TW201509986A - Polyester sheet, molded article produced from polyester sheet, and card - Google Patents

Abstract

The purpose of the present invention is to provide a polyester sheet having excellent heat resistance and moldability. The polyester sheet according to the present invention is characterized by having a layer containing a polyester (A) and is non-oriented, wherein the polyester (A) is a polyester comprising 1 to 60 mol% inclusive of an ethylene glycol component and 1 to 60 mol% inclusive of an isosorbide component wherein the total amount of the glycol components is 100 mol%.

Description

Polyester sheet, molded body made of polyester sheet and card Field of invention

The present invention relates to a polyester sheet excellent in heat resistance and moldability, and a molded body and a card obtained from the polyester sheet.

Background of the invention

A saturated polyester (especially a polyester resin typified by polyethylene terephthalate) is widely used as a sheet and a film polymer, and has recently been used for its excellent chemical resistance and low performance. Gas permeability is also gradually applied to beverage bottles such as carbonated drinks, juices, and beer, cosmetic containers, and food trays. Among them, the amorphous polyester sheet known as A-PET has attracted attention for its excellent recovery, low pollution and food safety. In recent years, it has been used as a substitute for vinyl chloride or polystyrene. The usage has increased rapidly. In addition to being used as a blister pack for foods, pharmaceutical containers, or groceries by thermoforming, the polyester sheet is also used as a transparent case for placing cosmetics or electronic instruments, etc., by utilizing its excellent transparency. However, A-PET has a low glass transition temperature and is inferior in heat resistance. For example, in the field of heat-resistant containers for microwave ovens, the practical use range is greatly limited.

As one of the means to solve such a problem, Patent Document 1 has A biaxially stretched polyester film is disclosed which is composed of a mixture of polytrimethylene terephthalate and a polyester resin as a main component.

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

Further, Patent Document 3 discloses a polyester sheet which is a polyester-based polymer having a specific composition in a specific ratio and inactive particles having a specific secondary particle system, and further blended with a plurality of hydroxy groups. An ester product of an alcohol and a carbon number of 12 or more aliphatic monocarboxylic acids and an ester product of a specific polyol and an aliphatic monocarboxylic acid.

Advanced technical literature Patent literature

Patent Document 1: Japanese Laid-Open Patent Publication No. 2012-1589

Patent Document 2: Japanese Laid-Open Patent Publication No. 2012-126821

Patent Document 3: Japanese Patent Laid-Open No. Hei 8-142293

Summary of invention

However, the biaxially stretched polyester film of the invention disclosed in Patent Document 1 has an oriented structure by the stretching step and thus has high rigidity and excellent mechanical properties, but is inferior in thermoformability. Further, Patent Document 1 does not describe the improvement of heat resistance by increasing the glass transition temperature of the polyester resin, and there is no suggestion at all. Further, Patent Document 2 describes the improvement of heat resistance by raising the glass transition temperature, but the biaxially stretched polyester film of the invention disclosed in Patent Document 2 is dried at a high temperature in a post-processing printing step. Only for When it is used, a crystalline polyester resin having a melting point is used, and since it is biaxially stretched, although the rigidity is high and the mechanical properties are excellent, there is a problem that the formability is poor. Further, the invention described in Patent Document 3 is an amorphous non-oriented polyester sheet, and the slidability, blocking property, and cutting property are obtained without impairing processing properties such as transparency, printability, and adhesion. Although it is improved, Patent Document 3 does not describe the improvement of heat resistance and the improvement of formability by raising the glass transition temperature, and there is no suggestion at all.

Therefore, the present invention has been made in view of the above problems, and is intended to provide a polyester sheet excellent in heat resistance and moldability.

In order to solve the above problems, the present invention has the following configuration.

(1) A polyester sheet comprising 1 mol% or more and 60 mol% or less of an ethylene glycol component and 1 mol% or more and 60 parts by weight of a total of 100 mol% of a glycol component. The polyester having the following isosorbide component of mol% is polyester A, and the polyester sheet has a layer containing polyester A and is non-oriented.

(2) The polyester sheet of (1) which is a laminated structure.

(3) The polyester sheet according to (1) or (2), wherein the layer of the polyester A containing more than 50% by mass and 100% by mass or less in 100% by mass of the total component of the layer is the A layer, The sheet has an A layer.

(4) The polyester sheet according to any one of (1) to (3), which contains 1 mol% or more and 60 mol% or less in a total of 100 mol% of the glycol component of the polyester A. The 1,4-cyclohexane dimethanol component.

(5) The polyester sheet according to any one of (1) to (4) wherein the aforementioned polyester A There is no melting point.

(6) The polyester sheet according to any one of (1) to (5), which is selected from the group consisting of polyethylene terephthalate, polylactic acid, polyethylene naphthalate, and polypair When any of the group consisting of butyl phthalate is polyester B, the layer of polyester B containing more than 50% by mass and 100% by mass or less of 100% by mass of the total component of the layer is B. For the layer, the sheet has a B layer.

(7) A polyester sheet according to (6), wherein the layer B contains the polyester A.

(8) A polyester sheet according to (6) or (7) which is a laminated structure of the A layer/B layer/A layer.

(9) A polyester sheet according to (8), which is a laminated structure of the A layer/B layer/A layer, and the laminate ratio is 1/3/1 to 1/20/1.

(10) The polyester sheet according to any one of (1) to (9) which contains 80 mol% or more and 100 mol% in a total of 100 mol% of the dicarboxylic acid component of the polyester A. The following terephthalic acid components.

(11) The polyester sheet according to any one of (1) to (10), which has a whiteness of 70% or more and 100% or less.

(12) The polyester sheet according to any one of (1) to (11), which has a dynamic friction coefficient μd of 0.20 or more and 0.40 or less.

(13) A formed body obtained by the polyester sheet of any one of (1) to (12).

(14) A card comprising a printed layer, and the printed layer is directly laminated with the layer A of the polyester sheet of any one of (3) to (12).

According to the present invention, a polyester sheet excellent in heat resistance and moldability can be provided.

1‧‧‧Sheet Central

2‧‧‧Sheet

3‧‧‧ pillar

4‧‧‧Sheet TD direction

5‧‧‧Sheet MD direction

6‧‧‧ Height at the right end (height from the ground to the center of the MD)

7‧‧‧The height of the left end (from the ground to the MD Height of direction center)

8‧‧‧ Height of the pillar

9‧‧‧The right end of the sheet in the MD direction

10‧‧‧The left end of the sheet in the MD direction

11‧‧‧The width of the pillar

12‧‧‧Length of the pillar

Fig. 1 is a schematic view showing an evaluation method of heat resistance of a sheet.

Detailed description of the preferred embodiment

The present invention is a polyester sheet characterized in that it contains 1 mol% or more and 60 mol% or less of ethylene glycol component and 1 mol% or more in a total of 100 mol% of the glycol component. And the polyester of the isosorbide component of 60 mol% or less is polyester A, and the polyester sheet has a layer containing polyester A and is non-oriented. The invention will be described below.

The polyester constituting the polyester sheet of the present invention is a generic term for a polymer compound in which an ester bond is mainly bonded in a main chain. Then, when a polyester is usually obtained by polycondensation reaction of a dicarboxylic acid and a diol, 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 a layer containing polyester A.

The polyester A means that an ethylene glycol component of 1 mol% or more and 60 mol% or less and 1 mol% or more and 60 mol% or less of isosorbide are contained in a total of 100 mol% of the glycol component. A polyester of an alcohol component. The polyester sheet of the present invention having such a layer can be suitably maintained as the strength or heat resistance of the sheet. From the viewpoint of strength, transparency, and heat resistance, the content of the ethylene glycol component in the glycol component of the polyester A is preferably 5 mol% or more and 50 mol% or less, and is 13 mol% or more. 45% or less is better than 20% by mole And 40 mol% or less is more preferable. Further, the isosorbide component content in the glycol component of the polyester A is preferably 5 mol% or more and 50 mol% or less, preferably 15 mol% or more and 40 mol% or less, preferably 22 mol%. More than % and more than 35 mol% is more preferable.

The isosorbide refers to a diol having a structure represented by the following formula (I), 1,4:3,6-dianhydro-D-sorbitol. Therefore, the isosorbide component is contained in the polyester A as a glycol component in the state of the following formula (II). Isosorbide can be easily obtained from sugars and starches derived from biomass components. For example, isosorbide can be obtained by hydrogenating and dehydrating D-glucose. Since the polyester sheet of the present invention uses a component derived from biomass, it can be made into an environmentally friendly sheet.

Further, the ethylene glycol used in the polyester sheet of the present invention is not particularly limited, but a sheet which is more environmentally friendly can be produced by using ethylene glycol derived from biomass.

