Modifier for resin sheet, polyester resin composition, polyester resin sheet, laminated sheet, and method for producing molded article

Abstract

The invention provides a modifier for a resin sheet, a polyester resin composition, a polyester resin sheet, a laminated sheet, and a method for producing a molded body. The purpose of the present invention is to provide: a modifier which is used in combination with a polyester resin and which provides a resin sheet having excellent surface sliding properties without deteriorating transparency; a polyester resin composition containing the modifier; a polyester resin sheet; a laminate sheet; this modifier for a resin sheet is used in the production of a resin sheet, and contains (A) an ester compound of a trivalent-hexavalent polyhydric alcohol and a fatty acid having a C8-22 hydrocarbon group, and (B) a compound containing elemental calcium, the content ratio of the elemental calcium being 0.1-3.0 mass% with respect to the modifier.

Description

[0001] This application is a divisional application of the invention patent application with application number 202111421214.2, application date November 26, 2021, entitled "Method for manufacturing a resin sheet modifier, a polyester resin composition, a polyester resin sheet, a laminated sheet and a molded article". Technical Field

[0002] This invention relates to a modifier used in the manufacture of polyester resin sheets with excellent transparency and surface smoothness, and to polyester resin compositions comprising the modifier, polyester resin sheets, laminates, and methods for manufacturing molded articles. Background Technology

[0003] Polyester resins, such as polyethylene terephthalate (PET), produce films or sheets with excellent transparency, allowing for easy bending, punching, and cutting. Therefore, these films or sheets can be thermoformed to manufacture containers and lids for food, pharmaceuticals, stationery, and various other products. In manufacturing these molded products, multiple polyester sheets stacked to a specified width and length are fed one by one into a thermoforming apparatus for processing. However, insufficient slippage or adhesion of the sheets can result in defective products or reduced productivity.

[0004] Additionally, for example, containers that have been processed and shaped are often transported stacked together, and then the items are stored inside the containers after they are removed one by one. However, when the resin raw material is not sufficiently slippery or sticky, multiple containers may sometimes be removed in an overlapping manner.

[0005] To address this problem, attempts have been made to improve surface properties, making the surface of the polyester sheet, and consequently the surface of the molded body, easier to slide. The following techniques are known.

[0006] Patent Document 1 discloses a non-stretched or low-ratio stretched polyester sheet, which is formed from a composition containing 0.04 to 1% by weight of slip agent particles (such as silica) with an average particle size of 8 to 50 micrometers and 99.0 to 99.96% by weight of polyester. Patent Document 2 discloses a biaxially stretched polyester film, characterized by protrusions formed from polyester with a maximum diameter of 5 μm or less at a density of 20 to 60 per μm. 2The density exists on the surface of the film. The polyester contains internal particles containing calcium and phosphorus elements and 50-750 ppm of silica particles, and the calcium content is 0.01-0.1% by weight, and the phosphorus content is 0.5-2 times the equivalent of calcium in terms of elemental molar ratio. Additionally, Patent Document 3 discloses a release-layer laminated polyester film for green sheets, characterized by having at least three layers in a laminated structure. The surface roughness (Ra) of one film surface is in the range of 0.001-0.005 μm, and the layer constituting this surface contains more than 1000 ppm of alumina particles. A release layer and a green sheet are sequentially provided on this surface. The surface roughness (Ra) of another film surface is in the range of 0.010-0.030 μm, wherein the number of depressions with a depth of 0.2 μm or more on the surface of this green sheet is less than one per 100 cm. 2 The surface layer contains polystyrene particles with a cross-linked structure achieved by compounds containing more than two carbon-carbon double bonds in a single molecule.

[0007] Existing technical documents

[0008] Patent documents

[0009] Patent Document 1: Japanese Patent Application Publication No. 5-17598

[0010] Patent Document 2: Japanese Patent Application Publication No. 6-313095

[0011] Patent Document 3: Japanese Patent Application Publication No. 2016-187963 Summary of the Invention

[0012] The problem the invention aims to solve

[0013] The object of the present invention is to provide: a modifier for use in combination with polyester resin to provide a resin sheet with excellent surface lubricity without impairing transparency, and a polyester resin composition comprising the modifier, a polyester resin sheet, a laminate, and a method for manufacturing a molded article.

[0014] Solution for solving the problem

[0015] The inventors have discovered that if a resin composition is obtained by combining a modifier containing a specific fatty acid ester and a calcium content of 0.1 to 3.0% by mass relative to the modifier with a polyester resin, a resin sheet with excellent surface lubricity without compromising transparency can be obtained.

[0016] The present invention is as follows.

[0017] The resin sheet modifier of the present invention is characterized in that it is a modifier for manufacturing resin sheets, comprising an ester compound of a tri- to hexa-membered polyol and a fatty acid having a hydrocarbon group having 8 to 22 carbon atoms as component (A), and a compound containing calcium as component (B), wherein the content of calcium is 0.1 to 3.0 by mass relative to the modifier.

[0018] Preferably, the above-mentioned component (B) includes at least one selected from talc and zeolite.

[0019] The polyester resin composition of the present invention is characterized in that it is a resin composition for manufacturing polyester resin sheets, comprising: polyester resin and the above-described resin sheet modifier of the present invention.

[0020] The polyester resin sheet of the present invention is characterized in that it contains: polyester resin and the above-mentioned resin sheet modifier of the present invention.

[0021] The laminate of the present invention is characterized by comprising: a resin layer formed from the polyester resin sheet of the present invention, and other resin layers.

[0022] The method for manufacturing the molded body of the present invention is characterized in that the polyester resin sheet or laminate of the present invention described above is used for molding processing.

[0023] The effects of the invention

[0024] In this invention, when a polyester resin composition is prepared by combining a resin sheet modifier with a polyester resin, the polyester resin composition can be formed into a molding material suitable for manufacturing polyester resin sheets with excellent transparency and surface lubricity. The polyester resin composition can be used directly in the manufacture of polyester resin sheets, or it can be formed into a composition (masterbatch) with an increased ratio of the resin sheet modifier to the polyester resin. Therefore, using this masterbatch in combination with polyester resin allows for efficient manufacture of polyester resin sheets. Furthermore, the laminate of this invention comprises a resin layer formed from a polyester resin sheet with excellent transparency and surface lubricity; therefore, the surface of this resin layer exhibits excellent lubricity.

