JP2005314557A - Reclaimed polyester sheet - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a reclaimed polyester sheet that utilizes, as a raw material, used PET resin reclaimed from the market, and has excellent transparency and molding properties as well as heat resistance. <P>SOLUTION: This substantially amorphous reclaimed polyester sheet is equipped with a reclaimed polyester resin layer comprising 10-90 mass% of a PET resin (A) reclaimed from the market and 90-10 mass% of a polyarylate resin composition (B) mainly composed of a copolymer or polymer alloy comprising 20-90 mass% of a polyester and 80-10 mol% of a polyarylate resin that has a Tg which is not less than 15°C higher than that of the PET resin (A) from the market. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a recycled polyester sheet made from a used polyethylene terephthalate resin collected from the market. In particular, the present invention relates to a recycled polyester sheet excellent in secondary processability, which is suitably used for display cases such as tobacco, display cans such as beverage cans, advertisement display boards with backlights, and the like disposed in vending machines.

Since polyethylene terephthalate (hereinafter also referred to as PET) is inherently crystalline, it may crystallize depending on the heating and cooling conditions during sheet formation, making secondary processing such as thermoforming difficult. , Mechanical strength may decrease or transparency may be lost. In particular, since used PET resins collected from the market may vary in quality, various problems resulting from crystallization are more prominent.
Further, since the PET resin has a low melt viscosity and a low melt tension, it is not easy to form a sheet by melt extrusion. However, in the case of a used PET resin, the viscosity is further reduced by hydrolysis. Therefore, sheet forming by melt extrusion becomes even more difficult.

  Conventionally, the following proposals have been made in order to solve various problems in using a used PET resin recovered from the market as a sheet raw material.

  For example, in Patent Document 1 (Japanese Patent Laid-Open No. 7-268113), a polyester sheet made from a market-recovered PET resin is highly crystallized, poor in elasticity, and has low impact. Therefore, 50 to 90% by mass of the market-recovered PET resin contains 5 to 20% by mass of rubber and further 10 to 45% by mass of an inert filler as an additive for reducing the tendency of PET to crystallize when heated. A molded sheet has been proposed.

  In Patent Document 2 (Japanese Patent Laid-Open No. 8-302170), a used PET resin alone has a very low viscosity and melt tension in a molten state, and it is difficult to extrude it into a thick sheet by itself. 10 to 50 parts by mass of a polyethylene resin having a flow rate (JIS K6760, g / 10 min) of 0.1 or less, 1 to 10 parts by mass of a compatibilizing agent, and 10 to 50 parts by mass of an amorphous thermoplastic polyester resin. There has been proposed a thermoforming sheet characterized in that a recycled polyester resin composition obtained by mixing is melt-extruded into a sheet shape and cooled while being nipped by a roll.

  Patent Document 3 (Japanese Patent Laid-Open No. 2000-297162) discloses a polyolefin for 57 to 96% by mass of a recycled material raw material mainly composed of polyethylene terephthalate in order to impart heat resistance and impact resistance to used PET. A polyester sheet obtained by adding 1 to 8% by mass of a resin, 3 to 35% by mass of a polyester elastomer resin, and less than 1% by mass of a modified polyolefin resin has been proposed.

  In Patent Document 4 (Japanese Patent Application Laid-Open No. 2003-119355), (A) polyethylene terephthalate is mainly used in order to obtain a molded article having excellent moldability and excellent mechanical strength because crystallization hardly proceeds during heat molding. A polyester resin sheet containing a recycled resin as a component and a polyethylene terephthalate resin in which 10 mol% or more of the glycol component (B) is modified with neopentyl glycol has been proposed.

JP 7-268113 A JP-A-8-302170 JP 2000-297162 A JP 2003-119355 A

  By the way, in general, a sheet for molding used for forming a display body such as a cigarette or a beverage can disposed in a vending machine, an advertising display board with a backlight, etc. Heat resistance that can withstand heat from light, a backlight, a heater for beverages, or the like is required.

Conventionally, many polycarbonates have been used for this type of application. In addition, a biaxially stretched PET film or an APET sheet (amorphous ethylene terephthalate resin sheet) is also used.
However, in the case of polycarbonate, since the glass transition temperature of the sheet is high, it is necessary to increase the molding temperature range, so that molding is not easy, and there is a problem that the time required for thermoforming and the molding cycle become long. In the case of a biaxially stretched PET film, moldability is a problem, and in the case of an APET sheet, heat resistance is often a problem.