[Chemical 2]

In the sheet of the present invention, the polyester A contains the ethylene glycol component and the isosorbide component in a specific range, whereby even in the temperature range where the conventional formulation softens at 90 ° C, sufficient Heat resistance. The reason why the heat resistance of the sheet of the present invention having a layer containing polyester A (which contains an isosorbide component) is improved is that the isosorbide component of the above formula (II) has a relatively straight structure. In addition, the free rotation of the isosorbide component in the molecular chain of the polyester is limited. Therefore, it is conceivable that the softening of the polyester molecular chain becomes difficult to occur, and the glass transition point temperature of the polyester A rises, and as a result, the heat resistance of the sheet of the present invention is improved.

The glycol component contained in the polyester A of the present invention may be, for example, a 1,2-propanediol component, a 1,3-propanediol component or a 1,3-butanediol, in addition to the ethylene glycol component and the isosorbide component. An aliphatic dihydroxy compound component such as a component, a 1,4-butanediol component, a 1,5-pentanediol component, a 1,6-hexanediol component, or a neopentyl glycol component; a diethylene glycol component; a polyoxyalkylene glycol component such as an ethylene glycol component, a polypropylene diol component, or a polytetramethylene glycol component; a fat such as a 1,4-cyclohexane dimethanol component or a spirodiol component; A cyclic dihydroxy compound component; an aromatic dihydroxy compound component such as a bisphenol A component or a bisphenol S component.

When the total amount of the glycol component in the polyester A is 100 mol%, From the viewpoint of transparency, the content of the glycol component (for example, 1,4-cyclohexanedimethanol component) other than the ethylene glycol component and the isosorbide component is preferably 1 mol% or more and 60 mol% or less. It is preferably 20 mol% or more and 54 mol% or less, more preferably 30 mol% or more and 52 mol% or less. Among these, the polyester A preferably contains a 1,4-cyclohexanedimethanol component from the viewpoints of transparency, impact resistance, and moldability at the time of post-forming thermoforming. As a glycol component.

From the viewpoint of cold resistance, heat sealability, and printability, the polyester A is preferably a polyester having no melting point. In order to obtain the polyester A having no melting point, 1,4-cyclohexane is contained in an amount of 30 mol% or more and 52 mol% or less in a total of 100 mol% of the glycol component of the polyester A. In the state of the methanol component, the melting point of the polyester A may become absent. The absence of the melting point of the polyester A means that the polyester A is an amorphous resin. A more preferred aspect of the polyester sheet of the present invention is formed by forming the polyester A in a state in which 20% by mole or more and 40% by mole of the total amount of the diol-based component is 100% by mole. The following ethylene glycol component, 22 mol% or more and 35 mol% or less of isosorbide component, and 30 mol% or more and 52 mol% or less of 1,4-cyclohexanedimethanol component.

Further, examples of the suitable dicarboxylic acid component of the polyester A of the present invention include the following dicarboxylic acid compound components: a terephthalic acid component, an isophthalic acid component, a phthalic acid component, and 2,6-naphthalene. An aromatic dicarboxylic acid component such as a carboxylic acid component, a diphenyldicarboxylic acid component, a diphenylguanidine dicarboxylic acid component, a diphenoxyethane dicarboxylic acid component, or a 5-pyridyl dicarboxylic acid component; an oxalic acid component, and amber An aliphatic dicarboxylic acid component such as an acid component, an adipic acid component, a sebacic acid component, a dimer acid component, a maleic acid component, or a fumaric acid component; 1,4-cyclohexanedicarboxylic acid An alicyclic dicarboxylic acid component such as a component; an oxycarboxylic acid component such as an oxygen benzoic acid component or the like. Further, examples of the dicarboxylic acid ester derivative component include esterified products of the above dicarboxylic acid compound, for example, dimethyl terephthalate component, diethyl terephthalate component, and 2-hydroxyethyl terephthalate. Methyl ester component, dimethyl 2,6-naphthalene dicarboxylate component, dimethyl isophthalate component, dimethyl adipate component, diethyl maleate component, dimethyl dimerate Ingredients, etc. Among these, from the viewpoint of moldability and workability, a terephthalic acid component is preferably used as the dicarboxylic acid component of the polyester A. Then, in the total of 100 mol% of the dicarboxylic acid component of the polyester A, the terephthalic acid component is preferably 80 mol% or more and 100 mol% or less, and is 90 mol% or more and 100 mol%. Preferably, it is preferably 95% or more and 100% by mole or less.

Further, the glass transition temperature of the polyester A of the present invention is preferably 85 ° C or more and 150 ° C or less, more preferably 100 ° C or more and 150 ° C or less, and more preferably 110 ° C or more and 150 ° C or less. By setting the glass transition temperature of the polyester A to 85 ° C or more and 150 ° C or less, a polyester sheet excellent in heat resistance can be obtained. In order to set the glass transition temperature to 85 ° C or more and 150 ° C or less, it is important to formulate the above-mentioned appropriate amount in accordance with the structure and content ratio of each component of the glycol component and the dicarboxylic acid component. As the polyester A, a commercially available raw material can be suitably used, for example, "ECOZEN" (manufactured by SK Chemical Co., Ltd.). When the heat resistance, the transparency, and the extrusion temperature at the time of producing a sheet are lowered, the polyester sheet of the present invention preferably has an A layer as defined below.

A layer: a layer of polyester A containing more than 50% by mass and not more than 100% by mass in 100% by mass of the total component of the layer.

In the total composition of the layer of 100% by mass, the layer A should preferably contain 60 masses. The layer of the polyester A of 100% by mass or more and 100% by mass is preferably 75 mass% or more and 100 mass% or less, more preferably 90 mass% or more and 100 mass% or less.

The polyester sheet of the present invention is preferably a laminated structure. In particular, if the moldability during hot forming is emphasized and the preheating temperature before molding is lowered, it is preferable to have a B layer as defined below.

B layer: a layer of polyester B containing more than 50% by mass and 100% by mass or less in 100% by mass of the total component of the layer.

Examples of the polyester B include polyhydroxyalkanoic acid such as polylactic acid and polyhydroxybutyrate; polycaprolactone, polyethylene terephthalate, polybutylene terephthalate, and polyethylene naphthalate. Ester, polyethylene succinate, polybutylene succinate, polyethylene adipate, polybutylene succinate adipate. Among these, it is preferably selected from any group consisting of polyethylene terephthalate, polylactic acid, polyethylene naphthalate, and polybutylene terephthalate. . Polyester B is a component other than polyester A.

In the case of 100% by mass of the total component of the layer, the layer B is preferably a layer of the polyester B containing 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 more preferably 90% by mass or more. More preferably 100% by mass or less.

In addition, the layer B containing more than 50% by mass and 100% by mass or less of the polyester B in the total mass of 100% by mass of the total layer of the layer means that the content is more than 50% by mass and 100% by mass or less. And polyhydroxyalkanoic acid, polycaprolactone, polyethylene terephthalate, polyethylene naphthalate, polybutylene terephthalate, polyethylene succinate, polysuccinic acid a layer composed of butadiene ester, polyethylene adipate, and polybutylene succinate adipate, Rather, it means that the layer having a total content of more than 50% by mass and 100% by mass or less is contained. The polyester B is preferably polyethylene terephthalate or polylactic acid. By using a polylactic acid derived from a biomass resin, an environmentally friendly polyester sheet can be produced. When the polyester sheet of the present invention has the layer A, in addition to the polyester A, the layer A may contain less than 50% by mass of the polyester B in 100% by mass of the total component of the layer A. When the heat resistance, the transparency, and the extrusion temperature at the time of producing a sheet are lowered, the layer A preferably does not contain the polyester B. When the moldability in the post-forming hot forming process is emphasized, and the preheating temperature at the time of post-forming hot forming can be lowered, the layer A preferably contains more than 0% by mass and less than 50% by mass of the polyester B. The polyester B contained in the layer A is preferably polyethylene terephthalate or polylactic acid from the viewpoint of lowering the preheating temperature in the post-forming hot forming process.

When the polyester sheet of the present invention has the B layer, the B layer may contain less than 50% by mass of the polyester A in 100% by mass of the total content of the B layer. When the moldability during hot forming is emphasized and the preheating temperature before molding can be lowered, the layer B preferably does not contain the polyester A. On the other hand, if the heat resistance and transparency are emphasized, and the extrusion temperature at the time of producing a sheet can be lowered, the layer B should preferably not contain the polyester A. When the layer A contains the polyester A, the layer B preferably contains more than 0% by mass and less than 50% by mass of the polyester A in 100% by mass of the total composition of the layer B.

In the method of including the polyester A in the layer B, in addition to the method of adding the polyester A which has not been used in the production of the polyester sheet, there is a method of adding the recovered raw material containing the polyester A. The term "unused polyester" as used herein means a polyester which has not been used at all in the film formation. Again, the so-called recycling The raw material means a sheet obtained by pulverizing the side of the sheet produced by the film forming step of the sheet or the waste sheet, and re-granulating it using an extruder or the like; or A sheet obtained by pulverizing chips (chips, scraps, and the like) generated when a molded article composed of the polyester sheet of the present invention is produced is regranulated using an extruder or the like.

