JP2012162586A - Oriented polyester film for molding - Google Patents

Oriented polyester film for molding Download PDF

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JP2012162586A
JP2012162586A JP2011021559A JP2011021559A JP2012162586A JP 2012162586 A JP2012162586 A JP 2012162586A JP 2011021559 A JP2011021559 A JP 2011021559A JP 2011021559 A JP2011021559 A JP 2011021559A JP 2012162586 A JP2012162586 A JP 2012162586A
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component
film
molding
spiroglycol
mol
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Inventor
Mikiya Hayashibara
Takumi Matsui
Mutsuo Nishi
Yoshinori Saimiya
芳紀 斎宮
匠 末井
幹也 林原
睦夫 西
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Toyobo Co Ltd
東洋紡績株式会社
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Abstract

PROBLEM TO BE SOLVED: To provide a substrate for molding that suitably combines moldability and form stability.SOLUTION: The oriented polyester film for molding includes: at least 50 mol% of a terephthalic acid component or a 2,6-naphthalenedicarboxylic acid component and an ethylene glycol component; 2-20 mol% of a spiroglycol component; and 5-30 mol% of a copolymerization component other than the spiroglycol component.

Description

  The present invention relates to a stretched polyester film for molding. Specifically, the present invention relates to a stretched polyester film for molding that has both form retention and moldability.

  Until now, an unstretched sheet made of polyester, polycarbonate and acrylic resin has been used as a base film suitable for molding. Especially, the unstretched sheet | seat which consists of polyester resins has good transparency, and is excellent in economical efficiency (patent document 1). However, since these are unstretched sheets, the solvent resistance is not sufficient and the high demands of the market have not been satisfied. It has also been proposed to use stretched polyethylene terephthalate having properties excellent in solvent resistance (Patent Document 2). However, it cannot meet the demand for high moldability. Then, in order to make solvent resistance and moldability compatible, a stretched polyester film has been proposed using a copolymerized polyester resin as a raw material (Patent Document 3).

  On the other hand, a film exhibiting heat resistance by using a spiroglycol component as a copolymer component is disclosed (Patent Document 4).

JP 2002-249652 A JP-A-11-268215. JP 2004-75713 A JP 2008-260965 A

  A molding film may be subjected to a molding process after being decorated such as printing. In recent years, from the viewpoint of improving production efficiency, an increasing number of methods for performing a drying process after printing at a high temperature in order to shorten the printing process. For example, the drying temperature has been about 60 ° C. so far, but the above method has been performed under the condition of about 80 to 90 ° C. Therefore, shape stability at a higher temperature (80 to 90 ° C.) is required for the molding film. On the other hand, moldability is also required in a relatively low temperature range of 100 to 120 ° C. However, the polyester film for molding obtained in Patent Documents 1 to 3 has a tendency to bend easily at a temperature of 90 ° C. or lower, or lacks softness in a temperature range of 100 to 120 ° C. Moreover, the film obtained by patent document 4 was highly brittle, and did not have a moldability.

  The object of the present invention is to provide a film that can be molded at a relatively low temperature while maintaining the stability at a relatively high temperature by coexisting the moldability at 100 ° C. or higher and the shape stability at 90 ° C. or lower. There is to do.

  The stretched polyester film for molding of the present invention capable of solving the above-mentioned problems has the following configuration.

The first invention of the present invention comprises a terephthalic acid component or 2,6-naphthalenedicarboxylic acid component, an ethylene glycol component of 50 mol% or more, a spiro glycol component of 2 to 20 mol%, and a co-polymer other than the spiro glycol component. It is a stretched polyester film for molding containing 5 to 30 mol% of a polymerization component.
2nd invention of this invention is the stretched polyester film for a shaping | molding whose glass transition temperature of the said film is 80-150 degreeC, and melting | fusing point is 200-255 degreeC.
3rd invention of this invention is the stretched polyester film for a shaping | molding whose elasticity modulus in the longitudinal direction and the width direction of a film is 1-5 GPa in all at 25 degreeC.
4th invention of this invention is the stretched polyester film for shaping | molding formed by mixing the copolyester containing copolymer components other than a spiroglycol component and spiroglycol, and a homopolyester.
According to a fifth aspect of the present invention, the stretched polyester for molding is obtained by mixing a copolymer polyester containing a spiro glycol component as a copolymer component, a copolymer polyester containing a copolymer component other than spiro glycol, and a homopolyester. It is a film.
The sixth aspect of the present invention is the above-described molding stretching, wherein the copolymer component other than the spiroglycol includes any one of branched aliphatic glycol, alicyclic glycol, sophthalic acid, naphthalenedicarboxylic acid, and adipic acid. It is a polyester film.
7th invention of this invention is the stretched polyester film for a shaping | molding which contains a ultraviolet absorber in a film.

