JP2017170902A - Multilayered polyester sheet and molded article of the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a multilayered polyester sheet which is excellent in secondary workability heat resistance, printability and moldability, and in particular, is suitably used in a display article such as an advertisement displaying plate with back light in a vending machine, a display case of a tobacco and the like and a display can such as a beverage can or a packaging sheet of cosmetics, foods and the like.SOLUTION: A multilayered polyester sheet has a substrate layer containing a polyester resin, and a coating layer which is provided on at least one surface of the substrate layer and contains the polyester resin. The polyester resin of the coating layer contains 1,4-cyclohexanedimethanol and isosorbide, and is obtained by reacting a diol component in which a content ratio of the isosorbide is 10-50 mol% based on the total diol component with a dicarboxylic acid component.SELECTED DRAWING: None

Description

The present invention relates to a multilayer polyester sheet having high heat resistance and excellent secondary processability such as printability and moldability, and a molded article formed by molding the multilayer polyester sheet.
The multi-layer polyester sheet of the present invention is particularly suitable for transparent display cases and thermoformed products that have been folded for display products such as advertising display plates and display cases around display vending machines, display cans, packaging for cosmetics and foods, etc. For example, it is suitably used.

In general, advertising display plates and display molded products around vending machines are required to have heat resistance that can withstand heat sources such as heaters for heating products such as sunlight, backlight, or beverages. Conventionally, many polycarbonate sheets have been used to satisfy the required heat resistance characteristics. However, since the polycarbonate sheet has a high heat distortion temperature, the molding temperature range is high, the molding is not easy, the time required for thermoforming and the molding cycle are long; In order to improve the scratch resistance, it is common to use a masking film attached (Patent Document 1). However, in such a case, when printing or the like, the work efficiency is extremely poor. There is.
In addition, biaxially stretched polyethylene terephthalate (PET) film (Patent Document 2) and non-stretched PET sheet are also partially employed. However, the former has poor moldability and the latter has insufficient heat resistance. There were problems such as.

  Furthermore, vending machines are installed throughout the country, and advertisement display sheets and display supplies are frequently changed and exchanged, such as for sales promotion and product replacement at seasonal changes. There are also environmental problems such as the generation of waste, and especially polycarbonate sheets have problems such as environmental hormones.

  Therefore, heat resistance that can withstand the heat in the vending machine, secondary processability and workability such as printability and moldability, and the use of plant-derived resin, recycling, incineration disposal, and other waste disposal sheets Is desired.

  On the other hand, for packaging sheets for cosmetics and foods, heat resistance may be required during filling and transportation of contents, and a sheet with excellent heat resistance, printability, and formability is also desired. Has been.

JP 2004-345344 A JP 2004-75713 A

  The present invention is excellent in secondary processability such as heat resistance, printability, and moldability, and in particular, an advertising display plate with backlight in a vending machine, a display case such as cigarette, a display can such as a beverage can, etc. It is an object of the present invention to provide a multilayer polyester sheet that is suitably used as a display product of the above, or a packaging sheet for cosmetics, foods, and the like, and a molded product formed by molding the multilayer polyester sheet.

  As a result of intensive studies to solve the above-mentioned problems, the present inventors have determined that, in a multilayer polyester sheet having a coating layer and a base layer, 1,4-cyclohexanedimethanol and a predetermined proportion of isosorbide are used as the polyester resin of the coating layer. It has been found that the above-described problems can be solved by using a polyester resin obtained using a diol component containing.

  The present invention has been achieved on the basis of such findings, and the gist thereof is as follows.

[1] In a multilayer polyester sheet having a base layer containing a polyester resin and a coating layer containing a polyester resin provided on at least one surface of the base layer, the polyester resin of the coating layer is 1,4-cyclohexane. It is a polyester resin obtained by reacting a diol component and a dicarboxylic acid component, which contain dimethanol and isosorbide, and the content ratio of isosorbide is 10 mol% or more and 50 mol% or less with respect to all diol components. Multi-layer polyester sheet.