[0025] By applying the polyester resin sheet or laminate of the present invention to conventional molding processes, a molded body of a specified shape can be easily obtained. When multiple molded bodies are overlapped, adhesion can be suppressed. Detailed Implementation

[0026] The resin sheet modifier of the present invention is a modifier for manufacturing resin sheets, containing component (A) a tri- to hexa-membered polyol and an ester compound of a fatty acid having a hydrocarbon group having 8 to 22 carbon atoms, and component (B) a compound containing calcium.

[0027] The above-mentioned component (A) is an ester compound of polyol and fatty acid, preferably an organic compound formed by carbon atoms, hydrogen atoms and oxygen atoms and containing ester bonds.

[0028] The polyol used in the formation of the above component (A) is a compound having 3 to 6 hydroxyl groups.

[0029] Examples of the aforementioned polyols include trimethylolethane, trimethylolpropane, glycerol, diglycerol, triglycerol, tetraglycerol, di(trimethylol)ethane, di(trimethylol)propane, pentaerythritol, dipentaerythritol, hexanetriol, sorbitol, sorbitol, erythritol, mannitol, galactitol, idotitol, tarottitol, and allitol. Among these, glycerol and pentaerythritol are preferred.

[0030] The fatty acid used in the formation of the above-mentioned component (A) is an alkyl compound having 8 to 22 carbon atoms and containing a carboxyl group. In order to form the component (A) of the above-mentioned preferred embodiment, the fatty acid is optionally an aliphatic compound containing a carbon / carbon unsaturated bond, that is, a compound in which one hydrogen atom of an aliphatic saturated hydrocarbon or unsaturated hydrocarbon is replaced by a carboxyl group.

[0031] Examples of the aforementioned fatty acids include octanoic acid, capric acid, dodecanoic acid, tridecanoic acid, tetradecanoic acid, pentadecanoic acid, hexadecanoic acid, 9-hexadecenoic acid, heptadecanoic acid, octadecanoic acid, cis-9-octadecenoic acid, 11-octadecenoic acid, eicosanoic acid, and docosanoic acid. Among these, dodecanoic acid, tridecanoic acid, tetradecanoic acid, pentadecanoic acid, hexadecanoic acid, heptadecanoic acid, and octadecanoic acid, which are saturated fatty acids with 12 to 18 carbon atoms in the alkyl group, are preferred.

[0032] The above-mentioned component (A) is an esterification of the above-mentioned polyol and fatty acid. The component (A) contained in the resin sheet modifier of the present invention may be only one type or may be two or more types.

[0033] The resin sheet modifier of the present invention contains calcium. When the total amount of the resin sheet modifier is set to 100% by mass, the content of calcium in the resin sheet modifier is 0.1 to 3.0% by mass, preferably 0.3 to 3.0% by mass, and particularly preferably 0.5 to 2.0% by mass.

[0034] The calcium element contained in the resin sheet modifier may be a calcium element derived from a compound containing the calcium element of the above-mentioned component (B), or may be a calcium element other than that.

[0035] In this invention, the calcium content in the modifier for resin sheets only needs to be within the above-mentioned range. When used in combination with polyester resin, a polyester resin composition is formed, thereby making it easy to manufacture molded articles such as resin sheets with excellent surface smoothness without compromising transparency.

[0036] As a method for quantifying the calcium content in the resin sheet modifier of the present invention, conventional determination methods can be applied. For example, fluorescence X-ray analysis can be used.

[0037] In the resin sheet modifier of the present invention, the compound containing calcium element of the above-mentioned component (B) is not particularly limited, and can be either an inorganic compound or an organic compound. Among these, inorganic compounds are preferred, and known talc or zeolite are preferred. Component (B) contained in the resin sheet modifier of the present invention can be any one of them, or both.

[0038] The above-mentioned component (B) is preferably in particulate form. In terms of the average particle size based on the laser / diffraction scattering method, from the viewpoint of obtaining a resin sheet with excellent surface smoothness without compromising transparency, it is preferably 0.5 to 20 μm in the case of talc and 1 to 10 μm in the case of zeolite.

[0039] In the resin sheet modifier of the present invention, when the total content of the above-mentioned components (A) and (B) is set to 100% by mass, their content ratios are preferably 40-80% by mass and 20-60% by mass, respectively.

[0040] The resin sheet modifier of the present invention may contain other components as needed, as long as the transparency of the resin molded body can be obtained. For example, it may contain fillers (hereinafter referred to as "other fillers") other than the above-mentioned component (B), plasticizers, antioxidants, ultraviolet absorbers, weathering agents, heat stabilizers, antistatic agents, lubricants, flame retardants, crystal nucleating agents, etc.

[0041] Other fillers include silica, talc (containing no calcium), diatomaceous earth, titanium dioxide, alumina, zirconium oxide, zinc oxide, strontium oxide, strontium carbonate, iron oxide, ferrite, zeolite, pyrophyllite, montmorillonite, vermiculite, wollastonite, mica, and clay. It should be noted that the other fillers contained in the resin sheet modifier of this invention may be only one type or may be two or more types.

[0042] The preferred composition of the resin sheet modifier of the present invention is described below.

[0043] (1) Modifier formed from component (A) and component (B)

[0044] (2) Modifier formed from component (A), component (B) and other fillers

[0045] The resin sheet modifier of the present invention can preferably be manufactured as follows: by mixing component (A), component (B) and other components to be used in combination as needed using a conventionally known mixing device.

[0046] The resin sheet modifier of the present invention contains the above-mentioned components (A) and (B), and is suitable as a raw material for manufacturing resin compositions that provide transparent polyester resin sheets and the like with smooth surfaces.

[0047] The polyester resin composition of the present invention is used to manufacture polyester resin sheets, comprising: polyester resin and the resin sheet modifier of the present invention. There is no limitation on the amount of the resin sheet modifier of the present invention added to the resin composition of the present invention; however, when the content of polyester resin is set to 100 parts by weight, it is preferable to contain the modifier of the present invention at a ratio of 0.1 to 45 parts by weight. When the content of polyester resin is set to 100 parts by weight, the polyester resin composition of the present invention containing the resin sheet modifier of the present invention at a ratio of 10 to 45 parts by weight can form a masterbatch.

[0048] The resin sheet modifier and polyester resin contained in the polyester resin composition of the present invention may be only one type or two or more types.

[0049] The aforementioned polyester resin is a thermoplastic resin, which can be any of aromatic polyester resin and aliphatic polyester resin, or a combination of both. Furthermore, these polyester resins can be any of homopolymer polyester and copolymer polyester.