  The stretched polyester film for molding of the present invention has good shape stability even in a temperature range of about 90 ° C., and also exhibits good moldability even in a temperature range of 100 ° C. or higher. Therefore, it is suitable for molding applications.

  In addition, by incorporating an ultraviolet absorber in the film and reducing the transmittance in the ultraviolet region, light resistance can be imparted, particularly for applications used outdoors (members for automobile exteriors or building materials). It is useful as a molding material.

  The stretched polyester film for molding of the present invention comprises a terephthalic acid component or a 2,6-naphthalenedicarboxylic acid component and an ethylene glycol component of 50 mol% or more, a spiro glycol component of 2 to 20 mol%, and other than the spiro glycol component. It consists of the polyester resin composition which contains a copolymerization component 5-30 mol%, It is characterized by the above-mentioned.

  The polyester resin composition constituting the film of the present invention comprises a terephthalic acid component or 2,6-naphthalenedicarboxylic acid component as a dicarboxylic acid component and an ethylene glycol component as a glycol component in an amount of 50 mol% or more, preferably 60 mol% or more. More preferably, it contains 70 mol% or more. Thereby, the film of this invention can hold | maintain suitably the intensity | strength and transparency as a polyester film. These components may be copolymerized with other dicarboxylic acid components / glycol components in the polyester resin composition, or may be included as a homopolyester. Examples of the homopolyester include polyethylene phthalate or polyethylene naphthalate.

  The polyester resin composition constituting the film of the present invention contains 2 to 20 mol%, preferably 3 to 15 mol%, of a spiroglycol component. Spiroglycol is a diol 3,9-bis (2-hydroxy-1,1-dimethylethyl) -2,4,8,10-tetraoxaspiro [5.5] having the structure shown in the following chemical formula 1. Undecane. The spiroglycol component contains a spiro ring structure in the polyester as a copolymer component of the glycol component. Spiroglycol can be obtained commercially from, for example, Mitsubishi Gas Chemical Company.

  In addition, in Table 1 of the below-mentioned Example, although the molar ratio of each component is divided and displayed on an acid component and a glycol component, the molar ratio (mol%) prescribed | regulated by this invention is the acid component which comprises a polyester resin, and It is specified as a ratio to the total amount of components including the glycol component. Since the polyester resin contains the same amount of the glycol component and the acid component, when it is calculated separately for the acid component and the glycol component, the number is twice the molar ratio of the total amount of the acid component and the glycol component.

  In the present invention, by including such a specific glycol component in the above range, sufficient heat resistance can be obtained even in the region of 90 ° C., which is a softening temperature in the conventional formulation. The reason why heat resistance is obtained by the spiroglycol component is that the spiroglycol component has a relatively rigid structure. Furthermore, the spiroglycol component is limited in free rotation in the polyester molecular chain. Therefore, it is considered that the softening of the polyester molecular chain hardly occurs and the glass transition temperature rises, and as a result, the heat resistance is improved. Spiroglycol components are relatively bulky and a large free space is secured around the molecule. Therefore, good results can be achieved in terms of moldability. When the content of the spiroglycol component is at least the above lower limit, the effect of improving heat resistance by the spiroglycol component is likely to be obtained. Moreover, it is preferable that the spiroglycol component is not more than the above upper limit in that the shape is stably maintained even at room temperature.

  The polyester resin composition constituting the film of the present invention contains 5 to 30 mol%, preferably 8 to 25 mol%, more preferably 10 to 20 mol% of a copolymer component other than the spiroglycol component. The spiroglycol component has a relatively rigid structure. Therefore, when it has only a spiroglycol component as a copolymerization component, it becomes easy to produce brittleness and it will become easy to produce a fracture | rupture at the time of film forming. By including a copolymer component other than the spiroglycol component in the above range, the present invention can reduce breakage in film formation and exhibit good moldability in a temperature range of 100 ° C. or higher. When the copolymer component other than the spiroglycol component is at least the above lower limit, brittleness is suppressed and molding becomes easy. On the other hand, when the copolymerization component other than the spiroglycol component is not more than the above upper limit, the melting point of the polyester resin composition is kept low, and good shape stability is easily maintained even in a temperature range of about 90 ° C.

  The copolymer component other than the spiroglycol component is spiroglycol, ethylene glycol, and terephthalic acid when the terephthalic acid component is used as the acid component (or 2,6-naphthalenedicarboxylic acid when the 2,6-naphthalenedicarboxylic acid component is used) ) Other than the glycol component or dicarboxylic acid component, and one kind or two or more kinds may be used in combination. The copolymer component other than the spiroglycol component suitable for use in the present invention includes a branched aliphatic glycol or alicyclic glycol in the glycol component, and the dicarboxylic acid component is an aromatic dicarboxylic acid component or a long-chain aliphatic system. Dicarboxylic acid is mentioned. Since all of these copolymer components have a bulky molecular structure, it becomes possible to rapidly soften above the glass transition temperature, and moldability at 100 ° C. or higher can be suitably obtained.