  Therefore, the present invention uses recycled PET resin collected from the market as a raw material, and has excellent transparency and moldability (particularly secondary processability), and also has heat resistance that can withstand the heat in the vending machine. A polyester sheet is to be provided.

  The present invention relates to a market-recovered PET resin (A) of 10 to 90% by mass based on an ethylene terephthalate polyester resin composed mainly of a dicarboxylic acid component containing terephthalic acid as a main component and a glycol component containing ethylene glycol as a main component. And a substantially non-crystalline regenerated polyester sheet comprising a regenerated polyester resin layer comprising 90 to 10% by mass of a polyarylate resin having a glass transition temperature of 15 ° C. or more higher than the market-recovered PET resin (A). Claim 2) is proposed.

  In addition, the present invention provides a market-recovered PET mainly comprising an ethylene terephthalate-based polyester resin comprising a dicarboxylic acid component containing terephthalic acid as a main component and a glycol component containing ethylene glycol as a main component, as a more preferred recycled polyester sheet. It is a copolymer or polymer alloy comprising 10 to 90% by weight of resin (A), 20 to 90% by weight of polyester and 80 to 10% by mole of polyarylate resin, and has a glass transition temperature from the market-recovered PET resin (A). A substantially non-crystalline regenerated polyester comprising a regenerated polyester-based resin layer comprising 90 to 10% by mass of a polyarylate resin composition (B) whose main component is a copolymer or polymer alloy having a temperature of 15 ° C. or higher. A sheet (claim 1) is proposed.

The recycled polyester sheet of the present invention is made from used PET resin recovered from the market, has secondary processability such as excellent transparency and thermoformability, and also has heat resistance that can withstand the heat in the vending machine. Since it is provided, it can be suitably used as a sheet for molding such as a display body such as a cigarette or a beverage can disposed in a vending machine, or an advertising display board with a backlight.
Especially, what uses the resin composition which has as a main component the copolymer or polymer alloy of polyester and a polyarylate-type resin as a polyarylate resin composition (B) is preferable. In general, PET resin and polyarylate resin are difficult to mix, so when polymer blended, it tends to be opaque at normal melt extrusion temperature, and even more opaque when using market recovered PET resin (A). easy. On the other hand, as the polyarylate resin composition (B), since a copolymer or polymer alloy of polyester and polyarylate resin having a predetermined ratio is used, even if it is a market-recovered PET resin (A) Mixing is easy, sufficient transparency can be obtained even at a normal melt extrusion temperature, and sufficient heat resistance can be secured.

The regenerated polyester sheet of the present invention can be a single-layer sheet composed only of a regenerated polyester resin layer or a multilayer sheet provided with a regenerated polyester resin layer.
In the case of a multilayer sheet, it is preferable that the recycled polyester resin layer occupies 30% or more of the total thickness of the sheet.
In addition, as a preferable configuration example of the multilayer sheet, for example, a configuration in which an inert particle-containing resin layer in which inert particles are included in a polyester resin is formed on at least one side of a recycled polyester resin layer is provided. A multilayer sheet can be mentioned. By laminating the resin layer containing inert particles in this way, irregularities are formed on the sheet surface and the paper feeding property can be improved, and blocking of ink can be prevented by preventing blocking.

  The recycled polyester sheet of the present invention can be used as an advertising display sheet by forming a pattern layer on the sheet surface, a pattern layer is formed on the sheet surface and then bent to form a display case, or a pattern layer on the sheet surface. And can be thermoformed to form a molded product for display. As described above, it is excellent in transparency and heat resistance, and is particularly suitable for display cases and displays disposed in vending machines. For example, it can be suitably used for molded processed products, for example, advertising display boards with backlights, display cases such as cigarettes, and display cans such as beverage cans. However, it is not limited to these uses.

In the present invention, “the main component” is the meaning of a component occupying at least 50 mol%, preferably 70 to 100 mol%.
Further, in the present invention, “substantially non-crystalline” means non-crystalline which becomes non-crystalline by quenching with a cast roll. From the viewpoint of crystallinity, the crystallinity is 10 % Or less.