[0050] The aforementioned polyester resin is typically obtained through polycondensation of dicarboxylic acid components and dihydroxy components, polycondensation of dicarboxylic acid components, dihydroxy components, and hydroxycarboxylic acid components, or ring-opening polymerization of lactone components.

[0051] Examples of dicarboxylic acid components include aromatic dicarboxylic acids or their derivatives with approximately 8 to 16 carbon atoms, such as terephthalic acid, isophthalic acid, phthalic acid, naphthalenedicarboxylic acid (e.g., 2,6-naphthalenedicarboxylic acid), diphenyl dicarboxylic acid, diphenyl ether dicarboxylic acid, diphenylmethane dicarboxylic acid, diphenyl ethane dicarboxylic acid, and diphenyl ketone dicarboxylic acid; alicyclic dicarboxylic acids or their derivatives with approximately 8 to 12 carbon atoms, such as cyclohexanedicarboxylic acid, hexahydrophthalic acid, hexahydroisophthalic acid, hexahydroterephthalic acid, and humic acid; and aliphatic dicarboxylic acids or their derivatives with approximately 2 to 40 carbon atoms, such as adipic acid, pimelic acid, octanoic acid, azelaic acid, sebacic acid, dodecanedicarboxylic acid, hexadecanedicarboxylic acid, and dimer acids.

[0052] In addition, examples of the aforementioned dihydroxy components include aliphatic alkylene glycols such as ethylene glycol, trimethylene glycol, propylene glycol, 1,3-butanediol, 1,4-butanediol, neopentyl glycol, hexanediol, octanediol, and decanediol, which are straight-chain or branched alkylene glycols with approximately 2 to 12 carbon atoms; alicyclic glycols such as cyclohexanediol, cyclohexanediethanol, and hydrogenated bisphenol A; aromatic glycols such as hydroquinone, resorcinol, dihydroxybenzene, naphthalenediol, and dihydroxydiphenyl ether; and adducts obtained by adding ethylene oxide, propylene oxide, and other epoxides to bisphenol A (such as diethoxylated bisphenol A); as well as polyalkylene glycols such as diethylene glycol, triethylene glycol, polyethylene glycol, bis(tetramethylene glycol), dipropylene glycol, tripropylene glycol, and polypropylene glycol.

[0053] Examples of hydroxycarboxylic acid components include lactic acid, glycolic acid, 2-hydroxy-n-butyric acid, 3-hydroxybutyric acid, 4-hydroxybutyric acid, 4-hydroxyvalerate, 2-hydroxyhexanoic acid, 2-hydroxyisohexanoic acid, 6-hydroxyhexanoic acid, 2-hydroxy-3,3-dimethylbutyric acid, 2-hydroxy-3-methylbutyric acid, hydroxybenzoic acid, hydroxynaphthoic acid, diphenylene hydroxycarboxylic acid, and other hydroxycarboxylic acids and their derivatives.

[0054] Examples of lactones mentioned above include ε-propiolactone, δ-butyrolactone, β-butyrolactone, γ-butyrolactone, neopentyllactone, δ-pentyllactone, and ε-caprolactone.

[0055] When the above-mentioned polyester resin is an aromatic homopolymer polyester, it is preferably a condensation polymer of dicarboxylic acid component and dihydroxy component.

[0056] The preferred dicarboxylic acid component is terephthalic acid, naphthalenedicarboxylic acid, etc., and the preferred dihydroxy component is ethylene glycol, diethylene glycol, butanediol, cyclohexanediol, etc. Representative homopolymer polyesters include polyethylene terephthalate (PET), polypropylene terephthalate (PPT), polybutylene terephthalate (PBT), polyhexene terephthalate, poly(1,4-cyclohexanediol) terephthalate, polypentyl terephthalate, etc., as well as alkylene terephthalates such as polyethylene isophthalate, polyethylene naphthalate, polybutylene naphthalate, and polyhexene naphthalate. Among these, PET is particularly preferred.

[0057] In addition, when the above-mentioned polyester resin is an aromatic copolyester, it is preferably a condensation polymer of dicarboxylic acid component, dihydroxy component and hydroxycarboxylic acid component.

[0058] The dicarboxylic acid component is preferably selected from one or more of isophthalic acid, phthalic acid, terephthalic acid, naphthalenedicarboxylic acid, adipic acid, sebacic acid, etc., and the dihydroxy component is preferably selected from one or more of ethylene glycol, diethylene glycol, propylene glycol, butanediol, 4-cyclohexanediol, neopentyl glycol, etc., and the hydroxycarboxylic acid is, for example, p-hydroxybenzoic acid. Representative copolyester resins include condensates formed from terephthalic acid, ethylene glycol, and 4-cyclohexanediol (sometimes called "PETG resin"), polyethylene terephthalate / ethylene isophthalate resins, etc.

[0059] When the aforementioned polyester resin is an aliphatic polyester resin, it is preferably a resin obtained through ring-opening polymerization of cyclic lactones, condensation polymerization of aliphatic hydroxycarboxylic acids (hydroxycarboxylic acids), condensation polymerization of aliphatic dicarboxylic acids (succinic acid, adipic acid, azelaic acid, sebacic acid, α,ω-dodecanoic acid, dodecenylsuccinic acid, octadecenylsuccinic acid, cyclohexanedicarboxylic acid, etc.) and / or esterifying compounds (dimethyl succinate, dimethyl adipate, dimethyl azelate, dimethyl sebacate, etc., aliphatic compounds with functional groups having two or more ester bond-forming properties in the molecule), and condensation polymerization of aliphatic diols (ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, neopentyl glycol, 1,4-cyclohexanediol, cyclohexanediol, etc.).

[0060] Examples of aliphatic polyester resins obtained by ring-opening polymerization of cyclic lactones include poly(ε-propiolactone) resin, poly(δ-butyrolactone) resin, poly(β-butyrolactone) resin, poly(γ-butyrolactone) resin, poly(neovaleractone) resin, poly(δ-valeractone) resin, and poly(ε-caprolactone) resin.

[0061] Examples of aliphatic polyester resins obtained through the polycondensation reaction of aliphatic hydroxycarboxylic acids (hydroxycarboxylic acids) include polylactic acid resin, polyglycolic acid resin, poly(3-hydroxybutyric acid) resin, poly(4-hydroxybutyric acid) resin, and poly(4-hydroxyvalerate) resin.

[0062] The aforementioned polyester resin preferably comprises an aromatic polyester resin.

