebis (2-methyl-4H, 3,1-benzoxazin-4-one), 6,6'-methylenebis (2-phenyl-4H, 3,1-benzoxazin-4-one), 6,6 '-Ethylenebis (2-methyl-4H, 3,1-benzoxazin-4-one), 6,6'-ethylenebis (2-phenyl-4H, 3,1-benzoxazin-4-one), 6 , 6'-Butylenebis (2-methyl-4H, 3,1-benzoxazin-4-one), 6,6'-Butylenebis (2-phenyl-4H, 3,1-benzoxazin-4-one), 6 , 6'-oxybis (2-methyl-4H, 3,1-benzoxazin-4-one), 6,6'-oxybis (2-phenyl-4H, 3,1-benzoxazin-4-one), 6 , 6'-sulfonylbis ( -Methyl-4H, 3,1-benzoxazin-4-one), 6,6'-sulfonylbis (2-phenyl-4H, 3,1-benzoxazin-4-one), 6,6'-carbonylbis (2-methyl-4H, 3,1-benzoxazin-4-one), 6,6'-carbonylbis (2-phenyl-4H, 3,1-benzoxazin-4-one), 7,7'- Methylenebis (2-methyl-4H, 3,1-benzoxazin-4-one), 7,7'-methylenebis (2-phenyl-4H, 3,1-benzoxazin-4-one), 7,7'- Bis (2-methyl-4H, 3,1-benzoxazin-4-one), 7,7'-ethylenebis (2-methyl-4H, 3,1-benzoxazin-4-one), 7,7 ' -Oxybis (2-methyl-4H, 3,1- Benzoxazin-4-one), 7,7'-sulfonylbis (2-methyl-4H, 3,1-benzoxazin-4-one), 7,7'-carbonylbis (2-methyl-4H, 3 1-benzoxazin-4-one), 6,7'-bis (2-methyl-4H, 3,1-benzoxazin-4-one), 6,7'-bis (2-phenyl-4H, 3 1-benzoxazin-4-one), 6,7'-methylenebis (2-methyl-4H, 3,1-benzoxazin-4-one), and 6,7'-methylenebis (2-phenyl-4H, 3 , 1-benzoxazin-4-one), and the like.

  When blending the organic ultraviolet absorber into the base film, it is exposed to a high temperature in the extrusion process, and therefore, it is necessary to use an ultraviolet absorber having a thermal decomposition starting temperature of 290 ° C. or higher when forming the film. It is preferable in reducing process contamination. If an ultraviolet absorber having a thermal decomposition start temperature of 290 ° C or lower is used, the decomposed product of the ultraviolet absorber adheres to the roll group of the manufacturing apparatus during film formation, and may reattach to the film or be damaged. This is not preferable because it causes optical defects.

  Examples of inorganic ultraviolet absorbers include ultrafine particles of metal oxides such as cerium oxide, zinc oxide, and titanium oxide, but are not particularly limited thereto. In addition, as the polymer ultraviolet absorber, the product name NOVAPEX U-110 of Mitsubishi Chemical, the product name PUVA of Otsuka Chemical, and the product name ULS of Otsuka Kogyo Co., Ltd. are commercially available. In addition, reactive UV absorbers incorporating reactive UV-absorbing functional groups into the polymer chain can be used, and trade names RUVA-93 and RUVA-100 are commercially available from Otsuka Chemical.

  As another method capable of reducing the light transmittance at a wavelength of 380 nm to 50% or less, there is a method of using, for example, naphthalenedicarboxylic acid having absorption in this wavelength region as a polyester copolymerization component.

  The polyester film for molding according to the present invention has the above polyester film as a base material, and an easy-printing coating layer A made of an adhesive modified resin on one side of the base material contains particles and / or waxes on the other side. A configuration in which the slipping coating layer B is laminated is a preferred embodiment. This configuration is excellent in sheet feeding stability, ink adhesion, dampening water suitability, etc. in a high-speed UV offset printing press for multicolor printing, and enables high-quality printing. For example, a high-quality printing surface as a member for a dummy container or the like. It is suitable for fields that require feeling and printing economy.

  In the present invention, the easy-printing coating layer A is not particularly limited as long as it has a function of improving the printability of the polyester film for molding the base material. The coating layer A is (a) a polyester-based graft copolymer obtained by grafting an acid anhydride having at least one double bond to a hydrophobic copolyester resin, and (b) an average particle size of 1.0 to 5 A configuration comprising a composition containing 0.0 μm particles is a preferred embodiment.

  In the present invention, the easy-sliding coating layer B is not particularly limited as long as it has a function of improving the slipping property of the polyester film for molding the base material, and is optional (c) A preferred embodiment comprises a composition comprising a copolyester resin, (d) a compound having a sulfonate group, (e) particles having an average particle size of 1.0 to 5.0 μm, and (f) a polymer wax. It is an aspect.

  The “polyester-based graft copolymer obtained by grafting an acid anhydride having at least one double bond to a hydrophobic copolymerized polyester resin”, which is a constituent component of the easy-printing coating layer A, will be described in detail.

  “Grafting” of a polyester-based graft copolymer is to introduce a branched polymer composed of a polymer different from the main chain into the main chain of the main polymer. Graft polymerization is generally carried out by reacting at least one radical polymerizable monomer using a radical initiator in a state where a hydrophobic copolyester resin is dissolved in an organic solvent.

  The reaction product after completion of the grafting reaction includes a graft copolymer of a desired hydrophobic copolymerized polyester resin and a radically polymerizable monomer, a hydrophobic copolymerized polyester resin not subjected to grafting, and a hydrophobic polymer. It also contains a radical polymerizable monomer that has not been grafted to the copolymerizable polyester resin.

  The polyester-based graft copolymer is not only the above-mentioned polyester-based graft copolymer, but in addition to this, a hydrophobic copolymerized polyester resin that has not undergone grafting, and a radical polymerizability that has not been grafted. A reaction mixture containing monomers and the like is also included.

It is preferable that the acid value of a reaction product obtained by graft polymerization of a radically polymerizable monomer on a hydrophobic copolyester resin is 600 eq / 10 ⁶ g or more. More preferably, the acid value of the reactant is 1200 eq / 10 ⁶ g or more. When the acid value of the reaction product is less than 600 eq / 10 ⁶ g, the adhesion with the printing layer applied to the primer layer (the aforementioned easy-printing coating layer A) tends to be insufficient.

  The mass ratio of the hydrophobic copolymerized polyester resin and the radical polymerizable monomer is preferably in the range of polyester / radical polymerizable monomer = 40/60 to 95/5, more preferably 55/45 to 93 /. 7, particularly preferably in the range of 60/40 to 90/10.

  When the mass ratio of the hydrophobic copolymerized polyester resin is less than 40% by mass, the excellent adhesion of the polyester resin cannot be exhibited. On the other hand, when the mass ratio of the hydrophobic copolyester resin is larger than 95% by mass, blocking, which is a defect of the polyester resin, easily occurs.

  The graft polymerization reaction product is in the form of an organic solvent solution or dispersion or an aqueous solvent solution or dispersion. In particular, a dispersion of an aqueous solvent, that is, a form of a water-dispersible resin is preferable from the viewpoint of work environment and applicability. In order to obtain such a water-dispersible resin, usually, a radically polymerizable monomer containing a hydrophilic radically polymerizable monomer is grafted onto the hydrophobic copolymerized polyester resin in an organic solvent, and then It is achieved by adding water, distilling off the organic solvent.

  The water-dispersible resin means a resin having an average particle diameter of 500 nm or less measured by a laser light scattering method and exhibiting a translucent or milky white appearance. By adjusting the polymerization method, water-dispersible resins having various particle sizes can be obtained. The particle size is suitably 10 to 500 nm, and is preferably 400 nm or less, more preferably 300 nm or less in terms of dispersion stability. It is. When the average particle diameter exceeds 500 nm, the gloss of the coating film surface is lowered, and the transparency of the coating is lowered. When the average particle diameter is less than 10 nm, the water-resistant adhesion tends to be lowered.

