JP2015131407A - Polyester sheet, molding, and card - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polyester sheet excellent in heat resistance, transparency, fabricability, cold resistance, heat sealability and printability.SOLUTION: The polyester sheet has an A layer and a B layer, when polyester having no melting point is defined as polyester A, a polyester A-based layer is defined as the A layer, the polyester other than the polyester A is defined as polyester B, and a polyester B-based layer is defined as the B layer. The polyester sheet has 100-3,000 MPa storage modulus in the longitudinal direction and width direction thereof at 100°C and is a non-oriented sheet.

Description

  The present invention relates to a polyester sheet excellent in heat resistance, transparency, moldability, cold resistance, heat sealability, and printability.

  Saturated polyester, particularly polyester resin represented by polyethylene terephthalate, is widely used as a polymer for sheets and films, starting with fibers, but by utilizing its excellent chemical resistance and low gas permeability, carbonated beverages, juices, It has come to be applied to beverage bottles such as beer, cosmetic containers, and food trays. Among them, an amorphous polyester sheet called A-PET has attracted attention for its excellent recyclability, low pollution, and food safety, and its usage is rapidly increasing in recent years as a packaging material replacing vinyl chloride and polystyrene. This polyester sheet is used as a blister pack for food and medicine containers and miscellaneous goods by thermoforming, and also used as a clear case for putting cosmetics, electrical equipment, etc. taking advantage of its excellent transparency. However, since A-PET has a low glass transition temperature, it is inferior in heat resistance. For example, in the field of heat-resistant containers used in microwave ovens, the practical use range is greatly limited.

  As one means for solving such a problem, Patent Document 1 discloses a biaxially stretched polyester film mainly composed of a mixture of polytrimethylene terephthalate and a polyester resin.

  Patent Document 2 discloses a biaxially stretched polyester film for molding containing an isosorbide component.

  Moreover, in patent document 3, the polyester resin produced using 1, 4- cyclohexane dimethanol and isosorbide as a glycol component, and its manufacturing method are disclosed.

JP 2012-1589 A JP2012-126721A Special table 2013-504650 gazette

  However, although the invention described in Patent Document 1 has an oriented structure by the stretching process, the rigidity is high and the mechanical properties are excellent, but the thermoformability is inferior. Moreover, there is no description about the heat resistance improvement by the glass transition temperature improvement, and it is not suggested at all. The invention described in Patent Document 2 uses a crystalline polyester resin having a melting point in order to use it after drying at a high temperature in a post-processing printing step, although there is a description about heat resistance improvement. Since the axial stretching is performed, the rigidity becomes high and the mechanical properties are excellent, but there is a problem that the moldability is poor. In addition, the invention described in Patent Document 3 has a description of improving heat resistance and impact strength by using 1,4-cyclohexanedimethanol and isosorbide together as a glycol component, but transparency when used as a sheet, There is no description on improvement of thermoformability and no suggestion is made.

  Then, this invention is made | formed in view of the said problem, and it aims at providing the polyester sheet excellent in heat resistance, transparency, a moldability, cold resistance, heat-sealing property, and printability.

In order to solve the above problems, the present invention has the following configuration. That is:
(1) When the polyester having no melting point is polyester A, a layer mainly composed of polyester A is a layer A, and when a polyester other than the polyester A is polyester B, a layer mainly composed of polyester B When it is set as B layer, it has A layer and B layer,
The storage elastic modulus in the sheet longitudinal direction and the sheet width direction at 100 ° C. is from 100 MPa to 3,000 MPa,
A polyester sheet characterized by being non-oriented.
(2) The polyester sheet according to (1), which has a layered structure of A layer / B layer / A layer.
(3) The polyester sheet according to (1) or (2), wherein the layer thickness ratio of A layer / B layer / A layer is 1/3/1 to 1/18/1.
(4) In a total of 100 mol% of the glycol component of the polyester A, the ethylene glycol component is 1 mol% to 60 mol%, the isosorbide component is 5 mol% to 60 mol%, and the 1,4-cyclohexanedimethanol component is The polyester sheet according to any one of (1) to (3), comprising 30 mol% or more and 52 mol% or less.
(5) A total of 100 mol% of the glycol component of the polyester A contains 1 mol% to 90 mol% of ethylene glycol component and 5 mol% to 60 mol% of spiroglycol component, The polyester sheet according to any one of (3) to (3).
(6) In a total of 100 mol% of the glycol component of polyester A, 1,4-cyclohexanedimethanol component is 5 mol% or more and 90 mol% or less, 2,2,4,4-tetramethyl-1,3-cyclobutane The polyester sheet according to any one of (1) to (3), comprising a diol component in an amount of 5 mol% to 60 mol%.
(7) The polyester sheet according to any one of (1) to (6), wherein the polyester B is polyethylene terephthalate.
(8) The polyester sheet according to any one of (1) to (7), wherein the B layer contains 5% by mass or more and less than 50% by mass of the polyester A.
(9) The polyester sheet according to any one of (1) to (8), wherein the haze is 10% or less.
(10) The polyester sheet according to any one of (1) to (9), wherein the dynamic friction coefficient μd is 0.20 or more and 0.40 or less.
(11) A molded product obtained from the polyester sheet according to any one of (1) to (10).
(12) A card having a printed layer, wherein the printed layer is directly laminated with the A layer of the polyester sheet according to any one of (1) to (11).

  According to the present invention, it is possible to provide a polyester sheet excellent in heat resistance, transparency, moldability, cold resistance, heat sealability, and printability.

Schematic diagram showing the heat resistance evaluation method of the sheet

  In the present invention, when a polyester having no melting point is polyester A, a layer mainly composed of polyester A is a layer A, and when a polyester other than the polyester A is polyester B, a layer mainly composed of polyester B A polyester sheet characterized by having an A layer and a B layer, a storage elastic modulus in a sheet longitudinal direction and a sheet width direction at 100 ° C. of 100 MPa to 3000 MPa, and non-orientation. It is. The present invention will be described below.

  The polyester constituting the polyester sheet of the present invention is a general term for polymer compounds in which the main bond in the main chain is an ester bond. The polyester is usually obtained by polymerizing dicarboxylic acid and glycol, and the polyester after polymerization is composed of a dicarboxylic acid component and a glycol component.

  It is important that the polyester sheet of the present invention has the A layer when the polyester having no melting point is the polyester A and the layer mainly composed of the polyester A is the A layer. By having A layer, the polyester sheet of this invention has the advantage that it is excellent in cold resistance, heat-sealing property, and printability. A method for preventing the melting point of the polyester from being present is not particularly limited, and examples thereof include a method using polyester A1, polyester A2, or polyester A3 described later as polyester A.

  In addition, the layer which has polyester A as a main component means that it is a layer which contains the polyester A 50 to 100 mass% in all the components of 100 mass%.

  And considering the heat resistance of the sheet obtained, transparency, and the point that the extrusion temperature when producing the sheet can be lowered, the content of the polyester A in the A layer is 100% by mass of all the components of the A layer. The polyester A is preferably 60% by mass or more and 100% by mass or less, more preferably 75% by mass or more and 100% by mass or less, and further preferably 90% by mass or more and 100% by mass or less.

  It is important that the polyester sheet of the present invention has a B layer when the polyester other than the polyester A is a polyester B and a layer mainly composed of the polyester B is a B layer.

  The polyester B means a polyester other than the polyester A, that is, a polyester different from the polyester A. Here, the polyester different from the polyester A means a polyester in which at least one of the dicarboxylic acid component or the glycol component is different from the dicarboxylic acid component or the glycol component constituting the polyester A. That is, the dicarboxylic acid component and the glycol component are the same component, those having different contents and molecular weights, those having different types and contents of additives, and those having different intrinsic viscosities mean the same polyester. . As the polyester B, as long as it is a polyester other than the polyester A, both a polyester having no melting point and a polyester having a melting point are applicable. However, it is preferable to use a polyester having a melting point as the polyester B from the viewpoint of handleability and heat resistance.

  The layer mainly composed of polyester B means a layer containing 50% by mass or more and 100% by mass or less of polyester B in 100% by mass of all components of the layer.

  And considering the point that the preheating temperature before molding can be lowered when the resulting sheet is thermoformed, the content of the polyester B in the B layer is 100% by mass of all components of the B layer. Polyester B is preferably 60% by mass or more and 100% by mass or less, more preferably 75% by mass or more and 100% by mass or less, and further preferably 90% by mass or more and 100% by mass or less.

The polyester A is not particularly limited as long as it is a polyester having no melting point, but it is preferable to use the following A1), A2), or A3) from the viewpoint of heat sealability, printability, heat resistance, and moldability. .

A1) In a total of 100 mol% of the glycol component of polyester A, the ethylene glycol component is 1 mol% to 60 mol%, the isosorbide component is 5 mol% to 60 mol%, and the 1,4-cyclohexanedimethanol component is 30 mol. % To 52 mol% or less polyester. (Hereinafter referred to as polyester A1)
A2) A polyester containing 1 mol% to 90 mol% of an ethylene glycol component and 5 mol% to 60 mol% of a spiro glycol component in a total of 100 mol% of the glycol component of polyester A. (Hereinafter referred to as polyester A2)
A3) In 100 mol% of the total glycol component of polyester A, 1,4-cyclohexanedimethanol component is 5 mol% or more and 90 mol% or less, 2,2,4,4-tetramethyl-1,3-cyclobutanediol component Containing 5 mol% or more and 60 mol% or less. (Hereinafter referred to as polyester A3)

Therefore, polyester A1 will be described below.