  Examples of the branched aliphatic glycol include neopentyl glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, and the like. Examples of the alicyclic glycol include 1,4-cyclohexanedimethanol and tricyclodecane dimethylol. Among these, neopentyl glycol and 1,4-cyclohexanedimethanol are particularly preferable from the viewpoint of compatibility with the spiroglycol component.

  As the aromatic dicarboxylic acid, terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid or ester-forming derivatives thereof are suitable. Further, as the long chain aliphatic dicarboxylic acid, succinic acid, adipic acid, azelaic acid, sebacic acid and the like are suitable. Among these, isophthalic acid, naphthalenedicarboxylic acid, and adipic acid are particularly preferable from the viewpoint of compatibility with the spiroglycol component.

  The copolymer polyester in the polyester resin composition constituting the film comprises a terephthalic acid component or 2,6-naphthalenedicarboxylic acid component as a dicarboxylic acid component, an ethylene glycol component as a glycol component, a spiroglycol component and / or the above spiroglycol. A copolymer component other than the components is used as a constituent component. The copolymerized polyester used in the present invention may contain a spiroglycol component and a copolymerized component other than the spiroglycol component as a copolymerized component, or a copolymerized polyester other than the spiroglycol component and a copolymerized component other than the spiroglycol component. A blend of copolyesters may also be used. The mixing ratio in this case can be appropriately controlled within the range of the mol% ratio of the above components. Among these, a copolyester containing both a spiroglycol component and a copolymer component other than the above spiroglycol component is preferred for compatibility with each component, and more suitable for both moldability and form stability than a blend. Yes.

  The polyester resin composition constituting the film of the present invention may be a copolyester containing a spiroglycol component and a copolymer component other than spiroglycol, or may contain a copolymer component other than the spiroglycol component and spiroglycol. A blend of a copolymerized polyester and a homopolyester may be used, or a copolymerized polyester containing a spiroglycol component as a copolymerized component and a copolymerized polyester containing a copolymerized component other than spiroglycol and a homopolyester. It may be a blend. Forming a film by blending is preferable for achieving transparency and high melting point (heat resistance) while maintaining moldability. In any case, it is important that the mol% of each component is within the above range. In addition, content of each said component can be measured by the NMR component analysis and mass spectrometry of a film sample.

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

  When manufacturing the said 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 polyester preferably has an intrinsic viscosity of 0.50 dl / g or more, more preferably 0.55 dl / g or more, particularly preferably 0.60 dl / g or more from the viewpoint of moldability and film-forming stability. is there. If the intrinsic viscosity is less than 0.50 dl / g, the moldability tends to decrease. In addition, when a filter for removing foreign substances is provided in the melt line, the upper limit of the intrinsic viscosity is preferably 1.0 dl / g from the viewpoint of ejection stability during extrusion of the molten resin.

  The melting point of the polyester film of the present invention is preferably 200 ° C. or higher and lower than 255 ° C. from the viewpoint of heat resistance and moldability, more preferably 210 ° C. or higher and 254 ° C. or lower, and 220 ° C. or higher and 253 ° C. or lower. Further preferred. By setting the melting point within the above range, moldability in a temperature range of 100 ° C. or higher is suitably achieved. When the melting point is not less than the above lower limit, it is preferable from the viewpoint of shape retention, and when the melting point is less than the above upper limit, it is preferable from the viewpoint of moldability. In order to control the melting point within the above range, it is preferable to adjust the content of copolymer components other than spiroglycol. Specifically, when the content of copolymer components other than spiroglycol increases, the melting point of the polyester film decreases.

  The glass transition temperature of the polyester film of the present invention is preferably 80 ° C. or higher and 150 ° C. or lower, more preferably 82 ° C. or higher and 140 ° C. or lower, and 85 ° C. or higher and 130 ° C. from the viewpoint of maintaining the shape at high temperature. The following is more preferable. By setting the glass transition temperature in the above range, the form stability in a temperature range of about 90 ° C. is suitably achieved. When the glass transition temperature is equal to or higher than the lower limit, it is preferable from the viewpoint of shape retention, and when the glass transition temperature is lower than the upper limit, it is preferable from the viewpoint of moldability. In order to control the glass transition temperature within the above range, it is preferable to adjust the content of spiroglycol. Specifically, when the content of spiroglycol increases, the glass transition temperature of the polyester film increases.