  The hydrophilic radical polymerizable monomer used for the polymerization of the water-dispersible resin means a radical polymerizable monomer having a hydrophilic group or a group that can be changed to a hydrophilic group later. Examples of the radical polymerizable monomer having a hydrophilic group include a radical polymerizable monomer containing a carboxyl group, a hydroxyl group, a phosphoric acid group, a phosphorous acid group, a sulfonic acid group, an amide group, a quaternary ammonium base and the like. be able to.

  On the other hand, examples of the radical polymerizable monomer having a group that can be changed to a hydrophilic group include radical polymerizable monomers containing an acid anhydride group, a glycidyl group, a chloro group, and the like. Among these, from the viewpoint of water dispersibility, a carboxyl group is preferable, and a radical polymerizable monomer having a carboxyl group or a group capable of generating a carboxyl group is preferable. Moreover, it is preferable that the radically polymerizable monomer which has a carboxyl group or has a group which generate | occur | produces a carboxyl group is contained from the point which can raise an acid value.

  The glass transition temperature of the polyester-based graft copolymer is not particularly limited, but is preferably 20 ° C. or higher, more preferably 40 ° C. or higher, from the viewpoint of adhesion in a high temperature and high humidity environment.

  The above-mentioned hydrophobic copolyester resin needs to be essentially water-insoluble which does not inherently disperse or dissolve in water. When a polyester resin that is dispersed or dissolved in water is used for graft polymerization, adhesion and water-resistant adhesion deteriorate.

  The composition of the dicarboxylic acid component of this hydrophobic copolyester resin is as follows: aromatic dicarboxylic acid 60 to 99.5 mol%, aliphatic dicarboxylic acid and / or alicyclic dicarboxylic acid 0 to 40 mol%, polymerizable unsaturated dicarboxylic acid. It is preferable that it is 0.5-10 mol% of dicarboxylic acid containing a heavy bond. When the aromatic dicarboxylic acid is less than 60 mol%, or when the aliphatic dicarboxylic acid and / or alicyclic dicarboxylic acid exceeds 40 mol%, the adhesive strength tends to decrease.

  Moreover, when the dicarboxylic acid containing a polymerizable unsaturated double bond is less than 0.5 mol%, it becomes difficult to carry out efficient grafting of the radical polymerizable monomer to the polyester resin. If it exceeds 1, the viscosity will increase too late in the grafting reaction, which tends to hinder the uniform progress of the reaction. More preferably, the aromatic dicarboxylic acid is 70 to 98 mol%, the aliphatic dicarboxylic acid and / or the alicyclic dicarboxylic acid is 0 to 30 mol%, and the dicarboxylic acid containing a polymerizable unsaturated double bond is 2 to 7 mol%. It is.

  Examples of the aromatic dicarboxylic acid include terephthalic acid, isophthalic acid, orthophthalic acid, naphthalene dicarboxylic acid, and biphenyl dicarboxylic acid. It is preferable not to use a hydrophilic group-containing dicarboxylic acid such as 5-sodiumsulfoisophthalic acid from the viewpoint that the water-resistant adhesion decreases.

  Examples of the aliphatic dicarboxylic acid include succinic acid, adipic acid, azelaic acid, sebacic acid, dodecanedioic acid, and dimer acid. Examples of the alicyclic dicarboxylic acid include 1,4-cyclohexanedicarboxylic acid. 1,3-cyclohexanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid and acid anhydrides thereof.

  Examples of dicarboxylic acids containing polymerizable unsaturated double bonds include α, β-unsaturated dicarboxylic acids such as fumaric acid, maleic acid, maleic anhydride, itaconic acid, citraconic acid, unsaturated double bonds As examples of the alicyclic dicarboxylic acid containing 2,5-norbornene dicarboxylic acid anhydride and tetrahydrophthalic anhydride can be given. Of these, fumaric acid, maleic acid and 2,5-norbornene dicarboxylic acid are preferred from the viewpoint of polymerizability.

  On the other hand, the glycol component is composed of an aliphatic glycol having 2 to 10 carbon atoms and / or an alicyclic glycol having 6 to 12 carbon atoms and / or a glycol having an ether bond, but as an aliphatic glycol having 2 to 10 carbon atoms. Is, for example, ethylene glycol, 1,2-propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, neopentyl glycol, 1,6-hexanediol, 3-methyl- Examples include 1,5-pentanediol, 1,9-nonanediol, and 2-ethyl-2-butylpropanediol. Examples of the alicyclic glycol having 6 to 12 carbon atoms include 1,4-cyclohexanedi Mention may be made of methanol.

  Examples of glycols having an ether bond include diethylene glycol, triethylene glycol, dipropylene glycol, and glycols obtained by adding ethylene oxide or propylene oxide to two phenolic hydroxyl groups of bisphenols, such as 2,2 Mention may be made of -bis (4-hydroxyethoxyphenyl) propane. Polyethylene glycol, polypropylene glycol, and polytetramethylene glycol can also be used as necessary.

  Moreover, you may copolymerize 0-5 mol% trifunctional or more polycarboxylic acid and / or a polyol further to the said polyester-type graft copolymer. Examples of the tri- or more functional polycarboxylic acid include trimellitic anhydride, pyromellitic anhydride, benzophenone tetracarboxylic anhydride, trimesic acid, ethylene glycol bis (anhydro trimellitate), glycerol tris (anhydro trimellitate) ) Is used. On the other hand, as the trifunctional or higher functional polyol, for example, glycerin, trimethylolethane, trimethylolpropane, and pentaerythritol are used. The trifunctional or higher polycarboxylic acid and / or polyol is preferably copolymerized to a maximum of 5 mol%, particularly preferably 0 to 3 mol%, based on the total acid component or total glycol component. If the copolymerization ratio exceeds 5 mol%, gelation during polymerization tends to occur, which is not preferable.

  The hydrophobic copolyester resin preferably has a weight average molecular weight in the range of 5,000 to 50,000. If the weight average molecular weight is less than 5,000, the adhesive strength tends to decrease, and conversely if it exceeds 50,000, problems such as gelation during polymerization tend to occur.

  Examples of the polymerizable unsaturated monomer include (1) monoester or diester of fumaric acid such as (1) fumaric acid, monoethyl fumarate, diethyl fumarate, dibutyl fumarate, and (2) maleic acid and its anhydride. Monoester or diester of maleic acid such as monoethyl maleate, diethyl maleate, dibutyl maleate, (3) itaconic acid and its anhydride, monoester or diester of itaconic acid, (4) maleimide such as phenylmaleimide, 5) Styrene derivatives such as styrene, α-methyl styrene, t-butyl styrene, chloromethyl styrene, and other examples include vinyl toluene and divinyl benzene.

  Examples of the acrylic polymerizable monomer include alkyl acrylate and alkyl methacrylate (wherein the alkyl group is methyl group, ethyl group, N-propyl group, isopropyl group, N-butyl group, isobutyl group, t- Butyl group, 2-ethylhexyl group, cyclohexyl group, phenyl group, benzyl group, phenylethyl group, etc.); hydroxy-containing such as 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate Acrylic monomer; acrylamide, methacrylamide, N-methyl methacrylamide, N-methyl acrylamide, N-methylol acrylamide, N-methylol methacrylamide, N, N-dimethylol acrylamide, N-meth Amide group-containing acrylic monomers such as cymethylacrylamide, N-methoxymethylmethacrylamide and N-phenylacrylamide; Amino group-containing acrylic monomers such as N, N-diethylaminoethyl acrylate and N, N-diethylaminoethyl methacrylate; Epoxy group-containing acrylic monomers such as glycidyl acrylate and glycidyl methacrylate; acrylic monomers containing carboxyl groups such as acrylic acid, methacrylic acid and their salts (sodium salt, potassium salt, ammonium salt) or salts thereof It is done. Preferred are maleic anhydride and esters thereof. The said monomer can be copolymerized using 1 type, or 2 or more types.