[0063] The polyester resin composition of the present invention only needs to achieve the transparency of the resin sheet. Other components may be included as needed, such as fillers, plasticizers, antioxidants, ultraviolet absorbers, weathering agents, heat stabilizers, antistatic agents, lubricants, flame retardants, crystal nucleating agents, etc., other than component (B).

[0064] When the polyester resin composition of the present invention is a masterbatch, it may have, for example, a cylindrical shape, a prismatic shape, a spherical shape, an ellipsoidal shape, etc.

[0065] The masterbatch described above can be manufactured as follows: a mixture containing the resin sheet of the present invention and a modifier and a polyester resin is heated to form a melt compound, which is then fed into a conventionally known extrusion method. The specific manufacturing method is as follows.

[0066] Method (1): The above-mentioned resin sheet modifier and polyester resin of the present invention are added to a mixer such as a drum mixer, Henschel mixer, or super mixer and mixed. Then, the mixture is melt-blended and granulated using an extruder such as a single screw extruder or a multi-screw extruder to obtain the masterbatch.

[0067] Method (2): Polyester resin is melted using an extruder such as a single-screw extruder or a multi-screw extruder. The resin is then mixed with the resin sheet modifier and additives of the present invention through side feeding or liquid injection. The mixture is then melt-blended and granulated to obtain a masterbatch.

[0068] The polyester resin sheet of the present invention comprises the resin sheet modifier of the present invention described above. It contains the resin sheet modifier in a transparent polyester resin sheet with a smooth surface at a preferred ratio. That is, when the content of polyester resin is set to 100 parts by weight, it is preferable to contain the resin sheet modifier at a ratio of 0.1 to 1.5 parts by weight. Component (A) is contained at a ratio of 0.02 to 1.2 parts by weight, preferably 0.04 to 1.2 parts by weight. Calcium is contained at a ratio of 0.0001 to 0.045 parts by weight, preferably 0.0003 to 0.045 parts by weight, more preferably 0.0005 to 0.03 parts by weight.

[0069] The thickness of the polyester resin sheet of the present invention is not particularly limited, but is preferably 100-800 μm, more preferably 300-500 μm.

[0070] The polyester resin sheet of the present invention is transparent, and when subjected to a haze measurement according to the method of JIS K 7136, the haze is preferably 10% or less, more preferably 5% or less. Therefore, the visual visibility of articles on opposite sides is excellent through this resin sheet.

[0071] Furthermore, when the polyester resin sheet of the present invention is subjected to static friction coefficient measurement according to the method of JIS K 7125, the static friction coefficient is preferably 0.40 or less, more preferably 0.35 or less. Because the polyester resin sheet of the present invention has the above-mentioned properties, its surface is smooth, and when multiple resin sheets are overlapped, they do not stick together and can be easily removed one by one.

[0072] The polyester resin sheet of the present invention can be manufactured by subjecting the above-described polyester resin composition of the present invention to conventional molding methods such as calendering, T-die molding, blow molding, and blow molding, and can be stretched as needed. Subsequently, the polyester resin sheet of the present invention is subjected to two processing steps such as vacuum forming, air-forming, punching, and assembly, thereby manufacturing a molded body with a specified shape, such as a container.

[0073] Furthermore, the polyester resin sheet of the present invention described above can be used to manufacture multi-layered resin sheets, i.e., laminated sheets. In the present invention, a three-layer laminated sheet can be formed, consisting of a transparent, smooth-surfaced polyester resin sheet and other resin layers. For example, the surface layers on one side and the other side are both formed of the polyester resin sheet of the present invention, while the middle layer is composed of other resins. In this type of laminated sheet, when the HAZE is preferably 10% or less, more preferably 5% or less, the visual distinguishability of articles on opposite sides is excellent. The laminated sheet of the present invention is not limited to a three-layer laminated sheet; it can be a two-layer laminated sheet or a laminated sheet formed of four or more layers.

[0074] The aforementioned three-layer laminated sheets can be manufactured using co-extrusion, lamination, or similar methods. In the co-extrusion method, a molding material (thermoplastic resin composition) containing polyester resin and the resin sheet modifier of the present invention, used to form surface layers on one side and the other side, and a molding material (thermoplastic resin composition) used to form the intermediate layer can be subjected to blow molding or T-die molding; stretching can also be performed as needed. Furthermore, lamination methods include dry lamination, sandwich lamination, and extrusion lamination. When manufactured using these lamination methods, lamination can be performed with an adhesive sandwiched between a polyester resin sheet containing polyester resin and the resin sheet modifier of the present invention used to form surface layers on one side and the other side, and a resin film used to form the intermediate layer.

[0075] The laminated sheet of the present invention, like the polyester resin sheet of the present invention described above, can be subjected to two processes such as vacuum forming, air forming, punching, and assembly, thereby enabling the manufacture of molded bodies with a specified shape, such as containers.

[0076] Example

[0077] The following examples illustrate the implementation of the present invention in further detail. However, the present invention is not limited to these examples. Here, parts and percentages are used as mass standards unless otherwise specified.

[0078] 1. Quantitative determination of raw materials and calcium element in the modifier for resin tablets.

[0079] The following shows the raw materials used in the manufacture of the resin sheet modifier. The average particle size of the filler is a value determined based on laser diffraction / scattering.

[0080] (1) Fatty acid esters

[0081] A-1: Pentaerythritol Tetrastearate

[0082] A-2: Glyceryl tristearate

[0083] A-3: Sorbitol Tristearate

[0084] A-4: Glyceryl monostearate

[0085] A-5: Diglyceryl monolaurate

[0086] A-6: Pentaerythritol distearate

[0087] a-1: Glycol monostearate

[0088] a-2: Decaglyceryl monolaurate

[0089] (2) Filler (a compound containing calcium)

[0090] B-1: Zeolite particles (average particle size: 7μm, Ca content: 5.73%)

[0091] B-2: Zeolite particles (average particle size: 5μm, Ca content: 5.20%)

[0092] B-3: Zeolite particles (average particle size: 3μm, Ca content: 5.26%)

[0093] B-4: Zeolite particles (average particle size: 10 μm, Ca content: 5.40%)

[0094] B-5: Talc particles (average particle size: 4μm, Ca content: 0.19%)

[0095] B-6: Talc particles (average particle size: 6μm, Ca content: 0.29%)

[0096] B-7: Talc particles (average particle size: 10μm, Ca content: 0.10%)

[0097] B-8: Talc particles (average particle size: 15μm, Ca content: 0.27%)

[0098] B-9: Zeolite particles (average particle size: 12μm, Ca content: 5.54%)

[0099] B-10: Zeolite particles (average particle size: 0.5 μm, Ca content: 5.20%)

[0100] (3) Other fillers

[0101] C-1: Silica particles (average particle size: 3μm)

[0102] C-2: Talc particles (average particle size: 8μm, Ca-free)

[0103] C-3: Silica particles (average particle size: 8μm)

[0104] C-4: Silica particles (average particle size: 3μm)

[0105] C-5: Silica particles (average particle size: 0.5μm)

[0106] (4) Quantitative analysis of calcium

[0107] The calcium content of the resin sheets in the examples and comparative examples was quantified using a fluorescence X-ray analysis device “ZSX101e” manufactured by Rigaku Co., Ltd.