In view of the transparency of the polyester sheet when the layer B contains the polyester A, polyethylene terephthalate is preferably used for the polyester B of the layer B. That is, since the compatibility between the polyester A and the polyethylene terephthalate is good, even if the recycled raw material containing the polyester A is added to the layer B to obtain the polyester sheet of the present invention, the increase in haze can be suppressed. A sheet with good transparency is obtained.

From the viewpoint of reducing the environmental load, the polyester sheet of the present invention may contain a recycled raw material without departing from the performance of the present invention. The content of the recovered raw material is 5% by mass or more and less than 50% by mass, and preferably 10% by mass or more and 40% by mass or less, and more preferably 15% by mass or more and 35% by mass or less, based on 100% by mass of the total component of the layer. .

Moreover, when the polyester sheet of the present invention is in the form of a laminated structure of the A layer/B layer/A layer, the B layer in the intermediate layer preferably contains a recycled raw material from the viewpoint of heat resistance and transparency. Because of the active use of recycled raw materials, environmental impact can be reduced, and environmentally friendly sheets can be made.

The polylactic acid used in the present invention is mainly composed of an L-lactic acid component and/or a D-lactic acid component. In the case where the L-lactic acid component and/or the D-lactic acid component are the main component, the lactic acid component is 70% by mass or more and 100% by mass or less based on 100% by mass of all the monomer components constituting the polymer. It is preferred to use substantially the same composition of L-lactic acid component and/or D-lactic acid component. Homo polylactic acid.

The polylactic acid used in the present invention preferably has crystallinity. The polylactic acid has crystallinity, and when the DSC measurement is performed, the melting point derived from polylactic acid can be observed. Generally, the higher the optical purity of the homopolylactic acid, the higher the melting point or crystallinity. The melting point or crystallinity of the polylactic acid is affected by the molecular weight or the catalyst used in the polymerization. However, in general, the polylactic acid having an optical purity of 98 mol% or more has a melting point of about 170 ° C and a high crystallinity. Further, as the optical purity is lowered, the melting point or crystallinity is lowered. For example, homopolylactic acid having an optical purity of 88 mol% has a melting point of about 145 °C. The homopolylactic acid having an optical purity of 75 mol% has a melting point of about 120 °C. A homopolylactic acid having an optical purity lower than 70 mol% becomes non-crystalline which does not exhibit a clear melting point.

The polylactic acid to be used in the present invention may be mixed with a crystalline polymorphic polylactic acid and an amorphous homopolylactic acid for the purpose of imparting or enhancing the function according to the use. In this case, the ratio of the amorphous homopolylactic acid may be determined in a range that does not impair the effects of the present invention. In the case of forming a sheet, at least one of the polylactic acid to be used preferably contains polylactic acid having an optical purity of 97 mol% or more in the case where high heat resistance is to be imparted. When it is desired to impart impact resistance, at least one of the polylactic acid to be used preferably contains polylactic acid having an optical purity of less than 97 mol%.

In the present invention, the weight average molecular weight of the polylactic acid is not particularly limited, and in view of mechanical properties, it is preferably in the range of 100,000 or more and 300,000 or less. The range of 120,000 or more and 280,000 or less is better, and the range of 130,000 or more and 270,000 or less is better, and the range is 140,000 or more and 260,000 or less. It is especially good.

Further, the polylactic acid may contain other components than the lactic acid component (L-lactic acid component or D-lactic acid component) insofar as the performance of the present invention is not impaired. Examples of the other components include a polyvalent carboxylic acid component, a polyvalent alcohol component, a hydroxycarboxylic acid component, and a lactone component, and specific examples thereof include a succinic acid component, an adipic acid component, a sebacic acid component, and a transbutylene component. Acid component, terephthalic acid component, isophthalic acid component, 2,6-naphthalenedicarboxylic acid component, sodium 5-sulfonate isophthalic acid component, 5-sulfonic acid tetrabutylphosphonium isophthalate component, etc. a polyvalent carboxylic acid or a derivative thereof; an ethylene glycol component, a propylene glycol component, a butanediol component, a pentanediol component, a hexanediol component, an octanediol component, a neopentyl glycol component, a glycerin component, a trimethylolpropane component, a neopentyl alcohol component; a polyvalent alcohol component in which an ethylene oxide component or a propylene oxide component is added to a trimethylolpropane component or a pentaerythritol component; An aromatic polyvalent alcohol component in which an oxyethylene component is subjected to an addition reaction; a polyhydric alcohol such as a diethylene glycol component, a triethylene glycol component, a polyethylene glycol component, or a polypropylene glycol component, or a derivative thereof; Acetic acid component, 3-hydroxybutyric acid component, 4-hydroxybutyric acid component, 4-hydroxyshikimate component, 6- Hydroxycarboxylic acid such as hydroxycaproic acid component, glycoside component, ε-caprolactone glycoside component, ε-caprolactone component, β-caprolactone component, δ-butyrolactone component, β- or γ-butane A lactone such as an ester component, a neopentyl lactone component or a δ-valerolactone component.

The polyethylene terephthalate used in the present invention may be a dicarboxylic acid component obtained from terephthalic acid or an ester derivative thereof, and a glycol obtained from ethylene glycol or an ester derivative thereof. The ingredients are manufactured using conventional methods.

In the production of polyethylene terephthalate, a dicarboxylic acid other than terephthalic acid may be used in small amounts in addition to terephthalic acid in the surface of the dicarboxylic acid component.

Examples of such a dicarboxylic acid include the following dicarboxylic acid compound components: an isophthalic acid component, a phthalic acid component, a 2,6-naphthalenedicarboxylic acid component, and a diphenyldicarboxylic acid component. An aromatic dicarboxylic acid component such as a diphenyl sulfonium dicarboxylic acid component, a diphenoxy ethane dicarboxylic acid component, or a 5-pyridyl dicarboxylic acid component; an oxalic acid component, a succinic acid component, an adipic acid component, and a bismuth dioxide component; An aliphatic dicarboxylic acid component such as an acid component, a dimer acid component, a maleic acid component or a fumaric acid component; an alicyclic dicarboxylic acid component such as a 1,4-cyclohexanedicarboxylic acid component; and p-oxybenzoic acid An oxycarboxylic acid component such as a component. Further, the dicarboxylic acid ester derivative component may, for example, be an esterified product of the above dicarboxylic acid compound, for example, a dimethyl terephthalate component, a diethyl terephthalate component, or a 2-hydroxyethyl terephthalate. Methyl ester component, dimethyl 2,6-naphthalene dicarboxylate component, dimethyl isophthalate component, dimethyl adipate component, diethyl maleate component, dimethyl dimerate Ingredients, etc. The dicarboxylic acid component other than the terephthalic acid component is preferably 10 mol% or less in a total of 100 mol% of the dicarboxylic acid component contained in the polyethylene terephthalate.

In the production of polyethylene terephthalate, in addition to the ethylene glycol component, a glycol component other than the ethylene glycol component may be used in a small amount (but the isosorbide component is excluded). Examples of such a glycol component include a 1,2-propylene glycol component, a 1,3-propanediol component, a 1,3-butanediol component, a 1,4-butanediol component, and a 1,5-pentane group. An aliphatic dihydroxy compound component such as a diol component, a 1,6-hexanediol component or a neopentyl glycol component; a polyoxyalkylene glycol component such as a diol component, a polyethylene glycol component, a polypropylene glycol component, or a tetramethylene glycol component; a fat such as a 1,4-cyclohexane dimethanol component or a spirodiol component; A cyclic dihydroxy compound component; an aromatic dihydroxy compound component such as a bisphenol A component or a bisphenol S component. The glycol component other than the ethylene glycol component is preferably 40 mol% or less and 10 mol% in a total of 100 mol% of the glycol component contained in the polyethylene terephthalate. The following is better.

For the polyethylene terephthalate, commercially available various raw materials can be used, and the product name is "NOVAPEX" (Mitsubishi Chemical Co., Ltd.) and the product name: "VYLON" (Dongyang Textile Co., Ltd.) )), the product name: "BELLPET" (manufactured by Bell Polyester), and the product name: "TEXPET" (Dayu Japan Co., Ltd.).

When the polyester sheet of the present invention is used for the purpose of concealability, the whiteness is preferably 70% or more and 100% or less. In order to set the whiteness to 70% or more and 100% or less, it is preferable to use the following method: in the case of the polyester sheet having the A layer, it is preferable that the layer A contains 100% by mass of the total component of the layer A. 20% by mass or more of the method of polylactic acid; or a polyester sheet having the selected layer of polylactic acid as the B layer of the polyester B, in the 100% by mass of the total composition of the layer B, it is preferable to make the polyester A A method of containing 20% by mass or more and less than 50% by mass. At this time, the sheet loses transparency, and the obtained polyester sheet becomes cloudy, and the whiteness can be made 70% or more and 100% or less.