  In this invention, melting | fusing point of a polyester film falls by containing copolymerization components other than spiroglycol, and suitable moldability is obtained. However, since only the copolymer component causes a decrease in the glass transition temperature, the shape retention at a high temperature decreases. Therefore, in the present invention, by using a spiroglycol component having a rigid structure in combination, the glass transition temperature can be maintained, and both moldability and form retention at high temperatures can be achieved.

  When printing is performed on the film, the printed layer is deteriorated by sunlight in an outdoor environment. In addition, when used in a long-term outdoor environment, the film itself deteriorates due to sunlight. Therefore, in order to impart light resistance of the film in an outdoor environment, it is preferable to blend an ultraviolet absorber with the molding polyester film. The ultraviolet absorber may be either inorganic or organic as long as it has an ultraviolet absorbing action. Examples of organic ultraviolet absorbers include benzotoazole, benzophenone, cyclic imino ester, and combinations thereof. From the viewpoint of heat resistance, benzotoazole and cyclic imino ester are preferred. 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 inorganic ultraviolet absorbers include ultrafine particles of metal oxides such as cerium oxide, zinc oxide, and titanium oxide.

  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, etc. is not.

  Examples of the cyclic imino ester ultraviolet absorber include 2,2 ′-(1,4-phenylene) bis (4H-3,1-benzoxazin-4-one), 2-methyl-3,1-benzoxazine. -4-one etc. are mentioned.

  The addition amount of the ultraviolet absorber is preferably 0.01% by mass to 10% by mass, more preferably 0.05% by mass to 5% by mass, and further preferably 0.1% by mass to 3% by mass. When used outdoors for a long time, if the amount of UV absorber added is less than the above upper limit, the film is deteriorated by UV rays, which is not preferable. Moreover, since the transparency of a film will become low when there is much addition amount, it is unpreferable.

  Moreover, in order to improve handling properties, such as the slipperiness and winding property of a film, it is preferable to form an unevenness | corrugation on the film surface. 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 internal particles having an average particle size of 0.01 to 10 μm, external 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 and transparency 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. The lower limit of the average particle diameter of the particles is more preferably 0.10 μm, particularly preferably 0.50 μm, from the viewpoint of handling properties such as slipping property and winding property. On the other hand, the average particle diameter of the particles is more preferably 5 μm, particularly preferably 2 μm, from the viewpoint of transparency and reduction of film defects due to coarse protrusions.

  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 external particles include wet and dry silica, colloidal silica, aluminum silicate, titanium oxide, calcium carbonate, calcium phosphate, barium sulfate, alumina, mica, kaolin, clay, hydroxyapatite and the like, and styrene, silicone, acrylic Organic particles or the like containing acids as constituent components 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 characteristics defined in the present invention are not impaired.

  Furthermore, the content of the particles in the film is preferably 0.001 to 10% by mass, more preferably 0.01 to 5% by mass, and still more preferably 0.1 to 1% 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 formation of coarse protrusions, deterioration of film forming property and transparency.

  Moreover, since the particle | grains contained in a film generally differ in refractive index from polyester, it becomes a factor which reduces the transparency of a film. In many cases, the molded product is printed on the surface of the film before the film is molded in order to improve the design. Since such a printing layer is often applied to the back side of a molding film, it is desired that the transparency of the film is high from the viewpoint of printing clarity.

  Therefore, in order to obtain a high degree of transparency while maintaining the handleability of the film, the base film of the main layer does not substantially contain particles, and has a laminated structure containing particles only in the surface layer. It is effective to use a laminated film.

  In order to impart other functions, 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 the laminated film is not particularly limited. For example, the laminated film has an A / B two-kind two-layer structure, a B / A / B two-kind three-layer structure, and a C / A / B three-kind three-layer structure. A form is mentioned. When suppressing the bleeding out of the said ultraviolet absorber, the aspect which adds an ultraviolet absorber only to a center layer is also preferable. Moreover, the aspect which adds the said particle | grain only to a surface layer from the point of coexistence of transparency and workability is also preferable.

  In the molding polyester film of the present invention, the elastic modulus at 25 ° C. is an indicator of the form stability in a normal state. When the film is rolled and unwound, it is preferable to exhibit appropriate form stability that does not cause slack or stress. The elastic modulus at 25 ° C. of the film of the present invention is preferably 1 to 5 GPa, more preferably 1.2 to 4 GPa, and further preferably 1.5 to 3 GPa in both the longitudinal direction and the width direction.

  In the present invention, shape retention as a film can be suitably achieved by stretching the film. In addition, the presence or absence of stretching of the film can be specified by measuring the degree of plane orientation (ΔP), for example. Specifically, the degree of plane orientation (ΔP) of the film of the present invention is preferably 0.0001 or more, more preferably 0.001 or more, and still more preferably 0.01 or more.