[0108] 2. Manufacturing of modifiers for resin sheets

[0109] Example 1-1

[0110] Using a mixer, 38.5 parts of fatty acid ester A-1, 7.7 parts of zeolite particles B-1, 30.8 parts of talc particles B-5, 7.7 parts of silica particles C-1, and 15.3 parts of talc particles C-2 were stirred to obtain a resin sheet modifier (hereinafter referred to as "resin sheet modifier E-1") formed from a homogeneous mixture (see Table 1). Table 1 also records the ratio of components (A) and (B) of the present invention when the total is set to 100%, and the ratio of calcium element contained in the resin sheet modifier (Ca content).

[0111] Examples 1-2

[0112] Using 50 parts of fatty acid ester A-1, 15 parts of zeolite particles B-1, and 35 parts of talc particles C-2, the same operation as in Example 1-1 was performed to obtain a resin sheet modifier (hereinafter referred to as "resin sheet modifier E-2") (see Table 1).

[0113] Examples 1-3

[0114] Using 60 parts of fatty acid ester A-1, 2.5 parts of fatty acid ester A-4, 9.4 parts of zeolite particles B-1, and 28.1 parts of zeolite particles B-2, the same operation as in Example 1-1 was performed to obtain a resin sheet modifier (hereinafter referred to as "resin sheet modifier E-3") (see Table 1).

[0115] Examples 1-4

[0116] Using 60 parts of fatty acid ester A-2, 25 parts of zeolite particles B-2, and 15 parts of silica particles C-3, the same operation as in Example 1-1 was performed to obtain a resin sheet modifier (hereinafter referred to as "resin sheet modifier E-4") (see Table 1).

[0117] Examples 1-5

[0118] Using 40 parts of fatty acid ester A-2, 30 parts of zeolite particles B-4, and 30 parts of talc particles B-7, the same operation as in Example 1-1 was performed to obtain a resin sheet modifier (hereinafter referred to as "resin sheet modifier E-5") (see Table 1).

[0119] Examples 1-6

[0120] Using 59 parts of fatty acid ester A-1, 6.3 parts of zeolite particles B-3, and 34.7 parts of talc particles B-6, the same operation as in Example 1-1 was performed to obtain a resin tablet modifier (hereinafter referred to as "resin tablet modifier E-6") (see Table 1).

[0121] Examples 1-7

[0122] Using 40.5 parts of fatty acid ester A-1, 46.5 parts of zeolite particles B-3, and 13 parts of talc particles B-8, the same operation as in Example 1-1 was performed to obtain a resin sheet modifier (hereinafter referred to as "resin sheet modifier E-7") (see Table 1).

[0123] Examples 1-8

[0124] Using 27.3 parts of fatty acid ester A-2, 31.8 parts of zeolite particles B-3, and 40.9 parts of talc particles B-5, the same operation as in Example 1-1 was performed to obtain a resin sheet modifier (hereinafter referred to as "resin sheet modifier E-8") (see Table 1).

[0125] Examples 1-9

[0126] Using 70 parts of fatty acid ester A-2, 3.7 parts of fatty acid ester A-5, and 26.3 parts of zeolite particles B-9, the same operation as in Example 1-1 was performed to obtain a resin sheet modifier (hereinafter referred to as "resin sheet modifier E-9") (see Table 1).

[0127] Examples 1-10

[0128] Using 78.6 parts of fatty acid ester A-2, 1.4 parts of zeolite particles B-1, and 20 parts of talc particles B-5, the same operation as in Example 1-1 was performed to obtain a resin sheet modifier (hereinafter referred to as "resin sheet modifier E-10") (see Table 1).

[0129] Examples 1-11

[0130] Using 61.1 parts of fatty acid ester A-3 and 38.9 parts of zeolite particles B-10, the same operation as in Example 1-1 was performed to obtain a resin sheet modifier (hereinafter referred to as "resin sheet modifier E-11") (see Table 1).

[0131] Comparative Example 1-1

[0132] Using 47.4 parts of fatty acid ester A-1, 1.4 parts of zeolite particles B-1, and 51.2 parts of silica particles C-4, the same operation as in Example 1-1 was performed to obtain a resin sheet modifier (hereinafter referred to as "resin sheet modifier e-1") (see Table 1).

[0133] Comparative Examples 1-2

[0134] Using 25 parts of fatty acid ester A-6 and 75 parts of zeolite particles B-10, the same operation as in Example 1-1 was performed to obtain a resin sheet modifier (hereinafter referred to as "resin sheet modifier e-2") (see Table 1).

[0135] Comparative Examples 1-3

[0136] Using 62.5 parts of fatty acid ester a-1, 18.75 parts of zeolite particles B-1, and 18.75 parts of silica particles C-3, the same operation as in Example 1-1 was performed to obtain a resin sheet modifier (hereinafter referred to as "resin sheet modifier e-3") (see Table 1).

[0137] Comparative Examples 1-4

[0138] Using 30.3 parts of fatty acid ester a-2, 15.15 parts of zeolite particles B-2, 14.55 parts of talc particles C-2, and 40 parts of silica particles C-5, the same operation as in Example 1-1 was performed to obtain a resin sheet modifier (hereinafter referred to as "resin sheet modifier e-4") (see Table 1).

[0139] [Table 1]

[0140]

[0141] 3. Manufacturing of Masterbatch (Resin Composition)

[0142] Using the resin sheets obtained above as a modifier and polyethylene terephthalate "BG-80" (trade name) produced by Sinopec Yizheng Chemical Fiber Co., Ltd., a masterbatch (resin composition) is manufactured.