  The graft polymerization is generally carried out by reacting a radical initiator and a radical polymerizable monomer mixture in a state where a hydrophobic copolyester resin is dissolved in an organic solvent. The reaction product after completion of the grafting reaction includes a graft copolymer between the hydrophobic copolymerized polyester resin and the radical polymerizable monomer mixture, a hydrophobic copolymerized polyester resin that has not undergone grafting, and a hydrophobic polymer. Although the radical polymer which was not grafted to the copolyester resin is also contained, the above-mentioned polyester-based graft copolymer includes all of them.

  Examples of the graft polymerization initiator include organic peroxides and organic azo compounds known to those skilled in the art.

  Examples of the organic peroxide include benzoyl peroxide, t-butyl peroxypivalate, and examples of the organic azo compound include 2,2′-azobisisobutyronitrile, 2,2′-azobis (2, 4-dimethyl pareronitrile).

  The amount of the polymerization initiator used for graft polymerization is at least 0.2% by mass, preferably 0.5% by mass or more, based on the radical polymerizable monomer.

  In addition to the polymerization initiator, a chain transfer agent for adjusting the chain length of the branched polymer, for example, octyl mercaptan, mercaptoethanol, 3-tert-butyl-4-hydroxyanisole can be used as necessary. In this case, it is desirable to add in the range of 0 to 5% by mass with respect to the polymerizable monomer.

  The grafting reaction solvent is preferably composed of an aqueous organic solvent having a boiling point of 50 to 250 ° C. The aqueous organic solvent means a solvent having a solubility in water at 20 ° C. of at least 10 g / L or more, preferably 20 g / L or more. A solvent having a boiling point exceeding 250 ° C. is not preferable because the evaporation rate is extremely slow and it is difficult to sufficiently remove the solvent from the coating film even when the coating film is heated at a high temperature.

  Further, when the grafting reaction is carried out using the aqueous organic solvent as a solvent at a boiling point of less than 50 ° C, it is necessary to use an initiator that cleaves into radicals at a temperature of less than 50 ° C. Since it increases, it is not preferable.

The aqueous organic solvent can be roughly classified into two types.
First, the first aqueous organic solvent can dissolve the copolymer polyester resin well, and can dissolve the polymerizable monomer mixture containing the carboxyl group-containing polymerizable monomer and the polymer thereof relatively well. It is. This is the first group of aqueous organic solvents. Examples of the first group of aqueous organic solvents include esters such as ethyl acetate; ketones such as methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone; cyclic ethers such as tetrahydrofuran, dioxane and 1,3-dioxolane; ethylene glycol dimethyl ether; Glycol ethers such as propylene glycol methyl ether, propylene glycol propyl ether, ethylene glycol ethyl ether, ethylene glycol butyl ether; carbitols such as methyl carbitol, ethyl carbitol, butyl carbitol; ethylene glycol diacetate, ethylene glycol ethyl ether Glycols or lower esters of glycol ethers, such as acetate; Emissions alcohols; dimethylformamide, dimethylacetamide, substituted amides such as N- methylpyrrolidone.

  On the other hand, the second aqueous organic solvent hardly dissolves the copolyester resin, but relatively well dissolves the polymerizable monomer mixture containing the carboxyl group-containing polymerizable monomer and its polymer. It can be done. This is the second group of aqueous organic solvents. Examples of the second group of aqueous organic solvents include water, lower alcohols, lower carboxylic acids, and lower amines, with alcohols having 1 to 4 carbon atoms and glycols being particularly preferred.

  When the grafting reaction is carried out with a single solvent, only one of the first group of aqueous organic solvents can be selected. When using a mixed solvent, there are a case where a plurality of types are selected from only the first group of aqueous organic solvents and a case where at least one type is selected from the first group of aqueous organic solvents and at least one type is added from the second group of aqueous organic solvents.

  Graft polymerization reaction in both cases where the graft polymerization reaction solvent is a single solvent from the first group of aqueous organic solvents and when it is a mixed solvent consisting of each of the first group and the second group of aqueous organic solvents Can be performed.

  However, there are differences in the progress of the grafting reaction, the appearance and properties of the grafting reaction product and the aqueous dispersion derived therefrom, and a mixed solvent composed of each of the first group and the second group of aqueous organic solvents. Is preferred.

  In the first group of solvents, the molecular chain of the polyester-based graft copolymer is in a state where the chain having a large spread is extended, while in the mixed solvent of the first group / second group, the yarn chain having a small spread. It is in a state entangled in a shape. This can be confirmed by measuring the viscosity of the polyester-based graft copolymer in these solutions.

  Further, it is effective for preventing gelation by adjusting the dissolution state of the polyester-based graft copolymer and making intermolecular crosslinking difficult to occur. Coexistence of highly efficient grafting and gelation suppression is achieved in the latter mixed solvent system. The mass ratio of the mixed solvent of the first group / second group is preferably in the range of 95/5 to 10/90, more preferably 90/10 to 20/80, and particularly preferably 85/15 to 30/70. . The optimum mixing ratio is determined according to the solubility of the polyester used.

  The obtained grafting reaction product is preferably neutralized with a basic compound, and can be easily dispersed in water by neutralization.

  As the basic compound, a compound that volatilizes at the time of heating at the time of coating film formation or heat curing after blending the curing agent is desirable, and ammonia, organic amines and the like are preferable. Examples of the organic amine compound include triethylamine, N, N-diethylethanolamine, N, N-dimethylethanolamine, aminoethanolamine, N-methyl-N, N-diethanolamine, isopropylamine, iminobispropylamine, ethylamine, Diethylamine, 3-ethoxypropylamine, 3-diethylaminopropylamine, sec-butylamine, propylamine, methylaminopropylamine, dimethylaminopropylamine, methyliminobispropylamine, 3-methoxypropylamine, monoethanolamine, diethanolamine, tri Mention may be made of ethanolamine.

  The basic compound has a pH value of the aqueous dispersion in the range of 5.0 to 9.0 by at least partial neutralization or complete neutralization, depending on the carboxyl group content contained in the grafting reaction product. It is desirable to use it. If a basic compound with a boiling point of 100 ° C. or lower is used, there are few residual basic compounds in the coating film after drying, adhesion of metals and inorganic deposited films, and water resistance adhesion when laminated with other materials Excellent heat and water resistance.

  In addition, when a basic compound of 100 ° C. or higher is used or the drying conditions are controlled, and the basic compound remains in the coated film after drying at 500 ppm or more, the transfer property of the printing ink is improved.

  In the obtained aqueous dispersion, the weight average molecular weight of the polymer of the radical polymerizable monomer is preferably 500 to 50,000.

  Generally, it is difficult to control the weight average molecular weight of the polymer of the radical polymerizable monomer to be less than 500, the grafting efficiency is lowered, and there is a tendency that hydrophilic groups are not sufficiently imparted to the copolymer polyester. is there. In addition, the graft polymer of the radical polymerizable monomer forms a hydrated layer of dispersed particles. In order to obtain a stable dispersion by providing a sufficiently thick hydrated layer, The weight average molecular weight of the graft polymer is desirably 500 or more.

  The upper limit of the weight average molecular weight of the graft polymer of the radical polymerizable monomer is preferably 50,000 from the viewpoint of polymerizability in solution polymerization. In order to set the weight average molecular weight of the graft polymer of the radical polymerizable monomer within the range of 500 to 50,000, the initiator amount, the monomer dropping time, the polymerization time, the reaction solvent, the monomer composition, or as required The chain transfer agent and the polymerization inhibitor are preferably combined appropriately.