  From the viewpoint of strength, transparency, and heat resistance, the content of the ethylene glycol component in the glycol component of polyester A1 is preferably 5 mol% or more and 50 mol% or less, more preferably 13 mol% or more and 45 mol% or less, Preferably they are 20 mol% or more and 40 mol% or less. The content of the isosorbide component in the glycol component of polyester A is preferably 10 mol% or more and 50 mol% or less, more preferably 15 mol% or more and 40 mol% or less, and further preferably 22 mol% or more and 35 mol% or less. is there.

  Isosorbide can be easily obtained from saccharides and starch that are biomass-derived components. For example, isosorbide can be obtained by hydrogenating D-glucose and performing a dehydration reaction. Since the polyester sheet of the present invention uses biomass-derived components, it can be an environmentally friendly sheet.

  Moreover, although ethylene glycol used for the polyester sheet of the present invention is not particularly limited, by using biomass-derived ethylene glycol, it can be made an environmentally friendly sheet.

  When the polyester A1 contains the ethylene glycol component and the isosorbide component in a specific range, sufficient heat resistance can be obtained even in the region of 100 ° C., which is the temperature at which the conventional formulation softens. When polyester A1 is used as the polyester A that is the main component of the A layer, the reason why the heat resistance of the sheet of the present invention is improved is that the isosorbide component has a relatively rigid structure. Furthermore, the isosorbide component is limited in free rotation in the polyester molecular chain. Therefore, it is considered that the heat resistance of the sheet of the present invention is improved as a result of the softening of the polyester molecular chain becoming difficult and the glass transition temperature of the polyester A1 increasing.

  The glycol component contained in the polyester A1 of the present invention includes 1,2-propanediol component, 1,3-propanediol component, 1,3 in addition to ethylene glycol component, isosorbide component, and 1,4-cyclohexanedimethanol component. -Butanediol component, 1,4-butanediol component, 1,5-pentanediol component, 1,6-hexanediol component, aliphatic dihydroxy compound components such as neopentyl glycol component, diethylene glycol component, polyethylene glycol component, polypropylene glycol Component, polyoxyalkylene glycol component such as polytetramethylene glycol component, alicyclic dihydroxy compound component such as spiroglycol component, aromatic dihydroxylation such as bisphenol A component and bisphenol S component Such things components.

  The glycol component other than the ethylene glycol component, isosorbide component, and 1,4-cyclohexanedimethanol component is preferably 40 mol% or less in a total of 100 mol% of the glycol components contained in the polyester A1, more preferably It is preferable that it is 10 mol% or less.

  Polyester A1 has an ethylene glycol component of 20 mol% to 40 mol%, an isosorbide component of 22 mol% to 35 mol%, and a 1,4-cyclohexanedimethanol component of 30 mol% in a total of 100 mol% of glycol components. By setting it as the aspect containing 52 mol% or less above, it becomes a more preferable aspect of the polyester sheet of this invention.

Hereinafter, polyester A2 will be described.

  From the viewpoint of strength, transparency, and heat resistance, the content of the ethylene glycol component in the glycol component of the polyester A2 is preferably 10 mol% or more and 90 mol% or less, more preferably 25 mol% or more and 85 mol% or less, Preferably they are 50 mol% or more and 80 mol% or less. The content of the spiroglycol component in the glycol component of polyester A2 is preferably 15 mol% or more and 60 mol% or less, more preferably 20 mol% or more and 55 mol% or less, and further preferably 30 mol% or more and 50 mol% or less. It is.

  Polyester A2 is a polyester according to the present invention, in which the ethylene glycol component is contained in an amount of 50 mol% to 80 mol% and the spiro glycol component is contained in an amount of 30 mol% to 50 mol% in a total of 100 mol% of the glycol component. This is a more preferable embodiment of the sheet.

  The glycol component contained in the polyester A2 of the present invention includes, for example, a trimethylene glycol component, a 2-methylpropanediol component, a 1,4-butanediol component, and a 1,5-pentanediol in addition to the ethylene glycol component and the spiroglycol component. Components, aliphatic diols such as 1,6-hexanediol component, diethylene glycol component, triethylene glycol component, propylene glycol component and neopentyl glycol component; polyether compounds such as polyethylene glycol component, polypropylene glycol component and polybutylene glycol component Trihydric or higher polyhydric alcohols such as glycerin component, trimethylolpropane component, pentaerythritol component; 1,3-cyclohexanedimethanol component, 1,4-cyclohexanedi Tanol component, 1,2-decahydronaphthalene diethanol component, 1,3-decahydro naphthalene diethanol component, 1,4-decahydro naphthalene diethanol component, 1,5-decahydro naphthalene diethanol component, 1,6 -Decahydronaphthalene diethanol component, 2,7-decahydro naphthalene diethanol component, tetralin dimethanol component, norbornane dimethanol component, tricyclodecane dimethanol component, 5-methylol-5-ethyl-2- (1,1 -Dimethyl-2-hydroxyethyl) -1,3-dioxane, alicyclic diols such as pentacyclododecane dimethanol component; 4,4 '-(1-methylethylidene) bisphenol component, methylene bisphenol (bisphenol F) component 4,4'-cyclohexylidene Alkylene oxide adducts of bisphenols such as sphenol (bisphenol Z) component, 4,4'-sulfonylbisphenol (bisphenol S) component; hydroquinone component, resorcin component, 4,4'-dihydroxybiphenyl component, 4,4'- Examples thereof include alkylene oxide adducts of aromatic dihydroxy compounds such as dihydroxydiphenyl ether components and 4,4′-dihydroxydiphenylbenzophenone components.

  Such a glycol component other than the ethylene glycol component and the spiro glycol component is preferably 40 mol% or less, more preferably 10 mol% or less, in a total of 100 mol% of the glycol components contained in the polyester A2. preferable.

Hereinafter, polyester A3 will be described.

  From the viewpoint of strength, transparency, and heat resistance, the content of 1,4-cyclohexanedimethanol component in the glycol component of polyester A3 is preferably 20 mol% or more and 80 mol% or less, more preferably 30 mol% or more and 75. The mol% or less, more preferably 40 mol% or more and 70 mol% or less. The content of 2,2,4,4-tetramethyl-1,3-cyclobutanediol component in the glycol component of polyester A2 is preferably 10 mol% or more and 55 mol% or less, more preferably 20 mol% or more and 50 mol%. The mol% or less, more preferably 25 mol% or more and 45 mol% or less.

Polyester A3 contains 1,4-cyclohexanedimethanol component at 40 mol% or more and 70 mol% or less, 2,2,4,4-tetramethyl-1,3-cyclobutanediol component at 100 mol% in total of glycol components. By setting it as the aspect containing 25 mol% or more and 45 mol% or less, it becomes a more preferable aspect of the polyester sheet of this invention.

The glycol component contained in the polyester A3 of the present invention includes a 1,2-propanediol component in addition to the 1,4-cyclohexanedimethanol component and the 2,2,4,4-tetramethyl-1,3-cyclobutanediol component. 1,3-propanediol component, 1,3-butanediol component, 1,4-butanediol component, 1,5-pentanediol component, 1,6-hexanediol component, aliphatic dihydroxy such as neopentylglycol component Compound component, diethylene glycol component, polyethylene glycol component, polypropylene glycol component, polyoxyalkylene glycol component such as polytetramethylene glycol component, alicyclic dihydroxy compound component such as spiro glycol component, bisphenol A component, bisphenol S component, etc. And aromatic dihydroxy compound components.

  The glycol component other than the 1,4-cyclohexanedimethanol component and 2,2,4,4-tetramethyl-1,3-cyclobutanediol component is 100 mol% in total of the glycol components contained in the polyester A3. It is preferably 40 mol% or less, more preferably 10 mol% or less.

The dicarboxylic acid component used in the polyester A of the present invention is not particularly limited, but the terephthalic acid component, isophthalic acid component, phthalic acid component, 2,6-naphthalenedicarboxylic acid component, diphenyldicarboxylic acid component, diphenylsulfone dicarboxylic acid component , Aromatic dicarboxylic acid components such as diphenoxyethane dicarboxylic acid component, 5-sodium sulfone dicarboxylic acid component, oxalic acid component, succinic acid component, adipic acid component, sebacic acid component, dimer acid component, maleic acid component, fumaric acid component Examples thereof include an aliphatic dicarboxylic acid component such as an alicyclic dicarboxylic acid component such as a 1,4-cyclohexanedicarboxylic acid component, and a dicarboxylic acid compound component such as an oxycarboxylic acid component such as a paraoxybenzoic acid component. Examples of the dicarboxylic acid ester derivative component include esterified products of the above dicarboxylic acid compounds, such as dimethyl terephthalate component, diethyl terephthalate component, 2-hydroxyethyl methyl terephthalate ester component, dimethyl 2,6-naphthalenedicarboxylate component, isophthalate. Examples thereof include a dimethyl acid component, a dimethyl adipate component, a diethyl maleate component, and a dimer acid dimethyl component. Among these, as the dicarboxylic acid component of polyester A, a terephthalic acid component is preferably used from the viewpoints of moldability and handleability. In the total 100 mol% of the dicarboxylic acid component of polyester A, the terephthalic acid component is preferably 80 mol% or more and 100 mol% or less, more preferably 90 mol% or more and 100 mol% or less, and still more preferably 95 mol%. More than 100 mol%.