[2] In the multilayer polyester sheet according to [1], the polyester resin of the base layer contains 1,4-cyclohexanedimethanol and isosorbide, and the content ratio of isosorbide is 1 mol% or more based on all diol components. And the multilayer polyester sheet characterized by being a polyester resin obtained by making the diol component and dicarboxylic acid component which are less than the content rate of the isosorbide in the diol component of the polyester resin of the said coating layer react.

[3] The multilayer polyester sheet according to [1] or [2], wherein at least one sheet surface is provided with surface irregularities having a maximum protrusion height (Rmax) of 0.5 to 5 μm. Multi-layer polyester sheet.

[4] The multilayer polyester sheet according to [3], wherein the surface irregularities are provided by embossing.

[5] In the multilayer polyester sheet according to [3], the surface irregularities are imparted by particles contained in the coating layer on the sheet surface provided with the surface irregularities, and the average particle size of the particles is 2 to 2. A multilayer polyester sheet, wherein the content of the particles in the coating layer is 15 to 5% by weight at 15 μm.

[6] The multilayer polyester sheet according to any one of [1] to [5], wherein at least one coating layer contains an antistatic agent and / or a lubricant, or at least one sheet surface has an antistatic agent. And / or a multi-layer polyester sheet coated with a lubricant.

[7] The multilayer polyester sheet according to any one of [1] to [6], wherein the thickness ratio of the coating layer is in the range of 1 to 50% of the thickness of the entire sheet. Polyester sheet.

[8] A molded product formed by molding the multilayer polyester sheet according to any one of [1] to [7].

[9] The molded product according to [8], which is an advertising display plate, a display product, a folded case for packaging, or a molded product for packaging.

  According to the present invention, it is excellent in secondary processability such as heat resistance, printability, and moldability, and in particular, an advertising display plate with backlight in a vending machine, a display case such as tobacco, and a display such as a beverage can. Provided is a multilayer polyester sheet suitably used as a display product such as a can or a packaging sheet for cosmetics, foods, and the like.

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

  The multilayer polyester sheet of the present invention is a multilayer polyester sheet having a base layer containing a polyester resin and a coating layer containing a polyester resin provided on at least one surface of the base layer, wherein the polyester resin of the coating layer is: A polyester resin obtained by reacting a diol component and a dicarboxylic acid component, which contain 1,4-cyclohexanedimethanol and isosorbide and the content ratio of isosorbide is 10 mol% or more and 50 mol% or less with respect to all diol components. It is characterized by being.

[Polyester resin constituting the coating layer]
The polyester resin constituting the coating layer of the multilayer polyester sheet of the present invention contains 1,4-cyclohexanedimethanol and isosorbide (hereinafter sometimes referred to as “ISB”), and the ISB content is 10 mol. % Or more and 50 mol% or less of a diol component and a dicarboxylic acid component are reacted with a polyester resin. That is, the polyester resin is obtained by polycondensation of a dicarboxylic acid component and a diol component, but the coating layer according to the present invention has at least 1,4-cyclohexane as the diol component as described above. An ISB copolymer polyester resin obtained by using a diol component containing dimethanol and isosorbide is used.

  The dicarboxylic acid component of the ISB copolymer polyester resin includes terephthalic acid, but a part of terephthalic acid may be substituted with another dicarboxylic acid. Examples of other dicarboxylic acids include oxalic acid, malonic acid, succinic acid, adipic acid, azelaic acid, sebacic acid, neopentylic acid, isophthalic acid, naphthalenedicarboxylic acid, diphenyl ether dicarboxylic acid, p-oxybenzoic acid and the like. The other dicarboxylic acid used may be one kind or a mixture of two or more kinds, and the amount of the other dicarboxylic acid to be substituted can be appropriately selected.

  On the other hand, the diol component contains 1,4-cyclohexanedimethanol and isosorbide as essential components, and this diol component may contain other diols. Other diols include ethylene glycol, propylene glycol, trimethylene glycol, tetramethylene glycol, hexamethylene glycol, dimethylene glycol, neopentyl glycol, polyalkylene glycol, glycerin, pentaerythritol, trimethylolpropane, methoxypolyalkylene glycol, etc. Is mentioned. These other diols may be one kind or a mixture of two or more kinds, and the amount of the other diols can be appropriately selected. In the present invention, isosorbide is added to the diol component in a predetermined manner. It is essential to include it as a percentage.

