JP2009179696A - Polyester resin composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a polyester resin composition capable of eliminating a flow mark that is generated by the difference in fluidity from other resins upon manufacturing a multilayer sheet, by compounding a specified fatty acid ester into a polyester resin containing a diol unit having a cyclic acetal skeleton. <P>SOLUTION: The polyester resin composition comprises: 80 to 99.995 wt% of a polyester resin (A) containing dicarboxylic acid units and diol units, in which 1 to 60 mol% of the diol units have a cyclic acetal skeleton; and 0.005 to 5 wt% of at least one kind of 10-30C fatty acid ester. A multilayered sheet is disclosed, having a layer comprising the above polyester resin composition. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a polyester resin composition containing a diol unit having a cyclic acetal skeleton, and more specifically, a specific fatty acid ester is blended with the polyester resin. The present invention relates to a polyester resin composition capable of eliminating generated flow marks.

  Polyester, especially polyethylene terephthalate (hereinafter sometimes referred to as “PET”), is a resin that balances mechanical performance, solvent resistance, fragrance retention, recyclability, etc., and is used for bottles, sheets, films, etc. It is used in large quantities in the center. However, since PET has high crystallinity, when it is attempted to produce a molded article or sheet having a thickness, whitening occurs due to crystallization, and transparency is impaired. Moreover, since the glass transition temperature of PET is about 80 ° C., high heat resistance and transparency are required, such as products used in automobiles, packaging materials for import / export, packaging materials for retort processing and microwave heating. It was not available for use.

  On the other hand, polyethylene naphthalate (hereinafter sometimes referred to as “PEN”), which is a transparent polyester resin having a chemical structure well similar to that of PET, is a polyester in which the dicarboxylic acid unit of PET is a naphthalene dicarboxylic acid unit. It is possible to process almost the same moldings (bottles, etc.) as possible, and has the possibility of recycling. Since PEN has a rigid molecular structure, it has features that are superior to PET in terms of heat resistance (glass transition temperature of about 110 ° C.), gas barrier properties, etc., but is very expensive. Similarly, since the crystallinity is high, there is a drawback that when a thick molded body or sheet is manufactured, whitening occurs due to crystallization and transparency is impaired.

  Therefore, low crystalline polyester resins such as modified PET partially copolymerized with 1,4-cyclohexanedimethanol and modified PET partially modified with isophthalic acid are used for applications requiring transparency. However, the glass transition temperature of these resins is around 80 ° C., and the heat resistance has not been improved as compared with PET.

  Polyester resins containing a diol having a cyclic acetal skeleton (for example, Patent Document 1, Patent Document 2, and Patent Document 3) are polyester resins that have improved heat resistance of PET and PEN while having high transparency. It can be used in applications where high performance is required.

There is an attempt to improve heat resistance, impact resistance, and scratch resistance by making a polyester sheet containing a diol having a cyclic acetal skeleton and other resins into a multilayer sheet (for example, Patent Document 1). However, when producing a multilayer sheet with a polyester resin containing a diol having a cyclic acetal skeleton and another resin (for example, PET) (for example, a two-layer / three-layer structure in which the polyester resin is a skin layer and PET is a core layer) A poor appearance on the sheet surface called a flow mark may occur due to a difference in flowability caused by a difference in viscosity between the two.
JP 2003-182014 A JP 2002-69165 A JP 2004-67830 A

  The object of the present invention occurs due to a difference in flowability from other resins, for example, during the production of a multilayer sheet, by blending a specific fatty acid ester with a polyester resin containing a diol having a cyclic acetal skeleton in view of the situation as described above. It is providing the polyester resin composition which can eliminate a flow mark.

  As a result of intensive studies, the present inventors have found that the resin viscosity during molding can be adjusted by adding a specific fatty acid ester to a polyester resin containing a diol unit having a cyclic acetal skeleton. Reached.

  That is, the present invention provides a polyester resin (A) containing a dicarboxylic acid unit and a diol unit, wherein 1 to 60 mol% of the diol unit is a diol unit having a cyclic acetal skeleton, 80 to 99.995 wt%, and carbon number It is a polyester resin composition characterized by containing 0.005 to 5% by weight of at least one of 10 to 30 fatty acid esters.