  The production method of the stretched polyester film is not particularly limited. For example, after drying the polyester resin as necessary, it is supplied to a melt extruder, extruded into a sheet form from a slit-shaped die, and a casting drum by a method such as electrostatic application. An example is a method in which the unstretched sheet is uniaxially or biaxially stretched after being brought into close contact with and cooled and solidified to obtain an unstretched sheet.

  As the biaxial stretching method, a method is employed in which an unstretched sheet is stretched and heat-treated in the longitudinal direction (MD) and width direction (TD) of the film to obtain a biaxially stretched film having a desired in-plane orientation degree. . 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. In the case of the simultaneous biaxial stretching method, a tenter driven by a linear motor may be used. 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. More preferably, the stretching ratio in the longitudinal direction is 2.8 to 4.0 times, and the stretching ratio in the width direction is 3.0 to 4.5 times.

  As the stretching conditions for producing the molding polyester film of the present invention, it is preferable to select, for example, the following conditions.

  In the longitudinal stretching, it is more preferable that the stretching temperature is 80 to 120 ° C. and the stretching ratio is 1.6 to 4.0 times so that the subsequent lateral stretching can be performed smoothly.

  As described above, by using the polyester film for molding of the present invention, it is difficult to mold with a conventional polyester film, and vacuum molding or compressed air under a low molding pressure of 10 atm or less during molding. Also in a molding method such as molding, a molded product with good finish can be obtained. In addition, these molding methods are advantageous in terms of economy in the production of molded products because the molding costs are low. Therefore, application to these molding methods can most effectively exert the effect of the molding polyester film of the present invention.

  On the other hand, although the mold and the molding apparatus are expensive and disadvantageous in terms of economy, mold molding is characterized in that a molded product having a more complicated shape than that of the molding method is molded with high accuracy. Therefore, when molding using the molding polyester film used in the present invention, molding is possible at a lower molding temperature than conventional polyester films, and the finished quality of the molded product is improved. A remarkable effect is expressed.

  Furthermore, the molded product thus molded has excellent elasticity and shape stability (heat shrinkage characteristics, thickness unevenness) when used in a room temperature atmosphere, and also has excellent solvent resistance and heat resistance, as well as environmental impact. Therefore, it can be suitably used as a molding member for home appliance nameplates, automobile nameplates, dummy cans, building materials, decorative plates, decorative steel plates, transfer sheets and the like.

  The molding polyester film of the present invention is also suitable as a molding material that is molded using a molding method such as press molding, laminate molding, in-mold molding, draw molding, or bending molding, in addition to the above-described molding methods. is there.

  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) Haze Based on JIS-K7136-2000, it measured using the haze meter (the Nippon Denshoku Industries Co., Ltd. make, 300A). In addition, the measurement was performed twice and the average value was calculated | required.

(2) Film thickness Using Millitron, a total of 15 points were measured, 5 points per sheet, and the average value was determined.

(3) Elastic modulus The sample was cut into a strip shape having a length of 20 mm and a width of 5 mm, respectively, with a single-blade razor in the longitudinal direction and the width direction of the film. Subsequently, it evaluated using the Vibron testing machine (made by IT measurement control Co., Ltd.). The value of the storage elastic modulus obtained by the evaluation was taken as the elastic modulus.

  The measurement was performed under the conditions of a temperature range of 20 ° C. to 200 ° C., a temperature increase rate of 10 ° C./min, and a frequency of 10 Hz, and the elastic modulus at 25 ° C. was measured.

(4) Glass transition temperature (Tg) and melting point (Tm)
Using a differential scanning calorimeter (Mac Science, DSC3100S), about 7 mg of the raw material extruded under the conditions of each example was placed in a sample pan, the pan was capped, and the temperature was increased from room temperature to 300 ° C. in a nitrogen gas atmosphere. The temperature was measured at a temperature increase rate of 20 ° C./min. Tg (° C.) was determined based on JIS-K7121-1987, 9.3, and the melting point was determined by the melting peak temperature (Tpm) defined in 9.1.

(5) Light resistance In the dark box, the printed sample that was offset printed at a position 3 cm directly below the fluorescent lamp (manufactured by Matsushita Electric Co., Ltd., U-type fluorescent lamp FUL9EX) Put it on. Next, light was continuously irradiated 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 the light 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. Those having a color difference (ΔE value) of 0.5 or less were marked with ◯, and those with more than that were marked with ×. The color difference (ΔE value) is calculated by the following formula.
ΔE = √ (Δa 2 + Δb 2 + ΔL 2 )

(6) Formability (A) Vacuum forming After 5 mm square printing is performed on the film, the film is heated for 10 to 15 seconds with an infrared heater heated to 500 ° C and then vacuumed at a mold temperature of 30 to 100 ° C. Molding was performed. In addition, the heating conditions selected the optimal conditions within the said range with respect to each film. The shape of the mold was a cup shape, the opening had a diameter of 50 mm, the bottom part had a diameter of 40 mm, the depth was 50 mm, and all corners were curved with a diameter of 0.5 mm. .