[0143] Example 2-1

[0144] Using a roller, 100 parts of the above-mentioned polyethylene terephthalate (PET) and 35.1 parts of resin sheets were stirred with modifier E-1, and then melt-blended at 250°C to 270°C using a twin-screw compounding extruder "TEX30α" (model name) manufactured by Nippon Steel Works Co., Ltd., to obtain masterbatch M-1 (refer to Table 2).

[0145] Example 2-2

[0146] Using 100 parts of the above-mentioned polyethylene terephthalate (PET) and 25.0 parts of resin sheet modifier E-2, the same operation as in Example 2-1 was performed to obtain masterbatch M-2 (refer to Table 2).

[0147] Example 2-3

[0148] Using 100 parts of the above-mentioned polyethylene terephthalate (PET) and 25.0 parts of resin sheet modifier E-4, the same operation as in Example 2-1 was performed to obtain masterbatch M-3 (refer to Table 2).

[0149] Examples 2-4

[0150] Using 100 parts of the above-mentioned polyethylene terephthalate (PET) and 25.0 parts of resin sheet modifier E-5, the same operation as in Example 2-1 was performed to obtain masterbatch M-4 (see Table 2).

[0151] Examples 2-5

[0152] Using 100 parts of the above-mentioned polyethylene terephthalate (PET) and 22.7 parts of resin sheet modifier E-7, the same operation as in Example 2-1 was performed to obtain masterbatch M-5 (see Table 2).

[0153] Examples 2-6

[0154] Using 100 parts of the above-mentioned polyethylene terephthalate (PET) and 22.0 parts of resin sheet modifier E-11, the same operation as in Example 2-1 was performed to obtain masterbatch M-6 (see Table 2).

[0155] [Table 2]

[0156]

[0157] 4. Preparation of resin compositions and resin sheets and their evaluation

[0158] A resin composition for forming resin sheets is manufactured using the above-mentioned polyethylene terephthalate (PET) and the resin sheet modifier or masterbatch obtained above.

[0159] Example 3-1

[0160] Using a roller, 100 parts of the above-mentioned polyethylene terephthalate (PET) and 0.50 parts of resin sheet were stirred with modifier E-1, and then melt-blended at 250°C to 270°C using a twin-screw compounding extruder "TEX30α" (model name) manufactured by Nippon Steel Works Co., Ltd., to obtain a composition for manufacturing resin sheet (hereinafter referred to as "resin composition T-1"). Next, the melt-blended resin composition T-1 was extruded from a T-die onto a cooling roller with the temperature adjusted to 40°C to obtain a resin sheet with a thickness of 300 μm (hereinafter referred to as "resin sheet S-1") (see Table 3).

[0161] The obtained resin sheet S-1 was evaluated for its slip properties and transparency using the following method, and the results are recorded in Table 3.

[0162] (1) Sliding

[0163] For the resin sheets, after 24 hours of humidity conditioning at 20°C and 65%RH, the static coefficient of friction was measured under the same atmosphere using a friction testing machine "TR-2" (model name) manufactured by Toyo Seiki Co., Ltd., according to JIS K7125. Measurements were taken on any surface of three resin sheets, and the average of the three points was used to evaluate the sliding properties based on the following criteria.

[0164] ◎◎: 0.35 or less

[0165] ◎: Above 0.35 and below 0.40

[0166] 〇: Above 0.40 and below 0.60

[0167] ×: Exceeding 0.60

[0168] (2) Transparency

[0169] The haze of the resin sheets was measured using a haze meter "NDH5000" (model name) manufactured by Nippon Denshoku Kogyo Co., Ltd., according to JIS K7136. Measurements were taken at arbitrary locations on five resin sheets, and the average value of the five points was used to evaluate the transparency based on the following criteria.

[0170] ◎: 5% or less

[0171] 〇: More than 5% but less than 10%

[0172] ×: More than 10%

[0173] Example 3-2

[0174] Using 99.60 parts of the above-mentioned polyethylene terephthalate (PET) and 0.54 parts of masterbatch M-1, resin composition T-2 was prepared in the same manner as in Example 3-1. Then, resin sheet S-2 as shown in Table 3 was manufactured. Subsequently, its slip properties and transparency were evaluated (see Table 3).

[0175] Example 3-3

[0176] Resin composition T-3 was prepared in the same manner as in Example 3-1, except that 96.58 parts of the above-mentioned polyethylene terephthalate (PET) and 4.62 parts of masterbatch M-1 were used. Then, resin sheet S-3 as shown in Table 3 was prepared. Subsequently, the slip properties and transparency were evaluated (refer to Table 3).

[0177] Examples 3-4

[0178] Using 100 parts of the above-mentioned polyethylene terephthalate (PET) and 1.01 parts of resin sheet modifier E-1, resin composition T-4 was prepared in the same manner as in Example 3-1. Then, resin sheet S-4 as shown in Table 3 was prepared. Subsequently, the slip properties and transparency were evaluated (refer to Table 3).

[0179] Examples 3-5

[0180] Using 100 parts of the above-mentioned polyethylene terephthalate (PET) and 0.60 parts of resin sheet modifier E-2, resin composition T-5 was prepared in the same manner as in Example 3-1. Then, resin sheet S-5 as shown in Table 3 was prepared. Subsequently, the slip properties and transparency were evaluated (refer to Table 3).

[0181] Examples 3-6

[0182] Using 98.48 parts of the above-mentioned polyethylene terephthalate (PET) and 1.90 parts of masterbatch M-2, resin composition T-6 was prepared in the same manner as in Example 3-1. Then, resin sheet S-6 as shown in Table 3 was manufactured. Subsequently, its slip properties and transparency were evaluated (refer to Table 3).

[0183] Examples 3-7

[0184] Using 100 parts of the above-mentioned polyethylene terephthalate (PET) and 0.91 parts of resin sheet modifier E-3, resin composition T-7 was prepared in the same manner as in Example 3-1. Then, resin sheet S-7 as shown in Table 3 was prepared. Subsequently, the slip properties and transparency were evaluated (refer to Table 3).

[0185] Examples 3-8

[0186] Using 100 parts of the above-mentioned polyethylene terephthalate (PET) and 0.55 parts of resin sheet modifier E-4, resin composition T-8 was prepared in the same manner as in Example 3-1. Then, resin sheet S-8 as shown in Table 3 was prepared. Subsequently, the slip properties and transparency were evaluated (refer to Table 3).