  Furthermore, the glass transition temperature of the polyester A of the present invention is preferably 85 ° C or higher and 150 ° C or lower, more preferably 90 ° C or higher and 150 ° C or lower, and further preferably 100 ° C or higher and 150 ° C or lower. .

  In order to set the glass transition temperature of the polyester A to 85 ° C. or more and 150 ° C., it is important to set the above-described preferable amounts for the constitution and content ratio of each component in the glycol component and the dicarboxylic acid component. Such a polyester A is a commercially available raw material, for example, as a trade name, “ECOZEN” (manufactured by SK Chemical Co., Ltd.) as polyester A1, “ALTERSTER” (manufactured by Mitsubishi Gas Chemical Co., Ltd.), polyester as polyester A2. As A3, “TRITAN” (manufactured by EASTMAN Chemical Co., Ltd.) can be preferably used.

  The polyester B is not particularly limited as long as it is a polyester other than the polyester A, but is preferably polyethylene terephthalate from the viewpoint of ease of handling and preheating temperature during thermoforming. The glass transition temperature of polyethylene terephthalate is more preferably less than 85 ° C.

The A layer of the polyester sheet of the present invention may contain less than 50% by mass of polyester B in addition to polyester A in 100% by mass of all components of the A layer. In view of heat resistance, transparency, and the point that the extrusion temperature at the time of producing the sheet can be lowered, it is preferable that the A layer does not contain the polyester B. In view of the fact that the preheating temperature during post-processing thermoforming can be lowered, the A layer preferably contains polyester B in an amount of more than 0% by mass and less than 50% by mass.

  The B layer of the polyester sheet of the present invention may contain less than 50% by mass of polyester A in 100% by mass of all components of the B layer. When emphasizing that the preheating temperature before molding can be lowered when thermoforming, the B layer preferably does not contain polyester A. On the other hand, if importance is attached to heat resistance, transparency, and the point that the extrusion temperature at the time of producing the sheet can be lowered, the B layer preferably contains the polyester A, and when the B layer contains the polyester A, The B layer preferably contains 5% by mass or more and less than 50% by mass of the polyester A in 100% by mass of all components of the B layer.

  As a method of including polyester A in layer B, there is a method of adding a recovered raw material containing polyester A in addition to a method of adding unused polyester A at the time of producing a polyester sheet. The term “unused polyester” as used herein means a polyester that has never been used for sheet film formation. The recovered material is a flake obtained by crushing a sheet ear or scrap sheet generated in the sheet forming process, a product re-pelletized using an extruder, or the polyester of the present invention. Flakes obtained by pulverizing scraps (molded scraps, scrap scraps, etc.) generated during the production of compacts made of sheets, and re-pelletized products using an extruder Means.

  Considering the transparency of the polyester sheet when the polyester A is contained in the B layer, it is preferable to use polyethylene terephthalate as the polyester B of the B layer. That is, since polyester A and polyethylene terephthalate have good compatibility, even if a recovered material containing polyester A is added to the B layer to obtain the polyester sheet of the present invention, the increase in haze can be suppressed and transparency is improved. This is because a good sheet can be obtained. That is, by using polyethylene terephthalate as the polyester B of the B layer and partially including the polyester A in the B layer, the haze of the polyester sheet of the present invention can be reduced to 10% or less. In addition, from the viewpoint of further compatibility between polyester A and polyethylene terephthalate, it is preferable to use polyester A1 as polyester A, which suppresses an increase in haze of the sheet and further improves transparency.

  The polyester sheet of the present invention can contain a collected raw material in the A layer and / or the B layer as long as the performance of the present invention is not impaired for the purpose of reducing the environmental load. The content of the recovered raw material is 5% by mass or more and less than 50% by mass, more preferably 10% by mass or more and 40% by mass or less, and most preferably 15% by mass or more, in 100% by mass of all components of the A layer and / or B layer. 35% by mass or less.

Further, when the polyester sheet of the present invention is an embodiment of a layered structure of A layer / B layer / A layer, it is more preferable that the recovered material is contained in the B layer of the intermediate layer from the viewpoint of heat resistance and transparency. . Since the recovered raw materials can be used positively, the environmental load can be reduced and an environmentally friendly sheet can be obtained.

The polyethylene terephthalate used for the polyester B of the present invention can be produced by a known method using a dicarboxylic acid component derived from terephthalic acid or an ester derivative thereof and a glycol component derived from ethylene glycol or an ester derivative thereof.

When producing the polyethylene terephthalate used for the polyester B of the present invention, a small amount of dicarboxylic acid other than terephthalic acid may be used as the dicarboxylic acid component in addition to terephthalic acid.
Examples of such dicarboxylic acids include isophthalic acid components, phthalic acid components, 2,6-naphthalenedicarboxylic acid components, diphenyldicarboxylic acid components, diphenylsulfone dicarboxylic acid components, diphenoxyethane dicarboxylic acid components, and 5-sodium sulfone dicarboxylic acid. Aromatic dicarboxylic acid components such as components, oxalic acid components, succinic acid components, adipic acid components, sebacic acid components, dimer acid components, maleic acid components, fumaric acid components and other aliphatic dicarboxylic acid components, 1,4-cyclohexanedicarboxylic acid Examples thereof include dicarboxylic acid compound components such as alicyclic dicarboxylic acid components such as acid components and oxycarboxylic acid components such as paraoxybenzoic acid components. Examples of the dicarboxylic acid ester derivative component include esterified products of the above dicarboxylic acid compounds, such as dimethyl terephthalate component, diethyl terephthalate component, 2-hydroxyethyl methyl terephthalate ester component, dimethyl 2,6-naphthalenedicarboxylate component, isophthalate. Examples thereof include a dimethyl acid component, a dimethyl adipate component, a diethyl maleate component, and a dimer acid dimethyl component. Such a dicarboxylic acid component other than the terephthalic acid component is preferably 10 mol% or less when the total of the dicarboxylic acid components contained in polyethylene terephthalate is 100 mol%.

  When producing the polyethylene terephthalate used in the polyester B of the present invention, as a glycol component, in addition to an ethylene glycol component, a glycol component other than an ethylene glycol component (however, an isosorbide component, a spiroglycol component, 2, 2, 4, A small amount of 4-tetramethyl-1,3-cyclobutanediol component may be used. Examples of such glycol components include 1,2-propanediol component, 1,3-propanediol component, 1,3-butanediol component, 1,4-butanediol component, 1,5-pentanediol component, 1 1,6-hexanediol component, aliphatic dihydroxy compound component such as neopentyl glycol component, diethylene glycol component, polyethylene glycol component, polypropylene glycol component, polyoxyalkylene glycol component such as polytetramethylene glycol component, 1,4-cyclohexanedimethanol Examples thereof include aromatic dihydroxy compound components such as components, bisphenol A components, and bisphenol S components. Such a glycol component other than the ethylene glycol component is preferably 40 mol% or less, more preferably 10 mol% or less, in a total of 100 mol% of the glycol components contained in polyethylene terephthalate.

  As the polyethylene terephthalate used in the polyester B of the present invention, various commercially available raw materials can be preferably used. For example, trade name: “Novapex” (manufactured by Mitsubishi Chemical Corporation), trade name: “Byron” (Toyobo ( Product name: "Belpet" (manufactured by Bell Polyester Co., Ltd.), product name: "Tex Pet" (manufactured by Daewoo Japan Co., Ltd.), product name: "Easter PETG · 6763" (Corporation) Eastman Chemical Co., Ltd.).

It is important that the polyester sheet of the present invention has a laminated structure having an A layer and a B layer. That is, examples of the layer configuration of the present invention include, for example, A layer / B layer, A layer / B layer / A layer, and the like. And as this invention, from the point which can lower the extrusion temperature at the time of producing heat resistance, transparency, and a sheet | seat, and can perform the preheating temperature before shaping | molding at the time of thermoforming, A layer / The configuration of B layer / A layer is particularly preferable.

  That is, the polyester sheet of the present invention has an A layer in the outermost layer, which has excellent heat resistance and transparency, and can lower the extrusion temperature during sheet production, and lowers the preheating temperature before molding during thermoforming. By making it the structure which has B layer which can be formed in an inner layer, it can be set as the sheet | seat which is excellent in heat resistance and transparency, can lower the extrusion temperature at the time of sheet preparation, and can reduce the preheating temperature before shaping | molding.

  In consideration of the transparency and molding processability of the sheet, the polyester sheet of the present invention having a layered structure of A layer / B layer / A layer is between A layer and B layer, between A layer and A layer, B It is particularly preferred that the layer and the B layer have an aspect in which they are directly laminated without any other layers. That is, the polyester sheet of the present invention preferably has no adhesive layer or the like. Therefore, the polyester sheet of the present invention having the A layer and the B layer is preferably produced by coextrusion. From the viewpoint of interlayer adhesion, it is more preferable to use polyester A1 for polyester A and polyethylene terephthalate for polyester B. A method for measuring the interlayer adhesion will be described later.