From the viewpoint of heat resistance and formability, the polyester sheet of the present invention preferably has a storage elastic modulus in the sheet width direction at 100 ° C of 200 MPa or more and less than 3,000 MPa. If the storage elastic modulus is less than 200 MPa at 100 ° C, The heat resistance of the polyester sheet of the present invention and the heat resistance of the molded article produced using the sheet may be lowered. On the other hand, when the storage elastic modulus is 3,000 MPa or more, the heat resistance is excellent, but the formability may be deteriorated.

In other words, from the viewpoint of heat resistance, the storage elastic modulus in the sheet width direction at 100 ° C is preferably 200 MPa or more, and more preferably 600 MPa or more, and more preferably 1200 MPa or more. Moreover, in order not to lower the moldability, the storage elastic modulus in the sheet width direction at 100 ° C is preferably less than 3,000 MPa, and more preferably 2,000 MPa or less.

In the polyester sheet of the present invention, the method of setting the storage elastic modulus at 100 ° C to 200 MPa or more and less than 3,000 MPa is not particularly limited, and for example, in the polyester sheet of the present invention having the layer A, The polyester A contained in the layer A is a polyester having a glass transition temperature of 110° C. or more and 150° C. or less, and contains 60% by mass or more and 100% by mass or less of the total component 100% by mass of the layer A. Ester A.

As described above, it is important that the polyester sheet of the present invention has a layer containing the polyester A. The polyester sheet of the present invention may have a single layer structure composed only of the layer or a laminate structure having at least one layer of the layer as long as it has a layer containing the polyester A. In the present invention, a single layer structure including only a layer containing polyester A, a single layer structure including an A layer to be described later, a laminated structure having an A layer and a B layer to be described later, and a B layer to be described later are exemplified. A single layer structure containing polyester A or the like. That is, as an example of the layer structure of the present invention, for example, A layer, B layer containing polyester A, A layer/B layer, A layer/B layer/A layer, B layer/A layer/B layer , A layer / A layer, A layer / A layer / A layer, B layer / B layer containing polyester A, B layer / B layer / B layer containing polyester A, B layer / B containing polyester A Layer/B layer, etc. And this hair In view of heat resistance and transparency, the extrusion temperature at the time of producing a sheet can be lowered, the formability at the time of post-forming thermoforming, and the preheating temperature before molding can be lowered. It is particularly preferable to have the structure of the A layer/B layer/A layer.

That is, the polyester sheet of the present invention has an A layer having excellent heat resistance and transparency at a maximum outer layer and which can lower the extrusion temperature at the time of producing a sheet, and has a post-machining hot forming process in the inner layer. The B layer having a moldability and a temperature at which the preheating temperature before molding can be lowered during the hot forming process can be made into a sheet having the following characteristics: heat resistance and transparency are excellent. The extrusion temperature at the time of producing the sheet is lowered, the formability at the time of post-forming thermoforming, and the preheating temperature before molding can be lowered.

Further, in consideration of the transparency and the formability of the sheet, the polyester sheet of the present invention having a laminated structure is particularly between the A layer and the B layer, between the A layer and the A layer, and between the B layer and the B layer. It is better to have no other layers but to directly stack these layers. That is, the polyester sheet of the present invention preferably does not have an 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 co-extrusion. Further, from the viewpoint of interlayer adhesion, the polyester B is preferably polyethylene terephthalate.

The thickness of the polyester sheet of the present invention is not particularly limited, but is preferably 50 μm or more and 2000 μm or less, more preferably 100 μm or more and 1500 μm or less, and still more preferably 200 μm or more and 750 μm or less.

In addition, the laminate ratio of the polyester sheet of the laminated structure of the present invention is not particularly limited. However, in consideration of the formability of the sheet, in the case of the laminated structure of the A layer and the B layer, the laminate ratio is also That is, "A layer thickness is combined "/"B layer thickness total" should be 1/15~20/1 ratio, preferably 1/15~6/1, 1/5~2/1 better, 1/10~2 /3 is especially good. Here, for example, the "thickness total" means that the thickness of the A layer is only one layer in the A layer, and the two layers or more in the A layer. The sum of the layer thicknesses.

Moreover, when the polyester sheet of the present invention is in the form of a laminated structure of the A layer/B layer/A layer, the stacking ratio, that is, "A total thickness of the A layer" / "Total thickness of the B layer" / "Total thickness of the A layer" is preferably It is 1/3/1~1/20/1, and 1/4/1~1/18/1 is better, 1/5/1~1/16/1 is better, 1/6/1 ~1/15/1 is especially good. The "total thickness" is as described above.

The resin or polyester sheet used in the present invention can be dissolved in hexafluoroisopropanol (HFIP) or a mixed solvent of HFIP and chloroform, and ¹ H-NMR and ¹³ C-NMR can be used to characterize the dicarboxylic acid component or the second. Alcohol content and quantitative content. When the polyester sheet of the present invention has a laminated structure, it can be similarly evaluated by scraping each layer of the sheet.

The polyester A used in the present invention preferably has an intrinsic viscosity of 0.40 dl/g or more and 0.50 dl/g or more, from the viewpoints of moldability and film stability during hot working. It is preferably 0.55 dl/g or more. Further, when a filter is provided to remove foreign matter, the upper limit of the intrinsic viscosity is preferably 1.0 dl/g from the viewpoint of the discharge stability when the molten resin is extruded.

From the characteristics of the moldability at the time of hot forming which imparts cold resistance, heat sealability, printability, and post-processing, even in the case of a single-layer structure including only the layer of polyester A, even At least with polyester In the laminated structure of the layer A, it is important that the polyester sheet of the present invention is non-oriented. Here, whether or not the polyester sheet is non-oriented can be judged by the degree of plane orientation: ΔP. That is, if the degree of orientation of the surface: ΔP is 0 or more and 0.008 or less, it means that the polyester sheet is non-oriented. The method for making the non-alignment is not particularly limited as long as the effect of the present invention is not impaired, and it is preferable to use a T-die casting method in which a resin is extruded by a T-die. Surface orientation degree: The measurement method of ΔP will be described later.

The polyester sheet of the present invention may contain various additives without departing from the scope of the object of the present invention.

Examples of the additive which the polyester sheet of the present invention may contain include fillers (glass fibers, carbon fibers, metal fibers, natural fibers, organic fibers, glass flakes, glass beads, ceramic fibers, ceramic beads, asbestos, ash). Stone, talc, clay, mica, sericite, zeolite, bentonite, montmorillonite, synthetic mica, dolomite, kaolin, micronized citric acid, feldspar powder, potassium titanate, shale-swelling porous body (Sirasu balloon), carbonic acid Calcium, magnesium carbonate, barium sulfate, calcium acidate, alumina, acidified titanium, aluminum silicate, cerium oxide, gypsum, homogeneous quartzite, soda ash or clay, etc.; ultraviolet absorber (resorcinol, water) Salicylate, benzotriazole, benzophenone, etc.; thermal stabilizer (hindered phenol, hydroquinone, phosphite and such substitutes); slip agent; release agent (octadecanoic acid) And its salt, its ester, its monoester; stearyl alcohol, stearylamine and polyethylene wax, etc.; coloring agent containing dye (aniline black, etc.) and pigment (cadmium sulfide, phthalocyanine, etc.); Agent (phosphite, hypophosphite, etc.); flame retardant (red phosphorus, phosphate, Brominated polystyrene, brominated polyphenylene ether, brominated polycarbonate, magnesium hydroxide, melamine and cyanuric acid or a salt thereof, cerium compound, etc.; conductive agent or coloring agent (carbon black, etc.); Sex modifier (graphite, fluorine An antistatic agent or the like may be contained in one or two or more kinds.

Among them, in order to impart slidability to the polyester sheet of the present invention, the polyester sheet of the present invention preferably contains inorganic particles such as talc, alumina, aluminum niobate or cerium 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, considering the slidability and the windability of the sheet, it is preferably 0.1 μm or more, less than 3 μm, and 0.5. It is preferably not less than μm and less than 2 μm. In addition, the "average particle diameter of the inorganic particles" can be measured using a Coulter counter (for example, manufactured by Nippon Scientific Machinery Co., Ltd.), and the average particle diameter is obtained when the cumulative mass fraction is 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. However, in consideration of the slidability and the windability of the sheet, the layers constituting the polyester sheet of the present invention are used in each layer. The content of 100% by mass of the total component is preferably 0.05% by mass or more and 1.0% by mass or less, and more preferably 0.1% by mass or more and 0.7% by mass or less.

Further, even when a plurality of kinds of inorganic particles are used in combination, the average particle diameter and the content are in the above range, and can be suitably used.

The method of containing the inorganic particles is not particularly limited, and a known method can be employed. For example, it may be added during polymerization; after mixing, a mixer is used for mixing; a high-concentration master batch of inorganic particles is prepared in advance, and then diluted and added.

Further, if necessary, one or two or more kinds of nucleating agents may be added to the polyester sheet of the present invention without departing from the object of the present invention. In the case of a nucleating agent suitable for use in the polyester sheet of the present invention, an inorganic system such as talc may be mentioned. Nucleating agent; an organic amide compound such as ethyl bis-laurate decylamine, ethyl bis-dihydroxy-sodium hydroxystearate and tricyclohexyl decyl phthalate; copper phthalocyanine and pigment yellow-110 A pigment-based nucleating agent; an organic carboxylic acid metal salt, zinc phenylphosphonate or the like.