  A reaction product obtained by graft-polymerizing a radically polymerizable monomer to a hydrophobic copolymerized polyester resin has a self-crosslinking property and thus exhibits a high degree of solvent resistance. Although it does not crosslink at room temperature, it undergoes intermolecular reactions such as hydrogen abstraction by thermal radicals with heat during drying, and crosslinks without a crosslinking agent. For the first time, adhesion and water-resistant adhesion can be exhibited. The crosslinkability of the coating film can be evaluated by various methods, and examples thereof include a method of measuring the insoluble fraction in a chloroform solvent that dissolves both the hydrophobic copolyester resin and the radical polymer.

  Specifically, the insoluble fraction of the coating film obtained by drying at 80 ° C. or less and heat-treating at 120 ° C. for 5 minutes is preferably 50% by mass or more, more preferably 70% by mass or more. When the insoluble content of the coating film is less than 50% by mass, not only the adhesion and water-resistant adhesion are not sufficient, but also the frequency of occurrence of blocking is increased.

  The copolyester resin forming the slippery coating layer B is a copolyester resin having at least one dicarboxylic acid component, at least one diol component, and an ester-forming component as structural units, The same kind of polyester resin as that of the easy-printing coating layer A (hereinafter sometimes referred to as a printing layer) or a commonly used copolyester resin may be used.

  Examples of the dicarboxylic acid component that is a constituent component of the copolyester resin used for the slippery coating layer B include (1) terephthalic acid, isophthalic acid, 2,6-naphthalenedicarboxylic acid, and 4,4′-biphenylenedicarboxylic acid. , Aromatic dicarboxylic acids such as 5-sodiumsulfoisophthalic acid, (2) aliphatic dicarboxylic acids such as succinic acid, adipic acid, azelaic acid and sebacic acid, (3) 1,4-cyclohexanedicarboxylic acid, 1,2- Mention may be made of alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid, and (4) unsaturated dicarboxylic acids such as maleic acid, fumaric acid and tetrahydrophthalic acid. Of these, terephthalic acid and isophthalic acid are preferable, and other dicarboxylic acids may be added in other small amounts.

  Examples of the diol component that is the other component of the copolymer polyester resin used for the slippery coating layer B include (1) ethylene glycol, diethylene glycol, propylene glycol, 1,3-propanediol, and 1,4-butane. Diols, neopentyl glycol, 1,6-hexanediol, aliphatic diols such as polyethylene glycol, (2) alicyclic diols such as 1,4-cyclohexanedimethal, (3) 4,4′-bis (hydroxyethyl) ) Aromatic diols such as bisphenol A, and bis (polyoxyethylene glycol) bisphenol ether. Of these, ethylene glycol and diethylene glycol are most preferable, and a small amount of other diol components may be used.

  In addition to the dicarboxylic acid component, it is preferable to use 5-sodium sulfoisophthalic acid in the range of 1 to 10 mol% in order to impart water dispersibility to the copolyester used in the slippery coating layer B. In addition, sulfoterephthalic acid, 4-sulfoisophthalic acid, 4-sulfonaphthalene-2,6 dicarboxylic acid, 5- (4-sulfophenoxy) isophthalic acid, and the like can be used.

  The resin components of these easy-printing coating layer A and easy-sliding coating layer B are preferably contained in the coating layer in the range of 30 to 95% by mass. When the amount is less than 30% by mass, the film strength is insufficient, and the film easily falls off when an external force such as friction is applied. Furthermore, the particles are likely to fall off. On the other hand, when it exceeds 95% by mass, the strength as a film is improved, but the intended performance such as antistatic performance and slipperiness is hardly exhibited. Preferably it is 50-90 mass%.

The compound having a sulfonate group used in the slippery coating layer B is a compound used for the purpose of imparting antistatic properties. For example, an unsaturated monomer having a sulfonate group (for example, sodium vinyl sulfonate) , Sodium methallyl sulfonate, sodium styrene sulfonate, ammonium vinyl sulfonate, potassium methacryl sulfonate, lithium styrene sulfonate, etc.) and a polymer-type antistatic agent comprising R-SO ₃ X (Here, R represents an alkyl group, an aryl group, or an aromatic group having an alkyl group, and X represents a metal ion (eg, Li, Na, K, etc.), ammonium ion, amine ion, or phosphate ester ion) Low molecular weight antistatic agents and dimers thereof, but sulfonate groups with excellent heat resistance And, have a function of antistatic property is exhibited, but it is not limited to the compound.

  Examples of the alkyl sulfonate include sodium pentane sulfonate, sodium octane sulfonate, lithium octane sulfonate, potassium octane sulfonate, and sodium tetradecyl sulfonate.

  Examples of the aryl sulfonate include sodium benzyl sulfonate, sodium toluyl sulfonate, and sodium naphthyl sulfonate. Furthermore, examples of the aromatic sulfonate having an alkyl group include alkyl (carbon number: 8 to 20) benzenesulfonic acid metal salts (for example, Li, K, Na salts) such as sodium dodecylbenzenesulfonate, and alkylnaphthalene. Examples include sodium sulfonate and sodium alkylphenyl ether disulfonate.

  The polymer antistatic agent comprising a polymer of an unsaturated monomer having a sulfonate group uses, for example, a styrene resin containing a sulfonate group component in the molecule such as polystyrene sulfonate. It is preferable.

  This polymer antistatic agent is characterized by the high hydrophilicity of its sulfonic acid component. Examples of the styrene resin containing a sulfonate group component in the molecule include homopolymers such as sodium salt, potassium salt, lithium salt, ammonium salt, and phosphonium salt of polystyrene sulfonic acid, acrylic acid ester, and methacrylic acid ester. Examples include a copolymer of an acrylic monomer and a styrene sulfonic acid monomer.

  The polystyrene sulfonate has a weight average molecular weight of 1,000 to 150,000, preferably 10,000 to 70,000. When the molecular weight is less than 1,000, it becomes difficult to obtain water-resistant adhesion of the coating film, and when it exceeds 150,000, uniform mixing with the copolymerized polyester tends to be difficult.

When the sulfonate group-containing compound is a low molecule, the mixing ratio in each layer is preferably 0.5 to 15% by mass, particularly preferably 2 to 10% by mass. Further, when the sulfonate group-containing compound is a polymer, it is preferably 5 to 50% by mass, particularly preferably 10 to 30% by mass. A mixture of the low molecular compound and the high molecular compound may be used. Further, the surface resistivity of the coating layer containing the compound having a sulfonate group is not less than 10 ¹² Ω / □ under the conditions of 23 ° C. and 50% RH. The slipperiness becomes insufficient under a low load, and the transportability such as double feeding in a high-speed printer tends to deteriorate. On the other hand, when the content of the compound having a sulfonate group is too large, the printed surface is likely to be contaminated due to set-off or particle dropout.

  In the present invention, commercially available inorganic particles and / or organic particles can be used as the particles having an average particle diameter of 1 to 5 μm that can be contained in the coating layer. The average particle diameter is more preferably in the range of 1 to 3 μm. The average particle size of the particles is taken by taking a plurality of photographs of at least 200 particles by electron microscopy, tracing the outline of the particles on an OHP film, and converting the trace image to an equivalent circle diameter with an image analyzer. To calculate.

  Examples of the inorganic particles include silica, calcium carbonate, and alumina, and examples of the organic particles include, but are not limited to, polyolefin, acrylic, styrene, urethane, polyamide, and polyester.