  Since the polyester resin composition of the present invention can arbitrarily reduce the resin viscosity, the flow mark is eliminated by matching the flowability with other resins (for example, PET) at the time of producing a multilayer sheet, for example. It is possible to improve the releasability from the mold during the secondary processing using the sheet.

Ｒ^１、Ｒ^２、及びＲ^３はそれぞれ独立して、炭素数が１〜１０の脂肪族炭化水素基、炭素数が３〜１０の脂環式炭化水素基、及び炭素数が６〜１０の芳香族炭化水素基からなる群から選ばれる炭化水素基を表す。一般式（１）及び（２）の化合物としては３，９−ビス（１，１−ジメチル−２−ヒドロキシエチル）−２，４，８，１０−テトラオキサスピロ〔５．５〕ウンデカン、または５−メチロール−５−エチル−２−（１，１−ジメチル−２−ヒドロキシエチル）−１，３−ジオキサンが特に好ましい。 The present invention is described in detail below. The polyester resin used in the polyester resin composition of the present invention is a polyester resin (A) containing a dicarboxylic acid unit and a diol unit, wherein 1 to 60 mol% of the diol unit is a diol unit having a cyclic acetal skeleton. The diol unit having a cyclic acetal skeleton is preferably a unit derived from a compound represented by the following general formula (1) or (2).

R ¹ , R ² , and R ³ are each independently an aliphatic hydrocarbon group having 1 to 10 carbon atoms, an alicyclic hydrocarbon group having 3 to 10 carbon atoms, and 6 to 10 carbon atoms. Represents a hydrocarbon group selected from the group consisting of aromatic hydrocarbon groups. As the compounds of the general formulas (1) and (2), 3,9-bis (1,1-dimethyl-2-hydroxyethyl) -2,4,8,10-tetraoxaspiro [5.5] undecane, or 5-methylol-5-ethyl-2- (1,1-dimethyl-2-hydroxyethyl) -1,3-dioxane is particularly preferred.

  In addition, the diol unit other than the diol unit having a cyclic acetal skeleton is not particularly limited, but ethylene glycol, trimethylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, diethylene glycol Aliphatic diols such as propylene glycol and neopentyl glycol; polyether diols such as polyethylene glycol, polypropylene glycol and polybutylene glycol; 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, 1,2- Decahydronaphthalene diethanol, 1,3-decahydronaphthalene diethanol, 1,4-decahydronaphthalene diethanol, 1,5-decahydronaphthalene diethanol, 1,6-decahydronaphthalene Cycloaliphatic diols such as dimethanol, 2,7-decahydronaphthalene diethanol, tetralin dimethanol, norbornane dimethanol, tricyclodecane dimethanol, pentacyclododecane dimethanol; 4,4 ′-(1-methylethylidene ) Bisphenols such as bisphenol, methylene bisphenol (bisphenol F), 4,4′-cyclohexylidene bisphenol (bisphenol Z), 4,4′-sulfonyl bisphenol (bisphenol S); alkylene oxide adducts of the above bisphenols; hydroquinone , Aromatic dihydroxy compounds such as resorcin, 4,4′-dihydroxybiphenyl, 4,4′-dihydroxydiphenyl ether, 4,4′-dihydroxydiphenylbenzophenone; Alkylene oxide adducts of hydroxy compounds can be exemplified. Ethylene glycol, diethylene glycol, trimethylene glycol, 1,4-butanediol and 1,4-cyclohexanedimethanol are preferable from the viewpoint of mechanical performance and economical efficiency of the polyester resin of the present invention, and ethylene glycol is particularly preferable. The exemplified diol units can be used alone or in combination.

  In addition, the dicarboxylic acid unit of the polyester resin (A) used in the polyester resin composition of the present invention is not particularly limited, but succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid Aliphatic carboxylic acids such as dodecanedicarboxylic acid, cyclohexanedicarboxylic acid, decanedicarboxylic acid, norbornane dicarboxylic acid, tricyclodecanedicarboxylic acid, pentacyclododecanedicarboxylic acid; terephthalic acid, isophthalic acid, phthalic acid, 2-methylterephthalic acid, Examples thereof include aromatic dicarboxylic acids such as 1,4-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, biphenyldicarboxylic acid, and tetralindicarboxylic acid. From the viewpoint of mechanical performance and heat resistance of the polyester resin of the present invention, terephthalic acid, isophthalic acid, 1,4-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid and 2,7- Aromatic dicarboxylic acids such as naphthalenedicarboxylic acid are preferred, and terephthalic acid, 2,6-naphthalenedicarboxylic acid, and isophthalic acid are particularly preferred. Among these, terephthalic acid is most preferable from the viewpoint of economy. The illustrated dicarboxylic acids can be used alone or in combination.