  When the polyester sheet of the present invention is thermoformed, the preheating temperature before molding is preferably a low temperature from the viewpoints of energy reduction and molding cycle improvement, and the sheet temperature is preferably 90 ° C. or higher and 150 ° C. or lower. 90 ° C. or more and 140 ° C. or less is more preferable, and 90 ° C. or more and 130 ° C. or less is more preferable. The method for satisfying the preferable range of the preheating temperature before molding is not particularly limited. For example, as described above, polyethylene terephthalate having a glass transition temperature of less than 85 ° C. can be used as polyester B. It is preferable to use polyethylene terephthalate having a glass transition temperature of less than 85 ° C. for the polyester B of the present invention because the preheating temperature before molding when the sheet is thermoformed can be lowered and the molding cycle is improved.

It is important that the polyester sheet of the present invention is non-oriented from the viewpoint that good moldability can be imparted. Here, whether or not the polyester sheet is non-oriented can be determined by the degree of plane orientation: ΔP. That is, when the degree of plane orientation: ΔP is 0 or more and 0.008 or less, it means that the polyester sheet is non-oriented. The method for non-orienting is not particularly limited as long as the effects of the present invention are not impaired, but it is preferable to use a T die casting method in which a resin is extruded using a T die. A method for measuring the degree of plane orientation: ΔP will be described later.

In the polyester sheet of the present invention, it is important that the storage elastic modulus in the sheet longitudinal direction and the sheet width direction at 100 ° C. is 100 MPa or more and 3,000 MPa or less, respectively. If the storage elastic modulus in the sheet longitudinal direction and the sheet width direction at 100 ° C. is less than 100 MPa, the heat resistance of the polyester sheet of the present invention and the heat resistance of the molded body produced using the sheet may be lowered. . Conversely, when the storage elastic modulus in the sheet longitudinal direction and the sheet width direction at 100 ° C. exceeds 3,000 MPa, the heat resistance is excellent, but the moldability may be deteriorated.

  That is, from the viewpoint of heat resistance, the storage elastic modulus in the sheet longitudinal direction and the sheet width direction at 100 ° C. is preferably 100 MPa or more, more preferably 200 MPa or more, further preferably 400 MPa or more, and 600 MPa or more. Most preferred. In order not to lower the moldability, the storage elastic modulus in the sheet longitudinal direction and the sheet width direction at 100 ° C. is preferably 3,000 MPa or less, more preferably 2,600 MPa or less, and 2,200 MPa. The following is most preferable.

  In the polyester sheet of the present invention, the method for setting the storage elastic modulus at 100 ° C. to 100 MPa or more and 3,000 MPa or less is not particularly limited. For example, it is a non-oriented sheet having an A layer and a B layer. A polyester having a glass transition temperature of 100 ° C. or higher and 150 ° C. or lower and having no melting point is used as the main polyester A, and the polyester A is contained in 60% by mass or more and 100% by mass or less in 100% by mass of all components of the A layer. A method is mentioned.

Although there is no restriction | limiting in particular in the thickness of the polyester sheet of this invention, It is preferable that they are 50 micrometers or more and 2,000 micrometers or less, More preferably, it is 100-1,500 micrometers, More preferably, it is 200-750 micrometers.

  In addition, the lamination thickness ratio of the polyester sheet of the laminated structure of the present invention is not particularly limited, but in the case of an aspect of the laminated structure of A layer / B layer / A layer, heat resistance, transparency, and moldability are considered. Then, the lamination thickness ratio is preferably 1/3/1 to 1/18/1, more preferably 1/4/1 to 1/17/1, still more preferably 1/5/1 to 1/16. / 1, most preferably 1/6/1 to 1/15/1.

The polyester A used in the present invention preferably has an intrinsic viscosity of 0.40 dl / g or more, more preferably 0.50 dl / g or more, particularly preferably 0.55 dl from the viewpoint of moldability and film-forming stability. / G or more. In addition, when a filter for removing foreign substances is provided, the upper limit of the intrinsic viscosity is preferably 1.0 dl / g from the viewpoint of ejection stability during extrusion of the molten resin.

The polyester sheet of the present invention can contain various additives as long as the object of the present invention is not impaired.

  Examples of additives that can be contained in the polyester sheet of the present invention include fillers (glass fiber, carbon fiber, metal fiber, natural fiber, organic fiber, glass flake, glass bead, ceramic fiber, ceramic bead, asbestos, wallastite. , Talc, clay, mica, sericite, zeolite, bentonite, montmorillonite, synthetic mica, dolomite, kaolin, fine silicic acid, feldspar powder, potassium titanate, shirasu balloon, calcium carbonate, magnesium carbonate, barium sulfate, calcium oxide, oxidation Aluminum, titanium oxide, aluminum silicate, silicon oxide, gypsum, novaculite, dosonite or clay, ultraviolet absorbers (resorcinol, salicylate, benzotriazole, benzophenone, etc.), heat stabilizers (hinders) Dophenol, hydroquinone, phosphites and substituted products thereof), lubricant, mold release agent (such as montanic acid and its salt, its ester, its half ester, stearyl alcohol, stearamide and polyethylene wax), dye (such as nigrosine) And pigments (including cadmium sulfide and phthalocyanine), anti-coloring agents (phosphite, hypophosphite, etc.), flame retardants (red phosphorus, phosphate esters, brominated polystyrene, brominated polyphenylene ether, bromine) Polycarbonate, magnesium hydroxide, melamine and cyanuric acid or salts thereof, silicon compounds, etc.), conductive agents or colorants (carbon black, etc.), slidability improvers (graphite, fluororesins, etc.), antistatic agents, etc. Including one or more It can be.

  Among them, in order to impart slip properties to the polyester sheet of the present invention, the polyester sheet of the present invention preferably contains inorganic particles such as talc, aluminum oxide, aluminum silicate, and silicon oxide.

  The average particle diameter of the inorganic particles is not particularly limited as long as the effect of the polyester sheet of the present invention is not impaired. However, in consideration of the slipperiness and winding property of the sheet, it is preferably 0.1 μm or more and 3 μm or less, more preferably 0.5 μm. It is 2 μm or less. The “average particle diameter of the inorganic particles” can be measured using a Cole counter (for example, manufactured by Nippon Chemical Machinery Co., Ltd.) and can be obtained as the average particle diameter when the cumulative mass fraction becomes 50%.

  The content of the inorganic particles is not particularly limited as long as the effect of the polyester sheet of the present invention is not impaired, but considering the slipperiness and winding property of the sheet, in each layer constituting the polyester sheet of the present invention, all components of each layer In 100 mass%, 0.05 mass% or more and 1.0 mass% or less are preferable, and 0.1 mass% or more and 0.7 mass% or less are more preferable.

  In addition, even if it uses in combination of multiple types of inorganic particle | grains, if an average particle diameter and content are in the said range, it can use preferably.

  As a method for containing the inorganic particles, a known method can be adopted, and it is not particularly limited. For example, it can be added at the time of polymerization, mixed using a blender after polymerization, or a high-concentration master batch of inorganic particles prepared in advance and diluted.

  Moreover, the polyester sheet of this invention can add 1 type (s) or 2 or more types of crystal nucleating agents in the range which does not impair the objective of this invention as needed. Examples of the crystal nucleating agent suitably used for the polyester sheet of the present invention include inorganic nucleating agents such as talc, organic bisuluric acid amide, ethylene bis-12-dihydroxystearic acid amide, trimesic acid tricyclohexyl amide and the like. Examples thereof include amide compounds, pigment nucleating agents such as copper phthalocyanine and pigment yellow 110, organic carboxylic acid metal salts, and zinc phenylphosphonate.

The dynamic friction coefficient μd of the polyester sheet of the present invention is preferably 0.20 or more and 0.40 or less. If μd is less than 0.20, winding deviation and meandering may occur. On the other hand, if μd is larger than 0.40, sheets with different surfaces laminated in order during molding may not slide, and a feeding failure may occur, resulting in a reduction in processing efficiency.

  The method for satisfying the preferred range of the above-mentioned dynamic friction coefficient in the polyester sheet of the present invention is not particularly limited. For example, as described above, the method for containing inorganic particles in the sheet, particularly the outermost layer containing inorganic particles. The method etc. can be mentioned.

The polyester sheet of the present invention preferably has a haze of 0.3% to 10%. If the haze is in the above range, a molded article using such a sheet can be preferably used as a sheet or container having high design properties such as excellent visibility of contents and good appearance as a product. . If the haze is less than 0.3%, the sheet is easily scratched, and the appearance may deteriorate when the sheet is used as a container. If the haze is greater than 10%, the transparency is insufficient. Yes, it may not be preferable for practical use. The haze of the polyester sheet of the present invention is more preferably 0.3% or more and 8% or less, further preferably 0.3% or more and 6% or less, and most preferably 0.3% or more and 5% or less.