  Moreover, content with respect to the resin component of the said particle | grain in a coating layer is 0.3-10 mass%, Preferably it is 0.7-5 mass%. When the average particle size is less than 1 μm or the particle content is less than 0.3% by mass, it is difficult to form appropriate irregularities on the surface of the coating layer. As a result, when it is a sheet-fed film, it is difficult for an air layer to accumulate between the films, the friction immediately after releasing the load cannot be reduced, and it becomes difficult to increase the printing speed. When the average particle diameter exceeds 5 μm, or when the particle content exceeds 10% by mass, the haze of the film increases, the transparency is deteriorated, or the particles are dropped, resulting in a print surface stain, a problem of print quality, The frequency of machine stand contamination increases.

  The polymer wax component (f) used for the slippery coating layer B is not particularly limited as long as it does not impair the transparency, and conventionally known ones can be used. For example, a polyethylene type, a polypropylene type, and a fatty acid type are mentioned. The weight average molecular weight of these wax components is preferably 1,000 to 10,000, more preferably 1,500 to 6,000. When the molecular weight is less than 1,000, oozing from the inside of the coating layer to the surface tends to cause transfer contamination to the printing surface, which may adversely affect the ink adhesion.

  When the weight average molecular weight of the polymer wax exceeds 10,000, the effect of improving slipperiness may be insufficient. As for content of the wax component in a coating layer, 1-10 mass% is preferable with respect to a resin component, Most preferably, it is 2-8 mass%. When the content of the polymer wax component in the slippery coating layer B is less than 1% by mass with respect to the resin component, the friction coefficient cannot be lowered sufficiently, and the printing speed is difficult to increase. When the content of the high molecular weight wax component in the slippery coating layer B exceeds 10% by mass with respect to the resin component, the loss of the wax component leads to contamination on the printed surface, and further deterioration of transparency and haze. Cheap.

  In a polyester film for molding in which an easy-printing coating layer A is laminated on one side of the polyester base film and a coating layer is formed on both sides of the polyester film, the slipping property of the film is, for example, high-speed UV It is only necessary to provide sheet feeding stability in an offset printing machine. Specifically, it is a preferred embodiment that the static friction coefficient and the dynamic friction coefficient when the easy-printing coating layer A and the slippery coating layer B are overlapped are 0.5 or less.

  If the coefficient of dynamic friction exceeds 0.5, the slipperiness becomes insufficient, and therefore the frequency of occurrence of poor conveyance during sheet feeding on a sheet-fed printing press increases. Generally, the static friction coefficient shows a maximum value when the film is rubbed, and is higher than the dynamic friction coefficient. However, when the lubricant is included in at least one of the coating layers, the coefficient of friction rises gently with friction running, so that the value of the static friction coefficient becomes equal to or lower than the dynamic friction coefficient. A low coefficient of static friction makes the beginning of movement during sheeting smoother. As a result, the sheet-fed printing press can improve the printing speed.

  When manufacturing the polyester film for molding of the present invention, the method of forming the coating layers A and B on both sides of the polyester base film is not limited and is arbitrary, but a method carried out by a coating method is suitable. As the step of applying the coating solution in this method, a method of coating on an unstretched film and then stretching in at least one direction, a method of coating after longitudinal stretching, a method of coating on the film surface after the orientation treatment, etc. Either method is possible. In particular, when manufacturing a polyester base film, the so-called in-line coating method is applied before the crystal orientation of the film is completed, and then stretched in at least one direction and then the crystal orientation of the polyester film is completed. The effect obtained by stacking the layers can be expressed more significantly, which is preferable.

  In the slippery coating layer B, the copolymerized polyester resin (c) and the compound (d) having a sulfonate group are easily separated due to a difference in hydrophilicity between them. Therefore, the coating solution for forming the slippery coating layer B is applied to the substrate within 2 seconds immediately after applying a shear rate of 1000 (1 / second) or more immediately before application, and then 70 ° C. or less and humidity within 2 seconds. It is preferable to carry out by a method of drying at 90 ° C. or higher after preliminary drying for 1 to 3 seconds at 50% RH and a wind speed of 10 to 20 m / second. By coating by this method, the copolymer polyester resin and the compound having a sulfonate group are uniformly dispersed, and a good surface resistance value can be obtained.

  When the in-line coating method is used, the base film and the graft copolymer are not thermally deteriorated in order to develop the self-crosslinking property of the polyester-based graft copolymer that is a component of the easy-printing coating layer A. Within the range, it is preferable to employ heating conditions that increase the amount of heat in the heat setting treatment step after stretching. Specifically, it is 200 ° C to 250 ° C, preferably 220 ° C to 250 ° C. However, by increasing the heat setting time, sufficient self-crosslinking property can be exhibited even at a relatively low temperature.

  As the method for providing the coating layers A and B, a gravure coating method, a kiss coating method, a dip method, a spray coating method, a curtain coating method, an air knife coating method, a blade coating method, a reverse roll coating method and the like are usually used. Can be applied

  Although the thickness of the coating layers A and B is not particularly limited, in the present invention, the final thickness after drying is preferably 0.05 to 1.0 μm, more preferably 0.07 to 0.5 μm, Especially preferably, it is 0.09-0.3 micrometer.

  For the coating layers A and B, known additives such as a surfactant, an antioxidant, a heat stabilizer, a weather stabilizer, an ultraviolet absorber, and an organic lubricant are used as long as the effects of the present invention are not impaired. May be included.

  In the present invention, the slipperiness between the easy-printing coating layer A and the slippery coating layer B on the opposite side is very good as compared with a conventionally known method. This remarkable improvement in slipperiness when films are stacked in sheet form is as follows: (1) Air retention between films due to surface irregularities caused by particles having an average particle diameter of 1 to 10 μm contained in the coating layers on both sides Effects, (2) anti-static adhesion effect by the sulfonic acid metal salt contained in the slippery coating layer B, and (3) lowering of the static friction coefficient by the polymer wax component further contained in the slippery coating layer B It is. If these three effects are not all available, the cut film will not be smooth enough when it starts to move from a stationary state, the transportability from a stack of sheets in a sheet-like state, and the biting stability during feeding will be inferior. The printing speed cannot be increased.

  A laminated film having a normal coating layer has inert particles for forming irregularities on the film surface for the purpose of improving handling properties (e.g., slipperiness, winding property, blocking resistance) and scratch resistance. Contained. However, the laminated polyester film of the present invention preferably contains particles in the coating layer to improve transparency, and the content of particles in the base film is preferably reduced. It is particularly preferable not to contain it. The phrase “substantially does not contain particles” means that the content of the main component elements constituting the particles in the base film is below the detection limit of the fluorescent X-ray analysis method.

  In the present invention, high transparency can be obtained while having a coating layer on both sides by using a base film substantially containing no particles inside. As a result, the brightness when illuminated by transmitted light is excellent, and the sharpness of characters and images when the printed surface is viewed through the film from the easy-smooth surface (coating layer B / non-printed surface) side is obtained. It is done.

  Further, in the present invention, the adhesion strength with the coating layer A for commonly used UV curable printing ink and solvent-type printing ink is 1 mm square in cross-cut evaluation with a grid according to JIS-K5400. The residual ratio of the number of eyes is preferably 90% or more, particularly preferably 96% or more.

  If the adhesion force (remaining ratio of the number of squares) is less than 90%, ink dropout after printing occurs, leading to deterioration in appearance and transportability. In general, offset printing makes it difficult for ink to drop off because the ink thickness is 1 μm to several μm. However, screen printing may be several μm to 10 μm or more, and the printing performance has adhesion that can be applied to screen printing ink. Necessary for transparent polyester film.

  If the adhesion is less than 90%, ink dropout occurs after printing, leading to deterioration in appearance and transportability. In general, offset printing makes it difficult for ink to drop off because the ink thickness is 1 μm to several μm. However, screen printing may be several μm to 10 μm or more, and the printing performance has adhesion that can be applied to screen printing ink. Necessary for transparent polyester film.