  Content of a polyester resin (A) is 80-99.995 weight% with respect to a polyester resin composition, Preferably it is 83-99.99 weight%, More preferably, it is 85-99.95 weight%. When the content of the polyester resin (A) exceeds 99.995% by weight, the fatty acid ester cannot be contained in a sufficient amount, so that the effect of viscosity reduction and releasability is insufficient. When the content of the polyester resin (A) is less than 80%, the excellent characteristics of the polyester resin (A) may not be exhibited. The polyester resin (A) is a resin that has high transparency and improved heat resistance of PET and PEN, and can be used in fields where transparency and heat resistance are required.

The polyester resin composition of the present invention contains a fatty acid ester having 10 to 30 carbon atoms. As the fatty acid ester, those described in Kao Corporation “Kao Plastics Additives” and the like and Rikenmar series manufactured by Riken Vitamin Co., Ltd. can be used. Examples thereof include stearic acid monoglyceride, behenic acid monoglyceride, palmitic acid monoglyceride, lauric acid monoglyceride, oleic acid monoglyceride, capric acid monoglyceride, myristic acid monoglyceride, linolenic acid monoglyceride, stearyl stearate and the like. Of these, stearic acid monoglyceride, behenic acid monoglyceride, palmitic acid monoglyceride, and lauric acid monoglyceride can be preferably used. These fatty acid esters can be used alone or in combination.
The content of the fatty acid ester is 0.005 to 5% by weight, preferably 0.01 to 3% by weight, more preferably 0.05 to 2% by weight, based on the polyester resin composition. When the fatty acid ester content exceeds 5% by weight, volatilization from a vent port or a discharge port of an extruder, for example, occurs at a high temperature or precipitation occurs on the surface of the molded product to obtain a transparent molded product. Will not be able to. When the content is less than 0.005% by weight, the effects of viscosity reduction and releasability are insufficient.

  The method for adding the fatty acid ester used in the present invention is not particularly limited, but is a method for containing the polyester resin (A) in the presence of the fatty acid ester, or melting before extraction from the polymerization vessel in the polymerization step. A method of adding a fatty acid ester to a polyester resin (A) in a state, a method of dry blending a fatty acid ester after pelletizing the polyester resin (A), a method of melt-kneading the dry blended product with an extruder, etc., extrusion A method of adding a fatty acid ester to the melted polyester resin (A) using a machine or the like is employed. Among these, since it is easy to arbitrarily adjust the addition amount, a method of dry blending the fatty acid ester into the pellet and melt-kneading with an extruder or the like is preferable.

  A known apparatus can be used for mixing and kneading the polyester resin (A) and the fatty acid ester. For example, a tumbler, high-speed mixer, nauter mixer, ribbon blender, mixing roll, kneader, intensive mixer, single screw extruder And a mixing and kneading apparatus such as a twin-screw extruder. Moreover, liquid mixing apparatuses, such as a gate mixer, a butterfly mixer, a universal mixer, a dissolver, and a static mixer, can also be used. Further, a resin containing a high-concentration fatty acid ester and a polyester resin can be mixed by the above method and apparatus.

The melt viscosity of the polyester resin (A) used in the present invention is in the range of 700 to 5000 Pa · s when measured at a measurement temperature of 240 ° C. and a shear rate of 100 s ⁻¹ . If the melt viscosity is in the above range, it can be easily adjusted to a desired viscosity with a fatty acid ester depending on the purpose, and a polyester resin composition having excellent moldability can be obtained. For example, when manufacturing two types and three layers of multi-layer sheets, it is possible to adjust and improve the viscosity of the flow mark that occurs due to the difference in viscosity by appropriately selecting the type, combination, addition amount, etc. of the fatty acid ester. It becomes.