  Hereinafter, preferred embodiments of the present invention will be described, but the scope of the present invention is not limited to the embodiments described below.

  The regenerated polyester sheet of the present invention is a regenerated polyester sheet comprising a polymer blend of a market-recovered PET resin (A) and a polyarylate resin composition (B) based on a polyester or polyarylate resin copolymer or polymer alloy. It is the reproduction | regeneration polyester sheet | seat provided with the polyester-type resin layer.

[Market collected PET resin (A)]
Market-recovered PET resin (A) is a resin obtained from plastic products collected from the market, such as plastic bottles, plastic sheets, plastic containers including cups and trays collected from the market. Any resin mainly composed of an ethylene terephthalate-based polyester resin composed of a dicarboxylic acid component and a glycol component mainly composed of ethylene glycol can be used as the raw material of the present invention.

This market-recovered PET resin (A) does not particularly limit the regeneration method. Generally, for example, flakes obtained by removing (separating) dissimilar resins and dissimilar materials other than resin from collected products collected separately by local governments and supermarkets throughout the country, etc. Or the thing etc. which re-pelletized it using the extruder etc. can be used.
Note that the market-recovered PET resin (A) is a resin other than the above-mentioned ethylene terephthalate-based polyester resin, such as a PET bottle, because of the nature of undergoing a market recovery process. Since some of the containers are made of other resins, or non-resinous materials are mixed into the PET sheet, resins other than the above-mentioned ethylene terephthalate-based polyester resins may be mixed into the market-collected PET resin. is there. In particular, recently, PET bottles in which a layer containing a resin other than ethylene terephthalate-based polyester resin or a layer containing a different material other than resin, such as a container for hot beverages, has been put on the market, ethylene terephthalate-based polyester It can be said that the market-recovered PET resin (A) is characterized by a small amount of a different resin or a different material other than the resin. However, it is preferable to use those having a mixing ratio of these different resins and different materials of less than 3%, more preferably less than 1%.

[Polyarylate resin composition (B)]
As the polyarylate resin composition (B), it is preferable to use a polyarylate resin composition mainly composed of a copolymer or polymer alloy of a polyarylate resin and polyester.
For example, a copolymer or polymer alloy comprising 80 to 10% by weight of a polyarylate resin and 20 to 90% by mole of a polyester resin, particularly preferably 70 to 20% by weight of a polyarylate resin and 30 to 80% by mole of a polyester resin. A polyarylate resin composition comprising a copolymer or polymer alloy of 60 to 40% by mass of a polyarylate-based resin and 40 to 60 mol% of a polyester-based resin. .
Examples of the copolymer of the polyarylate-based resin and the polyester-based resin include a copolymer in which a part of the divalent phenol of the polyarylate-based resin is substituted with an aliphatic diol.

In the case of such a polyarylate resin composition (B) mainly composed of a copolymer or a polymer alloy, compatibility between the market recovered PET resin (A) and the polyarylate resin composition (B) is improved. Even if it is melt-extruded at about 270 ° C., which is the extrusion temperature of a normal polyester resin, transparency can be obtained well.
However, it is also possible to use, as the polyarylate resin composition (B), a polyarylate resin alone or a resin composition in which the polyarylate resin accounts for more than 80 mass%. In this case, since the compatibility between the market-recovered PET resin (A) and the polyarylate-based resin composition (B) is poor and transparency may be lowered, the extrusion temperature at the time of melt extrusion depending on the application It is necessary to raise the transparency to a level that does not cause a problem in use, for example, by raising the temperature above the extrusion temperature of a normal polyester resin. In this case, the transparency having no problem in use means that the haze value is less than 15%, more preferably less than 8% when finally formed into a sheet.
Moreover, it is preferable that the glass transition temperature (Tg) of a component (B) is 15 degreeC or more higher especially market recovery PET resin (A), especially 25 degreeC or more. As a component (B), the glass transition temperature should just be 15 degreeC or more higher than market collection PET resin (A), for example, the polyester-type resin which comprises component (B), a polyarylate resin, or the glass transition temperature of the component It can be low.
In the present invention, “polymer alloy” means a polymer blend in which the compatibility of different polymers is enhanced, and a state in which a certain fine affinity is applied to the interface between the component polymers to form a homogeneous fine and stable dispersion structure. Specifically, it refers to a polymer blend exhibiting a microphase separation structure composed of a dispersed phase having a size of 1 μm or less.

