JP2017171906A - Thermoplastic resin oriented film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a thermoplastic resin oriented film excellent in flexibility and capable of being applied to molding application excellent in moldability at a low temperature, a protective film, a process film or the like.SOLUTION: There is provided a thermoplastic resin oriented film having an average of elongation in a film length direction and a direction orthogonal to the same at 70°C of 400% or more and 1000% or less and an average of Young modulus in the film length direction and the direction orthogonal to the same at 70°C of 50 MPa or more and 1000 MPa or less.SELECTED DRAWING: None

Description

  The present invention relates to a thermoplastic resin oriented film.

Thermoplastic resin films, especially biaxially oriented polyester films, have excellent properties such as mechanical properties, electrical properties, dimensional stability, transparency, and chemical resistance. Widely used as a substrate film in applications.
However, since the biaxially oriented polyester film is a strong film, it is inferior in flexibility, low-temperature workability and the like. Therefore, unstretched sheets, biaxially oriented films (Patent Document 1), and laminated polyester films (Patent Document 2) using resins such as polyolefins, nylons, and copolyesters are disclosed for applications in which those characteristics are important. .

JP 2003-113259 A JP 2008-030475 A

  However, in order to obtain a molded body by molding the biaxially oriented film and the laminated polyester film disclosed in Patent Document 1 and Patent Document 2, it is necessary to mold at a high temperature. There is a problem that it cannot be used for process film applications that are co-stretched with multiple materials.

  Then, this invention aims at providing the thermoplastic resin orientation film which can be employ | adopted for the molding use excellent in the softness | flexibility and the moldability in low temperature, a protective film, a process film, etc.

In order to solve the above problems, the oriented thermoplastic resin film of the present invention employs the following means.
(1) The average value of the elongation in the film length direction at 70 ° C. and the direction perpendicular thereto is 400% or more and 1000% or less, and the average of the Young's modulus in the film length direction at 70 ° C. and the direction perpendicular thereto A thermoplastic resin oriented film having a value of 50 MPa to 1000 MPa.
(2) The thermoplastic resin oriented film according to (1), wherein a resin constituting the thermoplastic resin oriented film has a polyester resin as a main component.
(3) The thermoplastic resin oriented film according to (1) or (2), wherein the glass transition temperature of the resin constituting the thermoplastic resin oriented film is 30 ° C. or higher and 70 ° C. or lower.
(4) The thermoplastic resin oriented film is a laminated film including a layer made of polyester resin A (hereinafter referred to as A layer) and a layer made of polyester resin B (hereinafter referred to as B layer), wherein the A layer is at least one of The thermoplastic resin oriented film according to any one of (1) to (3), which is the outermost layer.
(5) The thermoplastic resin oriented film according to (4), which is a three-layer laminated film composed of A layer / B layer / A layer.
(6) The thermoplastic resin oriented film according to (4) or (5), wherein the polyester resin A and the polyester resin B satisfy the following (I) and (II):

(I) Glass transition temperature of polyester resin A> Glass transition temperature of polyester resin B (II) Melting point of polyester resin A> Melting point of polyester resin B (7) The polyester resin B has a polybutylene terephthalate resin as a main component. The thermoplastic resin oriented film according to any one of (4) to (6).

  ADVANTAGE OF THE INVENTION According to this invention, it is possible to provide the thermoplastic resin orientation film which was excellent in the softness | flexibility, and was excellent in the moldability in low temperature, and the drawability.

  In the oriented thermoplastic resin film of the present invention, the average value of the elongation in the direction perpendicular to the film length direction at 70 ° C. is 400% or more and 1000% or less, and the film length direction at 70 ° C. is orthogonal to the film length direction. The average value of the Young's modulus in the direction to be is 50 MPa or more and 1000 MPa or less.

  Hereinafter, each requirement of the present invention will be described.

  In the thermoplastic resin oriented film of the present invention, it is important that the average value of the elongation in the film length direction at 70 ° C. and the direction perpendicular thereto is 400% or more and 1000% or less. From the viewpoint of improving handling after molding and co-stretchability with multiple materials, the average value of the elongation in the film length direction at 70 ° C. and the direction perpendicular thereto is particularly preferably 500% or more and 700% or less.

  In the oriented thermoplastic resin film of the present invention, the average value of Young's modulus in the direction perpendicular to the film length direction at 70 ° C. in at least one direction in the plane is important to be 50 MPa or more and 1000 MPa or less. From the viewpoint of improving handling after molding and co-stretchability with multiple materials, 50 MPa or more and 700 MPa or less are more preferable, and 100 MPa or more and 600 MPa or less are particularly preferable.

  The thermoplastic resin oriented film of the present invention can be preferably employed, whether it is a single film or a laminated film, but a laminated film is particularly preferred from the viewpoints of flexibility, moldability, and stretchability. In particular, from the viewpoint of flexibility, moldability, and stretchability, it is preferably a laminated film including a layer made of polyester resin A (hereinafter referred to as A layer) and a layer formed of polyester resin B (hereinafter referred to as B layer). The A layer is preferably located on at least one surface from the viewpoint of releasability from the mold.

  As a preferable configuration in the case where the thermoplastic resin film of the present invention is a laminated film, since it has an A layer and a B layer and the A layer is located on at least one surface, for example, A layer / B 2 layer configuration of layer, 2 types 3 layer configuration of A layer / B layer / A layer, A layer / B layer / A layer / B layer, A layer / B layer / A layer / B layer / A layer, etc. It is also possible to take a multilayer structure. However, considering the manufacturing cost and problems such as blocking during storage of the thermoplastic resin film, the thermoplastic resin film is particularly preferably a two-layer / three-layer configuration of A layer / B layer / A layer.