[0187] Examples 3-9

[0188] Resin composition T-9 was prepared in the same manner as in Example 3-1, except that 95.60 parts of the above-mentioned polyethylene terephthalate (PET) and 5.50 parts of masterbatch M-3 were used. Then, resin sheet S-9 as shown in Table 3 was prepared. Subsequently, the slip properties and transparency were evaluated (refer to Table 3).

[0189] Examples 3-10

[0190] Using 100 parts of the above-mentioned polyethylene terephthalate (PET) and 0.70 parts of resin sheet modifier E-5, resin composition T-10 was prepared in the same manner as in Example 3-1. Then, resin sheet S-10 as shown in Table 3 was prepared. Subsequently, the slip properties and transparency were evaluated (refer to Table 3).

[0191] Example 3-11

[0192] Using 97.20 parts of the above-mentioned polyethylene terephthalate (PET) and 3.50 parts of masterbatch M-4, resin composition T-11 was manufactured in the same manner as in Example 3-1. Then, resin sheet S-11 as shown in Table 3 was manufactured. Subsequently, the slip properties and transparency were evaluated (refer to Table 3).

[0193] Example 3-12

[0194] Using 100 parts of the above-mentioned polyethylene terephthalate (PET) and 0.81 parts of resin sheet modifier E-6, resin composition T-12 was prepared in the same manner as in Example 3-1. Then, resin sheet S-12 as shown in Table 3 was prepared. Subsequently, the slip properties and transparency were evaluated (refer to Table 3).

[0195] Example 3-13

[0196] Using 100 parts of the above-mentioned polyethylene terephthalate (PET) and 0.50 parts of resin sheet modifier E-7, resin composition T-13 was prepared in the same manner as in Example 3-1. Then, resin sheet S-13 as shown in Table 3 was prepared. Subsequently, the slip properties and transparency were evaluated (refer to Table 3).

[0197] Example 3-14

[0198] Using 93.83 parts of the above-mentioned polyethylene terephthalate (PET) and 7.57 parts of masterbatch M-5, resin composition T-14 was manufactured in the same manner as in Example 3-1. Then, resin sheet S-14 as shown in Table 3 was manufactured. Subsequently, its slip properties and transparency were evaluated (refer to Table 3).

[0199] Example 3-15

[0200] Using 100 parts of the above-mentioned polyethylene terephthalate (PET) and 0.20 parts of resin sheet modifier E-8, resin composition T-15 was prepared in the same manner as in Example 3-1. Then, resin sheet S-15 as shown in Table 3 was prepared. Subsequently, the slip properties and transparency were evaluated (refer to Table 3).

[0201] Example 3-16

[0202] Using 100 parts of the above-mentioned polyethylene terephthalate (PET) and 1.32 parts of resin sheet modifier E-9, resin composition T-16 was prepared in the same manner as in Example 3-1. Then, resin sheet S-16 as shown in Table 3 was prepared. Subsequently, the slip properties and transparency were evaluated (refer to Table 3).

[0203] Example 3-17

[0204] Using 100 parts of the above-mentioned polyethylene terephthalate (PET) and 1.21 parts of resin sheet modifier E-10, resin composition T-17 was prepared in the same manner as in Example 3-1. Then, resin sheet S-17 as shown in Table 3 was prepared. Subsequently, the slip properties and transparency were evaluated (refer to Table 3).

[0205] Example 3-18

[0206] Using 100 parts of the above-mentioned polyethylene terephthalate (PET) and 1.01 parts of resin sheet modifier E-11, resin composition T-18 was prepared in the same manner as in Example 3-1. Then, resin sheet S-18 as shown in Table 3 was prepared. Subsequently, the slip properties and transparency were evaluated (refer to Table 3).

[0207] Example 3-19

[0208] Using 98.18 parts of the above-mentioned polyethylene terephthalate (PET) and 2.22 parts of masterbatch M-6, resin composition T-19 was manufactured in the same manner as in Example 3-1. Then, resin sheet S-19 as shown in Table 3 was manufactured. Subsequently, its slip properties and transparency were evaluated (see Table 3).

[0209] Comparative Example 3-1

[0210] Using 100 parts of the above-mentioned polyethylene terephthalate (PET) and 0.50 parts of resin sheet modifier e-1, resin composition t-1 was prepared in the same manner as in Example 3-1. Then, resin sheet s-1 as shown in Table 3 was prepared. Subsequently, the slip properties and transparency were evaluated (refer to Table 3).

[0211] Comparative Example 3-2

[0212] Using 100 parts of the above-mentioned polyethylene terephthalate (PET) and 0.30 parts of resin sheet modifier e-2, resin composition t-2 was prepared in the same manner as in Example 3-1. Then, resin sheet s-2 as shown in Table 3 was prepared. Subsequently, the slip properties and transparency were evaluated (refer to Table 3).

[0213] Comparative Example 3-3

[0214] Using 100 parts of the above-mentioned polyethylene terephthalate (PET) and 0.81 parts of resin sheet modifier e-3, resin composition t-3 was prepared in the same manner as in Example 3-1. Then, resin sheet s-3 as shown in Table 3 was prepared. Subsequently, the slip properties and transparency were evaluated (refer to Table 3).

[0215] Comparative Examples 3-4

[0216] Using 100 parts of the above-mentioned polyethylene terephthalate (PET) and 0.50 parts of resin sheet modifier e-4, resin composition t-4 was prepared in the same manner as in Example 3-1. Then, resin sheet s-4 as shown in Table 3 was prepared. Subsequently, the slip properties and transparency were evaluated (refer to Table 3).

[0217] [Table 3]

[0218]

[0219] As clearly shown in Table 3, in Examples 3-1 to 3-19, since resin compositions containing the resin sheet modifier of the present invention were used, sheets with excellent sliding properties while maintaining high transparency were obtained. Furthermore, Examples 3-2, 3-3, 3-6, 3-9, 3-11, 3-14, and 3-19 are examples of manufacturing polyester resin sheets using the masterbatches shown in Table 2. With the polyester resin content set to 100 parts by weight, polyester resin sheets can be suitably manufactured using masterbatches formed from resin compositions containing 10 to 45 parts by weight of the resin sheet modifier.

[0220] 5. Fabrication and evaluation of laminated wafers

[0221] Laminated sheets were manufactured using the polyester resin composition obtained above and polyethylene terephthalate "BG-80" (trade name) produced by Sinopec Yizheng Chemical Fiber Co., Ltd.