  The polyester resin composition of the present invention includes a light stabilizer, an ultraviolet absorber, an antioxidant, a plasticizer, an extender, a matting agent, a drying regulator, an antistatic agent, an antisettling agent, a surfactant, and a flow improver. Various additives such as additives, drying oils, waxes, fillers, colorants, reinforcing agents, surface smoothing agents, leveling agents, curing reaction accelerators, and molding aids can be added. In addition, resins such as polyolefin, polyester, polyamide, polycarbonate, acrylonitrile resin, vinyl chloride resin, vinyl acetate resin, polyacrylic acid, polymethacrylic acid, polystyrene, ABS resin, polyimide, AS resin, and oligomers may be added.

  The polyester resin composition of the present invention can be used in various applications such as injection molded articles, extruded molded articles, sheets, sheet molded articles, unstretched films, stretched films, injection blow bottles, direct blow bottles, and foams.

The multilayer sheet of the present invention has at least one layer made of the polyester resin composition. In addition, at least one layer other than the layer made of the polyester resin composition is a resin layer mainly made of a resin selected from the group consisting of a polyester resin, a polycarbonate resin, an acrylic resin, a polystyrene resin, and a polymethyl methacrylate-styrene resin. Preferably there is.
The multilayer sheet of the present invention comprises a polyester resin composition and at least one resin selected from a polyester resin excluding the polyester resin (A), a polycarbonate resin, an acrylic resin, a polystyrene resin and a polymethyl methacrylate-styrene resin. It is obtained by forming into a multilayer sheet.

  Polyester resins such as polyethylene terephthalate, polyethylene naphthalate, isophthalic acid-modified polyethylene terephthalate, 1,4-cyclohexanedimethanol-modified polyethylene terephthalate, polyarylate, and the like (polyester resin (A)) Except), polycarbonate resin, acrylic resin, polystyrene resin, polymethyl methacrylate-styrene resin, acrylonitrile-butadiene-styrene resin, vinyl chloride resin, alicyclic polyolefin resin, etc. Polyester resin (excluding polyester resin (A)), polycarbonate resin, acrylic resin, polystyrene resin and polymethyl methacrylate-styrene resin are preferred as (Except a polyester resin (A)) a polyester resin, a polycarbonate resin is particularly preferably used.

  As a method for producing the multilayer sheet of the present invention, known laminating techniques such as a coextrusion method, a coextrusion laminating method, an extrusion laminating method, and a dry laminating method can be used. Moreover, you may use the adhesive agent suitable between resin for these lamination | stacking, or adhesive resin.

  The thickness of each layer of the multilayer sheet of the present invention is determined according to the use, the type of resin forming the layer, the number of layers, etc., but is usually 10 μm to 10 mm. Moreover, the total thickness of a multilayer sheet changes with uses, for example, is 0.1-1 mm in the sheet | seat for foodstuffs, and is used by thickness of 1-40 mm in thick material sheets, such as a building material and a product display. The total number of layers of the polyester resin composition layer and other resin layers is usually up to six.

  Hereinafter, the present invention will be described in more detail with reference to examples. However, the scope of the present invention is not limited by these examples.

The raw materials used in the examples and comparative examples are shown below.
・ Stearate monoglyceride: manufactured by Riken Vitamin Co., Ltd., trade name: Riquemar S-100A
-Behenic acid monoglyceride: Riken Vitamin Co., Ltd., trade name: Riquemar B-100
・ Polyethylene terephthalate (PET): manufactured by Nihon Unipet Co., Ltd., trade name: UNIPET RT553C
Polycarbonate (PC): manufactured by Mitsubishi Engineering Plastics Co., Ltd., trade name: Iupilon H-3000

〔Evaluation methods〕
Next, the evaluation method of the multilayer sheet in a present Example and a comparative example is as follows.
(1) Multi-layer sheet flow mark (external appearance defect)
The unevenness on the surface of the multilayer sheet was visually observed. The abbreviations of the observation results in the table are as follows.
○: No flow mark Δ: Flow mark slightly generated ×: Flow mark generated vigorously (2) Heat resistant 0.8 mm thick multilayer sheet, extruding direction is vertical, width direction is horizontal, vertical, horizontal 100 mm A square test piece was cut out, and this test piece was heated in an oven in increments of 5 ° C. for 30 minutes to obtain a maximum temperature at which the shrinkage in the vertical and horizontal directions after heating did not exceed 10%.
(3) Total light transmittance and haze value Total light transmittance and haze value are determined according to JIS-K-7105, ASTM D1003, a 0.8 mm thick multilayer sheet is conditioned for 48 hours, then 23 ° C., relative humidity 50 % Atmosphere. The measuring apparatus used is a fog value measuring apparatus (model: COH-300A) manufactured by Nippon Denshoku Industries Co., Ltd.