(Polyarylate resin)
The polyarylate resin constituting the polyarylate resin composition (B) is a resin composed of an aromatic dicarboxylic acid and a dihydric phenol, and even if it is a polyarylate homopolymer, a plurality of aromatic dicarboxylic acids or divalent resins. It may be a copolymer made of phenol. Moreover, the mixture which consists of a combination of a different kind of polyarylate resin may be sufficient.
The polyarylate-based resin is distinguished from a polyester-based resin composed of an aliphatic glycol in that it is composed of an aromatic glycol, that is, a divalent phenol, as a diol component.

Examples of the aromatic dicarboxylic acid component as a constituent of the polyarylate-based resin include terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid, and the like. It is preferable in terms of the melt processability of arylate.
On the other hand, as the dihydric phenol component, bisphenols, particularly bisphenol A is preferred. The dihydric phenol component may be used alone or in combination of two or more dihydric phenols. For example, bisphenols may be used in combination with ethylene glycol, propylene glycol, or the like.

  The molecular weight of the polyarylate resin constituting the polyarylate resin composition (B) is preferably 10,000 or more, particularly preferably 15,000 or more.

(Polyester resin)
The polyester resin to be polymer blended with the polyarylate resin may be a polyester obtained by polycondensation of a dicarboxylic acid component and a diol component in an equimolar amount.

  Examples of the dicarboxylic acid component include terephthalic acid and those in which a part of terephthalic acid is substituted with another dicarboxylic acid. Examples of the other dicarboxylic acid components 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. be able to. The other dicarboxylic acid component to be 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.

  Examples of the diol component include ethylene glycol and those in which a part of ethylene glycol is substituted with another diol component. Other diol components include propylene glycol, trimethylene glycol, tetramethylene glycol, hexamethylene glycol, dimethylene glycol, neopentyl glycol, polyalkylene glycol, 1,4-cyclohexanedimethanol, glycerin, pentaerythritol, trimethylol. And methoxy polyalkylene glycol. In addition, the other diol component used may be one kind or a mixture of two or more kinds, and the amount of the other diol component to be substituted can be appropriately selected.

Preferable specific examples of the polyester resin to be polymer blended with polyarylate include polyethylene terephthalate obtained by condensation polymerization of terephthalic acid and ethylene glycol, or a part of terephthalic acid with another dicarboxylic acid component or part of ethylene glycol. An ethylene terephthalate-based copolyester resin that has been changed to another diol component can be used, and may be the same as or similar to the main component of the market-recovered PET resin (A).
Here, as the ethylene terephthalate copolymer polyester, 60% or more of the dicarboxylic acid component is terephthalic acid, and the remaining dicarboxylic acid component is replaced with another dicarboxylic acid component, and the diol component is 60%. A polyester obtained by condensation polymerization of a diol component in which mol% or more is ethylene glycol and the remaining diol component is substituted with another diol component is exemplified.

  The polyester resin to be polymer blended with polyarylate may be a mixture of polyethylene terephthalate and the ethylene terephthalate copolymer polyester, or may be a mixture of a plurality of types of ethylene terephthalate copolymer polyester. .

The intrinsic viscosity of the polyester resin constituting the polyarylate resin composition (B) is preferably 0.4 dl / g or more, more preferably 0.5 dl / g or more. If the intrinsic viscosity is 0.4 dl / g or more, the mechanical strength of the used product can be sufficiently obtained, and particularly the impact strength at a low temperature can be maintained, which is practically preferable.
The molecular weight of the polyester resin is preferably 10,000 or more, particularly 15,000 or more.

(Sheet configuration)
The regenerated polyester sheet of the present invention can be a single-layer sheet composed only of the regenerated polyester resin layer, but can also be a multilayer sheet having the regenerated polyester resin layer as a base layer.

  As a multilayer sheet provided with a recycled polyester resin layer as a base layer, for example, an inert particle-containing resin layer containing a polyester resin and inert particles is formed on at least one side of the recycled polyester resin layer. A multilayer sheet formed by forming the inert particle-containing resin layer as a surface layer on one side or both sides of the recycled polyester resin layer can be mentioned.