[0222] Example 4-1

[0223] The resin composition T-1 used for manufacturing resin sheet S-1, which is made in the same way as in Example 3-1, is used for the two outer layers, and the above-mentioned polyethylene terephthalate resin is used for the middle layer. The melt compound of each layer is co-extruded from the T die onto a cooling roller with the temperature adjusted to 40°C to obtain a 3-layer laminate with a thickness of 300 μm and a layer ratio of 1 / 8 / 1 (hereinafter referred to as "laminated sheet U-1") (see Table 4).

[0224] For the obtained laminate U-1, the sliding properties and transparency were evaluated using the same evaluation criteria as the resin sheet, and the results are recorded in Table 4.

[0225] Examples 4-2 to 4-19

[0226] Similar to Example 4-1, using the resin composition (T-2~T-19) for manufacturing the polyester resin sheets (S-2~S-19) shown in Table 3, the laminated sheets U-2~U-19 shown in Table 4 were obtained (refer to Table 4).

[0227] Comparative Examples 4-1 to 4-4

[0228] Similar to Example 4-1, using the resin compositions (t-1 to t-4) for manufacturing the polyester resin sheets (s-1 to s-4) shown in Table 3, the laminated sheets u-1 to u-4 shown in Table 4 were obtained (see Table 4).

[0229] [Table 4]

[0230]

[0231] As can be clearly seen from the results in Table 4, Examples 4-1 to 4-19 are laminates with a three-layer structure, in which polyethylene terephthalate resin is used as the intermediate layer and the surface layer (two surface layers) of the intermediate layer is made of a resin composition containing the resin sheet modifier of the present invention. Therefore, they are laminates with excellent sliding properties in a way that maintains high transparency.

[0232] 6. Manufacturing and evaluation of molded parts

[0233] The above-mentioned polyester resin sheets or laminates are used to manufacture molded bodies.

[0234] Example 5-1

[0235] Using the polyester resin sheet (S-1) shown in Table 3, vacuum forming was performed using an NGF-0912 vacuum forming machine manufactured by Fuse Vacuum Co., Ltd. at a resin temperature of 90°C to obtain a tray-shaped molded body (hereinafter referred to as "Molded Body V-1") with a length of 10cm × width of 15cm × depth of 3cm (refer to Table 5).

[0236] For the obtained molded body V-1, the bottom surface of the tray shape was cut out, and the sliding and transparency were evaluated using the same evaluation criteria as the resin sheet. The results are recorded in Table 5.

[0237] Examples 5-2 to 5-19

[0238] Similar to Example 5-1, the molded bodies V-2 to V-19 shown in Table 5 were obtained using the polyester resin sheets (S-2 to S-19) shown in Table 3 (refer to Table 5).

[0239] Examples 5-20 to 5-38

[0240] Similar to Example 5-1, using the laminated sheets (U-1~U-19) shown in Table 4, the molded bodies V-20~V-38 shown in Table 6 were obtained (refer to Table 6).

[0241] Comparative Examples 5-1 to 5-4

[0242] Similar to Example 5-1, the molded bodies v-1 to v-4 shown in Table 7 were obtained using the polyester resin sheets (s-1 to s-4) shown in Table 3 (refer to Table 7).

[0243] Comparative Examples 5-5 to 5-8

[0244] Similar to Example 5-1, using the laminated sheets (u-1~u-4) shown in Table 4, the molded bodies v-5~v-8 shown in Table 7 were obtained (refer to Table 7).

[0245] [Table 5]

[0246]

[0247] [Table 6]

[0248]

[0249] [Table 7]

[0250]

[0251] As can be clearly seen from the results in Tables 5 to 7, Examples 5-1 to 5-38 are molded articles obtained from resin sheets and laminates made from resin compositions containing the resin sheet modifier of the present invention. Therefore, they are molded articles with excellent sliding properties while maintaining high transparency.

[0252] Industrial availability

[0253] The resin sheet modifier and masterbatch of the present invention are suitable as raw materials for manufacturing resin compositions that produce polyester resin molded articles with excellent transparency and smooth surfaces. Furthermore, the polyester resin molded articles obtained by the present invention are suitable for films, sheets, caps, containers, bags for storing items, etc. Because of their smooth surface, these molded articles do not stick together when overlapped, and can be easily removed one by one or sheet by sheet.

Claims

1. A modifier for resin sheets, characterized in that, It is a modifier used in the manufacture of resin sheets. It contains the following components (A) and (B), and the modifier contains calcium at a ratio of 0.1 to 3.0% by mass. Component (A): An ester compound containing pentaerythritol, a tri- to hexa-membered polyol, and a fatty acid having 8 to 22 carbon atoms. Component (B): A compound containing calcium.

2. The resin sheet modifier according to claim 1, wherein, The fatty acid used in the formation of component (A) has a hydrocarbon group having 12 to 18 carbon atoms.

3. The resin sheet modifier according to claim 1 or 2, wherein, The component (B) comprises at least one selected from talc and zeolite.

4. The resin sheet modifier according to claim 3, wherein, When the total content ratio of the components (A) and (B) is set to 100% by mass, the components (A) are contained at a ratio of 40 to 80% by mass and the components (B) are contained at a ratio of 20 to 60% by mass.

5. A polyester resin composition, characterized in that, It is a resin composition used to manufacture polyester resin sheets. It contains: polyester resin and a resin sheet modifier according to any one of claims 1 to 4.

6. The polyester resin composition according to claim 5, wherein, When the content of the polyester resin is set to 100 parts by weight, the resin sheet modifier is contained at a ratio of 0.1 to 45 parts by weight.

7. The polyester resin composition according to claim 6, wherein, When the content of the polyester resin is set to 100 parts by weight, the resin sheet modifier is contained in a ratio of 10 to 45 parts by weight.

8. A polyester resin sheet, characterized in that, Contains: polyester resin and a resin sheet modifier according to any one of claims 1 to 4.

9. The polyester resin sheet according to claim 8, wherein, When the content of the polyester resin is set to 100 parts by weight, the resin sheet modifier is contained at a ratio of 0.1 to 1.5 parts by weight.

10. A laminated sheet, characterized in that, It comprises: a resin layer formed from the polyester resin sheet as described in claim 8 or 9, and other resin layers.

11. A method for manufacturing a molded article, characterized in that, The polyester resin sheet according to claim 8 or 9 is used for molding.

12. A method for manufacturing a molded article, characterized in that, The laminated sheet of claim 10 is used for molding.

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