  The polyester resin constituting the coating layer contains isosorbide as a diol component for the purpose of improving heat resistance, but from the viewpoint of heat resistance, the content ratio of isosorbide in all diol components used for producing the polyester resin is 10 mol%. It is above, Preferably it is 15 mol% or more. Even if the diol component contains more than 50 mol% of isosorbide, the effect of improving the heat resistance is not only small, but if it is contained more than this, the physical properties are lowered, so it is used for the production of a polyester resin. The content ratio of isosorbide in all diol components is 50 mol% or less, preferably 40 mol% or less.

  1,4-cyclohexanedimethanol is contained in the diol component for the purpose of improving physical properties such as impact resistance and compatibility with other polyester resins. Although there is no restriction | limiting in particular in the content, It is preferable that it is the same mol% or more as isosorbide in all the diol components used for manufacture of a polyester resin, and it is 1 with respect to the isosorbide in all the diol components used for manufacture of a polyester resin. It is preferable to contain -5 mol times, especially 1-2 mol times.

  The intrinsic viscosity of the polyester resin used for the coating layer according to the present invention is preferably 0.4 dL / g or more, particularly 0.5 dL / g or more. When the intrinsic viscosity is less than this lower limit, the mechanical strength of the resulting multilayer polyester sheet becomes insufficient, particularly the impact strength at a low temperature is lowered, and there is a possibility that it cannot be used practically. The upper limit of the intrinsic viscosity of the polyester resin is usually 1.2 dL / g.

The polyester resin used for the coating layer may be only one kind of the above-mentioned ISB copolymer polyester resin, and the content ratio, intrinsic viscosity, etc. of 1,4-cyclohexanedimethanol and ISB of dicarboxylic acid component and diol component are different. It may be a mixture of two or more ISB copolymer polyester resins. Further, the polyester resin of the coating layer may be a mixed polyester resin of the above ISB copolymer polyester resin and a polyester resin other than the ISB copolymer polyester resin.
However, even when two or more polyester resins are used, the content ratio of isosorbide in all diol components constituting the mixed polyester resin is in the above range, and preferably the content ratio of 1,4-cyclohexanedimethanol In addition, the intrinsic viscosity of the mixed polyester resin should be within the above range.

  In addition, there is no restriction | limiting in particular in the manufacturing method of the polyester resin which comprises a coating layer, It can manufacture according to a conventional method.

[Polyester resin constituting base layer]
The polyester resin constituting the base layer of the multilayer polyester sheet of the present invention is not particularly limited. Specifically, polyethylene terephthalate (PET) obtained by condensation polymerization of terephthalic acid and ethylene glycol, or a part of terephthalic acid is used. A PET copolymer polyester resin or the like in which another dicarboxylic acid or a part of ethylene glycol is changed to another diol can be used. As PET-based copolyester resin, 60% or more of the total dicarboxylic acid component is terephthalic acid, the remaining dicarboxylic acid component substituted with another dicarboxylic acid, and 60 mol% or more of all diol components is ethylene glycol. And a polyester resin obtained by polycondensation with a diol component whose remaining part is substituted with another diol.

  Here, examples of the other dicarboxylic acid include those exemplified as the dicarboxylic acid of the polyester resin constituting the coating layer, and may be one kind or a mixture of two or more kinds. The amount of the other dicarboxylic acid to be made can be appropriately selected.

  Other diols include isosorbide, propylene glycol, trimethylene glycol, tetramethylene glycol, hexamethylene glycol, dimethylene glycol, neopentyl glycol, polyalkylene glycol, 1,4-cyclohexanedimethanol, glycerin, pentaerythritol, Trimethylolpropane, methoxypolyalkylene glycol and the like can be mentioned, and the other diol may be one kind or a mixture of two or more kinds, and the amount of other diol to be substituted can be appropriately selected. As for isosorbide, it is preferable to make it less than the content of isosorbide in the total diol component of the polyester resin constituting the coating layer in terms of ensuring physical properties such as impact resistance and moldability of the multilayer polyester sheet. In particular the diol component of the polyester resin constituting the substrate layer, the following 2/3 of the content of isosorbide in the diol component of the polyester resin constituting the coating layer, it is preferred especially is 1/2 or less.