In order to impart design properties to the polyester sheet of the present invention, a printing layer can be formed on the surface layer of the polyester sheet depending on the purpose. The printing layer is preferably laminated directly with the A layer from the viewpoint of the adhesion between the ink and the sheet. In addition, since the polyester which becomes the main body of A layer is polyester A without melting | fusing point, it can adhere | attach the printing layer and the polyester sheet of this invention more firmly. By doing in this way, the card | curd excellent in adhesiveness can be obtained from the polyester sheet of this invention. In other words, the card of the present invention has a print layer, and the print layer is directly laminated with the A layer of the polyester sheet.

  The print layer is formed by printing a desired print pattern made up of characters, figures, symbols, patterns, etc. From the viewpoint of improving the adhesion between the ink used in the printing layer and the surface layer of the sheet of the present invention, the surface layer is subjected to corona treatment under air, nitrogen, carbon dioxide atmosphere, plasma treatment, ozone treatment, flame treatment, etc. The pretreatment may be performed. The printing can be formed by various known printing methods such as gravure printing, offset printing, letterpress printing, screen printing, transfer printing, flexographic printing, and ink jet printing. The ink used for printing may be either water-based ink or non-water-based ink such as solvent-based ink. Although there is no restriction | limiting in particular in the thickness of a printing layer, it is preferable that it is 0.1 micrometer-10 micrometers from a viewpoint of printing appearance, More preferably, they are 0.2 micrometer-3 micrometers, More preferably, they are 0.4 micrometer-1 micrometer.

Hereinafter, as an example of the method for producing the polyester sheet of the present invention, a method for producing the polyester sheet of the present invention in which the A layer and the B layer are directly laminated in this order will be described.

  Resin, which is the raw material of layer A and layer B, is melt-extruded into each extruder, and after removing foreign matter with a wire mesh and adjusting the flow rate with a gear pump, supply them to a multi-manifold base or a feed block installed on the top of the base. To do. It is important that the multi-manifold base or the feed block is provided with a desired number of channels having a desired shape in accordance with a required sheet layer configuration. The molten resin extruded from each extruder is merged by the multi-manifold die or the feed block as described above, and coextruded into a sheet form from the die. The sheet is brought into close contact with the casting drum by an air knife or a method such as electrostatic application, and is cooled and solidified to form an unstretched sheet, or is discharged between a pair of casting drums and a polishing roll to be in close contact with the casting drum. It can be manufactured by a method using a touch roll method in which it is cooled and solidified to produce an unstretched sheet.

  Here, it is preferable to use a wire mesh mesh of 50 to 400 mesh in order to prevent surface roughness due to mixing of foreign matters such as gels and thermally deteriorated materials.

  Since the polyester sheet of the present invention is excellent in moldability, it can be suitably used as a molded article. That is, the molded product of the present invention is a molded product obtained from the polyester sheet of the present invention. Here, the molded product means a product obtained by subjecting a sheet to some processing including punching, cutting, ruled line processing, bending processing, and thermoforming processing.

  As molding methods for obtaining a molded body using the polyester sheet of the present invention, various molding methods such as vacuum molding, vacuum pressure molding, plug assist molding, straight molding, free drawing molding, plug and ring molding, skeleton molding, etc. Can be applied. The sheet preheating method in various molding methods includes the indirect heating method and the hot plate direct heating method. The indirect heating method is a method in which the sheet is preheated by a heating device installed at a position away from the sheet, and the hot plate is directly heated. The system is a system in which the sheet is preheated by contacting the sheet and the hot plate, but the polyester sheet of the present invention is a vacuum forming process of an indirect heating system, a vacuum / pressure forming process, or a vacuum / pressure forming process of a hot plate direct heating system. It can be preferably used for processing.

  The polyester sheet of the present invention is excellent in heat resistance and moldability, and in addition, has reduced environmental impact, so packaging containers, various electronic and electrical equipment, OA equipment, vehicle parts, machine parts, and other agriculture It is useful for various uses such as materials, fishery materials, transport containers, playground equipment and sundries. Among these, it can be preferably used for applications requiring heat resistance and moldability, such as food molded containers and beverage cup lids. More preferably, since polyester A, which does not have a melting point, is used, it has excellent cold resistance, heat sealability, and printability, so that cold resistance is particularly required for refrigerated / frozen food packaging applications, frozen dessert food packaging applications, and heat seals. For example, it can be suitably used for a clear case in which performance is particularly required, a card application in which clear files and printability are particularly required, and a display case. The card here means an ID card, a membership card, a cash card, a credit card, a commuter pass, a pass ticket, and the like. The display case here means a backlit advertisement display board, a display case such as a cigarette, a display can such as a beverage can.

[Methods for measuring physical properties and methods for evaluating effects]
The physical property measuring method and the effect evaluating method in the present invention are as follows.

1. A sample was cut out from the center portion in the stack thickness ratio sheet width direction. Using an ultramicrotome, an ultrathin section was sampled at −100 ° C. using an ultramicrotome as an observation surface by an embedding method using an epoxy resin. A sheet cross-sectional photograph of the thin film section of the sheet cross section was taken at a magnification of 1,000 times (magnification can be adjusted as appropriate) using a scanning electron microscope, and the thickness of each layer was measured. The observation location was changed, measurements were taken at 10 locations, the average value of the obtained values was taken as the thickness (μm) of each layer, and the lamination thickness ratio of the sheets was determined from the thickness of each layer.

2. Thickness dial gauge thickness gauge (JIS B7503 (1997), UPAIGHT DIAL GAUGE made by PEACOCK (0.001 × 2 mm), No. 25, measuring element 5 mmφ flat type) at intervals of 10 cm in the longitudinal direction and the width direction of the sheet 10 points at a time, and the average value was taken as the thickness (μm) of the sheet.

3. Transparency: Haze (%)
The haze value of the sheet was measured using a haze meter HGM-2DP type (manufactured by Suga Test Instruments Co., Ltd.). A sample for measuring the haze value was cut out from the center of the sheet. The measurement was performed 5 times per sample, and the average value (average haze) of the 5 measurements was taken.

4). Impact resistance: Impact (N · m / mm)
Using a film impact tester (manufactured by Toyo Seiki Seisakusho), the impact of the sheet was measured using a hemispherical impact head having a diameter of 1/2 inch in an atmosphere of a temperature of 23 ° C. and a humidity of 65% RH. A sheet sample was prepared in a size of 100 mm × 100 mm, and the measurement was performed 5 times per sample. Further, the impact value for each time was divided by the thickness of the measurement sample, and the impact per unit thickness was obtained from the average value of five measurements. The sample thickness was measured with a digital micrometer.

5. Storage elastic modulus A sheet is cut into a rectangle of 60 mm (longitudinal direction) × width 5 mm (width direction), 60 mm (width direction) × width 5 mm (longitudinal direction), and each sample is used for measurement in the longitudinal direction, sample for width direction measurement, and did. Using a dynamic viscoelasticity measuring apparatus (Seiko Instruments, DMS6100), storage elastic modulus (E ′) at 100 ° C. in the longitudinal direction and the width direction was determined under the following conditions.

Frequency: 10 Hz, test length: 20 mm, minimum load: about 100 mN, amplitude: 10 μm,
Measurement temperature range: −50 ° C. to 200 ° C., heating rate: 5 ° C./min.

6). DSC measurement (melting point, glass transition temperature)
The melting point and glass transition temperature of the resin were subjected to DSC measurement and analysis according to JIS K7121-1987 and JIS K7122-1987, using a differential scanning calorimeter (Seiko Denshi Kogyo's RDC220). The measurement conditions are 5 mg of the sample, a nitrogen atmosphere, a temperature increase rate of 20 ° C./min, and a temperature decrease rate of 20 ° C./min.

  The melting point of the resin was the temperature at the top of the endothermic peak. Also, the glass transition temperature is obtained by reading the specific heat change based on the transition from the glass state to the rubber state, and the straight line equidistant from the extended straight line of each baseline in the vertical axis (axis indicating heat flow) It was set as the temperature of the intermediate point of the point where the curve of the step-like change part intersects. The measurement was performed under the following conditions.

  Condition: In DSC measurement, the temperature was increased from 30 ° C. to 300 ° C. at a temperature increase rate of 20 ° C./min in the first heating step, then cooled to 30 ° C. at a temperature decrease rate of 20 ° C./min. When the temperature is increased from 30 ° C. to 300 ° C. at a temperature increase rate of 20 ° C./min in the heating step, the melting point and glass transition temperature are measured.

7). Intrinsic viscosity Intrinsic viscosity was measured by dissolving a resin in ortho-chlorophenol at 150 ° C. at a concentration of 0.12% by mass, and using a Ubbelohde viscometer in a constant temperature bath at 35 ° C.

8). Plane orientation degree: Δ P (discrimination of orientation state)
As described in “Materials” Vol. 43, No. 495, pp. 1520-1524, Dec. 1994, using an automatic birefringence meter KOBRA-21ADH manufactured by Oji Scientific Instruments Co., Ltd. According to the conditions, birefringences Δ x, Δ y, Δ z in the three principal axis directions of the sheet-like sample are obtained, and Δ x = γ−β, Δ y = γ−α, Δ z = α−β (γ ≧ β, α The degree of plane orientation: Δ P was determined from the following equation based on the relationship of the refractive index in the thickness direction of the sheet.
ΔP = {(γ + β) / 2} −α
= (Δy−Δz) / 2
Discrimination / orientation of orientation state: degree of plane orientation: ΔP is greater than 0.008.
Non-orientation: degree of plane orientation: ΔP is 0 or more and 0.008 or less.

