JP2014069384A - Laminate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a laminate which is provided with a polyester film having a specific plane orientation coefficient on both sides of a metal foil and can obtain a molded product which can be deeply drawn and is excellent in shape holding property and durability.SOLUTION: There is provided a laminate which is obtained by laminating a polyester film on both sides of a metal foil (A) having a thickness of 10 μm or more and 100 μm or less, wherein the plane orientation coefficient (fn) is 0.161 or more and 0.178 or less in any of the polyester films and the absolute value of the difference between the plane orientation coefficients of the polyester films laminated on both sides is 0.01 or less.

Description

  The present invention relates to a laminate in which a polyester film is provided on both sides of a metal foil, and more particularly to a laminate that can be suitably used for battery exteriors and pharmaceutical packaging applications that are subjected to molding processing.

  Metals such as aluminum, stainless steel, gold, silver, and copper make use of the mechanical properties, thermal properties, optical properties, electrical properties, and physical properties unique to each metal to provide electrical materials, packaging materials, decorative materials, Widely used in various applications such as building materials and optical materials. In particular, metal gas barrier properties and water vapor barrier properties are being applied to packaging applications such as battery outer packaging, pharmaceutical packaging, capacitor outer packaging, and food packaging. Since there is a high need for an increase in volume due to the transformation, deep drawability of metal foil is necessary. For pharmaceutical packaging, the molding process is performed according to the contents, and the processability of the metal foil is important.

  For example, as a method for forming metal foil for battery exterior use, a method of laminating a polyamide film as a thermoplastic resin film on one side of the metal foil and processing the metal foil by following the formation of the polyamide film is adopted. (For example, see Patent Document 1). Moreover, the laminated body which laminates | stacks the polyester film with high piercing strength on metal foil, and improves a moldability is proposed (for example, refer patent document 2). Furthermore, a configuration in which a polyamide film or a polyester film is laminated on both sides of the metal foil has been proposed in order to enhance the shape retention and durability of the molded product after molding (for example, Patent Document 3).

  In addition, for medical packaging, there is a growing need for packaging forms with metal foil to prevent deterioration of the contents. Improvement of metal foil moldability and molded product shape retention after molding according to the shape of the contents. There is a need for improved durability.

JP 2006-236938 A JP 2011-204673 A JP 2004-327042 A JP 2011-138793 A

  However, in Patent Document 1, since the polyamide film is laminated on one side of the metal foil, the molded body warps to the polyamide film side after molding, or delamination occurs between the film and the metal foil during long-time storage. There was a problem to do.

Moreover, although patent document 2 has laminated | stacked the polyester film with high piercing strength on the one side of metal foil, since a lamination | stacking only on the one side of metal foil, a moldability is inadequate, and it shape | molds like patent document 1. There was a problem that the molded body was later warped toward the polyester film.
The laminate described in Patent Document 3 has insufficient moldability of the polyester film used in the laminate, making it difficult for the molded body to achieve sufficient moldability, and durability after molding. There was also a problem.

  Moreover, since the laminated body of patent document 4 is using the polyamide film laminated | stacked on both sides of metal foil, and the polyester film, the elongation at break, a breaking point as a laminated body are used. The strength was insufficient, and the deep drawability and pinhole resistance during molding were not satisfactory.

  An object of the present invention is to eliminate the above-described problems. That is, a polyester film having a specific plane orientation coefficient is provided on both sides of a metal foil to provide a laminate capable of obtaining a molded product that can be deep drawn and has excellent shape retention and durability. There is to do.

The present invention for solving the above problems has the following configuration.
(1) A laminate formed by laminating a polyester film on both sides of a metal foil (A) having a thickness of 10 μm or more and 100 μm or less,
In any of the polyester films, the plane orientation coefficient (fn) is 0.161 or more and 0.178 or less,
The laminated body whose absolute value of the difference of the plane orientation coefficient of the said polyester film laminated | stacked on both sides is 0.01 or less.
(2) The laminate according to (1), wherein the thermal shrinkage rate after heat treatment at 190 ° C. for 10 minutes is 5% or more in both the longitudinal direction and the width direction in any of the polyester films.
(3) In any of the polyester films, the thermal shrinkage ratio after heat treatment at 190 ° C. for 10 minutes exceeds 6% in both the longitudinal direction and the width direction.
(4) When the thickness of the polyester film is 9 μm or more and 40 μm or less, respectively, the polyester film (B) having a small thickness and the polyester film (C) having a large polyester film,
The laminate according to claim 1, wherein a thickness ratio (H) of the polyester film (B) and the polyester film (C) satisfies the following formula.
0.5 ≦ H _B / H _C <1 (I)
(5) The laminate according to (1), wherein the thickness of each polyester film is 9 μm or more and 40 μm or less, and the thickness is the same.
(6) The laminate according to any one of (1) to (5), wherein the metal foil (A) and the polyester film are laminated via an adhesive layer having a thickness of 4 μm or less.
(7) The polyester film (B) or the polyester film (C) of the laminate according to any one of (1) to (6) is further used with a thermoplastic resin having a lower melting point than the resin constituting the polyester film. A laminate obtained by laminating the thermoplastic resin layer (D).
(8) The laminate according to any one of (1) to (7), wherein the metal foil (A) is a foil containing aluminum.
(9) The laminate according to any one of (1) to (8), which is used for battery exterior applications.
(10) The laminate according to (9), which is used for battery exterior use for automobiles.
(11) The laminate according to any one of (1) to (8), which is used for medical packaging applications.
(12) The laminate according to any one of (1) to (8) or (11), which is used for press-through package packaging for tablets.