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 the μd is smaller than 0.20, there may be a case where a winding shift or a meander occurs. On the other hand, when μd is larger than 0.40, there is a possibility that the surface is not slipped between the surfaces of the sequentially laminated layers during the forming process, and the processing failure is caused.

In the polyester sheet of the present invention, the method for satisfying the above-described dynamic friction coefficient to a suitable range is not particularly limited, and examples thereof include a method of containing inorganic particles in the sheet as described above, in particular, inorganic substances are contained in the outermost layer. In the case of the polyester sheet having the layer A, a method in which the layer A contains 20% by mass or more of polylactic acid in 100 parts by mass of the total component of the layer A.

In order to impart design properties to the polyester sheet of the present invention, a printing layer may be formed on the surface layer of the polyester sheet depending on the purpose. From the viewpoint of the adhesion between the ink and the sheet, the printed layer should be laminated directly to the A layer. Further, in order to make the printed layer and the polyester sheet of the present invention better, it is effective to use the polyester A which does not have a melting point in the polyester A used in the layer A. By doing so, it is possible to obtain a card which is excellent in the adhesion of each layer as described later. That is, the card of the present invention is characterized in that it has a printing layer which is directly laminated with the A layer of the polyester sheet.

The printed layer is printable by text, graphics, symbols, patterns, and He formed the composition of the desired print. From the viewpoint of contributing to the adhesion of the ink used in the printing layer to the surface layer of the sheet of the present invention, corona treatment in an air, nitrogen, carbon dioxide gas atmosphere in the surface layer; plasma treatment; ozone treatment; flame Pre-processing such as processing is also possible. Printing can be formed by various printing methods such as gravure printing, lithography, letterpress printing, screen printing, transfer printing, offset printing, inkjet printing, and the like. Further, the ink used for printing may be either a water-based ink or a non-aqueous ink such as a solvent-based ink. The thickness of the printed layer is not particularly limited, and is preferably from 0.1 μm to 10 μm, more preferably from 0.2 μm to 3 μm, even more preferably from 0.4 μm to 1 μm, from the viewpoint of printing appearance.

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

The resin of the raw materials of the A layer and the B layer is melted and extruded in each extruder, and the foreign matter is removed by the mesh metal mesh, and the flow rate is adapted by the gear pump, and then supplied to the manifold tube or supplied to the manifold tube. A feed block is placed on the upper part of the die. Further, in the above-described multiple branch pipe die or feed zone, it is important to set the flow path of the desired number and desired shape as required for the sheet layer construction. The molten resin extruded from each of the extruders is joined to the multiple branch tube die or the supply zone as described above, and is coextruded into a sheet shape from the die. The sheet can be produced by a method in which it is adhered to a casting drum by means of an air knife or externally applied static electricity, and is cooled and solidified to form an unstretched sheet; or a pair of casting drums Discharged from the polishing roller to make it adhere to the casting drum and cooled and solidified to produce unstretched A method of using a contact roll method for a sheet.

Here, in order to prevent surface roughness caused by the incorporation of foreign matter such as a gel or a thermally deteriorated material, a metal mesh of 50 to 400 mesh is preferably used.

Since the polyester sheet of the present invention is excellent in moldability, it can be suitably used as a molded body. That is, the molded body of the present invention is a molded body obtainable from the polyester sheet of the present invention. Here, the molded body means that any processing including press working, cutting, boundary processing, bending processing, and hot forming processing is applied to the sheet.

In terms of a forming method for obtaining a shaped body, which is a polyester sheet using the present invention, vacuum forming, vacuum press forming, plunger assisted forming, linear forming, no drawing forming, inserts and rings can be applied. Various forming methods such as forming and skeleton forming. In terms of the preheating method of the sheet in various forming methods, there is an indirect heating method and a direct heating method of the hot plate, and the indirect heating method is a method of preheating the sheet by using a heating device disposed at a position separated from the sheet; The direct heating method of the board is a method of preheating the sheet by contacting the sheet with the hot plate. The polyester sheet of the present invention can be suitably subjected to vacuum forming processing by indirect heating, vacuum pressure forming, or direct heating by a hot plate. The method of vacuum pressure forming.

The polyester sheet of the present invention is excellent in heat resistance and moldability, and is used in packaging containers, various electronic and electric machines, OA machines, vehicle parts, machine parts, other agricultural materials, fishery materials, and the like, in order to reduce environmental load. It is useful for various purposes such as transporting containers, game tools, and miscellaneous goods. Among these, it is particularly suitable for use in a food molding container, a beverage cap, or the like which requires heat resistance and formability. Further, the poly layer used in the A layer In the case of the ester A, when the polyester A having no melting point is used, the polyester sheet of the present invention is excellent in cold resistance, heat sealability, and printability, and therefore can be suitably used in refrigerated and frozen foods which are particularly resistant to cold resistance. Packaging use, cold snack food packaging use; or especially heat sealability is a necessary transparent box, clear file; or especially for card use and display box use. Here, the card means an ID card, a membership card, a cash card, a credit card, a regular ticket, a pass ticket, and the like. The so-called display box herein means a display panel for backlighting, a display box for cigarettes, a display can for beverage cans, and the like.

Example

[Method for measuring physical properties and evaluation method of effects]

The method for measuring the physical properties and the method for evaluating the effects in the present invention are as follows.

Stack ratio

The sample was cut out from the center of the sheet width direction (hereinafter referred to as the TD direction). By using an epoxy resin resin embedding method, an ultrathin slicer was used to make the sample piece long-hand direction (hereinafter referred to as MD direction) - the thickness direction section was an ultra-thin section at -100 ° C for the observation surface. The film section of the sheet profile was taken using a scanning electron microscope at a magnification of 1,000 times (the magnification was appropriately adjusted), and the thickness of each layer was measured. The observation position was changed, and measurement was performed at 10 points, and the average value of the obtained values was defined as the thickness (μm) of each layer, and the laminate ratio of the sheets was determined from the thickness of each layer.

2. Thickness

Use disc thickness gauge (JIS B7503 (1997), UPRIGHT DIAL GAUGE (0.001×2mm) made by PEACOCK, No.25, good gauge head 5mmφ In the flat shape, 10 points were measured at intervals of 10 cm in the MD direction and the TD direction of the sheet, and the average value thereof was defined as the thickness (μm) of the sheet.

3. Transparency: haze value (%)

The haze value of the sheet was measured using a haze meter HGM-2DP type (manufactured by Suga Test Machine Co., Ltd.). Further, the 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 value) of 5 measurements was made.

4. Impact resistance: impact value (N.m/mm)

The sheet impact value was measured using a film impact tester (manufactured by Toyo Seiki Co., Ltd.) using a hemispherical punch having a diameter of 1/2 Torr in an environment of a temperature of 23 ° C and a humidity of 65% RH. The sheet sample was made into 100 mm × 100 mm, and the measurement was performed 5 times per sample. Further, the impact value per one time was divided back to the thickness of the measurement sample, and the impact value per unit thickness was determined, and the average value of the five measurements was obtained. The sample thickness is measured by a digital micrometer.

5. Storage viscoelasticity

The sheet was cut into a rectangle of 60 mm (TD direction) × width 5 mm (MD direction) to prepare a sample for measurement in the TD direction. Using a dynamic viscoelasticity measuring apparatus (manufactured by Seiko Instruments, DMS6100), the storage elastic modulus (E') at a temperature of 100 °C in the TD direction was determined under the following conditions.

Frequency: 10 Hz, sample length: 20 mm, minimum load: about 100 mN, amplitude: 10 μm, measurement temperature range: -50 ° C to 200 ° C, temperature increase rate: 5 ° C / min.

6. DSC measurement (melting point, glass transition temperature)

The melting point of the resin, the glass transition temperature, is the use of differential scanning calorimeter (Seiko Electronics Co., Ltd., RDC220), and DSC measurement and analysis were carried out based on JIS K7121-1987 and JIS K7122-1987. The measurement conditions were as follows: a sample of 5 mg, a nitrogen atmosphere, a temperature increase rate of 20 ° C / min, and a temperature drop rate of 20 ° C / min.

Let the temperature at the apex of the endothermic peak be the melting point of the resin. Further, the glass transition temperature is set to read the temperature change from the glass state to the rubber state, and the temperature at the intermediate point of the intersection of the following two lines: the straight line extending from each reference line on the vertical axis (the axis representing the heat flow) There is a straight line in the direction, and a curve of the stepwise change of the glass transition. Further, it was measured under the following conditions.

Condition: When measuring DSC, the temperature is raised from 30 ° C to 300 ° C at a temperature increase rate of 20 ° C / min in the first heating step, and then cooled to 30 ° C at a cooling rate of 20 ° C / min, and further in the second heating step. The melting point and the glass transition temperature were measured at a temperature increase rate of 20 ° C / min from 30 ° C to 300 ° C.