  When the thermoplastic resin oriented film of the present invention is a laminated film having a three-layer structure of A layer / B layer / A layer, it is preferable that the polyester resin A and the polyester resin B satisfy the following (I) and (II): .

(I) Glass transition temperature of polyester resin A> Glass transition temperature of polyester resin B (II) Melting point of polyester resin A> Melting point of polyester resin B If the glass transition temperature of the polyester resin is within this range, it is co-stretched with other materials. In this case, the co-stretchability is good, and in the case of forming a molded body in the mold forming process, the peelability from the mold at the time of molding is good, which is preferable.
Also, if the melting point of the polyester resin is within this range, when it is co-stretched with other materials, the co-stretchability is good, and when forming into a molded body in the mold molding process, the moldability is good even at low temperatures. preferable.

  Further, the method for adjusting the orientation of the thermoplastic resin film of the present invention at 70 ° C. to 400% to 1000% and the Young's modulus at 70 ° C. to 50 MPa to 1000 MPa is not particularly limited. A method in which a resin having a transition temperature of 30 ° C. or higher and 70 ° C. or lower is melt-coextruded into a sheet and then stretched and heat-treated, and polyester resin A and polyester resin B satisfying the above (I) and (II) are laminated. This can be preferably achieved by a method in which the sheet is melt-coextruded into a sheet and then subjected to stretching and heat treatment.

The thermoplastic resin used for the thermoplastic resin film of the present invention is not particularly limited, and examples thereof include polyester resins such as polyethylene terephthalate and polyethylene naphthalate, polyester elastomers, polyamide resins such as nylon 6 and nylon 66, and polyamide elastomers. Polyolefin resins such as polypropylene and polyethylene, polyolefin elastomers, polyurethane, polylactic acid, and the like can be used. Further, these thermoplastic resins may be copolymerized thermoplastic resins. Furthermore, the thermoplastic resin may be a single type of thermoplastic resin or a mixture of a plurality of thermoplastic resins.
In particular, when a thermoplastic resin oriented film is molded at a low temperature or stretched at a low temperature, a polyester resin can be preferably used as the thermoplastic resin from the viewpoint of flexibility and low temperature deformability.

  The polyester resin means a polymer composed of a dicarboxylic acid component and a glycol component.

  Examples of the dicarboxylic acid component include isophthalic acid component, terephthalic acid component, diphenyl-4,4′-dicarboxylic acid component, 2,6-naphthalenedicarboxylic acid component, naphthalene-2,7-dicarboxylic acid component, naphthalene-1 , 5-dicarboxylic acid component, diphenoxyethane-4,4′-dicarboxylic acid component, diphenylsulfone-4,4′-dicarboxylic acid component, diphenyl ether-4,4′-dicarboxylic acid component, malonic acid component, 1,1 -A dimethylmalonic acid component, a succinic acid component, a glutaric acid component, an adipic acid component, a sebacic acid component, a decamethylene dicarboxylic acid component, etc. can be used.

  Examples of the glycol component include fats such as an ethylene glycol component, a tetramethylene glycol component, a hexamethylene glycol component, a neopentyl glycol component, a 1,3-propanediol component, a 1,4-butanediol component, and a spiroglycol component. Glycol components such as aliphatic glycol components, cycloaliphatic dimethanol components, alicyclic glycol components, bisphenol-A components, aromatic glycol components such as bisphenol-S components, polyethylene glycol components, polypropylene glycol components, polytetramethylene glycol components An ethylene glycol-propylene glycol copolymer component or the like can be used.

  Specific examples of the polyester resin include polyethylene terephthalate (PET), isophthalate copolymerized PET (PET / I), 1,4-cyclohexanedimethanol copolymerized PET (PETG), spiroglycol copolymerized PET, polypropylene terephthalate (PPT). ), Polybutylene terephthalate (PBT), isophthalate copolymerized PBT (PBT / I), polyhexamethylene terephthalate (PHT), polyethylene naphthalate (PEN), polypropylene naphthalate (PPN), polybutylene naphthalate (PBN), Examples include polycyclohexanedimethylene terephthalate (PCT), polyhydroxybenzoate (PHB), polylactic acid (PLA), and ethylene glycol copolymerized polylactic acid.

  The glass transition temperature of the resin constituting the thermoplastic resin oriented film of the present invention is preferably 30 ° C. or higher and 70 ° C. or lower, more preferably 50 ° C. or higher and 70 ° C. from the viewpoint of maintaining stress during molding at low temperature or stretching. It is as follows. As a method of setting the glass transition temperature of the polyester resin within this range, it can be achieved by adopting the polyester resin described above, but adjusting the glass transition point by using two or more resins having different glass transition temperatures in combination. However, it can be preferably achieved, but it can also be preferably achieved by adding a resin plasticizer shown below. Specific examples of the plasticizer include polyester plasticizers such as polypropylene glycol sebacate, polyalkylene ether plasticizers, ether ester plasticizers, and acrylate plasticizers. In addition, when the thermoplastic resin oriented film of the present invention is composed of a plurality of resins, the value at which the glass transition point temperature is most observed is the glass transition temperature.