  The molding polyester film of the present invention is used by applying heat, pressure, or the like to be deformed. Examples of the molding means include pressure molding, press molding, laminate molding, vacuum molding, vacuum / pressure molding, in-mold molding, drawing molding, and bending molding. The molded body molded in this way is used for molding members such as home appliance nameplates, automobile nameplates, dummy containers, building materials, decorative boards, decorative steel plates, transfer sheets, etc., but it is used as a dummy container member. Since the effects of the present invention can be suitably expressed, this is a preferred embodiment.

  Hereinafter, the present invention will be described in detail by way of examples. The film properties obtained in each example were measured and evaluated by the following methods.

(1) Intrinsic viscosity 0.1 g of the chip sample was precisely weighed and dissolved in 25 ml of a mixed solvent of phenol / tetrachloroethane = 6/4 (mass ratio), and measured at 30 ° C. using an Ostwald viscometer. In addition, the measurement was performed 3 times and the average value was calculated | required.

(2) Thickness unevenness A continuous tape-like sample having a length of 3 m in the transverse stretching direction and a length of 5 cm in the longitudinal stretching direction is taken up, and the thickness of the film is measured with a continuous film thickness measuring machine (manufactured by Anritsu Corporation). To record. From the chart, the maximum value (dmax), minimum value (dmin), and average value (d) of the thickness were obtained, and the thickness unevenness (%) was calculated by the following formula. In addition, the measurement was performed 3 times and the average value was calculated | required. Moreover, when the length of a horizontal extending direction is less than 3 m, it joins and performs. The connecting part is deleted from the data.
Unevenness of thickness (%) = ((dmax−dmin) / d) × 100

(3) Haze Based on JIS-K7136, it measured using the haze meter (Nippon Denshoku Industries Co., Ltd. make, 300A). In addition, the measurement was performed twice and the average value was calculated | required.

(4) Film Thickness Using a millitron, a total of 15 points were measured, 5 points per sheet, and the average value was determined.

(5) Stress at 100% elongation, elongation at break With respect to the longitudinal direction and width direction of the biaxially stretched film, a sample was cut into a strip shape having a length of 180 mm and a width of 10 mm, respectively, with a single-blade razor, and the sample was pulled. The sample was pulled using Toyo Seiki Co., Ltd., and the stress at 100% elongation (MPa) and elongation at break (%) in each direction were determined from the obtained load-strain curve.

  The measurement was performed in an atmosphere of 25 ° C. under the conditions of an initial length of 40 mm, a distance between chucks of 100 mm, a crosshead speed of 100 mm / min, a recorder chart speed of 200 mm / min, and a load cell of 25 kg. The measurement was performed 10 times and the average value was used.

  In addition, a tensile test was performed under the same conditions as described above even in an atmosphere at 100 ° C. At this time, the sample was held for 30 seconds in an atmosphere at 100 ° C. and then measured. The measurement was performed 10 times and the average value was used.

(6) Thermal contraction rate at 150 ° C. A strip sample having a length of 250 mm and a width of 20 mm is cut out in the longitudinal direction and the width direction of the film, respectively. Two marks are marked at intervals of 200 mm in the length direction of each sample, and the distance A between the two marks is measured under a constant tension (tension in the length direction) of 5 g. Subsequently, one side of each strip-shaped sample is hung with a clip on a basket under no load, and placed in a gear oven under an atmosphere of 150 ° C., and time is taken. After 30 minutes, the basket is removed from the gear oven and left at room temperature for 30 minutes. Next, for each sample, under a constant tension of 5 g (tension in the length direction), the interval B between the two marks is read with a gold finger in units of 0.25 mm. From the read intervals A and B, the thermal shrinkage rate at 150 ° C. of each sample is calculated by the following formula.
Thermal contraction rate (%) = ((A−B) / A) × 100

(7) Formability After printing on the film, after heating at 130 ° C. for 5 seconds, press molding was performed at a mold temperature of 80 ° C. and a pressure holding time of 5 seconds. ABS resin was poured into the molding material at 210 ° C. (injection molding), and a key top having a height of 3.0 mm, the surface of which was covered with a film, was created. The printing misalignment at this time was measured, and the molding state was visually observed and ranked according to the following criteria. In addition, ◎ and ○ were accepted and x was rejected.

◎: Printing deviation is less than 0.1 mm and the appearance is very good. ○: Printing deviation is 0.1 mm or more and less than 0.2 mm, and some wrinkles are seen.
No problem for practical use ×: Printing misalignment of 0.2 mm or more, film breakage, or large wrinkles and poor appearance

(8) Static friction coefficient μs and dynamic friction coefficient μd
Based on JIS-C2151, the following conditions evaluated.
-Test piece for flat plate: 130mm in width and 250mm in length, using non-printing surface side-Test piece for warping: 120mm in width, using printing surface side in length of 120mm-Measuring atmosphere: 23 ° C, 50% RH
・ Sled weight: 200g
・ Test speed: 150mm / min

(9) Surface resistivity The surface resistivity in the atmosphere of 23 ° C. and 50% RH using a surface resistance meter (manufactured by Mitsubishi Yuka Co., Ltd., HIRESUTA MCP HT-260) on the printed surface of the sample film and the opposite surface. (Ω / □) was measured under the following conditions.
・ Applied voltage: 500V
・ Measurement time: 10 seconds ・ Probe used: Type HRS

(10) Ink Adhesion Strength According to the cross-cut evaluation method described in 8.5.1 of JIS-K5400, the ink adhesion strength of the printed surface of the film (easily printable coating layer A in the present invention) was evaluated. Specifically, after printing the following ink on the printing surface of the film, using a crosscut guide, 100 pieces of 1 mm squares were created on the printing surface with a cutter blade, and then an adhesive tape (product name cellophane tape, manufactured by Nichiban Co., Ltd.). ) Was affixed to the printed surface and completely adhered so that no air remained. Next, after the adhesive tape was peeled off vertically, the remaining number of squares on the printed surface was evaluated as the adhesion (remaining number / 100).

  The adhesive strength with the UV curable ink is 100 mJ after printing with a RI tester on the coating layer surface (easily printable coating layer A of the present invention) using a UV curable ink (manufactured by Toka Dye, Best Cure 161). UV was irradiated and evaluated according to the above method. Also, using another UV curable ink (Seiko Advance, UVA), the surface of the coating layer (easily printable coating layer A of the present invention) was irradiated with 500 mJ of UV after # 300 screen printing, and the above method According to the same evaluation.

  Adhesive strength with solvent-type ink is solvent-type ink (Toyo Ink, TSP-400G). It is left to dry for 24 hours after printing on the coating layer surface (easily printable coating layer A of the present invention) with an RI tester. And evaluated according to the above method. Also, using another solvent-based ink (Tetron, manufactured by Jujo Ink Co., Ltd.), it was left to dry for 24 hours after screen printing # 250 on the coating layer surface (easily printable coating layer A of the present invention), according to the above method. Evaluation was performed in the same manner.

(11) Suitability for fountain solution When printing with a RI tester on the coating layer surface (easily printable coating layer A of the present invention) using a solvent-type offset printing ink (manufactured by Toyo Ink Co., Ltd., TSP-400G) After the film printing surface before color is pressure-bonded with a Molton roller moistened with 0.2 ml, 0.4 ml, and 0.6 ml of ion-exchanged water using a dropoid, the ink is developed and the ink transfer failure Presence / absence was comprehensively evaluated and judged by ○ and х.

(12) Feeding stability Using a sheet-fed offset printing machine (Heidelberg, Speedmaster, 8-color printing machine), stacking sheets of Kikuzen size (636 x 939 mm) size sheets at low printing speed The sheet feeding stability was evaluated when feeding and printing at (4,000 sheets / hour) and at high speed (8,000 sheets / hour). ◯ when the paper could be fed stably, and х when troubles such as double feeding and clogging occurred during feeding.