[Production of polyester resins (A-1) and (A-2)]
Charged terephthalic acid and ethylene glycol in the amounts shown in Table 1 into a 150 liter polyester resin production system equipped with a packed column rectification column, a partial condenser, a full condenser, a cold trap, a stirrer, a superheater, and a nitrogen introduction pipe The esterification reaction was carried out by a conventional method. Ethylene glycol for depolymerization and germanium dioxide in the amounts shown in Table 1 were added to the obtained ester, and depolymerization was performed at 225 ° C. under a nitrogen stream. After reacting for 3 hours while distilling off the water produced, ethylene glycol was distilled off at 215 ° C. and 13.3 kPa. Tetra-n-butyl titanate, potassium acetate, triethyl phosphate, and SPG described in Table 1 were added to the obtained ester, and the reaction was performed at 225 ° C. and 13.3 kPa for 3 hours. The resulting ester is heated and depressurized, and finally subjected to a polycondensation reaction at 270 ° C. and high vacuum (300 Pa or less). When the predetermined melt viscosity is reached, the reaction is terminated to obtain a polyester resin (A). It was.
In addition, the meaning of the abbreviation in a table | surface is as follows.
PTA: terephthalic acid SPG: 3,9-bis (1,1-dimethyl-2-hydroxyethethyl) -2,4,8,10-tetraoxaspiro [5.5] undecane EG: ethylene glycol GeO2: Germanium dioxide TBT: Tetra-n-butyl titanate AcOK: Potassium acetate TMP: Trimethyl phosphate

The evaluation methods of the polyester resins (A-1) and (A-2) are as follows.
(1) Ratio of diol units having a cyclic acetal skeleton The ratio of diol units having a cyclic acetal skeleton in a polyester resin is calculated from ¹ H-NMR measurement and peak area ratio by dissolving 20 mg of a polyester resin in 1 g of heavy chloroform. did. The measuring apparatus used JNM-AL400 by JEOL Co., Ltd., and measured it at 400 MHz.
(2) Glass transition temperature The glass transition temperature of the polyester resin is DSC / TA-50WS manufactured by Shimadzu Corporation. About 10 mg of a sample is placed in an aluminum non-sealed container, and the temperature rising rate in a nitrogen gas (30 ml / min) airflow is 20 The glass transition temperature was measured at a temperature of ° C / min and the temperature changed by ½ of the difference in baseline before and after the transition of the DSC curve.
(3) Molecular weight (number average molecular weight Mn, weight average molecular weight Mw, molecular weight distribution Mw / Mn)
Polyester resin (2 mg) was dissolved in 20 g of chloroform, measured by gel permeation chromatography (GPC), and calibrated with standard polystyrene as Mn and Mw / Mn. GPC was measured by connecting TOSOH 8020 manufactured by Tosoh Corporation with two columns GMHHR-L manufactured by Tosoh Corporation and one TSK G5000HR and measuring the column temperature at 40 ° C. As an eluent, chloroform was flowed at a flow rate of 1.0 ml / mn, and measurement was performed with a UV detector.
(4) The melt viscosity is measured using Toyo Seiki Capirograph 1C (capillograph), temperature: 240 ° C., preheating time: 1 min, nozzle diameter: 1 mm, nozzle length: 10 mm, shear rate: 100 (1 / sec). went.

[Production of polyester resin composition]
Various fatty acid esters were dry blended with the polyester resin (A-1) or (A-2), and then melt-kneaded with an extruder to produce polyester resin compositions shown in Tables 2 and 3.