7. Intrinsic viscosity

The intrinsic viscosity was measured by dissolving the resin at a concentration of 0.12% by mass in o-chlorophenol at 150 ° C, and then measuring it in a 35 ° C thermostat using an Ubbelohde viscometer.

8. Surface orientation: △P (discrimination of orientation state)

Using the automatic birefringence meter KOBRA-21ADH manufactured by Oji Scientific Instruments Co., Ltd., according to the conditions described in "Materials" Vol.43, No.495, pp.1520-1524, Dec.1994, the relevant sheet samples were obtained. 3 main axis birefringence Δx, Δy, Δz, and using △ x = γ - β, Δy = γ - α, Δz = α - β (γ ≧ β, α is the refractive index of the thickness direction of the sheet The relationship between The orientation of the surface is: △P.

△P={(γ+β)/2}-α=(△y-Δz)/2

Discrimination of orientation state

. Orientation: Surface orientation: ΔP is greater than 0.008.

. Non-orientation: Surface orientation: ΔP is 0 or more and 0.008 or less.

9. Heat resistance of the sheet

The heat resistance of the sheet was measured as shown in Fig. 1. That is, the sheet was cut into 150 mm (TD direction) × 50 mm (MD direction) to prepare a sheet sample for heat resistance measurement. Further, in the direction of the sheet TD, the mark stroke line is made into three parts, and the area in the middle is set as the center portion of the sheet. A double-sided tape is attached to the pillar (50 mm (width) × 50 mm (width)), and the sheet is attached to the pillar so that the region of the central portion of the sheet overlaps with the pillar. The pillars to which the sheets were attached were placed in an oven set to 100 ° C for 30 minutes. Thereafter, the height difference between the pillar height and the both ends of the sheet was read, and the amount of deflection was set as follows.

In addition, the height of the right end is set to the height from the ground to the center of the right end of the MD direction; the height of the left end is set to the height from the ground to the center of the left end of the MD direction; the heights of the two ends of the sheet are set to the height of the right end and the height of the left end. The average value. The heat resistance of the sheet was evaluated by comparing the amount of deflection before and after storage in an oven. If the evaluation of heat resistance is B or more, it can be used practically without any problem.

Flexing amount = height of the pillar - height of the ends of the sheet

Heat resistance of sheet

S: The deflection amount before and after storage in the oven is less than 4mm

A: The amount of deflection before and after storage in the oven is 4 mm or more and less than 8 mm.

B: The amount of deflection before and after storage in the oven is 8 mm or more and less than 12 mm.

C: The amount of deflection before and after storage in the oven was 12 mm or more.

10. Evaluation of heat resistance and formability of a molded body and a molded body

A sheet sample of 320 mm (MD direction) × 460 mm (TD direction) was produced: a small vacuum forming machine made of Chengguang Industry Co., Ltd., which was equipped with a tray-shaped mold having an opening of 150 mm × 210 mm, a bottom surface of 105 mm × 196 mm, and a height of 50 mm. The Model 300X is preheated and formed at a temperature condition in which the sheet temperature during molding is in the range of 110 ° C to 160 ° C.

The obtained molded body was placed in a hot air oven set at 100 ° C for 30 minutes so that the bottom surface portion of the molded body was placed thereon, and the heat resistance of the molded body was evaluated in three stages at a high maintenance rate. Further, the height of the molded body is set such that the molded body is placed with the bottom surface portion thereon, and the height of the bottom surface portion when viewed from the measuring surface. If the heat resistance level is B or more, it can be used without any problem in practical use.

Heat resistance of the formed body

S: 95% or more and 100% or less of the original height (50mm)

A: 90% or more of the original height (50mm), less than 95%

B: 85% or more of the original height (50mm), less than 90%

C: 85% less than the original height (50mm)

Formability of the formed body

S (very good): the sheet can be sufficiently formed until the bottom surface of the tray-shaped formed body, and the thickness of the sheet at the central portion of the bottom surface is maintained in the original film. More than 30% of the thickness.

A (good): The sheet can be sufficiently fitted until the bottom portion of the tray shape, but the sheet thickness of the central portion of the bottom surface is less than 30% of the original film thickness.

C (Molding failure): The sheet was not sufficiently molded until the bottom portion of the tray shape, or even if it was possible to mix and match, it was confirmed that the sheet at the bottom portion was broken.

The moldability was evaluated by measuring the fit of the bottom surface portion when the tray-shaped molded body was produced and the thickness of the sheet at the center portion of the bottom surface. If it is S or A, it can be formed without any problem in practical use.

11. Heat sealability (heat seal strength measurement)

The heat-sealing strength of the sheet was measured by using a heat sealer (TP-701S HEAT SEAL TESTER, TESTER SANGYO CO, LTD) in a residence time of 2.1 kgf/cm ² for 1 second, together with Teflon ( The heated flat upper heat seal fixture of the registered trademark) and the non-heated lower heat seal fixture covered with a glass cloth. The sheet is at a temperature of 80, 90, 100, 110, 120, 130, 140, 150, 160, 170 ° C of a predetermined heat sealing temperature, when the layer A is in the form of the outermost layer or in the form of the layer A/layer B. Heat sealing between each other on the A layer side; when the B layer is in the form of the outermost layer, heat sealing is performed on the B layer side, and the tensile testing machine manufactured by the British Scientific Precision mechanism is used to measure at each temperature. The outermost seal strength. (Examples 1 to 8, 10 to 12, 14 to 49, Comparative Examples 2 and 3 were printed on the A layer; and Examples 9 and 13 and Comparative Example 1 were heat-sealed on the B layer side.)

The peeling test was carried out as follows: the heat-sealed sample was cut out of a 25 mm wide strip, and the two ends that were not heat sealed were mounted on an Instron strength tester. The upper and lower clamps were supported at an angle of 90° to the opposite ends of the unheated seal, and a 90° peel test was performed.

The conditions of the peel test were set as follows. In the peel force curve, the heat seal strength is set by reading the value.

. Peeling test machine: British scientific precision mechanism to do the tensile testing machine

. Peeling angle: 90°

. Peeling speed: 200mm/min

. Recorder (chart) speed: 20mm / min

. Peeling direction: longitudinal direction

. Sample width: 25mm

Three test pieces were taken for the same sample, and the same measurement was performed three times. The average value of the obtained values was defined as heat seal strength (g/25 mm).

The heat sealability was judged on the basis of the following criteria. Among the heat seals at temperatures of 80, 90, 100, 110, 120, 130, 140, 150, 160, and 170 ° C, the highest heat seal strength was used for judgment. In terms of practicality, if it is B or more, it can be used without any problem.

S: 300g/25mm or more

A: 200g/25mm or more and less than 300g/25mm

B: 100g/25mm or more and less than 200g/25mm

C: less than 100g/25mm

12. Printability

The nitrocellulose ink CCST made by Toyo Ink Co., Ltd. was printed on the surface of layer A or layer B with a gravure roll, and placed in a 40 ° C, 90% relative humidity environment for 24 hours. Tape peel test. use "Cellotape" (registered trademark). Examples 1 to 8, 10 to 12, 14 to 49, and Comparative Examples 2 and 3 were printed on the A layer, and Examples 9 and 13 and Comparative Example 1 were printed on the B layer. The evaluation criteria are shown below. In terms of practicality, if it is B or more, it can be used without any problem.

S: There is no peeling at all.

A: The printed portion of the ink having an area ratio of more than 5% and less than 10% is peeled off on the side of the celluloid tape.

B: The printed portion of the ink having an area ratio of more than 10% and less than 15% is peeled off on the side of the celluloid tape.

C: The printed portion of the ink having an area ratio of more than 15% is peeled off on the side of the celluloid tape.

13. Dynamic friction coefficient: μd

Based on JIS-K-7125 (1999), a slip tester (manufactured by Toyo TESTER Industrial Co., Ltd.) was used to make a load of 200 g, depending on the resistance value (resistance) of the stable region after slipping out. Use the following formula to find the value of the friction coefficient: μd.

Here, in the case of a single film structure of only the A layer or a laminated structure such as the A layer/B layer/A layer, when the A layer is formed into the outermost layer of both sides, the A layers are combined and measured. On the other hand, in the laminated structure such as the A layer/B layer, when the A layer and the B layer are the outermost layer, the A layer and the B layer are combined and measured.

Dynamic friction coefficient: μd = resistance value / load

14. Whiteness

The L, a, and b values were obtained using a spectroscopic color difference meter SE-2000 (manufactured by Nippon Denshoku Industries Co., Ltd.), and the whiteness was obtained by the following formula.

Whiteness (%) = 100 - [(100-L) ² + a ² + b ² ] ^1/2

The measurement was performed three times for each sample and was obtained from the average of three measurements.