(13) Print quality The print appearance of the print sample used in the feed stability evaluation was visually determined. At this time, the appearance was visually judged through the film from the back side, not from the printed surface. A sample having a clear feeling and printability satisfying the following criteria was evaluated as “Good”.
(Clear feeling)
The printed design looks clear without being blocked by the base film or coating layer (printability)
Color unevenness and missing due to poor transfer of printing ink

(14) Light transmittance The light transmittance in the ultraviolet region of a wavelength of 380 nm was measured using a spectrophotometer (manufactured by Shimadzu Corporation, UV-1200).

(15) Light resistance Print samples used for evaluation of paper feed stability at a position 3 cm directly under fluorescent lamp lamps (manufactured by Matsushita Electric Co., Ltd., U-type fluorescent lamp FUL9EX) in a dark box It was placed with the side facing away. Next, irradiation was continued for 2000 hours, and the color difference (ΔE value) was measured according to JIS Z 8730 based on the color (a *, b *, L *) before and after irradiation on the printing surface side. The smaller the color difference (ΔE value), the smaller the color change before and after the light irradiation, that is, the better the light resistance. In the present invention, the acceptable level of light resistance was set to 0.5 or less in terms of color difference (ΔE value) and indicated by ◯. The color difference (ΔE value) is calculated by the following formula.
ΔE = √ (Δa ² + Δb ² + ΔL ² )

Example 1
(Preparation of hydrophobic copolyester resin)
In a stainless steel autoclave equipped with a stirrer, thermometer and partial reflux condenser, 218 parts by mass of dimethyl terephthalate, 194 parts by mass of dimethyl isophthalate, 488 parts by mass of ethylene glycol, 200 parts by mass of neopentyl glycol and tetra-N-butyl titanate 0.5 parts by mass was charged, and a transesterification reaction was performed from 160 ° C. to 220 ° C. over 4 hours. Next, 13 parts by mass of fumaric acid and 51 parts by mass of sebacic acid were added, and the temperature was raised from 200 ° C. to 220 ° C. over 1 hour to carry out an esterification reaction. Next, the temperature was raised to 255 ° C., and the reaction system was gradually depressurized, and then reacted for 1 hour 30 minutes under a reduced pressure of 0.22 mmHg to obtain a hydrophobic copolyester resin. The obtained hydrophobic copolyester was light yellow and transparent.

(Preparation of water-dispersed polyester graft copolymer)
In a reactor equipped with a stirrer, thermometer, refluxing device and quantitative dropping device, 75 parts by mass of hydrophobic copolymer polyester, 56 parts by mass of methyl ethyl ketone and 19 parts by mass of isopropyl alcohol are heated and stirred at 65 ° C. Dissolved. After the resin was completely dissolved, 15 parts by mass of maleic anhydride was added to the polyester solution. Subsequently, a solution prepared by dissolving 10 parts by mass of styrene and 1.5 parts by mass of azobisdimethylvaleronitrile in 12 parts by mass of methyl ethyl ketone was dropped into the polyester solution at 0.1 ml / min, and stirring was further continued for 2 hours. After sampling for analysis from the reaction solution, 5 parts by mass of methanol was added. Next, 300 parts by mass of ion-exchanged water and 15 parts by mass of triethylamine were added to the reaction solution and stirred for 1.5 hours. Thereafter, the reactor internal temperature was raised to 100 ° C., and methyl ethyl ketone, isopropyl alcohol, and excess triethylamine were distilled off to obtain a water-dispersed polyester graft copolymer. The obtained polyester-based graft copolymer was light yellow and transparent, and the glass transition temperature was 40 ° C.

(Preparation of coating liquid A for easy-printing coating layer A)
As a sulfonated metal salt, a polyester-based graft copolymer dispersed in water in a mixed solvent of ion-exchanged water and isopropyl alcohol (mass ratio: 60/40) so that the total solid concentration is 5% by mass. Sodium dodecyl diphenyl oxide disulfonate (manufactured by Matsumoto Yushi Co., Ltd., anionic antistatic agent), styrene-benzoguanamine-based spherical organic particles (manufactured by Nippon Shokubai Co., Ltd.) having an average particle size of 2.2 μm, and particles having an average particle size of 0.02 μm Colloidal silica (manufactured by Catalyst Kasei Co., Ltd.) was mixed so as to have a mass ratio of 50 / 1.5 / 1/3, respectively, to prepare coating solution A.

(Preparation of coating solution B for slippery coating layer B)
In a mixed solvent of ion-exchanged water and isopropyl alcohol (mass ratio: 60/40), a water-dispersible polyester copolymer (manufactured by Toyobo Co., Ltd. MD-16), sodium dodecyl diphenyloxide disulfonate (manufactured by Matsumoto Yushi Co., Ltd., an anionic antistatic agent) as a metal salt of sulfonic acid, polyethylene emulsion wax (manufactured by Toho Chemical Co., Ltd.) as a polymer wax agent, and particles Styrene-benzoguanamine-based spherical organic particles (manufactured by Nippon Shokubai Kogyo Co., Ltd.) having an average particle size of 2.2 μm and colloidal silica (manufactured by Nissan Chemical Co., Ltd.) having an average particle size of 0.04 μm in a solid content mass ratio of 50 / 2.5 / The mixture was mixed to 2.5 / 0.5 / 5 to prepare coating solution B.

(Preparation of laminated polyester film)
It consists of 100 mol% of terephthalic acid units as the aromatic dicarboxylic acid component, 85 mol% of ethylene glycol units and 15 mol% of neopentylglycol units as the diol component, 400 ppm of amorphous silica with an average particle size of 1.5 μm and benzotriazole A copolyester having an intrinsic viscosity of 0.69 dl / g, containing 1 part by mass of a UV absorber (manufactured by Ciba Specialty Chemicals, TINUVIN326) with respect to 100 parts by mass of the polyester, was produced. The copolyester was pre-crystallized, then dried, melt-extruded at 280 ° C. using an extruder having a T die, and rapidly cooled and solidified on a drum having a surface temperature of 40 ° C. to obtain an amorphous sheet.

  Next, this cast film was stretched 3.5 times at 80 ° C. in the longitudinal direction between a heating roll and a cooling roll to obtain a uniaxially oriented polyester film.

  Subsequently, said coating liquid A was apply | coated to the one surface of the uniaxially-oriented polyester film, and the coating liquid B was apply | coated to the other surface by the reverse coat method. In addition, each coating liquid applied a shear rate of 1000 (1 / second) or more between the roll gaps, applied to the substrate film within 2 seconds, and in an environment of 65 ° C., 60% RH, and wind speed of 15 m / second, Dry for 2 seconds. Further, it was dried for 3 seconds in an environment of 130 ° C. and a wind speed of 20 m / second to remove moisture.

  Next, the film edge is continuously held by a clip and guided to a tenter, preheated at 100 ° C. for 15 seconds, the first half of transverse stretching is stretched 3.6 times at 115 ° C. and the latter half is 95 ° C., 7% Then, heat treatment was performed at 205 ° C. while relaxing in the transverse direction to obtain a biaxially stretched polyester film having a thickness of 188 μm.

Comparative Example 1
In Example 1, the film was longitudinally stretched 3.7 times at 90 ° C., then transversely stretched 4.0 times at 120 ° C., and then heat-treated at 200 ° C. while relaxing 10% in the transverse direction. Except for this, a biaxially stretched polyester film was obtained in the same manner as in Example 1.

Comparative Example 2
In Example 1, the film was longitudinally stretched 3.5 times at 125 ° C., then transversely stretched 3.5 times at 130 ° C., and then heat treated at 230 ° C. An axially stretched polyester film was obtained.
Comparative Example 3
In Example 1, a biaxially stretched polyester film was obtained in the same manner as in Example 1 except that the ultraviolet ray absorbent was not included in the polyester as the raw material for the base film.