  As a composition of the said inert particle containing resin layer, what added an inert particle to the polyester-type resin as a main component is preferable.

  Here, as the polyester resin constituting the inactive particle-containing resin layer, a polyester resin similar to the polyester resin polymer-blended with the polyarylate can be used.

As the inert particles, for example, inorganic particles such as silica, aluminosilicate, talc, and crosslinked particles of styrene resin can be used.
The average particle diameter of the inert particles is preferably 3 to 15 μm, particularly preferably 5 to 10 μm. If the average particle size is 3 μm or more, the unevenness of the sheet surface is not too small, and the paper feeding property during secondary processing such as printing can be maintained well. Moreover, if it is 15 micrometers or less, the unevenness | corrugation on the surface of a sheet | seat will not become large too much, and the external appearance and transparency of a sheet | seat will not be deteriorated. In addition, the average particle diameter of an inert particle is measured using a Cole counter (made by Nippon Chemical Machinery Co., Ltd.), and is an average particle diameter when a cumulative mass fraction becomes 50%.

As the inert particles, those having a refractive index in the range of 1.4 to 1.7 are preferably selected. The refractive index of the polyester resin is around 1.57. If inert particles having a large difference from the refractive index of the polyester resin are used, the appearance and transparency of the sheet are deteriorated, which is not preferable.
Here, the refractive index of the inert particles is determined by immersing the inert particles in a liquid having a known refractive index, and measuring the refractive index of the liquid immersed in the inert particles with an Abbe refractometer. The refractive index is calculated from the ratio.

The content of the inert particles is preferably 0.05 to 1 part by mass with respect to 100 parts by mass of the polyester resin. If it is 0.05 parts by mass or more, the effect of improving sheet slip can be sufficiently obtained, and if it is 1 part by mass or less, the appearance and transparency of the sheet are not deteriorated.
A plurality of types of inert particles can be used in combination.

  Various methods can be used as a method of blending the inert particles with the polyester resin, and the method is not particularly limited. For example, it is added at the time of polymerization, mixed with the polymerized resin using a blender, or a high-concentration master batch such as inert particles is prepared in advance and diluted and mixed with the resin.

(Sheet thickness)
The thickness of the recycled polyester sheet of the present invention is not particularly defined because it varies depending on the application, but it is preferably selected in the range of, for example, 50 to 2000 μm and 150 to 1000 μm or 1000 to 2000 μm depending on the application.
When constituting a multilayer sheet having a recycled polyester resin layer as a base layer, the base layer has a thickness of 30% or more, particularly 50% or more, and especially 70% or more of the total thickness of the sheet. It is preferably designed to occupy. If the thickness of the base layer is 30%, the sheet is less likely to be deformed under any use environment.

  As long as the gist of the present invention is not impaired, an organic lubricant, wax, antistatic agent, ultraviolet absorber, impact modifier is added to the base layer or surface layer, or an antistatic agent, silicone, wax, etc. are added to the sheet surface. You may make it coat.

The recycled polyester sheet of the present invention is preferably formed as a substantially amorphous unstretched sheet. Specifically, it can be obtained by putting the resin into an extruder, extruding from a T-die, and rapidly solidifying with a cast roll.
In the present invention, an 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 not stretched. It shall be included in the sheet.

  When the recycled polyester sheet of the present invention is a multilayer sheet, for example, when producing a multilayer sheet of three layers, (1) a method of pasting each layer in advance, and then laminating with heat or an adhesive, (2) A method in which the surface coating layer formed in advance is thermally bonded immediately after the base layer sheet is extruded from the T-die of the extruder. (3) Each layer is melt-extruded by a separate extruder and melt-bonded by a nip roll. Method (4) Each layer can be melted by a separate extruder, and can be performed by a method such as a method of melt lamination and extruding as a multilayer sheet using a multilayer die. Using a multilayer sheet forming apparatus equipped with a melt extruder, the above-described amorphous polyester resin (A) and amorphous polyester resin (B) are melt-extruded at the same time to obtain a polyester having a three-layer structure. Producing Le resin sheet.