Five molded products that were vacuum-molded under the optimum conditions were evaluated for moldability and finish, and ranked according to the following criteria. In addition, (circle) was set as the pass and x was set as the disqualification.
○: (i) The molded product is not torn,
(Ii) The corner radius of curvature is more than 1 mm and not more than 1.5 mm, or printing deviation is 0.1
greater than 0.2 mm and less than 0.2 mm,
(Iii) Further, there is no appearance defect corresponding to ×, and there is no problem in practical use. ×: The molded product is torn, or even if it is not torn, it falls under any of the following items (i) to (iv) (I) A corner with a radius of curvature exceeding 1.5 mm (ii) A poor appearance with large wrinkles (iii) A whitened film with reduced transparency (iv) A print misalignment of 0.2 mm More than

(B) Pressurized air formability After 5 mm square printing is performed on the film, the film is heated for 10 to 15 seconds with an infrared heater heated to 500 ° C., and then subjected to 4 atm at a mold temperature of 30 to 100 ° C. Crushing was performed under pressure. In addition, the heating conditions selected the optimal conditions within the said range with respect to each film. The shape of the mold is a cup shape, the opening has a diameter of 60 mm, the bottom has a diameter of 55 mm, a depth of 50 mm, and all corners are curved with a diameter of 0.5 mm. .

The moldability and finish of five molded products that were pressure-molded under optimal conditions were evaluated and ranked according to the following criteria. In addition, (circle) was set as the pass and x was set as the disqualification.
○: (i) The molded product is not torn,
(ii) The corner radius of curvature is more than 1 mm and not more than 1.5 mm, or printing deviation is 0.1
greater than 0.2 mm and less than 0.2 mm,
(iii) Further, there is no appearance defect corresponding to ×, and there is no problem in practical use. ×: The molded product is torn, or even if it is not torn, it falls under any of the following items (i) to (iv) What to do
(i) Corner radius of curvature exceeds 1.5mm
(ii) Large folds and poor appearance
(iii) The film is whitened and the transparency is lowered
(iv) Print misalignment exceeding 0.2 mm

(C) Mold formability After printing on the film, contact heating with a hot plate heated to 100 to 140 ° C for 4 seconds, followed by press molding at a mold temperature of 30 to 70 ° C and a holding time of 5 seconds It was. In addition, the heating conditions selected the optimal conditions within the said range with respect to each film. The shape of the mold is a cup shape, the opening has a diameter of 50 mm, the bottom has a diameter of 40 mm, a depth of 30 mm, and all corners are curved with a diameter of 0.5 mm. .

The moldability and finish of the five molded products molded under optimal conditions were evaluated and ranked according to the following criteria. In addition, (circle) was set as the pass and x was set as the disqualification.
○: (i) The molded product is not torn,
(ii) The corner radius of curvature is more than 1 mm and not more than 1.5 mm, or printing deviation is 0.1
greater than 0.2 mm and less than 0.2 mm,
(iii) Further, there is no appearance defect corresponding to ×, and there is no problem in practical use. ×: The molded product is torn, or even if it is not torn, it falls under any of the following items (i) to (iv) What to do
(i) Corner radius of curvature exceeds 1.5mm
(ii) Large folds and poor appearance
(iii) The film is whitened and the transparency is lowered
(iv) Print misalignment exceeding 0.2 mm

(7) Heat resistance The film was cut into 150 mm x 50 mm, the center part of the long side of the film was placed on a 50 mm wide support, and the amount of deflection was taken as the difference between the height of both ends of the sample and the height of the support. The sample was placed in an oven set at 90 ° C. together with the support for 30 minutes, and then the difference between the height of both ends of the sample and the height of the support was taken. The amount of bending before and after the oven treatment was compared.