  The intrinsic viscosity of the polyester resin used in the base layer according to the present invention is preferably 0.4 dL / g or more, particularly 0.5 dL / g or more. When the intrinsic viscosity is less than this lower limit, the mechanical strength of the resulting multilayer polyester sheet becomes insufficient, particularly the impact strength at a low temperature is lowered, and there is a possibility that it cannot be used practically. The upper limit of the intrinsic viscosity of the polyester resin is usually 1.2 dL / g.

The polyester resin used for the base layer may be only one kind of the above-mentioned PET or PET copolymer polyester resin, and two or more kinds of dicarboxylic acid components, types and contents of diol components, and different intrinsic viscosities. A mixed polyester resin of a polyester resin may be used.
However, even when two or more kinds of polyester resins are used, the content ratio in the total diol component constituting the mixed polyester resin is, as described above, of isosorbide in the total diol component constituting the polyester resin of the coating layer. The content is preferably less than the content ratio, and the intrinsic viscosity of the mixed polyester resin is preferably in the above range.

  There is no restriction | limiting in particular also about the manufacturing method of the polyester resin which comprises a base layer, It can manufacture in accordance with a conventional method.

[Other ingredients]
Various additives such as an antioxidant, a stabilizer, a lubricant, a wax, an antistatic agent, an ultraviolet absorber, and an impact modifier can be blended in the polyester resin constituting the coating layer and the base layer. In particular, in the case where surface irregularities described later are imparted to the sheet surface, an organic lubricant such as a fatty acid ester or a fatty acid amide or an antistatic agent such as a cationic, anionic or nonionic surfactant is added to the polyester resin of the coating layer. By adding, the slipperiness and antistatic property of the sheet can be improved, and the workability and handling can be further improved. In this case, the addition amount of the lubricant and the antistatic agent is preferably about 0.01 to 2% by weight as the content in the coating layer.

  Various methods can be used as a method of blending these additives with the polyester resin, and the method is not particularly limited. In the present invention, for example, it is added at the time of polymerization, or the resin after polymerization is mixed using a blender, or a high-concentration master batch of an additive is prepared in advance, and this is further diluted with a polyester resin and mixed. Various methods can be employed, such as.

Moreover, in the polyester resin of a coating layer, particle | grains can be mix | blended in order to provide surface unevenness to the multilayer polyester sheet of this invention so that it may mention later.
These particles will be described later.

  Furthermore, the polyester resin constituting the coating layer and the base layer is made of a resin other than the polyester resin, such as a polycarbonate resin, a polyarylate resin, a polystyrene resin, a polyamide resin, and a polyolefin resin, as long as the object of the present invention is not impaired. You may use 1 type or in mixture of 2 or more types. When these other resins are used, in order to effectively obtain the effects of the present invention by using the polyester resin, the amount used is 30% by weight or less based on the total of the polyester resin and the other resin. Is preferred.

[Production method]
The multilayer polyester sheet of the present invention is an unstretched sheet that is not substantially crystallized, and is obtained by, for example, extrusion molding, supplying to an extruder, extruding from a T die, and rapidly solidifying with a cast roll. . Here, the unstretched sheet means a sheet that is not actively stretched for the purpose of increasing the strength of the sheet. For example, a sheet that has been stretched to less than 2 times by a stretching roll during extrusion molding is included in the unstretched sheet. It is.