When the thermoplastic resin oriented film of the present invention is a laminated film having a three-layer structure of A layer / B layer / A layer, the polyester resin B constituting the B layer is polybutylene terephthalate because of low temperature moldability and stretchability. It is preferable to use a resin as a main component.
Here, polybutylene terephthalate includes 70 to 100 mol% of butylene glycol component in a total of 100 mol% of diol components, and 70 to 100 mol% of terephthalic acid component in a total of 100 mol% of dicarboxylic acid components. It is polyester containing 100 mol% or less. As the glycol component other than the butylene glycol component and the dicarboxylic acid component other than the terephthalic acid component, a copolymer component commonly used for polyester can be included. From the viewpoint of solvent resistance and heat resistance, polybutylene terephthalate contains 75 to 100 mol% of butylene glycol component in 100 mol% of the diol component, and terephthal in 100 mol% of dicarboxylic acid component. The acid component is preferably contained in an amount of 80 mol% to 100 mol%, the butylene glycol component is preferably contained in an amount of 85 mol% to 100 mol%, and the terephthalic acid component is preferably contained in an amount of 85 mol% to 100 mol%.

  Examples of the dicarboxylic acid component that can be copolymerized with polybutylene terephthalate include terephthalic acid, isophthalic acid, orthophthalic acid, naphthalenedicarboxylic acid, diphenylcarboxylic acid, diphenylsulfone dicarboxylic acid, diphenoxyethanedicarboxylic acid, and 5-sodium sulfoisophthalic acid. , Aromatic dicarboxylic acids such as phthalic acid, oxalic acid, succinic acid, eicoic acid, adipic acid, sebacic acid, dimer acid, dodecanedioic acid, aliphatic dicarboxylic acid such as maleic acid and fumaric acid, fat such as cyclohexanedicarboxylic acid And polyfunctional acids such as aromatic dicarboxylic acid, trimellitic acid, and pyromellitic acid. On the other hand, examples of diol components that can be copolymerized with polybutylene terephthalate include aliphatic glycols such as ethylene glycol, propanediol, butanediol, pentanediol, hexanediol, neopentyl glycol, and triethylene glycol, bisphenol A, and bisphenol S. And aromatic glycols such as diethylene glycol and polytetramethylene glycol. A plurality of these dicarboxylic acids and / or diol components can also be used.

  Whether the thermoplastic resin oriented film of the present invention is a single layer film or a laminated film, a crystal nucleating agent may be contained for the purpose of improving heat resistance. Examples of the crystal nucleating agent include inorganic nucleating agents such as talc, organic nucleating agents such as dibenzylidene sorbitol, sodium benzoate, and sodium montanate.

  Moreover, various particles can be contained according to the purpose and application. The particles to be contained are not particularly limited as long as they are inert to the polyester resin, and examples thereof include inorganic particles, organic particles, and crosslinked polymer particles. Two or more kinds of these particles may be added.

  The inorganic particles are not particularly limited, but include various carbonates such as calcium carbonate, magnesium carbonate and barium carbonate, various sulfates such as calcium sulfate and barium sulfate, various composite oxides such as kaolin and talc, lithium phosphate and calcium phosphate. Various phosphates such as magnesium phosphate, various oxides such as aluminum oxide, silicon dioxide, and titanium oxide, and various salts such as lithium fluoride can be used.

  As the organic particles, terephthalate such as calcium, barium, zinc, manganese, magnesium and the like can be used.

  Examples of the crosslinked polymer particles include homopolymers or copolymers of vinyl monomers such as divinylbenzene, styrene, acrylic acid, and methacrylic acid. In addition, organic particles such as polytetrafluoroethylene, benzoguanamine resin, thermosetting epoxy resin, unsaturated polyester resin, thermosetting urea resin, and thermosetting phenol resin are also preferably used.

  In addition, various additives such as flame retardants, heat stabilizers, antioxidants, UV absorbers, antistatic agents, plasticizers, tackifiers, fatty acid esters, organic lubricants such as waxes, or antifoaming agents such as polysiloxanes An agent can be appropriately blended within a range that does not impair the effects of the present invention.

  The thickness of the oriented thermoplastic resin film of the present invention is preferably 5 to 500 μm, more preferably 10 to 300 μm. When the thickness of the film is less than 5 μm, the strength of the molded body obtained by molding the oriented thermoplastic resin film may be inferior, and when it exceeds 500 μm, the moldability may be inferior.

In the thermoplastic resin oriented film of the present invention, the oriented film means a film having a plane orientation coefficient fn determined by a measurement method described later of 0.1 × 10 ⁻² or more. The plane orientation coefficient fn is preferably 0.3 × 10 ^{−2 to} 1.2 × 10 ^{−1 and} more preferably 0.5 × 10 ^{−2 to} 1.0 × 10 ⁻¹ from the viewpoint of film handling properties and strength. preferable.
May face orientation coefficient is deformed by stress generated in the process at the time of molding or during the stretching to lower the strength is less than 0.1 × 10 ^-2, molding exceeds 1.2 × 10 ^-1 And stretchability may be poor. As a method of setting the plane orientation coefficient fn to 0.1 × 10 ^{−2 to} 1.2 × 10 ^−1, after the thermoplastic resin of the present invention is melt-extruded into a sheet-like material, stretching and heat treatment are performed, Achievable.

  Next, a typical production method of the present invention will be described, but the present invention is not limited to this.

  The thermoplastic resin oriented film of the present invention is preferably manufactured by a manufacturing method having a step of forming a sheet-like material by a melt extrusion method, a step of stretching, and a step of performing a heat treatment in this order.

  The process for forming the thermoplastic resin oriented film into a sheet is not particularly limited, and can be produced by, for example, a melt extrusion method using a T die.

  That is, when the thermoplastic resin oriented film is a single film, the thermoplastic resin raw material is dried as necessary and then supplied to the melt extruder. Here, as an extruder, both a single screw extruder and a twin screw extruder can be used conveniently. The supplied resin raw material is melted at a temperature of the melting point of the resin, which is the main component of the raw material, at a temperature of 20 to 30 ° C., and then passed through a leaf disk filter or a wire mesh to remove foreign substances and coarse particles. Next, it is led to a slit-shaped T die and extruded into a sheet shape.