9. Heat resistance of sheet The heat resistance of the sheet was measured as shown in FIG. That is, the sheet was cut out to 150 mm (width direction) × 50 mm (longitudinal direction) to obtain a sheet sample for heat resistance measurement. Further, a line was drawn with a magic so as to be divided into three in the width direction, and the middle area was defined as the center of the sheet. A double-sided tape was affixed on the struts (50 mm (horizontal width) × 50 mm (vertical width)), and the sheet was affixed to the struts so that the region in the center of the sheet and the struts overlapped. The column with the sheet attached was placed in an oven set at 100 ° C. and stored for 30 minutes. Thereafter, the difference between the height of the column and the height of both ends of the sheet was read, and the amount of deflection was obtained as shown in the following formula.

The height of the right end is the height from the ground to the center of the right end in the longitudinal direction, the height of the left end is the height from the ground to the center of the left end of the longitudinal direction, and the height of both ends of the seat is the height of the right end. It was set as the average value of the height of the left end. The amount of deflection before and after storage in an oven was compared to evaluate the heat resistance of the sheet. When the evaluation of heat resistance is 2 or more in a five-step evaluation, it can be used practically without problems.
Deflection amount = height of column-height of both ends of sheet Heat resistance of sheet 5: Deflection amount before and after storage in oven is less than 2 mm 4: Deflection amount before and after storage in oven is 2 mm or more and less than 4 mm 3: In oven Deflection amount before and after storage is 4 mm or more and less than 7 mm 2: Deflection amount before and after storage in oven is 7 mm or more and less than 10 mm 1: Deflection amount before and after storage in oven is 10 mm or more

10. Molded body preparation, heat resistance evaluation of molded body, moldability evaluation 320 mm (longitudinal direction) x 460 mm (width direction) single wafer sample, opening 150 mm x 210 mm, bottom part 105 mm x 196 mm, height 50 mm tray Using a compact vacuum forming machine forming 300X type manufactured by Seiko Sangyo Co., Ltd. equipped with a mold, preheating and molding were performed under temperature conditions such that the sheet temperature during molding was in the range of 115 ° C to 180 ° C.

  The obtained molded body was placed in a hot air oven set at 100 ° C. for 30 minutes with the bottom surface of the molded body facing up, and the heat resistance of the molded body was evaluated in five stages by the height maintenance rate. The height of the molded body was determined to be the height of the bottom surface when the molded body was observed from the side, with the bottom surface of the molded body facing upward. When the heat resistance level is 2 or more in a five-step evaluation, it can be used practically without problems.

Heat resistance of molded article 5: 98% or more and 100% or less of original height (50 mm) 4: 96% or more and less than 98% of original height (50 mm) 3: 93% or more of original height (50 mm) Less than 96% 2: 90% or more of original height (50 mm) and less than 93% 1: Less than 90% of original height (50 mm)

Sheet moldability 5: The sheet is molded so as to sufficiently follow the bottom surface of the tray-shaped molded body, and the sheet thickness at the center of the bottom surface is kept thicker than 40% of the original film thickness. .
4: The sheet is molded so as to sufficiently follow the bottom surface of the tray-shaped molded body, but the sheet thickness at the center of the bottom surface is 30% or more and less than 40% of the original film thickness.
3: The sheet is molded so as to sufficiently follow the bottom surface of the tray-shaped molded body, but the sheet thickness at the center of the bottom surface is 20% or more and less than 30% of the original film thickness.
2: The sheet is molded so as to sufficiently follow the bottom surface of the tray-shaped molded body, but the sheet thickness at the center of the bottom surface is less than 20% of the original film thickness.
1 (deformation defect): Does not correspond to any of 2-5.

  The formability of the sheet was evaluated by measuring the followability to the bottom surface when a tray-shaped molded body was produced and the thickness of the sheet at the center of the bottom surface. If the level of formability is 2 or more in a five-step evaluation, it can be formed without any practical problems.

11. Heat sealability (heat seal strength measurement)
Using a heat sealer (TP-701S HEAT SEAL TESTER, TESTER SANGYO CO, LTD), a heating type flat top seal fixture coated with Teflon and a non-heated bottom seal coated with glass cloth A sample cut into a size of 297 mm (longitudinal direction) × 210 mm (width direction) is set between the fixtures, and a sample for heat seal measurement under conditions of 2.1 kgf / cm ² and a residence time of 1 second. Was made. The sheet has a predetermined sealing temperature of 80, 90, 100, 110, 120, 130, 140, 150, 160, and 170 ° C., and the A layer is the outermost layer or the A layer / B layer. In the case of heat sealing between the A layer sides, when the B layer is the outermost layer, heat seal is performed between the B layer sides, and when the C layer is the outermost layer, heat sealing is performed between the C layer sides. Then, the seal strength of the outermost layer at each temperature was measured with a tensile tester manufactured by British Scientific Instruments Seisakusho. (Examples 1-31, Comparative Examples 2 and 3 were heat-sealed on the A layer side, Comparative Example 1 was heat-sealed on the B layer side, and Comparative Examples 4 and 5 were heat-sealed on the C layer side.)

In the peel test, a heat-sealed sample is cut into a 25 mm wide strip, two unsealed ends are attached to the upper and lower clamps of the Instron tester, and the sealed ends are unsealed. The film was supported at an angle of 90 ° with respect to the part, and a 90 ° peel test was performed.

The conditions for the peel test were as follows. In the peel force curve, the value was read to obtain the heat seal strength.
・ Peel tester: Tensile Seiki Seisakusho tensile tester ・ Peel angle: 90 °
・ Peeling speed: 200 mm / min ・ Chart speed: 20 mm / min ・ Peeling direction: Longitudinal direction ・ Sample width: 25 mm
Three test pieces were collected from the same sample, and the same measurement was performed three times. The average value of the obtained values was defined as the heat seal strength (g / 25 mm).

The heat sealability was judged according to the following criteria.
A: A seal strength of 200 g / 25 mm or more can be achieved at any temperature.
X: A sealing strength of 200 g / 25 mm or more cannot be achieved at any sealing temperature.

12 Printability Nitrocellulose ink CCST manufactured by Toyo Ink Co., Ltd. is printed on the surface of layer A or layer B with a gravure roll, and left in a 40 ° C, 90% relative humidity atmosphere for 24 hours, and then the cello tape (registered trademark) is peeled off. Tested. (Examples 1-31, Comparative Examples 2 and 3 were printed on the A layer, Comparative Example 1 was printed on the B layer, and Comparative Examples 4 and 5 were printed on the C layer.) Shown in Practically, it can be used without problems if it is more than ○.
A: No peeling at all.
○: 5% or more and less than 10% of the ink printed part is peeled to the cellophane tape side.
X: 10% or more of the ink printed part is peeled off to the cellophane tape side.

13. Coefficient of dynamic friction: μd
According to JIS-K-7125 (1999), a slip tester (manufactured by Toyo Tester Kogyo Co., Ltd.) was used, the load was 200 g, different surfaces were combined, and the resistance in the stable region after sliding (μd: dynamic friction coefficient) is below. The value was calculated using the following formula.
Coefficient of dynamic friction: μd = resistance value / load

14 Cold resistance of sheet (cold impact resistance): Impact (N · m / mm)
Using a film impact tester (manufactured by Toyo Seiki Seisakusho), the impact of the sheet was measured using a hemispherical impact head having a diameter of ½ inch in an atmosphere of a temperature of −20 ° C. and a humidity of 65% RH. A sheet sample was prepared in a size of 100 mm × 100 mm, and the measurement was performed 5 times per sample. Further, the impact value for each time was divided by the thickness of the measurement sample, and the impact per unit thickness was obtained from the average value of five measurements. The sample thickness was measured with a digital micrometer.

15. Interlayer adhesion (interlayer adhesion strength measurement)
The longitudinal direction of the polyester sheet and the unstretched polypropylene film (CPP) was aligned and dry laminated under the following conditions.
CPP: “Trephan” (registered trademark) NO # 60 ZK93KM manufactured by Toray Film Processing Co., Ltd.
・ Adhesive: Toyo Morton Co., Ltd. AD503 / cat10
-Blending amount: AD503 / cat10 / ethyl acetate = 20/1/20 parts by mass-Application: Metabar # 12 was used, and an adhesive was applied to the corona-treated surface side of CPP.
Drying: 80 ° C., 45 seconds Lamination: After drying, the coated surface on the CPP was laminated to the A layer of the polyester sheet of the present invention.
Curing: 40 ° C., 48 hours A test piece having a width of 15 mm was taken out from a sample obtained by dry lamination, and a peel test was performed under the following conditions. Interlayer adhesion was measured by reading the value in the peel force curve.
・ Peel tester: Tensile Seiki Seisakusho tensile tester ・ Peel angle: 180 °
・ Peeling speed: 200 mm / min ・ Chart speed: 20 mm / min ・ Peeling direction: Longitudinal direction ・ Sample width: 15 mm
Three test pieces were collected from the same sample, and the same measurement was performed three times. The average value of the obtained values was defined as interlayer adhesion strength (g / 15 mm).