Example 2
In Example 1, the ultraviolet ray absorbent is not contained in the polyester which is the raw material of the base film, and the high molecular weight ultraviolet absorbent (NOVAPEX U-110, manufactured by Mitsubishi Chemical Co., Ltd.) is applied to the coating solution B of the slippery coating layer B. A biaxially stretched polyester film was obtained in the same manner as in Example 1 except that the amount was changed to 7 parts by mass with respect to 100 parts by mass of the solid content.

Example 3
It consists of 100 mol% of terephthalic acid units as aromatic dicarboxylic acid components, 90 mol% of ethylene glycol units and 10 mol% of 1,4-cyclohexanedimethanol units as diol components, and is a benzotriazole UV absorber (Ciba Specialty A copolyester having an intrinsic viscosity of 0.71 dl / g containing 1 part by mass of 100 parts by mass of TINUVIN 326) manufactured by Chemicals was produced. Next, the copolyester was pre-crystallized and then dried, melt-extruded at 280 ° C. using an extruder having a T die, and rapidly solidified on a drum having a surface temperature of 40 ° C. to obtain an amorphous sheet. .

  After the obtained sheet was stretched 3.0 times at 75 ° C. in the longitudinal direction between the heating roll and the cooling roll, the coating liquid A and The coating liquid B was applied, and the uniaxially stretched sheet was guided to a tenter. Next, preheating at 105 ° C. for 15 seconds, the first half of the transverse stretching is 125 ° C., the latter half is stretched 3.6 times at 98 ° C., and heat treatment is performed at 205 ° C. while relaxing 7% in the transverse direction. A biaxially stretched polyester film having a thickness of 250 μm was obtained.

Example 4
In Example 1, the amorphous dicarboxylic acid component consists of 100 mol% of terephthalic acid units, the diol component consists of 80 mol% of ethylene glycol units and 20 mol% of neopentylglycol units, and has an average particle size of 1.4 μm. Except that the copolyester having an intrinsic viscosity of 0.69 dl / g and the polyethylene terephthalate having an intrinsic viscosity of 0.70 dl / g were dried and pre-crystallized and then mixed at 1: 1 (mass ratio). In the same manner as in Example 1, a biaxially stretched polyester film was obtained.

Comparative Example 4
Intrinsic viscosity of 90 mol% terephthalic acid unit and 10 mol% of adipic acid as dicarboxylic acid component, 100 mol% of ethylene glycol unit as diol component, and 800 ppm of amorphous silica having an average particle size of 1.4 μm. A biaxially stretched polyester film was obtained in the same manner as in Example 1 except that a copolyester of .71 dl / g was used.

Comparative Example 5
The aromatic dicarboxylic acid component is composed of 100 mol% of terephthalic acid units, the diol component is composed of 95 mol% of ethylene glycol units, 3 mol% of 1,4-cyclohexanedimethanol units, and 2 mol% of diethylene glycol units. A copolyester having an intrinsic viscosity of 0.67 dl / g containing 2000 ppm of 6 μm aluminum silicate was pre-crystallized, then fully dried, and melt-extruded at 280 ° C. using an extruder having a T-die, and a surface temperature of 40 An amorphous sheet was obtained by rapid solidification on a ℃ drum.

  The obtained sheet was stretched 3.4 times at 96 ° C. in the longitudinal direction between the heating roll and the cooling roll, and then the uniaxially stretched sheet was led to a tenter. Next, it was preheated at 100 ° C. for 15 seconds, stretched 3.3 times in the transverse direction at 115 ° C., heat-treated at 180 ° C. while relaxing 5% in the transverse direction, and a biaxially stretched polyester film having a thickness of 188 μm Got.

Example 5
The films obtained in Examples 1 to 4 were cut to a size of Kikuzen (636 × 939 mm), and the obtained sheet-fed films were stacked, and a sheet-fed offset printing machine (Heidelberg, Speedmaster, 8-color printing machine). Then, the sheet was fed at a printing speed of 8,000 sheets / hour and printed on the surface A of the easily printable coating layer A using a UV curable ink. The printing operability and the printing characteristics of the printed product were good. The obtained printed polyester film for molding was press-molded at a mold temperature of 100 ° C. to produce a constricted dummy bottle having a constricted shape (a shape obtained by half-cutting an actual bottle). Molding operability and the appearance of the obtained dummy bottle were good.

  The evaluation results of the films obtained in Examples 1 to 4 and Comparative Examples 1 to 5 are shown in Tables 1 and 2.

  The polyester film for molding of the present invention is excellent in moldability at the time of heating, elasticity and shape stability (thickness unevenness, heat shrinkage characteristics) when used in a room temperature atmosphere as a molded body, and excellent in light resistance. Therefore, it is suitable as a film for various moldings such as in-mold molding, emboss molding, and vacuum molding. Furthermore, easy molding, which is a feature of the base material, is made by stacking the easy-printing coating layer A on one side of the base material and the easy-sliding coating layer B on the other side. In addition to the properties and light resistance, it is excellent in paper feeding stability, ink adhesion, dampening water suitability, etc. in a high-speed UV offset printing machine for multicolor printing, and can perform high-quality printing at high speed, so it is a member of a dummy container It is suitable as. Furthermore, it is also suitable as a member for nameplates of home appliances and automobiles, or a member for building materials.

Claims (12)

  A polyester film comprising a copolyester synthesized from an aromatic dicarboxylic acid component and a glycol component containing ethylene glycol and a branched aliphatic glycol and / or alicyclic glycol, the longitudinal direction and the width direction of the film 100% elongation stress at 25 ° C. is 180 to 1000 MPa and 100 ° C. is 1 to 100 MPa, and the light transmittance at a wavelength of 380 nm is 50% or less.   The polyester film for molding according to claim 1, wherein the branched aliphatic glycol is neopentyl glycol.   The polyester film for molding according to claim 1 or 2, wherein the alicyclic glycol is 1,4-cyclohexanedimethanol.   The polyester film for molding according to any one of claims 1 to 3, wherein the aromatic dicarboxylic acid component is terephthalic acid, naphthalenedicarboxylic acid, or an ester-forming derivative thereof.   The film has a 100% elongation stress ratio in the longitudinal direction and the width direction at 100 ° C (higher numerical value / lower numerical value) of 1.05 to 1.60. 4. The molding polyester film according to any one of 4 above.   The polyester film for molding according to any one of claims 1 to 5, wherein the film has a thickness unevenness of 5.5% or less.   The film for molding according to any one of claims 1 to 6, wherein the film has a thermal shrinkage in the longitudinal direction and the width direction at 150 ° C of 3.0% or less.   The film comprises a polyester film as a base material, and an easy-printing coating layer A made of an adhesive modified resin is laminated on one side of the base material, and an easy-sliding coating layer B containing particles and / or wax is laminated on the other side. It is made, The polyester film for shaping | molding in any one of Claims 1-7 characterized by the above-mentioned.   The easily printable coating layer A is (a) a polyester-based graft copolymer obtained by grafting an acid anhydride having at least one double bond to a hydrophobic copolymerized polyester resin, and (b) an average particle size of 1 The polyester film for molding according to claim 8, comprising a composition containing particles having a diameter of 0.0 to 5.0 μm.   The slippery coating layer B is (c) a copolymer polyester resin, (d) a compound having a sulfonate group, (e) particles having an average particle diameter of 1.0 to 5.0 μm, and (f) a polymer wax. The molding polyester film according to claim 8, comprising a composition comprising:   The static friction coefficient and dynamic friction coefficient when the easy-printing coating layer A and the easy-sliding coating layer B are overlapped are both 0.5 or less, for molding according to any one of claims 8 to 10 Polyester film.   A dummy container obtained from the molding polyester film according to claim 1.