15. Cold resistance (cold resistance): impact value (N.m/mm)

A sheet impact test was carried out using a film impact tester (manufactured by Toyo Seiki Co., Ltd.) using a hemispherical punch having a diameter of 1/2 inch, and measuring the sheet impact value in an environment of temperature: -20 ° C and humidity of 65% RH. The sheet sample was made into 100 mm × 100 mm, and the measurement was performed 5 times per sample. Further, the impact value per one time was divided back to the thickness of the measurement sample, and the impact value per unit thickness was determined, and the average value of the five measurements was obtained. The sample thickness is measured by a digital micrometer.

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

In the case of polyester A (A1, A2, A3, A4, A5, A1-MB), polyester B (B1, B2, B3, B4), and recycled raw materials (C1, C2), the following physical properties are used.

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

A2: Dicarboxylic acid component: terephthalic acid component = 100 mol%, glycol component: ethylene glycol component / 1,4-cyclohexane dimethanol component / isosorbide component = 28/48/24 Ear %, intrinsic viscosity = 0.65 dl / g, glass transition temperature =110 ° C, melting point = none. It was dried at 90 ° C for 5 hours in a rotary vacuum dryer before use.

A3: Dicarboxylic acid component: terephthalic acid component = 100 mol%, glycol component: ethylene glycol component / 1,4-cyclohexane dimethanol component / isosorbide component = 32/50/18 Mo Ear %, intrinsic viscosity = 0.64 dl / g, glass transition temperature = 95 ° C, melting point = none. It was dried at 90 ° C for 5 hours in a rotary vacuum dryer before use.

A4: Dicarboxylic acid component: terephthalic acid component = 100 mol%, glycol component: ethylene glycol component / 1,4-cyclohexane dimethanol component / isosorbide component = 20/36/44 Mo Ear %, intrinsic viscosity = 0.53 dl / g, glass transition temperature = 145 ° C, melting point = none. It was dried at 90 ° C for 5 hours in a rotary vacuum dryer before use.

A5: Dicarboxylic acid component: terephthalic acid component = 100 mol%, glycol component: ethylene glycol component / 1,4-cyclohexane dimethanol component / isosorbide component = 62/6/32 Ear %, intrinsic viscosity = 0.68 dl / g, glass transition temperature = 122 ° C, melting point = 263 ° C. It was dried at 90 ° C for 5 hours in a rotary vacuum dryer before use.

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. It was dried at 140 ° C for 5 hours in a rotary vacuum dryer before use.

B2: Polylactic acid ("Ingeo" 4043D by Nature Works; D-lactic acid content ratio = 5.0 mol%, Tg = 58 ° C, melting point = 153 ° C). It was dried at 90 ° C for 5 hours in a rotary vacuum dryer before use.

B3: Polylactic acid ("Ingeo" 4032D manufactured by Nature Works; D-lactic acid content ratio = 1.4 mol%, Tg = 58 ° C, melting point = 166 ° C). It was dried at 100 ° C for 5 hours in a rotary vacuum dryer before use.

B4: Polylactic acid ("Ingeo" 4060D manufactured by Nature Works; D lactic acid containing cut ratio = 12 mol%, Tg = 58 ° C, no melting point), and dried at 80 ° C for 5 hours in a rotary vacuum dryer before use.

A1-MB: In the above-mentioned A1, 95% by mass of the above A1 and 5% by mass of aluminum silicate "SILTON" JC-20 (average particle diameter: 2.0 μm) manufactured by Mizusawa Chemical Industry Co., Ltd. are blended. The small piece is set to A1-MB. It was dried at 90 ° C for 5 hours in a rotary vacuum dryer before use.

C1: A sheet obtained by pulverizing the edge of the sheet produced by the film forming step of the sheet or discarding the sheet, and the sheet is produced by the above-described Example 16. It was dried at 90 ° C for 5 hours in a rotary vacuum dryer before use.

C2: A sheet obtained by pulverizing chips (chips, scraps, and the like) generated when a molded article is produced, and the formed body is formed of a sheet made in Example 16 to be described later. It was dried at 90 ° C for 5 hours in a rotary vacuum dryer before use.

(Example 1)

In the resin used for the formation of the layer A, the vented extruder (1) is used, and the vacuum exhausted portion is degassed at 245 ° C, and the mixture is kneaded and melted by A1 (100% by mass) and extruded. The polymer meshed through a mesh mesh of 100 mesh, co-extruded from a T-die having a die temperature of 245 ° C in a single-layer die, and cooled to 40 ° C, respectively, in a pair Casting drum and polishing The spout is sprinkled between the rolls to be cooled and solidified in the casting drum, and after the unstretched sheet is produced, the sheet is taken up by a winder.

The obtained sheet was 250 μm, and the obtained sheet was produced by a method described in the molding system of [Method for Measuring Physical Properties and Effect Evaluation Method].

The characteristic values of the obtained sheet and the molded body are as shown in the table, and the sheet is non-oriented, and is excellent in transparency, impact resistance, heat sealability, printability, heat resistance, and cold resistance, and is excellent in heat resistance of the molded body. .

(Examples 2 to 8, 10 to 12, 45)

Except that the resin of the layer A, the extrusion temperature (°C) of the extruder (1), and the die temperature (°C) are changed as shown in the table, Examples 2 to 8, 10 to 12, and 45 are the same as the examples. 1 The same was obtained to obtain a sheet and a molded body. The physical properties of the obtained sheet and the molded body are shown in the table.

(Example 9)

In the resin used for the formation of the layer B, the vented extruder (2) is used to degas the vacuum exhaust unit at 270 ° C, and the mixture is melted and kneaded with A1 (30% by mass) and B1 ( 70% by mass) and extruded, the polymer was filtered through a mesh mesh of 100 mesh, co-extruded from a T-die having a die temperature of 270 ° C in a single-layer die, and cooled separately At 40 ° C, a pair of casting drums and a polishing roll were discharged and allowed to adhere to the casting drum to be cooled and solidified. After the unstretched sheet was produced, the sheet was taken up by a winder.

The obtained sheet was 250 μm, and the obtained sheet was produced by a method described in the molding system of [Method for Measuring Physical Properties and Effect Evaluation Method].

The characteristic values of the obtained sheet and the molded body are as shown in the table, and the sheet is non-oriented, and is excellent in transparency, impact resistance, and moldability of the molded body.

(Example 13)

Example 13 was obtained in the same manner as in Example 9 except that the resin of the layer B, the extrusion temperature (° C.) of the extruder (2), and the die temperature (° C.) were changed as shown in Table 9. . The physical properties of the obtained sheet and the molded body are shown in the table.

(Example 14)

In the resin used for the formation of the layer A, the vented extruder (1) is used, and the vacuum exhausted portion is degassed at 245 ° C, and the mixture is kneaded and melted by A1 (100% by mass) and extruded. The polymer is filtered through a mesh mesh of 100 mesh and supplied to two multi-layer tube die of three 3-layer laminate types. In addition, in the resin used for the layer B, the vented extruder (2) is used, and the vacuum exhaust unit is deaerated at 280 ° C, and the B1 (100% by mass) is melted and kneaded. Extrusion, in a different flow path from the extruder (1), after the polymer is filtered through a mesh mesh of 100 mesh, it is co-extruded from a T-die having a die temperature of 270 ° C, and is rotated. In the direction of the contact and cooling to 40 ° C, a pair of casting drums and a polishing roll are discharged and adhered to the casting drum to be cooled and solidified. After the unstretched sheet is produced, the sheet is taken up by a winder.

The obtained sheet was 250 μm, and the thickness structure and the thickness ratio were A layer/B layer/A layer=1/8/1, and the obtained sheet was formed by a molding system of [measuring method of physical property and evaluation method of effect]. Part of the method described to produce a shaped body.

The characteristic values of the obtained sheet and the molded body are as shown in the table, and the sheet is non-oriented, and has transparency, impact resistance, heat sealability, printability, heat resistance, It is excellent in cold resistance, and is excellent in moldability and heat resistance of a molded body.

(Examples 15 to 20, 24 to 30, 33 to 44, 46 to 49)

In addition to changing the extrusion temperature (°C) of the resin of the A layer and the B layer, the extruder (1), the extruder (2), the temperature of the die (°C), and the laminate, the embodiment 15~ 20, 24 to 30, 33 to 44, and 46 to 49 were obtained in the same manner as in Example 14 to obtain a sheet and a molded body. The physical properties of the obtained sheet and the molded body are shown in the table.

(Example 21)

In the resin used for the formation of the layer A, the vented extruder (1) is used, and the vacuum exhausted portion is degassed at 245 ° C, and the mixture is kneaded and melted by A1 (100% by mass) and extruded. The polymer was filtered through a mesh mesh of 100 mesh and supplied to two multi-layered tube die of three 3-layer laminate types. In addition, the resin used in the layer A is melted and kneaded with A1 (70% by mass) while degassing the vacuum exhaust unit at 260 ° C in a vented extruder (2). B1 (30 mass%) and extruded, in a different flow path from the extruder (1), after the polymer was filtered through a mesh mesh of 100 mesh, from a T-die having a die temperature of 250 ° C Co-extruded, and rotated to the direction of contact and cooled to 40 ° C, a pair of casting drum and polishing roller spit out and adhered to the casting drum to cool and solidify, after making the unstretched sheet, the coiler Take up the sheet.