  The extruded sheet is brought into close contact with a cooling roll and solidified by cooling. As a method for bringing the extruded sheet into close contact with the cooling roll, a method in which the entire surface of the sheet is sandwiched between a cast drum by a sleeve touch device composed of a roll and a metal belt, and a needle-like edge pinning device is used at both ends of the extruded sheet. Electrostatic application method that applies voltage to the sheet, pneumatic method that blows compressed air over the entire surface of the sheet using an air chamber device, electrostatic application method that applies voltage to the entire width of the sheet using a wire or tape electrostatic application device For example, an air knife method in which compressed air is blown to the entire width of the sheet using an air knife device, but from the viewpoint of cooling the sheet, a static voltage is applied to the entire width of the sheet using a wire type or tape type electrostatic application device. It is preferable to use an electric application method.

  The surface temperature of the cooling roll is preferably 30 ° C. or less from the viewpoint of crystallization and suppression of adhesion, more preferably 25 ° C. or less, and still more preferably 20 ° C. or less. The lower the lower limit of the surface temperature of the cooling roll, the better from the viewpoint of the effect of suppressing crystallization.

  Next, although stretching is not particularly limited, from the viewpoint of stretching accuracy, a method using a heating roll or a method using a tenter oven is preferable, and a method of stretching in the length direction using a heating roll and a tenter oven A sequential biaxial stretching method combined with a method of stretching in the transverse direction is particularly preferred from the viewpoint of achieving the object of the present invention.

  The stretching temperature in the stretching step is preferably the glass transition temperature (Tg) +5 to glass transition temperature (Tg) + 50 ° C. of the raw material having the highest glass transition temperature (Tg), more preferably glass transition temperature (Tg) +5 to glass. Transition temperature (Tg) + 40 ° C., more preferably glass transition temperature (Tg) +5 to glass transition temperature (Tg) + 30 ° C. If the stretching temperature is less than the glass transition temperature (Tg) + 5 ° C., the stretching stress may be high, and if it exceeds the glass transition temperature (Tg) + 50 ° C., the sheet may be softened and the thickness unevenness may be increased.

  The stretch ratio in each step of stretching is preferably 1.5 times to 5.0 times, more preferably 2.0 times to 4.0 times, from the viewpoint of thickness spots and film strength. If the draw ratio is less than 1.5 times, the thickness unevenness may become large, and if it exceeds 5.0 times, the subsequent formability and drawability may be poor.

  Further, after stretching, it is preferable to perform heat treatment for the purpose of reducing heat shrinkage at the time of molding. The melting point (Tg) -10 ° C is preferable, and the melting point (Tg) -40 ° C to the melting point (Tg) -10 ° C is more preferable. When the heat treatment temperature is less than the melting point (Tg) −60 ° C., the moldability at the time of molding may be poor, and when the heat treatment temperature exceeds the melting point (Tg) −10 ° C., the thickness unevenness of the film may increase. .

  Moreover, when the thermoplastic resin distribution film of this invention is a laminated | multilayer film, the polyester resin A (A raw material) which comprises A layer, and the polyester resin B (B raw material) which comprises B layer are each required. After drying, it is fed to a melt extruder. Here, as an extruder, both a single screw extruder and a twin screw extruder can be used conveniently. The supplied resin is melted at a temperature of the melting point of the resin, which is the main component of each raw material + 20 to 30 ° C., and then passed through a leaf disk filter or a wire mesh to remove foreign substances and coarse particles. Next, the feed block is passed so as to have a laminated structure of A raw material / B raw material / A raw material, led to a slit-shaped T die, and extruded into a sheet shape. The extruded sheet is cooled and solidified by being brought into close contact with a cooling roll in the same manner as in the single film.

  The sheet thus obtained can be stretched and heat-treated in the same manner and under the same conditions as the single film, whereby a thermoplastic resin oriented film can be obtained.

[Characteristic measurement method and effect evaluation method]
The characteristic measuring method and the effect evaluating method in the present invention are as follows.

(1) Glass transition temperature (Tg), melting point (Tm)
In the case of a raw material or a single film, 5 mg of a sample is collected, and in the case of a laminated film, 5 mg of a sample is collected for each layer by scraping each layer, and a differential scanning calorimeter DSCII manufactured by Seiko Instrument Co., Ltd. Using the mold, the peak temperature of the endothermic melting curve when the temperature was raised from −30 ° C. to 300 ° C. at a temperature rising rate of 20 ° C./min was defined as the melting point (Tm). Moreover, the glass transition temperature (Tg) was measured on the same measurement conditions.

(2) Young's modulus (MPa) and elongation (%) at 70 ° C
Samples were cut into strips having a length of 150 mm and a width of 10 mm in the direction perpendicular to the length direction and the length direction of the thermoplastic resin oriented film. Using a tensile tester (Orientec Tensilon UCT-100), an initial tensile chuck distance was set to 50 mm, and a tensile speed was set to 300 mm / min. The measurement was performed in an atmosphere at 70 ° C., and Young's modulus and elongation at break (elongation) were determined from the obtained load-strain curve. In addition, the measurement was performed 5 times for each sample, and the average value was evaluated.

(3) Plane orientation coefficient (fn)
The refractive indexes (Nx, Ny, and Nz, respectively) in the longitudinal direction, the width direction, and the thickness direction of the thermoplastic resin oriented film were measured with an Abbe refractometer, and calculated by the following equations.
fn = (Nx + Ny) / 2−Nz.