Interlayer adhesion was judged according to the following criteria.
○: Interlayer adhesion force is 200 g / 15 mm or more, or peeling between layers is difficult.
X: Interlayer adhesion is less than 200 g / 15 mm.

The raw materials used in the production examples, examples, and comparative examples of the present invention are as follows. In the production examples, examples, and comparative examples, the following abbreviations may be used.

  As polyester A, A1-1, A1-2, A1-3, A2, A3, A1-1-MB, A2-MB, A3-MB, polyester B as B1, B2, and other polyesters as C1 , C2, and D1, D2, D3, D4, D5, and D6 were used as recovered materials.

  A1-1: Dicarboxylic acid component: terephthalic acid component = 100 mol%, glycol component: ethylene glycol component / 1,4-cyclohexanedimethanol component / isosorbide component = 22/46/32 mol%, intrinsic viscosity = 0.58 dl / g, glass transition temperature = 120 ° C., melting point = none. Before use, it was dried at 90 ° C. for 5 hours in a rotary vacuum dryer.

  A1-2: Dicarboxylic acid component: terephthalic acid component = 100 mol%, glycol component: ethylene glycol component / 1,4-cyclohexanedimethanol component / isosorbide component = 28/48/24 mol%, intrinsic viscosity = 0.65 dl / g, Glass transition temperature = 110 ° C., melting point = none. Before use, it was dried at 90 ° C. for 5 hours in a rotary vacuum dryer.

  A1-3: Dicarboxylic acid component: terephthalic acid component = 100 mol%, glycol component: ethylene glycol component / 1,4-cyclohexanedimethanol component / isosorbide component = 20/36/44 mol%, intrinsic viscosity = 0.53 dl / g, Glass transition temperature = 145 ° C., melting point = none. Before use, it was dried at 90 ° C. for 5 hours in a rotary vacuum dryer.

  A2: Dicarboxylic acid component: terephthalic acid component = 100 mol%, glycol component: ethylene glycol component / spiroglycol component = 55/45 mol%, intrinsic viscosity = 0.66 dl / g, glass transition temperature = 112 ° C, melting point = none . Before use, it was dried at 90 ° C. for 5 hours in a rotary vacuum dryer.

  A3: Dicarboxylic acid component: terephthalic acid component = 100 mol%, glycol component: 1,4-cyclohexanedimethanol component / 2,2,4,4-tetramethyl-1,3-cyclobutanediol component = 60/40 mol% Intrinsic viscosity = 0.70 dl / g, glass transition temperature = 115 ° C., melting point = none. Before use, it was dried at 90 ° C. for 5 hours in a rotary vacuum dryer.

  B1: Dicarboxylic acid component: terephthalic acid component = 100 mol%, glycol component: ethylene glycol component = 100 mol%, glass transition temperature = 78 ° C., melting point = 266 ° C. Before use, it was dried for 5 hours at 140 ° C. in a rotary vacuum dryer.

  B2: Dicarboxylic acid component: terephthalic acid component = 100 mol%, glycol component: ethylene glycol component / 1,4-cyclohexanedimethanol component = 67/33 mol%, glass transition temperature = 82 ° C., melting point = none. Before use, it was dried at 90 ° C. for 5 hours in a rotary vacuum dryer.

C1: Dicarboxylic acid component: terephthalic acid component = 100 mol%, glycol component: ethylene glycol component / 1,4-cyclohexanedimethanol component / isosorbide component = 62/6/32 mol%, intrinsic viscosity = 0.68 dl / g, Glass transition temperature = 122 ° C., melting point = 263 ° C. Before use, it was dried at 90 ° C. for 5 hours in a rotary vacuum dryer.

  C2: Dicarboxylic acid component: naphthalene dicarboxylic acid component = 100 mol%, glycol component: ethylene glycol component = 100 mol%, glass transition temperature = 120 ° C., melting point = 262 ° C. Prior to use, it was dried at 150 ° C. for 5 hours in a rotary vacuum dryer.

A1-1-MB: In A1-1 above, 95% by mass of A1-1 and “Silton” JC-20 (average particle diameter: 2.0 μm), which is aluminum silicate manufactured by Mizusawa Chemical Industry Co., Ltd. A chip prepared by blending 5% by mass was designated as A1-1-MB. Before use, it was dried at 90 ° C. for 5 hours in a rotary vacuum dryer.

  A2-MB: In the above A2, 95% by mass of the above A2 and 5% by mass of “Silton” JC-20 (average particle size: 2.0 μm) which is aluminum silicate manufactured by Mizusawa Chemical Industry Co., Ltd. The produced chip was designated as A2-MB. Before use, it was dried at 90 ° C. for 5 hours in a rotary vacuum dryer.

  A3-MB: In A3 above, 95% by mass of the above A3 and 5% by mass of “Silton” JC-20 (average particle size: 2.0 μm) which is aluminum silicate manufactured by Mizusawa Chemical Industry Co., Ltd. The produced chip was designated as A3-MB. Before use, it was dried at 90 ° C. for 5 hours in a rotary vacuum dryer.

  D1: Flakes obtained by pulverizing sheet ears and scrap sheets generated in the film forming step of the sheet produced in Example 1 described later. Before use, it was dried at 90 ° C. for 5 hours in a rotary vacuum dryer.

  D2: Flakes obtained by pulverizing scraps (such as stamped scraps and scrap scraps) generated when a molded body made of a sheet manufactured in Example 1 described later is manufactured. Before use, it was dried at 90 ° C. for 5 hours in a rotary vacuum dryer.

  D3: Flakes obtained by pulverizing sheet ears and scrap sheets generated in the film forming step of the sheet prepared in Example 4 described later. Before use, it was dried at 90 ° C. for 5 hours in a rotary vacuum dryer.

  D4: Flakes obtained by pulverizing scraps (such as stamped scraps and scrap scraps) generated when a molded body made of a sheet manufactured in Example 4 described later is manufactured. Before use, it was dried at 90 ° C. for 5 hours in a rotary vacuum dryer.

  D5: Flakes obtained by pulverizing sheet ears and scrap sheets generated in the film forming step of the sheet prepared in Example 5 described later. Before use, it was dried at 90 ° C. for 5 hours in a rotary vacuum dryer.

  D6: Flakes obtained by pulverizing scraps (such as stamped scraps and scrap scraps) generated when a molded body made of a sheet manufactured in Example 5 described later is manufactured. Before use, it was dried at 90 ° C. for 5 hours in a rotary vacuum dryer.

Example 1
In the vent-type extruder (1), as a resin used for forming the A layer, 100% by mass of A1-1 was extruded while being melt-kneaded while degassing the vacuum vent part at 245 ° C., and the polymer was applied with a 100 mesh metal mesh. The mixture was filtered and supplied to a multi-manifold base of a two-kind three-layer stacking type. Further, 100% by mass of B1 as a resin used for forming the B layer is extruded into the vent type extruder (2) at 280 ° C. while being melt-kneaded while degassing the vacuum vent part, and is different from the extruder (1). A pair of casting drums, after the polymer is filtered through a mesh mesh of 100 mesh in the flow path, and co-extruded from a T-die die set at a die temperature of 270 ° C., rotated in a direction in contact with each other, and cooled to 40 ° C. The sheet was discharged between polishing rolls and adhered to a casting drum to be cooled and solidified to prepare an unstretched sheet, and then the sheet was wound up by a winder.

  The obtained sheet has a thickness of 250 μm, the thickness configuration is A layer / B layer / A layer = 1/8/1, and the obtained sheet is a molded product of [Method for measuring physical properties and method for evaluating effects]. A molded body was produced by the method described in the section.

  The characteristic values of the obtained sheet and molded product are as shown in the table, the sheet is non-oriented, and transparency, impact resistance, heat resistance, heat sealability, printability, cold resistance, interlayer adhesion The sheet was preheated at a low temperature of 125 ° C. when the molded body was produced, and the moldability and heat resistance of the molded body were excellent.

(Examples 2-14, 16-31)
Examples 2 to 14, 16 to 31 are A layer resin, B layer resin, extrusion temperature (° C.) of extruder (1), extrusion temperature (° C.) of extruder (2), die temperature (° C.), A sheet and a molded body were obtained in the same manner as in Example 1 except that the lamination thickness ratio was changed as shown in the table. The physical properties of the obtained sheet and molded product are shown in the table.

(Example 15)
In the vent-type extruder (1), as a resin used for forming the A layer, 100% by mass of A1-1 was extruded while being melt-kneaded while degassing the vacuum vent part at 245 ° C., and the polymer was applied with a 100 mesh metal mesh. The mixture was filtered and supplied to a multi-manifold base of two types and two layers. Further, as a resin used for forming the B layer, 100% by mass of B-1 is extruded into a vent-type extruder (2) at 270 ° C. while melting and kneading while degassing the vacuum vent portion, and the extruder (1). Is a pair of castings in which the polymer is filtered through a 100 mesh metal mesh in a separate channel, then co-extruded from a T die die with a die temperature set to 270 ° C., rotated in the direction of contact with each other, and cooled to 40 ° C. The sheet was discharged between a drum and a polishing roll, adhered to the casting drum, cooled and solidified to produce an unstretched sheet, and the sheet was wound up by a winder.