Although there is no restriction | limiting in particular as a manufacturing method of the multilayer polyester sheet of this invention, For example, it is preferable to be based on the method in any one of the following (1)-(4).
(1) A method in which each of the coating layer and the base layer is formed into a sheet in advance, and then bonded by heat or an adhesive. (2) Immediately after the base layer sheet is extruded from the T die of the extruder, Method of heat bonding (3) Method of melting and extruding each layer of coating layer and substrate layer with separate extruders and method of melting and bonding with nip roll (4) Melting each layer of coating layer and substrate layer with separate extruders, A method of melt lamination and extruding as a laminated sheet using a multilayer die

  Further, a trimming ear of a sheet or a scrap sheet generated in manufacturing may be mixed. In this case, it may be kneaded back into the base layer or the coating layer, but when it is kneaded back into the coating layer, the content ratio of isosorbide of the diol component in the polyester resin constituting the coating layer is 10 to 50 mol. The blending amount is adjusted so as not to deviate from%. The re-stretching is preferably performed on the base layer, and the re-rolling amount is not particularly specified, but it is preferably 60% by weight or less, particularly 40% by weight or less of the total resin constituting the base layer. Also in this case, when the base layer is blended with the polyester resin, the content of isosorbide in the total diol component of the polyester resin constituting the base layer is such that the isosorbide in the total diol component of the polyester resin constituting the coating layer It is preferable to adjust the amount of reconstitution so as not to exceed the content ratio of.

[Surface unevenness]
The multilayer polyester sheet of the present invention can be provided with surface irregularities on at least one surface of the sheet for the purpose of enhancing the slipperiness.

  In addition to embossing, the surface irregularities can be imparted by adding particles or the like to the polyester resin of the coating layer constituting the surface layer.

  The degree of surface irregularities is preferably 0.5 to 5 μm in terms of maximum protrusion height (Rmax) in order to achieve both slipperiness and appearance. When the maximum protrusion height (Rmax) is less than 0.5 μm, the slipperiness of the sheet is deteriorated and the workability is deteriorated, and when it exceeds 5 μm, the appearance such as transparency tends to be deteriorated.

  As a method of imparting surface irregularities by embossing, there are known methods such as a method of imparting by casting on an embossing roll during film formation, a method of applying a pre-collected sheet with an embossing roll by heating in an outline. Can be mentioned.

  On the other hand, when particles are added to the polyester resin constituting the coating layer to give surface irregularities, examples of the particles to be blended in the polyester resin include inorganic particles such as silica, alumina, aluminosilicate, talc, and styrene resins. Organic particles such as crosslinked particles can be used.

  As an average particle diameter of the particle | grains to be used, 2-15 micrometers is preferable. With particles having an average diameter less than the above lower limit, the effect of improving slipperiness due to surface irregularities is small when formed into a sheet, the paper feeding property at the time of secondary processing such as printing is insufficient, and conversely the average particle exceeding the above upper limit In the case of particles having a diameter, the maximum protrusion height (Rmax) of unevenness becomes larger than 5 μm when formed into a sheet, and the appearance and transparency of the sheet tend to be inferior. Here, the average particle size of the particles means the average particle size when the cumulative weight fraction is 50%, measured using a Coulter counter (manufactured by Nippon Chemical Machinery Co., Ltd.).

  Further, the refractive index of the particles to be used is not particularly defined, but from the viewpoint of maintaining transparency, it is preferably close to the refractive index of the polyester resin in which it is blended, preferably about 1.4 to 1.7, more preferably Is selected from 1.45 to 1.65. When particles having a large refractive index difference from the polyester resin are used, the appearance and transparency of the resulting sheet tend to be inferior.

  Further, the addition amount of the particles is preferably 0.01 to 5% by weight as the content in the coating layer. If the blending amount of the particles is less than the above lower limit, the effect of improving the slipperiness is small, and if it exceeds the above upper limit, the appearance and transparency of the sheet tend to be inferior.

  In addition, only 1 type may be used for a particle | grain and it does not interfere even if it uses combining several particle | grains from which a material, a refractive index, and an average particle diameter differ.

  Various methods can be used as a method of blending the particles with the polyester resin, and the method is not particularly limited. In the present invention, for example, it is added at the time of polymerization, or mixed with a resin after polymerization using a blender, or a master batch having a high concentration of particles is prepared in advance, and this is further diluted with a polyester resin and mixed. For example, various methods can be employed.