Further, the ears of the sheet or scrap sheets generated in the manufacturing may be mixed.
Even when it is a multilayer sheet, it may be kneaded back to any layer, but when kneaded back to the base layer, it is necessary to increase the blending amount so that the blending amount of the resin component (B) is not reduced. . The amount of remixing of the ears and scrap is not particularly specified, but is preferably 40% or less, more preferably 30% or less.

The regenerated polyester sheet thus obtained may be cut into a single sheet through a cutting device, or may be obtained by winding it into a coil.
Then, a pattern layer can be formed on the sheet surface to form an advertisement display sheet, for example, an advertisement base sheet for an electric decoration POP in a vending machine that requires heat resistance.
In addition, a picture layer can be formed on the surface of the recycled polyester sheet and bent to form a display case.
In addition, a pattern layer can be formed on the surface of the recycled polyester sheet and thermoformed to obtain a molded product for display. However, when thermoforming, although the conditions vary depending on the sheet thickness, generally, vacuum forming or pressure forming is performed in a preheating condition range in which the sheet surface temperature is 120 ° C to 160 ° C. It is preferable to heat the sheet for as short a time as possible so that crystallization of the sheet does not become significant.

  Examples of the present invention will be described below, but the scope of the present invention is not limited to the following examples.

(Examples 1-20, Comparative Examples 1-2)
Prepare the following raw materials, melt and mix each raw material in one or two twin-screw vent type extruders set at extrusion temperature of 270-280 ° C (condition α), single layer or two kinds After extrusion using a three-layer T-die, it was quenched with a cast roll having a mirror surface of 40 ° C. to obtain an amorphous polyester resin sheet.
About a single layer sheet, it produced as a winding roll sheet with a winder, and about 2 types and 3 layer sheets, it supplied to the cutting device and produced as a sheet-like sheet.
Examples 19 and 20 were performed under the conditions set at an extruder temperature of 320 ° C. (condition β).
The resin composition of each sheet is shown in Table 1, and the production conditions and various evaluation results of each sheet are shown in Table 2.
In Table 1, “c / a” in the resin composition of the polyarylate resin composition means the ratio of each component in the polymer alloy of component c and component a.

"material"
a: Polyethylene terephthalate obtained by condensation polymerization of terephthalic acid and ethylene glycol (glass transition temperature 70 ° C., intrinsic viscosity 0.75)
b: Copolyester obtained by polycondensation of a mixture of terephthalic acid as the dicarboxylic acid component and 70% ethylene glycol and 30 mol% 1,4-cyclohexanedimethanol as the diol component (glass transition temperature 81 ° C., intrinsic viscosity) 0.8))
c: Polyarylate homopolymer Utica U-100 (glass transition temperature 193 ° C.) manufactured by Unitika Ltd.
d: Polyarylate / polyester = 60/40 mass% alloy resin (U polymer U-8000 (glass transition temperature 120 ° C.) manufactured by Unitika Ltd.)
e: Polyarylate / polyester = 40/60 mass% alloy resin (U polymer U-8400 manufactured by Unitika Ltd. (glass transition temperature 98 ° C.))
f: Market recovered PET bottle recycled material (recycled material crushed and washed by a recycler) (glass transition temperature 70 ° C., intrinsic viscosity 0.67 to 0.69)

Unitika U polymer U-100 (trade name) is a polyarylate obtained by interfacial polymerization of terephthalic acid chloride / isophthalic acid chloride = molar ratio 1/1 and bisphenol A, and other grades of U polymer. The polymer is also an alloy resin of the polyarylate.

"Inert particles"
A: Aluminosilicate (refractive index 1.50, average particle size 8μm)
A: Aluminosilicate (refractive index 1.50, average particle size 2 μm)
C: Aluminosilicate (refractive index 1.50, average particle size 18 μm)
D: Silica (refractive index 1.46 average particle size 8μm)
E: Styrene cross-linked particles (refractive index 1.58 average particle size 8 μm)

"Evaluation methods"
1. Heat resistance test A sample of 100 mm × 100 mm was cut out and stored in a thermostat kept at 90 ° C. for 24 hours, and the dimensional change rate of the sheet and the degree of deformation of the sheet were measured.
The evaluation was made according to the following criteria, and indicated by symbols “◯” to “×”. Symbols “◯” and “Δ” are practical levels.