[Method for producing multilayer sheet]
The core layer material is extruded while venting devolatilization using a vented 65 mm twin screw extruder, while the skin layer material is extruded while venting devolatilization using a vented 30 mm twin screw extruder. Two types and three layers of multilayer sheets (total thickness of multilayer sheets: about 0.8 mm, skin layer thickness: about 0.1 mm) were manufactured using a die.
[Method for producing single-layer sheet]
Using a 65 mm extruder with a vent, PET was extruded while vent devolatilization, and a single layer sheet (sheet thickness: about 1.0 mm) was manufactured using a multi-manifold type die.

[Thermoforming of multilayer sheet]
The multilayer or single layer sheet produced in Examples 1 to 4 and Comparative Examples 1 to 3 was compression molded (thermoformed) to form a container having a flange portion.

(Releasability)
The releasability of the resin from the mold was visually observed, and the results are shown in Tables 2 and 3. The abbreviations of the observation results in the table are as follows.
○: Good releasability ×: Sticking of resin to the mold or poor smoothness of the molded product surface

[Examples 1-4, Comparative Examples 1-3]
The evaluation results of the multilayer sheet are shown in Tables 2 and 3.

  Since the polyester resin composition of the present invention can arbitrarily reduce the viscosity of the resin, it is possible to produce a multilayer sheet having no poor appearance (flow mark) with other resins having different viscosities. Industrial significance is great.

Claims (9)

80 to 99.995% by weight of a polyester resin (A) containing 1 to 60 mol% of a diol unit and containing a dicarboxylic acid unit and a diol unit and having a cyclic acetal skeleton, and a fatty acid ester having 10 to 30 carbon atoms A polyester resin composition containing 0.005 to 5% by weight of at least one of the following. 2. The polyester resin composition according to claim 1, wherein the fatty acid ester is at least one selected from the group consisting of stearic acid monoglyceride, behenic acid monoglyceride, palmitic acid monoglyceride, and lauric acid monoglyceride. The polyester resin composition according to claim 1 or 2, wherein the polyester resin (A) has a melt viscosity in a range of 700 to 5000 Pa · s when measured at a measurement temperature of 240 ° C and a shear rate of 100 s ^-1 . The diol unit having the cyclic acetal skeleton is represented by the general formula (1):

(In the formula, R ¹ and R ² are each independently an aliphatic hydrocarbon group having 1 to 10 carbon atoms, an alicyclic hydrocarbon group having 3 to 10 carbon atoms, and 6 to 10 carbon atoms. Represents a hydrocarbon group selected from the group consisting of aromatic hydrocarbon groups.)
Or general formula (2):

(In the formula, R ¹ is the same as above, R ³ is an aliphatic hydrocarbon group having 1 to 10 carbon atoms, an alicyclic hydrocarbon group having 3 to 10 carbon atoms, and 6 to 10 carbon atoms. Represents a hydrocarbon group selected from the group consisting of aromatic hydrocarbon groups of
The polyester resin composition according to any one of claims 1 to 3, which is a diol unit derived from a diol represented by formula (1). A diol unit having the cyclic acetal skeleton derived from 3,9-bis (1,1-dimethyl-2-hydroxyethyl) -2,4,8,10-tetraoxaspiro [5.5] undecane, Or a polyester resin composition according to any one of claims 1 to 3, which is a diol unit derived from 5-methylol-5-ethyl-2- (1,1-dimethyl-2-hydroxyethyl) -1,3-dioxane. object. Diol units derived from one or more diols selected from the group consisting of ethylene glycol, diethylene glycol, trimethylene glycol, 1,4-butanediol and 1,4-cyclohexanedimethanol, other than the diol unit having a cyclic acetal skeleton The polyester resin composition according to any one of claims 1 to 5. One or more dicarboxylic acid units selected from the group consisting of terephthalic acid, isophthalic acid, 1,4-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid and 2,7-naphthalenedicarboxylic acid The polyester resin composition according to claim 1, which is a dicarboxylic acid unit derived from dicarboxylic acid. At least 1 layer consists of a polyester resin composition in any one of Claims 1-7, The multilayer sheet characterized by the above-mentioned. The at least one layer other than the layer made of the polyester resin composition according to any one of claims 1 to 7 is mainly selected from the group consisting of a polyester resin, a polycarbonate resin, an acrylic resin, a polystyrene resin, and a polymethyl methacrylate-styrene resin. The multilayer sheet according to claim 8, wherein the multilayer sheet is a resin layer made of a resin.