[thickness]
The thickness of the sheet of the present invention is not particularly defined, but can be set according to the use, for example, in the range of 50 to 2000 μm, preferably 150 to 1000 μm.
Further, the thickness of the base layer and the coating layer is not particularly limited, but it is preferable that the ratio of the thickness of the coating layer is in the range of 1 to 50%, particularly 3 to 50% of the total thickness of the sheet. .
Here, the ratio of the thickness of the coating layer refers to the ratio of the total thickness of these coating layers when the coating layers are provided on both sides of the base layer.
When the coating layers are provided on both sides of the base layer, the thickness of each coating layer may be the same or different. However, in the present invention, the effect of the coating layer having excellent heat resistance is sufficient. Therefore, the thickness of the coating layer per layer is preferably 3 μm or more.

[Coating agent]
The multilayer polyester sheet of the present invention produced by the above-described method may be coated with an antistatic agent or a coating agent such as a lubricant such as silicone or wax on one or both surfaces. By applying, antistatic property and slipperiness can be further improved. In particular, when wax or silicone is applied, the slipperiness of the sheet can be further improved, and not only processability and handling, but also an improvement effect such as stacking properties when stacking molded products, etc. can be obtained. You can also.

[Usage]
Since the multilayer polyester sheet of the present invention is excellent in heat resistance, printability, moldability, processability, etc., display products such as advertisement display plates, display cases and display cans around vending machines, and cosmetics and foods. It is useful for transparent cases that have been folded for packaging, etc., and other thermoformed containers.
In addition, the multilayer polyester sheet of the present invention may be a roll of a long sheet, or may be cut into a sheet through a cutting device after being formed into a sheet.

  EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the following examples unless it exceeds the gist.

[Raw materials used]
The raw materials used such as resins and particles used in the following Examples and Comparative Examples are as follows.

<Polyester resin>
a: Copolyester resin (inherent viscosity) obtained by condensation polymerization of terephthalic acid and a mixture of 1,4-cyclohexanedimethanol 45 mol%, isosorbide 30 mol%, and ethylene glycol 25 mol% as a diol component : 0.6 dL / g)
b: Copolyester resin (inherent viscosity) obtained by condensation polymerization of terephthalic acid and a mixture of 1,4-cyclohexanedimethanol 45 mol%, isosorbide 25 mol%, and ethylene glycol 30 mol% as the diol component : 0.65 dL / g)
c: Copolyester resin (inherent viscosity) obtained by condensation polymerization of terephthalic acid and a mixture of 1,4-cyclohexanedimethanol 50 mol%, isosorbide 12 mol%, and ethylene glycol 38 mol% as a diol component : 0.7 dL / g)
d: Polyethylene terephthalate obtained by condensation polymerization of terephthalic acid and ethylene glycol (intrinsic viscosity 0.8 dL / g)
e: a copolymerized polyester resin (inherent viscosity 0.8 dL / g) obtained by condensation polymerization of terephthalic acid and a mixture of 70 mol% ethylene glycol and 30 mol% 1,4-cyclohexanedimethanol as a diol component )

<Particle>
A: Silica (refractive index 1.46, average particle size 8 μm)
A: Silica (refractive index 1.46, average particle size 1.5 μm)
C: Silica (refractive index 1.46, average particle size 18 μm)
D: Aluminosilicate (refractive index 1.50, average particle size 8 μm)
E: Styrene crosslinked particles (refractive index 1.58, average particle size 8 μm)

<Additives>
Lubricant: Glycerol monobehenate Antistatic agent: Sodium dodecylbenzenesulfonate

<Coating agent>
Lubricant: Silicone mold release agent “KM-9737” manufactured by Shin-Etsu Chemical Co., Ltd.
Antistatic agent: alkyltrimethylammonium salt

[Evaluation method]
The sheet evaluation method in each example and comparative example is as follows.

<Printability>
A sheet was set on a roll or a lithographic printing machine, and printing was performed using an ultraviolet curable ink.
Note that printing was performed using a roll in the case of an uncut long sheet, and using a lithographic printing machine in the case of a cut plate-like sheet.