(4) Warm water stretchability It determined as follows by the magnification at the time of extending | stretching until the thermoplastic resin oriented film fractured | ruptured in the length direction in the water tank filled with the hot water of 70 degreeC.
○: 5 times or more Δ: 4 times or more and less than 5 times ×: Less than 4 times

  Next, although this invention is demonstrated based on an Example and a comparative example, this invention is not limited to these.

  The raw materials used in the production examples, examples, and comparative examples of the present invention are as follows. In addition, the following polyester was used for the manufacture example, the Example, and the comparative example.

[Polybutylene terephthalate A (PBT-A)]
“Toraycon” (registered trademark) 1200M polybutylene terephthalate (glass transition temperature 45 ° C., melting point 225 ° C.) manufactured by Toray Industries, Inc. was used.

[Polybutylene terephthalate B (PBT-B)]
A polybutylene terephthalate copolymer of “Toraycon” (registered trademark) 1100E manufactured by Toray Industries, Inc. (glass transition temperature 45 ° C., melting point 195 ° C.) was used.

[Polyethylene terephthalate A (PET-A)]
To a mixture of 100 parts by mass of dimethyl terephthalate and 60 parts by mass of ethylene glycol, 0.09% by mass of magnesium acetate and 0.03 parts by mass of antimony trioxide are added to the amount of dimethyl terephthalate, and the temperature is increased by a conventional method. Then, a transesterification reaction was performed. Next, 0.20 part by mass of 85% aqueous solution of phosphoric acid is added to the transesterification product with respect to the amount of dimethyl terephthalate, and then transferred to a polycondensation reaction tank. Next, the reaction system was gradually depressurized while heating and heated, and a polycondensation reaction was performed at 290 ° C. under a reduced pressure of 1 mmHg to obtain polyethylene terephthalate having a glass transition temperature of 75 ° C. and a melting point of 257 ° C.

[Polyethylene terephthalate / isophthalate copolymer B (PET-B)]
A polyethylene terephthalate / isophthalate copolymer (glass transition temperature 75 ° C., no melting point) of “I-PET (registered trademark) IP252B” manufactured by Bell Polyester Products Co., Ltd. was used.

[Polylactic acid A (PLA-A)]
Manufactured by Nature Works (Ingeo® Biopolymer (polylactic acid resin) 4032 (D-lactic acid amount: 1.4 mol%)) (glass transition temperature 68 ° C., melting point 168 ° C.)
[Ethylene glycol copolymer polylactic acid B (PLA-B)]
Mixing 62 parts by mass of polyethylene glycol having a number average molecular weight of 8,000, 38 parts by mass of L-lactide, and 0.05 parts by mass of tin octylate, and a temperature of 160 ° C. in a nitrogen atmosphere in a reaction vessel equipped with a stirrer. For 3 hours to obtain an ethylene glycol copolymer polylactic acid having a polylactic acid segment having a number average molecular weight of 2,500 at both ends of polyethylene glycol having a number average molecular weight of 8,000.

Examples 1-3
A raw material mainly composed of polyethylene terephthalate (PET-A raw material) was dried under reduced pressure at 180 ° C. for 4 hours. A raw material mainly composed of polybutylene terephthalate (PBT-A raw material) was dried under reduced pressure at 150 ° C. for 4 hours. These two types of raw materials were blended 1: 1, and the raw material (PBT-) containing a polybutylene terephthalate copolymer as a main component was added to a single screw extruder (L / D = 28) set at an extrusion temperature of 275 ° C. B raw material) was dried under reduced pressure at 120 ° C. for 4 hours, and then charged into a single-screw extruder (L / D = 28) set at an extrusion temperature of 250 ° C. to obtain a blend of PET-A and PBT-A. A layer consisting of PBT-B, a layer consisting of a blend of PET-A and PBT-A, and a feed block laminating device through a feed block laminating apparatus so that the laminating ratio is 1/8/1. The sheet was extruded into a sheet shape, and the entire width of the extruded sheet was applied with a voltage using a wire-type electrostatic application device, brought into close contact with a casting drum cooled to 20 ° C. and solidified by cooling to obtain a laminated sheet. .

  The sheet thus obtained was led to a stretching machine comprising a preheating part having a preheating roll, a stretching part having a nip roll, and a cooling part comprising a cooling roll, and stretched in the length direction under the conditions and magnifications shown in Table 1. Thereafter, the film stretched in the length direction was guided to a tenter-type transverse stretching machine, and subjected to transverse stretching under the conditions and magnifications shown in Table 1 and heat treatment under the conditions shown in Table 1 to obtain oriented films having thicknesses shown in Table 3.

  The properties of the obtained oriented film are as shown in Table 2. The Young's modulus and elongation at 70 ° C. were satisfactory values, and the hot water stretchability was excellent.

Examples 4-6
In Example 1, the same except that the raw material mainly composed of polyethylene terephthalate (PET-A raw material) and the raw material mainly composed of polybutylene terephthalate (PBT-A raw material) were blended at 7: 3. Thus, a laminated sheet was obtained.
The sheet thus obtained was led to a stretching machine comprising a preheating part having a preheating roll, a stretching part having a nip roll, and a cooling part comprising a cooling roll, and stretched in the length direction under the conditions and magnifications shown in Table 1. Thereafter, the film stretched in the length direction was guided to a tenter type transverse stretching machine, and subjected to transverse stretching under the conditions and magnifications shown in Table 1 and heat treatment under the conditions shown in Table 1, to obtain an oriented film having a thickness shown in Table 2.

  The properties of the obtained oriented film are as shown in Table 3. The Young's modulus and elongation at 70 ° C. were satisfactory values, and the hot water stretchability was excellent.