(8) Solvent resistance The sample was immersed in toluene adjusted to 25 ° C. for 30 minutes, and the appearance change before and after immersion was determined according to the following criteria, and ○ was determined to be acceptable. The haze value was measured by the method described above.
○: Little change in appearance, change in haze value is less than 1% ×: Change in appearance is observed, or change in haze value is 1% or more

Example 1
The intrinsic viscosity is 0.69 dl / g, which is composed of 100 mol% of terephthalic acid unit as the aromatic dicarboxylic acid component, 20 mol% of ethylene glycol unit, 60 mol% of cyclohexanedimethanol unit and 20% of spiroglycol unit as the diol component. Copolyester chip (A), 0.08% by mass of amorphous silica having an intrinsic viscosity of 0.69 dl / g and an average particle size (SEM method) of 1.5 μm, and benzotriazole-based UV absorption Each of the polyethylene terephthalate chips (B) containing 1.0% by mass of the agent (N) (manufactured by Ciba Specialty Chemicals Co., Ltd., Tinuvin 326) was dried. Furthermore, the chip (A) and the chip (B) were mixed so as to have a mass ratio of 50:50. Subsequently, these chip mixtures were melt-extruded from the slit of the T die at 270 ° C. with an extruder, rapidly cooled and solidified on a chill roll having a surface temperature of 40 ° C., and at the same time, the amorphous mixture was adhered to the chill roll using an electrostatic application method. A stretched sheet was obtained.

  The obtained unstretched sheet was stretched 3.2 times at 100 ° C. in the longitudinal direction between the heating roll and the cooling roll. Next, the uniaxially stretched film was guided to a tenter and stretched 3.8 times at 110 ° C. Furthermore, heat setting was performed at 230 ° C. to obtain a biaxially stretched polyester film having a thickness of 100 μm.

Example 2
The intrinsic viscosity is 0.69 dl / g, which is composed of 100 mol% of terephthalic acid units as aromatic dicarboxylic acid components, 20 mol% of ethylene glycol units, 40 mol% of cyclohexanedimethanol units and 40% of spiroglycol units as diol components. Example 1 except that the copolymer polyester chip (C) and the polyethylene terephthalate chip (B) were mixed so as to have a mass ratio of 50:50, and the length was changed to 115 ° C. in the vertical direction. I went there.

Example 3
The intrinsic viscosity is 0.69 dl, comprising 50 mol% terephthalic acid unit and 50 mol% naphthalene dicarboxylic acid unit as the aromatic dicarboxylic acid component, and 88 mol% ethylene glycol unit and 12 mol% spiroglycol unit as the diol component. / G copolymer polyester chip (E) and polyethylene terephthalate chip (B) were mixed in the same manner as in Example 1 except that the mass ratio was 50:50.

Example 4
Intrinsic viscosity of 0.69 dl / g, comprising 60 mol% terephthalic acid units and 40 mol% adipic acid units as aromatic dicarboxylic acid components, and 70 mol% ethylene glycol units and 30 mol% spiroglycol units as diol components The copolymer polyester chip (E) and the polyethylene terephthalate chip (B) were mixed in a mass ratio of 50:50.

Example 5
Intrinsic viscosity of 0.69 dl / unit comprising 100 mol% of terephthalic acid unit as aromatic dicarboxylic acid component, 40 mol% of ethylene glycol unit, 40 mol% of neopentyl glycol unit and 20 mol% of spiro glycol unit as diol component This was carried out in the same manner as in Example 1 except that the g copolymerized polyester chip (E) and the polyethylene terephthalate chip (B) were mixed at a mass ratio of 50:50.

Example 6
Intrinsic viscosity is 0.69 dl / unit comprising 100 mol% of terephthalic acid unit as aromatic dicarboxylic acid component, 56 mol% of ethylene glycol unit, 24 mol% of neopentyl glycol unit and 20 mol% of spiro glycol unit as diol component. This was carried out in the same manner as in Example 1 except that the g copolymerized polyester chip (F) and the polyethylene terephthalate chip (B) were mixed at a mass ratio of 50:50.

Example 7
Intrinsic viscosity is 0.69 dl / g, comprising 80 mol% terephthalic acid units and 20 mol% isophthalic acid units as aromatic dicarboxylic acid components, and 92 mol% ethylene glycol units and 8 mol% spiroglycol units as diol components. This was carried out in the same manner as in Example 1 except that the copolyester chip (G) was used as a raw material.

Example 8
A benzotriazole ultraviolet absorber (80 mol% terephthalic acid unit and 20 mol% naphthalene dicarboxylic acid unit as the aromatic dicarboxylic acid component, 80 mol% ethylene glycol unit and 20 mol% spiroglycol unit as the diol component) N) Copolymer polyester chip (H) containing 1.0% by mass (manufactured by Ciba Specialty Chemicals Co., Ltd., Tinuvin 326) and having an intrinsic viscosity of 0.69 dl / g was used as a raw material. The same operation as in Example 1 was performed.

Comparative Example 1
This was carried out in the same manner as in Example 1 except that only a polyethylene terephthalate chip (B) was used.

Comparative Example 2
Copolymerized polyester chip having an intrinsic viscosity of 0.69 dl / g, comprising 100 mol% of terephthalic acid units as aromatic dicarboxylic acid components, 65 mol% of ethylene glycol units and 35 mol% of cyclohexanedimethanol units as diol components The same procedure as in Example 1 was performed except that (F) was used.