  The obtained sheet is 250 μm, the thickness structure is A layer / B layer = 2/8, and the obtained sheet is the method described in the molded article production part of [Method for measuring physical properties and method for evaluating effect] A molded body was prepared.

  The characteristic values of the obtained sheet and molded product are as shown in the table.

(Comparative Example 1)
In Comparative Example 1, 100% by mass of B1 as a resin used for forming the B layer was extruded into a vent type extruder (2) at 280 ° C. while being melt-kneaded while degassing the vacuum vent part, to form a mesh mesh of 100 mesh. The polymer is filtered and co-extruded from a T-die die with a die temperature set to 280 ° C into a single layer type die, cooled to 40 ° C, and discharged between a pair of casting drums and polishing rolls to adhere to the casting drum. After cooling and solidifying to produce an unstretched sheet, the sheet was wound up with a winder.

  The obtained sheet was 250 μm, and the obtained sheet was produced as a molded article by the method described in the molded article production part of [Method for measuring physical properties and method for evaluating effects].

  The characteristic values of the obtained sheet and molded product are as shown in the table, and the heat resistance, heat sealability, printability, and cold resistance of the sheet are inferior, and the sheet preheating temperature at the time of forming the molded product is 115 ° C. Although the temperature could be lowered, the heat resistance of the molded body was inferior.

(Comparative Example 2)
In the vent-type extruder (1), as a resin used for forming the A layer, 100% by mass of A1-1 was extruded while being melt-kneaded while degassing the vacuum vent part at 245 ° C., and the polymer was applied with a 100 mesh metal mesh. Filter and co-extrusion into a single layer type die from a T die die set at a die temperature of 245 ° C., cooled to 40 ° C. and discharged between a pair of casting drums and polishing rolls, closely attached to the casting drum and solidified by cooling did.

  The obtained unstretched sheet was stretched 3 times in the longitudinal direction at 85 ° C. with a roll stretching machine, and immediately cooled to room temperature. Next, the obtained uniaxially stretched film was introduced into a tenter, stretched 3.2 times in the width direction at 90 ° C. while holding both edges with clips, heat-set at 200 ° C., cooled, and wound up It was. The obtained sheet was 250 μm, and the characteristic values of the obtained sheet and molded body were as shown in the table. Since the sheet was biaxially stretched, the sheet was oriented. Since the rigidity of the obtained sheet was high, an attempt was made to produce a molded body, but the molding was poor and the molded body could not be obtained.

(Comparative Example 3)
In the vent-type extruder (1), as a resin used for forming the A layer, 100% by mass of A1-1 was extruded while being melt-kneaded while degassing the vacuum vent part at 245 ° C., and the polymer was applied with a 100 mesh metal mesh. The mixture was filtered and supplied to a multi-manifold base of a two-kind, three-layer type. In addition, 100 mass% of B1 was extruded into the vent type extruder (2) while melt-kneading while degassing the vacuum vent at 280 ° C., and 100 mesh metal mesh in a flow path different from the extruder (1). After the polymer is filtered at, the die is co-extruded from a T die die set at a base temperature of 270 ° C., rotated in a direction in contact with each other and cooled to 40 ° C., and discharged between a pair of casting drums and polishing rolls. And was solidified by cooling.

  The obtained unstretched sheet was stretched 3 times in the longitudinal direction at 85 ° C. with a roll stretching machine, and immediately cooled to room temperature. Next, the obtained uniaxially stretched film was introduced into a tenter, stretched 3.2 times in the width direction at 90 ° C. while holding both edges with clips, heat-set at 220 ° C., cooled, and wound up. It was. The obtained sheet is 250 μm, the thickness structure is A layer / B layer / A layer = 1/8/1, and the characteristic values of the obtained sheet and molded product are as shown in the table. Since it was axially stretched, the sheet was oriented. Since the rigidity of the obtained sheet was high, an attempt was made to produce a molded body, but the molding was poor and the molded body could not be obtained.

(Comparative Example 4)
In the vent type extruder (1), 100% by mass of C1 as a resin used for forming the C layer was extruded while being melt-kneaded while degassing the vacuum vent at 245 ° C., and the polymer was filtered through a 100 mesh metal mesh. This was supplied to a multi-manifold die of a two-kind, three-layer type. (Here, the C layer means a layer different from the A layer and the B layer.) Also, in the vent type extruder (2), 100% by mass of B1 is 280 ° C. as a resin used for forming the B layer. After extruding while melting and kneading while degassing the vacuum vent part, the polymer was filtered with a mesh mesh of 100 mesh in a flow path different from the extruder (1), and the die temperature was set to 270 ° C. Co-extruded from die die, rotated in the direction of contact with each other and cooled to 40 ° C., discharged between a pair of casting drums and a polishing roll, adhered to the casting drum, solidified by cooling, and produced an unstretched sheet. The sheet was wound up.

  The obtained sheet has a thickness of 250 μm, the thickness configuration is C layer / B layer / C layer = 1/8/1, and the obtained sheet is a molded product of [Method for measuring physical properties and method for evaluating effects]. A molded body was produced by the method described in the section.

  The characteristic values of the obtained sheet and molded product are as shown in the table, and the sheet is inferior in transparency, impact resistance, heat sealability, printability, cold resistance, and the sheet preheating temperature at the time of forming the molded product is The temperature was as high as 155 ° C., and the moldability of the molded product was poor.

(Comparative Example 5)
In Comparative Example 5, a sheet and a molded body were obtained in the same manner as in Comparative Example 4 except that the resin of the C layer, the extrusion temperature (° C.) of the extruder (1), and the die temperature (° C.) were changed as shown in the table. . The characteristic values of the obtained sheet and molded product are as shown in the table, and the sheet is inferior in transparency, impact resistance, heat sealability, printability, cold resistance, and the sheet preheating temperature at the time of forming the molded product is The temperature was as high as 160 ° C., and the moldability of the molded body was poor.

  In the table, A in the column of the lamination thickness ratio means A layer, B means B layer, and C means C layer.

  Since the polyester sheet of the present invention is excellent in heat resistance, transparency, moldability, cold resistance, heat sealability, printability, and in addition, the environmental load is reduced, packaging containers, various electronic and electrical equipment, It is useful for various uses such as OA equipment, vehicle parts, machine parts, other agricultural materials, fishing materials, transport containers, playground equipment, and miscellaneous goods. Among these, it can be preferably used for applications requiring heat resistance, transparency, and moldability, such as food containers and beverage cup lids.

DESCRIPTION OF SYMBOLS 1 Sheet | seat center part 2 Sheet | seat 3 Support | pillar 4 Sheet | seat width direction 5 Sheet | seat longitudinal direction 6 Height of the right end (height from the ground to the longitudinal direction center)
7 Height at the left end (height from the ground to the longitudinal center)
8 Height of the column 9 Center of the right edge in the longitudinal direction of the sheet 10 Center of the left edge in the longitudinal direction of the sheet 11 Horizontal width of the column 12 Vertical width of the column

Claims (12)

When the polyester having no melting point is polyester A, the layer mainly composed of polyester A is A layer, and when the polyester other than polyester A is polyester B, the layer mainly composed of polyester B is B layer. When having A layer and B layer,
The storage elastic modulus in the sheet longitudinal direction and the sheet width direction at 100 ° C. is from 100 MPa to 3,000 MPa,
A polyester sheet characterized by being non-oriented.   The polyester sheet according to claim 1, wherein the polyester sheet has a laminated structure of A layer / B layer / A layer.   The polyester sheet according to claim 1 or 2, wherein the layer thickness ratio of A layer / B layer / A layer is 1/3/1 to 1/18/1.   In a total of 100 mol% of the glycol component of polyester A, the ethylene glycol component is 1 mol% to 60 mol%, the isosorbide component is 5 mol% to 60 mol%, and the 1,4-cyclohexanedimethanol component is 30 mol%. The polyester sheet according to any one of claims 1 to 3, comprising 52 mol% or less.   The total of 100 mol% of the glycol component of the polyester A contains 1 mol% or more and 90 mol% or less of an ethylene glycol component, and 5 mol% or more and 60 mol% or less of a spiroglycol component. The polyester sheet in any one of.   In a total of 100 mol% of the glycol component of polyester A, 1,4-cyclohexanedimethanol component is 5 mol% to 90 mol%, 2,2,4,4-tetramethyl-1,3-cyclobutanediol component is The polyester sheet according to any one of claims 1 to 3, comprising 5 mol% or more and 60 mol% or less.   The polyester sheet according to claim 1, wherein the polyester B is polyethylene terephthalate.   B layer contains the said polyester A 5 mass% or more and less than 50 mass%, The polyester sheet in any one of Claims 1-7 characterized by the above-mentioned.   The polyester sheet according to any one of claims 1 to 8, wherein the haze is 0.3% or more and 10% or less.   The polyester sheet according to claim 1, wherein the dynamic friction coefficient μd is 0.20 or more and 0.40 or less.   The molded object obtained from the polyester sheet in any one of Claims 1-10. A card having a printed layer, wherein the printed layer is directly laminated with the A layer of the polyester sheet according to claim 1.

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