Examples 7-9
A raw material mainly composed of polyethylene terephthalate (PET-A raw material) was dried under reduced pressure at 180 ° C. for 4 hours. A raw material mainly composed of polybutylene terephthalate B (PBT-B) (PBT-B raw material) was dried under reduced pressure at 120 ° C. for 4 hours. These two types of raw materials were blended 1: 1, and the raw material (PBT-) containing a polybutylene terephthalate copolymer as a main component was added to a single screw extruder (L / D = 28) set at an extrusion temperature of 275 ° C. B raw material) was dried under reduced pressure at 120 ° C. for 4 hours, and then charged into a single-screw extruder (L / D = 28) set at an extrusion temperature of 250 ° C. to obtain a blend of PET-A and PBT-A. (Layer made of polyester resin A) / layer made of PBT-B raw material (polyester resin B) / layer made of a blend of PET-A and PBT-A (polyester resin A) with a lamination ratio of 1/8/1 The sheet was passed through a feed block laminating apparatus so as to form three layers, led to a T-die and extruded into a sheet shape, and the entire width of the extruded sheet was cooled to 20 ° C. by applying a voltage using a wire-type electrostatic application device. Caste In close contact it cooled and solidified to Ngudoramu to obtain a laminated sheet.

  The sheet thus obtained was led to a stretching machine comprising a preheating part having a preheating roll, a stretching part having a nip roll, and a cooling part comprising a cooling roll, and stretched in the length direction under the conditions and magnifications shown in Table 1. Thereafter, the film stretched in the length direction was guided to a tenter-type transverse stretching machine, and subjected to transverse stretching under the conditions and magnifications shown in Table 1 and heat treatment under the conditions shown in Table 1 to obtain oriented films having thicknesses shown in Table 3.

  The properties of the obtained oriented film are as shown in Table 3. The Young's modulus and elongation at 70 ° C. were satisfactory values, and the hot water stretchability was excellent.

Examples 10-12
In Example 7, the same procedure except that two raw materials, a raw material mainly composed of polyethylene terephthalate (PET-A raw material) and a raw material mainly composed of polybutylene terephthalate (PBT-B raw material) were blended at 7: 3. Thus, a laminated sheet was obtained.
The sheet thus obtained was led to a stretching machine comprising a preheating part having a preheating roll, a stretching part having a nip roll, and a cooling part comprising a cooling roll, and stretched in the length direction under the conditions and magnifications shown in Table 1. Thereafter, the film stretched in the length direction was guided to a tenter-type transverse stretching machine, and subjected to transverse stretching under the conditions and magnifications shown in Table 1 and heat treatment under the conditions shown in Table 1 to obtain oriented films having thicknesses shown in Table 3.

  The properties of the obtained oriented film are as shown in Table 3. The Young's modulus and elongation at 70 ° C. were satisfactory values, and the hot water stretchability was excellent.

Examples 13-15
A raw material mainly composed of polyethylene terephthalate (PET-B raw material) was dried under reduced pressure at 180 ° C. for 4 hours. A raw material mainly composed of polybutylene terephthalate (PBT-A raw material) was dried under reduced pressure at 150 ° C. for 4 hours. These two types of raw materials were blended 1: 1, and the raw material (PBT-) containing a polybutylene terephthalate copolymer as a main component was added to a single screw extruder (L / D = 28) set at an extrusion temperature of 275 ° C. B raw material) was dried under reduced pressure at 120 ° C. for 4 hours, and then charged into a single-screw extruder (L / D = 28) set at an extrusion temperature of 250 ° C., and a blend of PET-B and PBT-A. A layer consisting of PBT-B, a layer consisting of a blend of PET-B and PBT-A, and a feed block laminating device through a feed block laminating apparatus so that the laminating ratio is 3/8/1. The sheet was extruded into a sheet shape, and the entire width of the extruded sheet was applied with a voltage using a wire-type electrostatic application device, brought into close contact with a casting drum cooled to 20 ° C. and solidified by cooling to obtain a laminated sheet. .

  The sheet thus obtained was led to a stretching machine comprising a preheating part having a preheating roll, a stretching part having a nip roll, and a cooling part comprising a cooling roll, and stretched in the length direction under the conditions and magnifications shown in Table 1. Thereafter, the film stretched in the length direction was guided to a tenter-type transverse stretching machine, and subjected to transverse stretching under the conditions and magnifications shown in Table 1 and heat treatment under the conditions shown in Table 1 to obtain oriented films having thicknesses shown in Table 3.

  The properties of the obtained oriented film are as shown in Table 3. The Young's modulus and elongation at 70 ° C. were satisfactory values, and the hot water stretchability was excellent.

Examples 16-18
In Example 13, the same procedure except that two raw materials, a raw material mainly composed of polyethylene terephthalate (PET-B raw material) and a raw material mainly composed of polybutylene terephthalate (PBT-A raw material) were blended at 7: 3. Thus, a laminated sheet was obtained.
The sheet thus obtained was led to a stretching machine comprising a preheating part having a preheating roll, a stretching part having a nip roll, and a cooling part comprising a cooling roll, and stretched in the length direction under the conditions and magnifications shown in Table 1. Thereafter, the film stretched in the length direction was guided to a tenter-type transverse stretching machine, and subjected to transverse stretching under the conditions and magnifications shown in Table 1 and heat treatment under the conditions shown in Table 1 to obtain oriented films having thicknesses shown in Table 3.

  The properties of the obtained oriented film are as shown in Table 3. The Young's modulus and elongation at 70 ° C. were satisfactory values, and the hot water stretchability was excellent.