(Ink adhesion)
Immediately after printing, a tape peel test was conducted, the ratio of the peel area of the ink to the peel test area was examined, and evaluated according to the following criteria. “◯” and “△” are practical levels.
“◯”: The ink peel area is less than 30% of the peel test area.
“△”: The peel area of the ink is 30% or more and less than 70% of the peel test area.
“×”: The ink peel area is 70% or more of the peel test area.
(Sliding property (paper feeding property))
In printing with a lithographic printing machine, the slipperiness was evaluated according to the following criteria. “◎”, “◯”, and “△” are practical levels.
“◎”: The slipperiness was very good and the paper feeding was smooth.
“Good”: Good sliding property and smooth paper feeding.
“△”: The slipperiness is slightly bad, but paper feeding is possible.
“X”: Sliding property was poor and smooth paper feeding was not possible.

(Transparency (transparency of printed pattern))
The printed sheet was visually observed from the non-printed surface side, and the transparency of the printed pattern was evaluated according to the following criteria. “◯” and “Δ” are practical levels.
“◯”: The transparency of the printed pattern is good.
“Δ”: Transparency of printed pattern is slightly bad, but it is at a practical level.
“×”: The printed pattern has insufficient transparency.

<Thermoformability>
The sheet surface was heated and thermoformed using a vacuum forming machine, and the moldability and mold release properties were evaluated according to the following criteria. “◯” and “Δ” are practical levels.
A circular cup-shaped mold having a diameter of 100 mm and a depth of 30 mm was used as the molding die, and the molding temperature was determined by checking the surface temperature of the sheet immediately before molding.
(Formability)
“○”: Can be molded at a sheet heating temperature of 130 ° C. or less.
“X”: Cannot be molded unless the sheet heating temperature exceeds 130 ° C.
(Releasability)
“◯”: Good separation from the mold.
“Δ”: Although the mold separation from the mold is somewhat bad, it is at a practical level.
"X": The mold separation from the mold is poor, and the cooling time is long.

<Heat resistance>
The thermoformed product molded into a cup shape in the above-described evaluation of thermoformability was visually observed for deformation when left in an oven maintained at 90 ° C. for 6 hours, and evaluated according to the following criteria. “◯” and “△” are practical levels.
“○”… No deformation.
“△”: There is a slight deformation, but the shape is maintained.
“×”: A large deformation is seen.

<Surface unevenness>
The maximum protrusion height (Rmax) of the unevenness imparting surface by embossing or particle addition was measured.
The measurement method is a non-contact type three-dimensional roughness meter (512 by Micromap) using direct phase detection interferometry, so-called two-beam interferometry, and the PV value of the sheet surface in a measurement area of 428 μm × 320 μm is obtained. The measurement was performed over 10 points, and the PV values at the 10 points were averaged to obtain the maximum protrusion height (Rmax) of the film.

<Antistatic property>
Based on JISK-6911, the surface specific resistivity of the sheet was measured, and the value was evaluated according to the following criteria. In addition, the surface uneven | corrugated provision surface side was measured in the sheet | seat which provided the surface unevenness | corrugation.
“◯”: Surface resistivity of less than 1 × 10 ¹³ Ω “△”: Surface resistivity of 1 × 10 ¹³ Ω or more

[Examples 1-9, Comparative Examples 1-3]
Using the resin of the base layer and the coating layer shown in Table 1 as raw materials, each of the raw materials is melt-mixed in two twin-screw vent extruders set at an extrusion temperature of 270 ° C. After extrusion using a three-layer T die, sandwiched between two mirror-finished cast rolls set at 40 ° C., rapidly cooled, formed into a sheet, and the base layer and coating layer thicknesses shown in Table 1 are amorphous. A multilayered polyester sheet was obtained. The thickness of each layer was adjusted by the resin extrusion amount, and the thickness of each layer was confirmed by observing the sheet cross section.
In Table 1, the coating layer thickness of the two-type / three-layer sheet is the total thickness of the coating layers provided on both surfaces of the base layer, and the thickness of each coating layer was the same.
The printability, thermoformability, and heat resistance of the obtained sheet were evaluated, and the results are shown in Table 1.

[Examples 10 to 24]
In Example 1, a non-crystalline multilayer polyester sheet embossed on the coating layer was obtained in the same manner except that one of the two mirror-finished cast rolls was changed to an embossed roll having unevenness. . Furthermore, it supplied to the cutting apparatus and obtained the cut-plate-shaped multilayer polyester sheet.
The resulting sheet was evaluated for surface irregularities, printability, and antistatic properties, and the results are shown in Table 2.