Comparative Example 3
The intrinsic viscosity is 0.69 dl / g, which is composed of 100 mol% of terephthalic acid unit as an aromatic dicarboxylic acid component, 25 mol% of ethylene glycol unit, 20 mol% of cyclohexanedimethanol unit and 55% of spiroglycol unit as diol component. This was carried out in the same manner as in Example 1 except that the copolymer polyester chip (G) was used.

Comparative Example 4
The intrinsic viscosity is 0.69 dl / g, which is composed of 100 mol% of terephthalic acid unit as aromatic dicarboxylic acid component, 76 mol% of ethylene glycol unit, 20 mol% of cyclohexanedimethanol unit and 4% of spiroglycol unit as diol component. This was carried out in the same manner as in Example 1 except that the copolymer polyester chip (H) was used.

Comparative Example 5
The same procedure as in Example 1 was performed except that the film was not stretched.

  Regarding Examples 1 to 8 and Comparative Examples 1 to 5, the raw material compositions of the polymers used are shown in Table 1, and the production conditions and properties of the films are shown in Tables 2 and 3.

  The stretched polyester film for molding of the present invention has excellent moldability in the molding process, and can be used without being bent even when dried at a high temperature in the printing process, so that it is excellent in terms of shortening the drying time. ing. In addition, when used as a molded product in a normal temperature atmosphere, there are advantages that it is excellent in elasticity and form stability (heat shrinkage characteristics, thickness unevenness), excellent in solvent resistance and heat resistance, and has a small environmental load. Further, when unwinding a long film wound up in a roll shape at the time of post-processing, blocking and tearing are unlikely to occur, resulting in excellent productivity. Furthermore, since it is highly excellent in smoothness and transparency, the printing quality improving layer of the film has various types such as letterpress printing, intaglio printing, planographic printing, screen printing, offset printing, gravure printing, inkjet printing, flexographic printing, etc. Designs such as printing layers, design layers, etc. are applied by decoration methods such as printing decoration, printing, transfer, painting, painting, vapor deposition, sputtering, CVD, laminating, etc., then mold molding, pressure molding, vacuum molding, etc. It is suitable for a three-dimensional decoration method that is molded by various molding methods, and has excellent in-mold moldability and emboss moldability. Therefore, it is suitable as a member for nameplates or building materials of home appliances and automobiles, and contributes greatly to the industry.

  In addition, by incorporating an ultraviolet absorber in the film and reducing the transmittance in the ultraviolet region, light resistance can be imparted, particularly for applications used outdoors (members for automobile exteriors or building materials). It is suitable as a molding material.

Claims (7)

  1. A terephthalic acid component or 2,6-naphthalenedicarboxylic acid component and an ethylene glycol component of 50 mol% or more,
    Containing 2-20 mol% of spiroglycol component,
    Containing 5 to 30 mol% of a copolymer component other than the spiroglycol component,
    Stretched polyester film for molding.
  2.   The stretched polyester film for molding according to claim 1, wherein the film has a glass transition temperature of 80 ° C or higher and 150 ° C or lower and a melting point of 200 or higher and lower than 255 ° C.
  3.   The stretched polyester film for molding according to claim 1 or 2, wherein the elastic modulus in the longitudinal direction and the width direction of the film is 1 to 5 GPa at 25 ° C.
  4.   The stretched polyester film for molding according to claim 1, wherein a copolyester containing a spiroglycol component and a copolymerization component other than spiroglycol and a homopolyester are mixed.
  5.   The stretched polyester film for molding according to claim 1, which is obtained by mixing a copolymer polyester containing a spiro glycol component as a copolymer component, a copolymer polyester containing a copolymer component other than spiro glycol, and a homopolyester. .
  6.   The molding according to any one of claims 1 to 5, wherein the copolymer component other than the spiroglycol includes any one of branched aliphatic glycol, alicyclic glycol, isophthalic acid, naphthalenedicarboxylic acid, and adipic acid. Stretched polyester film.
  7.   The stretched polyester film for molding according to any one of claims 1 to 6, wherein the film contains an ultraviolet absorber.
JP2011021559A 2011-02-03 2011-02-03 Oriented polyester film for molding Pending JP2012162586A (en)

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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2003292593A (en) * 2002-04-04 2003-10-15 Mitsubishi Gas Chem Co Inc Polyester resin
JP2007254720A (en) * 2006-02-24 2007-10-04 Toray Ind Inc Polyester chip

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2003292593A (en) * 2002-04-04 2003-10-15 Mitsubishi Gas Chem Co Inc Polyester resin
JP2007254720A (en) * 2006-02-24 2007-10-04 Toray Ind Inc Polyester chip

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