Examples 19-21
A raw material mainly composed of polyethylene terephthalate (PET-B raw material) was dried under reduced pressure at 180 ° C. for 4 hours. A raw material mainly composed of polybutylene terephthalate (PBT-B raw material) was dried under reduced pressure at 150 ° C. for 4 hours. These two types of raw materials were blended 1: 1, and the raw material (PBT-) containing a polybutylene terephthalate copolymer as a main component was added to a single screw extruder (L / D = 28) set at an extrusion temperature of 275 ° C. B raw material) was dried under reduced pressure at 120 ° C. for 4 hours, and then charged into a single-screw extruder (L / D = 28) set at an extrusion temperature of 250 ° C., and a blend of PET-B and PBT-B. A layer consisting of PBT-B, a layer consisting of a raw material of PET-B and a layer consisting of a blend of PET-B and PBT-B. The sheet was extruded into a sheet shape, and the entire width of the extruded sheet was applied with a voltage using a wire-type electrostatic application device, brought into close contact with a casting drum cooled to 20 ° C. and solidified by cooling to obtain a laminated sheet. .

  The sheet thus obtained was led to a stretching machine comprising a preheating part having a preheating roll, a stretching part having a nip roll, and a cooling part comprising a cooling roll, and stretched in the length direction under the conditions and magnifications shown in Table 2. Thereafter, the film stretched in the length direction was guided to a tenter-type transverse stretching machine, and subjected to transverse stretching under the conditions and magnifications shown in Table 2 and heat treatment under the conditions shown in Table 2 to obtain oriented films having thicknesses shown in Table 4.

  The properties of the obtained oriented film are as shown in Table 4. The Young's modulus and elongation at 70 ° C. were satisfactory values, and the hot water stretchability was excellent.

Examples 22-24
Example 19 is the same as Example 19 except that two raw materials, a raw material mainly composed of polyethylene terephthalate (PET-B raw material) and a raw material mainly composed of polybutylene terephthalate (PBT-B raw material) were blended at 7: 3. Thus, a laminated sheet was obtained.
The sheet thus obtained was led to a stretching machine comprising a preheating part having a preheating roll, a stretching part having a nip roll, and a cooling part comprising a cooling roll, and stretched in the length direction under the conditions and magnifications shown in Table 2. Thereafter, the film stretched in the length direction was guided to a tenter-type transverse stretching machine, and subjected to transverse stretching under the conditions and magnifications shown in Table 2 and heat treatment under the conditions shown in Table 2 to obtain oriented films having thicknesses shown in Table 4.

  The properties of the obtained oriented film are as shown in Table 4. The Young's modulus and elongation at 70 ° C. were satisfactory values, and the hot water stretchability was excellent.

Examples 25 and 26
A polylactic acid (PLA-A) raw material and an ethylene glycol copolymer polylactic acid (PLA-B) raw material were blended so as to have a ratio of 7: 3, and then charged into a vent type twin screw extruder heated to 220 ° C. While adjusting the extrusion amount, it is guided to a T-die and extruded into a sheet shape, and the entire width of the extruded sheet is applied to a casting drum cooled to 20 ° C. by applying a voltage using a wire type electrostatic application device. The mixture was cooled and solidified to obtain a laminated sheet.

  The sheet thus obtained was led to a stretching machine comprising a preheating part having a preheating roll, a stretching part having a nip roll, and a cooling part comprising a cooling roll, and stretched in the length direction under the conditions and magnifications shown in Table 2. Thereafter, the film stretched in the length direction was guided to a tenter-type transverse stretching machine, and subjected to transverse stretching under the conditions and magnifications shown in Table 2 and heat treatment under the conditions shown in Table 2 to obtain oriented films having thicknesses shown in Table 4.

  The properties of the obtained oriented film are as shown in Table 4. The Young's modulus and elongation at 70 ° C. were satisfactory values, and the hot water stretchability was excellent.

Examples 27 and 28
A raw material mainly composed of polyethylene terephthalate (PET-A raw material) was dried under reduced pressure at 180 ° C. for 4 hours. A raw material mainly composed of polybutylene terephthalate (PBT-A raw material) was dried under reduced pressure at 150 ° C. for 4 hours. These two types of raw materials were blended 1: 1, and the raw material (PBT-) containing a polybutylene terephthalate copolymer as a main component was added to a single screw extruder (L / D = 28) set at an extrusion temperature of 275 ° C. B raw material) was dried under reduced pressure at 120 ° C. for 4 hours, and then charged into a single-screw extruder (L / D = 28) set at an extrusion temperature of 250 ° C., respectively. A feed block laminating device is passed through the feed block laminator so that the layer is composed of a blend of A and PBT-A / the layer composed of the PBT-B raw material and the laminating ratio is 1/8/1. Then, a voltage was applied to the entire width of the extruded sheet using a wire-type electrostatic application device, and the sheet was brought into close contact with a casting drum cooled to 20 ° C. to be cooled and solidified to obtain a laminated sheet.

  The sheet thus obtained was led to a stretching machine comprising a preheating part having a preheating roll, a stretching part having a nip roll, and a cooling part comprising a cooling roll, and stretched in the length direction under the conditions and magnifications shown in Table 2. Thereafter, the film stretched in the length direction was guided to a tenter-type transverse stretching machine, and subjected to transverse stretching under the conditions and magnifications shown in Table 2 and heat treatment under the conditions shown in Table 2 to obtain oriented films having thicknesses shown in Table 4.

  The properties of the obtained oriented film are as shown in Table 4. The Young's modulus and elongation at 70 ° C. were almost satisfactory values, and the hot water stretchability was excellent.