The obtained sheet was 250 μm, and the thickness structure and the thickness ratio were A layer/A layer/A layer=1/8/1, and the obtained sheet was formed by a molding system of [measurement method of physical properties and evaluation method of effect]. Part of the method described to produce a shaped body.

The characteristic values of the obtained sheet and molded body are shown in the table, and the sheet is It has no orientation, and is excellent in transparency, impact resistance, heat sealability, printability, heat resistance, and cold resistance, and is excellent in heat resistance.

(Examples 22, 31, 32)

In addition to changing the extrusion temperature (°C) of the resin of the A layer and the B layer, the extruder (1), the extruder (2), the die temperature (° C.), and the laminate, the embodiment 22, 31 and 32 were the same as in Example 21 to obtain a sheet and a molded body. The physical properties of the obtained sheet and the molded body are shown in the table.

(Example 23)

In the resin used for the formation of the layer A, the vented extruder (1) is used, and the vacuum exhausted portion is degassed at 245 ° C, and the mixture is kneaded and melted by A1 (100% by mass) and extruded. The polymer is filtered through a mesh mesh of 100 mesh and supplied to two types of two-layer laminated multi-tube nozzles. In addition, in the resin used for the formation of the B layer, the vented extruder (2) is melted and kneaded at a temperature of 270 ° C at a temperature of 270 ° C (100% by mass). Extrusion, in a different flow path from the extruder (1), after the polymer is filtered through a mesh mesh of 100 mesh, it is co-extruded from a T-die having a die temperature of 270 ° C, and is rotated. In the direction of the contact and cooling to 40 ° C, a pair of casting drums and a polishing roll were discharged and allowed to adhere to the casting drum to be cooled and solidified, and an unstretched sheet was produced, and then the sheet was taken up by a winder.

The obtained sheet is 250 μm, and the thickness structure and the thickness ratio are A layer/B layer=2/8, and the obtained sheet is a method described in the molding system of [Method for measuring physical properties and effect evaluation method]. To make a shaped body.

The characteristic values of the obtained sheet and molded body are shown in the table, and the sheet is It has no orientation, and is excellent in transparency, impact resistance, heat sealability, printability, and moldability of a molded body.

(Comparative Example 1)

In the case of the resin used for the formation of the layer B, Comparative Example 1 was a vented extruder (2), and at a temperature of 280 ° C, the vacuum exhausted portion was degassed and melted and kneaded B1 (100% by mass). And squeezing, the polymer is filtered through a mesh mesh of 100 mesh, and co-extruded from a T-die having a die temperature of 280 ° C in a single-layer die, and cooled to 40 ° C, respectively. A pair of casting drums and a polishing roll are discharged and adhered to the casting drum to be cooled and solidified. After the unstretched sheet is produced, the sheet is taken up by a winder.

The obtained sheet was 250 μm, and the obtained sheet was produced by a method described in the molding system of [Method for Measuring Physical Properties and Effect Evaluation Method].

The characteristic values of the obtained sheet and the molded body are as shown in the table, and the heat sealability, printability, heat resistance of the sheet, and heat resistance of the molded body are inferior.

(Comparative Example 2)

In the resin used for the formation of the layer A, the vented extruder (1) is used, and the vacuum exhausted portion is degassed at 245 ° C, and the mixture is kneaded and melted by A1 (100% by mass) and extruded. The polymer meshed through a mesh mesh of 100 mesh, co-extruded from a T-die having a die temperature of 245 ° C in a single-layer die, and cooled to 40 ° C, respectively, in a pair The casting drum and the polishing roller are spouted together and allowed to adhere to the casting drum for cooling and solidification.

The unstretched sheet obtained was stretched by 3 times in the MD direction at 85 ° C by a roll stretching machine, and immediately cooled to room temperature. Then, the list will be obtained The shaft-stretching film was introduced into a tenter, and while holding both sides with a jig, it was extended 3.2 times in the TD direction at 90 ° C, and then heat-set at 170 ° C, cooled, and then wound up. The obtained sheet was 250 μm, and the obtained sheet and molded body had characteristic values as shown in the table, and since the sheet was biaxially stretched, the sheet was oriented. Since the rigidity of the obtained sheet was high, it was attempted to produce a molded body, and the molding was poor, and the molded body could not be obtained. Moreover, since the molded body could not be obtained, the heat resistance of the molded body could not be evaluated.

(Comparative Example 3)

In the resin used for the formation of the layer A, the vented extruder (1) is used, and the vacuum exhausted portion is degassed at 245 ° C, and the mixture is kneaded and melted by A1 (100% by mass) and extruded. The polymer mesh is filtered through a 100 mesh mesh metal mesh and supplied to two 3-layer laminated multi-frozen tube die. Further, the vented extruder (2) was degassed at 280 ° C, and the kneaded B-1 was melted and melted at 100% by mass, and squeezed to be different from the extruder (1). The flow path is such that the polymer is filtered through a mesh mesh of 100 mesh, and is co-extruded from a T-die having a die temperature of 270 ° C, and rotated to the direction of contact and cooled to 40 ° C, a pair The casting drum and the polishing roller are spouted and adhered to the casting drum to be cooled and solidified. After the unstretched sheet is produced, the sheet is taken up by a winder.

The obtained sheet was 250 μm, the thickness structure and the thickness ratio were A layer/B layer/A layer=1/8/1, and the characteristic values of the obtained sheet and molded body were as shown in the table, because it was a biaxial extension. The sheet is therefore oriented. Since the rigidity of the obtained sheet was high, it was attempted to produce a molded body, and the molding was poor, and the molded body could not be obtained. Moreover, since the molded body could not be obtained, the heat resistance of the molded body could not be evaluated.

Table 1

In the table, the layer A indicates the A layer; the B layer means the B layer.

The polyester sheet of the present invention is excellent in heat resistance and moldability, and is used in packaging containers, various electronic and electric machines, OA machines, vehicle parts, machine parts, other agricultural materials, fishery materials, and the like, in order to reduce environmental load. It is useful for various purposes such as transporting containers, game tools, and miscellaneous goods. Among these, it is particularly suitable for use in a food molding container, a beverage cap, etc., which are required to have heat resistance and formability.

1‧‧‧Sheet Central

2‧‧‧Sheet

3‧‧‧ pillar

4‧‧‧Sheet TD direction

5‧‧‧Sheet MD direction

6‧‧‧ Height at the right end (height from the ground to the center of the MD)

7‧‧‧ Height of the left end (height from the ground to the center of the MD)

8‧‧‧ Height of the pillar

9‧‧‧The right end of the sheet in the MD direction

10‧‧‧The left end of the sheet in the MD direction

11‧‧‧The width of the pillar

12‧‧‧Length of the pillar

Claims (14)

A polyester sheet characterized by containing 1 mol% or more and 60 mol% or less of an ethylene glycol component and 1 mol% or more and 60 mol% in a total of 100 mol% of a glycol component. When the polyester of the isosorbide component of % or less is polyester A, the polyester sheet has a layer containing polyester A and is non-oriented. A polyester sheet according to claim 1, which is in a laminated structure. The polyester sheet of claim 1 or 2, wherein the layer of the polyester A having more than 50% by mass and less than 100% by mass in the total component of the layer is A layer, the sheet has A layer. The polyester sheet according to any one of claims 1 to 3, which contains 1 mol% or more and 60 mol% or less of 1,4-100% by mole of the diol component of the polyester A. Cyclohexane dimethanol component. The polyester sheet according to any one of claims 1 to 4, wherein the aforementioned polyester A does not have a melting point. The polyester sheet according to any one of claims 1 to 5, which is selected from the group consisting of polyethylene terephthalate, polylactic acid, polyethylene naphthalate and polybutylene terephthalate In the case where the polyester B is contained in any one of the groups of the esters, the layer of the polyester B containing more than 50% by mass and 100% by mass or less of 100% by mass of the total component of the layer is the B layer. The material has a B layer. A polyester sheet according to claim 6 wherein the layer B contains polyester A. A polyester sheet according to claim 6 or 7, which is a laminate structure of layer A/layer B/layer A. The polyester sheet of claim 8, which is a laminate structure of layer A/layer B/layer A, and has a laminate ratio of 1/3/1 to 1/20/1. The polyester sheet according to any one of claims 1 to 9, which contains 80 mol% or more and 100 mol% or less of terephthalic acid in a total of 100 mol% of the dicarboxylic acid component of the polyester A. ingredient. The polyester sheet according to any one of claims 1 to 10, which has a whiteness of 70% or more and 100% or less. The polyester sheet according to any one of claims 1 to 11, which has a dynamic friction coefficient μ d of 0.20 or more and 0.40 or less. A molded body obtained by the polyester sheet of any one of claims 1 to 12. A card having a printed layer, and the printed layer is directly laminated with the layer A of the polyester sheet of any one of claims 3 to 12.