[Examples 15 to 24]
In Example 1, the same manner as in Example 1 except that the particles shown in Table 2 were added to the polyester resin of the coating layers on both sides so that the content ratio in the coating layer was the ratio shown in Table 2 (however, In Example 20, the thickness of the base layer was 160 μm, the thickness of the coating layer was 20 μm, and the thickness of the sheet was 200 μm.) A non-crystalline multilayer polyester sheet was obtained. Furthermore, it supplied to the cutting apparatus and obtained the cut-plate-shaped multilayer polyester sheet. The particles were prepared in advance in a high concentration master batch with the polyester resin used in the coating layer, and this master batch was diluted with the polyester resin to obtain a predetermined addition amount.
The resulting sheet was evaluated for surface irregularities, printability, and antistatic properties, and the results are shown in Table 2.

[Example 25]
A non-crystalline multilayer polyester sheet was obtained in the same manner as in Example 17 except that 0.3% by weight of a lubricant and an antistatic agent were added to the polyester resin of the coating layer. In addition, the additive prepared the high concentration masterbatch with the polyester resin used for a coating layer previously, and diluted this masterbatch with the polyester resin to make predetermined addition amount.
The resulting sheet was evaluated for surface irregularities, printability, and antistatic properties, and the results are shown in Table 2.
As shown in Table 2, in Example 25, the antistatic property and slipperiness (paper feeding property) were improved as compared with Example 17.

[Examples 26 and 27]
A coating agent shown in Table 2 was applied to one side of an amorphous polyester sheet obtained in the same manner as in Example 17.
The resulting sheet was evaluated for surface irregularities, printability, and antistatic properties, and the results are shown in Table 2.
As shown in Table 2, in Example 26, the antistatic property was improved as compared with Example 17, and in Example 27, the slip property (paper feeding property) was improved as compared with Example 17.

[Comparative Examples 4 and 5]
Each of the following commercial products was evaluated, and the results are shown in Tables 1 and 2.
Comparative Example 4: Polycarbonate sheet (thickness 400 μm)
Comparative Example 5: Biaxially stretched polyethylene terephthalate sheet (thickness: 188 μm)

  In Tables 1 and 2, “ISB ratio” is the content ratio of isosorbide in all diol components of the polyester resin of each layer, and the description such as “d / b = 80/20” indicates that d and b are 80 : It shows that it mixed and used in the ratio of 20 (weight ratio).

  From Tables 1 and 2, the multilayer polyester sheet of the present invention is excellent in printability, thermoformability, and heat resistance, and is intended to further improve properties by imparting surface irregularities or using a lubricant or an antistatic agent. You can see that

On the other hand, the commercially available polycarbonate sheet (Comparative Example 4) has poor slip properties and poor thermoformability, and the biaxially stretched polyethylene terephthalate sheet (Comparative Example 5) is thermoformed. Impossible.
In Comparative Example 1 in which the polyester resin of the coating layer has a low isosorbide content and in Comparative Example 3 in which the polyester resin of the coating layer does not contain isosorbide, heat resistance is poor, and in Comparative Example 2 in which the coating layer is made of polyethylene terephthalate, thermoforming is performed. The mold release at the time is bad.

Claims (3)

In a multilayer polyester sheet having a base layer containing a polyester resin and a coating layer containing a polyester resin provided on at least one surface of the base layer,
The polyester resin of the coating layer contains 1,4-cyclohexanedimethanol and isosorbide,
The content ratio of isosorbide is 10 mol% or more and 50 mol% or less with respect to all diol components,
A multilayer polyester sheet, which is a polyester resin obtained by reacting a diol component containing 1,4-cyclohexanedimethanol in an amount of 1 to 5 moles with respect to isosorbide and a dicarboxylic acid component.   A molded article formed by molding the multilayer polyester sheet according to claim 1.   The molded article according to claim 2, which is an advertisement display plate, a display article, a folded case for packaging, or a molded article for packaging.