Examples 29 and 30
A raw material mainly composed of polyethylene terephthalate (PET-B raw material) was dried under reduced pressure at 180 ° C. for 4 hours. A raw material mainly composed of polybutylene terephthalate (PBT-A raw material) was dried under reduced pressure at 150 ° C. for 4 hours. These two types of raw materials were blended 1: 1, and the raw material (PBT-) containing a polybutylene terephthalate copolymer as a main component was added to a single screw extruder (L / D = 28) set at an extrusion temperature of 275 ° C. B raw material) was dried under reduced pressure at 120 ° C. for 4 hours, and then charged into a single-screw extruder (L / D = 28) set at an extrusion temperature of 250 ° C., respectively. B and PBT-A blended layer / PBT-B raw material layer with a lamination ratio of 1/8/1 through a feed block laminating device, led to a T die and extruded into a sheet Then, a voltage was applied to the entire width of the extruded sheet using a wire-type electrostatic application device, and the sheet was brought into close contact with a casting drum cooled to 20 ° C. to be cooled and solidified to obtain a laminated sheet.

  The sheet thus obtained was led to a stretching machine comprising a preheating part having a preheating roll, a stretching part having a nip roll, and a cooling part comprising a cooling roll, and stretched in the length direction under the conditions and magnifications shown in Table 2. Thereafter, the film stretched in the length direction was guided to a tenter-type transverse stretching machine, and subjected to transverse stretching under the conditions and magnifications shown in Table 2 and heat treatment under the conditions shown in Table 2 to obtain oriented films having thicknesses shown in Table 4.

  The properties of the obtained oriented film are as shown in Table 4. The Young's modulus and elongation at 70 ° C. were almost satisfactory values, and the hot water stretchability was excellent.

Comparative Examples 1-3
A raw material mainly composed of polyethylene terephthalate (PET-A raw material) was dried under reduced pressure at 180 ° C. for 4 hours. This raw material is put into a single-screw extruder (L / D = 28) set at an extrusion temperature of 280 ° C., guided to a T-die and extruded into a sheet shape, and the entire width of the extruded sheet is measured using a wire-type electrostatic application device. A single film sheet was obtained by applying a voltage to bring it into close contact with a casting drum cooled to 20 ° C. and solidifying by cooling.

  The sheet thus obtained was led to a stretching machine comprising a preheating part having a preheating roll, a stretching part having a nip roll, and a cooling part comprising a cooling roll, and stretched in the length direction under the conditions and magnifications shown in Table 2. Thereafter, the film stretched in the length direction was guided to a tenter-type transverse stretching machine, and subjected to transverse stretching under the conditions and magnifications shown in Table 2 and heat treatment under the conditions shown in Table 2 to obtain oriented films having thicknesses shown in Table 4.

  The properties of the obtained oriented film are as shown in Table 4. The Young's modulus and elongation at 70 ° C. were unsatisfactory values, resulting in poor hot water stretchability.

Comparative Examples 4 and 5
A raw material (PET-B) mainly composed of polyethylene terephthalate / isophthalate copolymer is put into a vent type twin screw extruder heated to 270 ° C., and is guided to a T die while adjusting the extrusion amount with a gear pump. A voltage was applied to the entire width of the extruded sheet using a wire-type electrostatic application device, and the sheet was brought into close contact with a casting drum cooled to 20 ° C. to be cooled and solidified to obtain a laminated sheet.

  The sheet thus obtained was led to a stretching machine comprising a preheating part having a preheating roll, a stretching part having a nip roll, and a cooling part comprising a cooling roll, and stretched in the length direction under the conditions and magnifications shown in Table 2. Thereafter, the film stretched in the length direction was guided to a tenter-type transverse stretching machine, and subjected to transverse stretching under the conditions and magnifications shown in Table 2 and heat treatment under the conditions shown in Table 2 to obtain oriented films having thicknesses shown in Table 4.

  The properties of the obtained oriented film are as shown in Table 4. The Young's modulus and elongation at 70 ° C. were unsatisfactory values, resulting in poor hot water stretchability.

The meanings of the abbreviations in the table are as follows: PET: Polyethylene terephthalate PBT: Polybutylene terephthalate PLA: Polylactic acid

Claims (7)

The average value of the elongation in the film length direction at 70 ° C. and the direction perpendicular thereto is 400% or more and 1000% or less, and the average value of the Young's modulus in the direction perpendicular to the film length direction at 70 ° C. is 50 MPa. The thermoplastic resin oriented film which is 1000 MPa or less. The thermoplastic resin oriented film according to claim 1, wherein a resin constituting the thermoplastic resin oriented film has a polyester resin as a main component. The thermoplastic resin oriented film according to claim 1 or 2, wherein a glass transition temperature of a resin constituting the thermoplastic resin oriented film is 30 ° C or higher and 70 ° C or lower. The thermoplastic resin oriented film is a laminated film including a layer made of polyester resin A (hereinafter referred to as A layer) and a layer made of polyester resin B (hereinafter referred to as B layer), wherein A layer is at least one outermost layer. The thermoplastic resin oriented film according to any one of claims 1 to 3. The thermoplastic resin oriented film according to claim 4, which is a three-layer laminated film comprising A layer / B layer / A layer. The thermoplastic resin oriented film according to claim 4 or 5, wherein the polyester resin A and the polyester resin B satisfy the following (I) and (II).
(I) Glass transition temperature of polyester resin A> Glass transition temperature of polyester resin B (II) Melting point of polyester resin A> Melting point of polyester resin B The thermoplastic resin oriented film according to any one of claims 4 to 6, wherein the polyester resin B contains a polybutylene terephthalate resin as a main component.