“◯”: The dimensional change rate is within ± 1%, and the warpage and floating when the sheet is placed on a flat surface is 2 mm or less.
“△”: The dimensional change rate is within ± 2%, and the warp and float when the sheet is placed on a flat surface is 4 mm or less.
“X”: The rate of dimensional change exceeds ± 2%, or the warpage or lift when the sheet is placed on a flat surface exceeds 4 mm.

2. Transparency appearance The transparency of the obtained sheet was confirmed with a haze meter in accordance with JIS K-7105.
Evaluation was performed according to the following criteria, and evaluation was performed using symbols “◯” to “×”. Symbols “◯” and “Δ” are practical levels.
“○”: Haze less than 5% “△”: Haze 5% or more but less than 10% “X”: Haze 10% or more

3. Secondary workability (1) Printability UV offset printing was performed on the obtained sheet-like sheet, and letterpress rotary UV printing was performed on the roll sheet. At this time, sheet feeding properties to the printing press (cut plate sheet target) and ink adhesion (tape peeling test) were observed and evaluated.
Each was evaluated according to the following criteria, and indicated by symbols “◯”, “Δ”, and “×”. The symbols “◯” and “Δ” are practical levels.

Feedability to the printing press (for cut sheet)
“◯”: The paper feeding to the printing machine was smooth and no paper feeding trouble occurred.
“△”: If the sheet was carefully rolled before printing, paper feeding was smooth.
“×”: Even if the sheet was carefully laid before printing, smooth feeding could not be performed, or problems such as feeding two sheets occurred frequently.

Ink adhesion (tape peeling test)
“◯”: In the tape peeling test, the ink was not peeled off at all or less than 0 to 10% of the peeling test surface was peeled off.
“Δ”: In the tape peeling test, 10% or more and less than 30% of the ink peeled off the peel test surface.
“×”: In the tape peeling test, ink was peeled off by 30% or more of the peeling test surface.

(2) Thermoformability Thermoformability was evaluated by the following criteria after heating the sheet surface to a predetermined temperature with a heater and then vacuum forming.
“○”: Can be molded at a sheet heating temperature of 130 ° C. or less “△”: Moldable at a sheet heating temperature of 150 ° C. or less “X”: Cannot be molded unless the sheet heating temperature exceeds 150 ° C.

Claims (8)

Market-recovered PET resin (A) of 10 to 90% by mass consisting mainly of an ethylene terephthalate-based polyester resin composed of a dicarboxylic acid component mainly composed of terephthalic acid and a glycol component mainly composed of ethylene glycol;
Polyarylate resin composition composed mainly of a copolymer or polymer alloy having a glass transition temperature of 15 ° C. or more higher than the market-recovered PET resin (A), comprising 20 to 90% by mass of polyester and 80 to 10 mol% of a polyarylate resin. Thing (B) 90-10 mass%,
A substantially non-crystalline regenerated polyester sheet comprising a regenerated polyester resin layer comprising:   2. The recycled polyester sheet according to claim 1, wherein the polyarylate resin composition (B) contains a polyarylate resin having a glass transition temperature higher by 15 ° C. or more than the market-recovered PET resin (A). Recycled polyester sheet.   3. The recycled polyester sheet according to claim 1, wherein the recycled polyester resin layer comprises a recycled polyester resin layer, and the recycled polyester resin layer occupies 30% or more of the thickness of the entire sheet. .   0.05 to 1 part by mass of inert particles having an average particle size of 3 to 15 μm and a refractive index of 1.4 to 1.7 with respect to 100 parts by mass of the polyester resin component on at least one side of the recycled polyester resin layer The regenerated polyester sheet according to any one of claims 1 to 3, further comprising an inert particle-containing resin layer.   The regenerated polyester sheet according to any one of claims 1 to 4, wherein a dimensional change rate of the sheet when left at 90 ° C for 24 hours is less than 2%.   The advertisement display sheet formed by forming a picture layer on the sheet | seat surface of the reproduction | regeneration polyester sheet in any one of Claims 1-5.   A display case formed by forming a pattern layer on a sheet surface of the recycled polyester sheet according to claim 1 and bending it. A molded product for display, which is formed by forming a pattern layer on the surface of the recycled polyester sheet according to any one of claims 1 to 5, and then thermoforming it.