  The laminated body of the present invention can be deep-drawn by having the above-described configuration, and can be suitably used for a battery exterior structural body and a medical packaging structural body corresponding to high capacity.

The laminated body of this invention has metal foil (A) from a viewpoint of gas barrier property, water vapor | steam barrier property, and intensity | strength.
The metal which comprises the metal foil (A) in this invention can be used according to the objectives, such as aluminum, stainless steel, copper, nickel, titanium, tin, silver, gold | metal | money, zinc. Especially, it is preferable that it is a layer containing aluminum from a viewpoint of a moldability, gas barrier property, water vapor | steam barrier property, intensity | strength, and economical efficiency. The metal foil (A) may be aluminum alone or an aluminum alloy to which copper, zinc, manganese, magnesium, silicon, lithium, iron or the like is added. The aluminum content is preferably 95% by weight or more with respect to the metal foil (A), and a pure aluminum system or an aluminum / iron alloy is preferably used.

  In the present invention, the metal foil (A) is preferably subjected to chemical conversion treatment on at least one side in order to improve the adhesion with the polyester film (B), the polyester film (C), or other layers. As a chemical conversion treatment method, chromic acid chromate treatment, phosphoric acid chromate treatment, coating-type chromate treatment, non-chromium (coating-type) chemical treatment such as zirconium, titanium, zinc phosphate, boehmite treatment, and the like are used.

Further, the metal foil (A) in the present invention needs to have a thickness of 10 μm or more and 100 μm or less.
When the thickness is less than 10 μm, the gas barrier property, water vapor barrier property and strength may be insufficient. On the other hand, when the thickness is 100 μm or more, the strength is too high and sufficient moldability may not be obtained. is there. There is also a demerit that increases the weight. The metal foil (A) is more preferably 20 μm or more and 80 μm or less, and most preferably 30 μm or more and 60 μm or less.

  The laminate of the present invention needs to be provided with a polyester film on both sides of the metal foil (A). The present invention has been found that by laminating a polyester film on both sides of the metal foil (A), both deep drawing followability and post-molding curl resistance can be achieved. In the case of a laminated body in which a polyester film is laminated only on one side of the metal foil (A), there is a limit in molding followability and it is difficult to cope with a deep drawing shape. Further, the molded body may curl to the polyester film side after molding, and may not be used for battery exterior use or pharmaceutical packaging use. Further, the durability becomes insufficient, for example, the molded body is deformed over time.

  In the present invention, the polyester constituting the polyester film is a general term for polymer compounds in which the main bonds in the main chain are ester bonds. The polyester resin can be usually obtained by polycondensation reaction of dicarboxylic acid or its derivative with glycol or its derivative. Here, the dicarboxylic acid unit (structural unit) or the diol unit (structural unit) means a divalent organic group from which a portion to be removed by polycondensation is removed, and is represented by the following general formula.

Dicarboxylic acid unit (structural unit): —CO—R—CO—
Diol unit (structural unit): —O—R′—O—
(Here, R and R ′ are divalent organic groups. R and R ′ may be the same or different.)

  Examples of glycols or derivatives thereof that provide the polyester used in the present invention include ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, 1,5- Aliphatic dihydroxy compounds such as pentanediol, 1,6-hexanediol, neopentyl glycol, diethylene glycol, polyethylene glycol, polypropylene glycol, polyoxyalkylene glycols such as polytetramethylene glycol, 1,4-cyclohexanedimethanol, spiro glycol, etc. Alicyclic dihydroxy compounds, aromatic dihydroxy compounds such as bisphenol A and bisphenol S, and derivatives thereof.

  Examples of the dicarboxylic acid or its derivative that gives the polyester used in the present invention include terephthalic acid, isophthalic acid, phthalic acid, 2,6-naphthalenedicarboxylic acid, diphenyldicarboxylic acid, diphenylsulfone dicarboxylic acid, diphenoxyethanedicarboxylic acid, 5 -Aliphatic dicarboxylic acids such as sodium sulfone dicarboxylic acid, oxalic acid, succinic acid, adipic acid, sebacic acid, dimer acid, maleic acid, fumaric acid and other aliphatic dicarboxylic acids, 1,4-cyclohexanedicarboxylic acid and other alicyclic rings Oxycarboxylic acids such as aliphatic dicarboxylic acids and paraoxybenzoic acids, and derivatives thereof. Examples of dicarboxylic acid derivatives include dimethyl terephthalate, diethyl terephthalate, 2-hydroxyethyl methyl terephthalate, dimethyl 2,6-naphthalenedicarboxylate, dimethyl isophthalate, dimethyl adipate, diethyl maleate, and dimethyl dimer. An esterified product can be mentioned.

  The polyester film of the present invention is preferably a biaxially oriented polyethylene terephthalate film from the viewpoints of moldability, strength, and economy.

  Here, the polyethylene terephthalate film is a polyester film composed of ethylene glycol as a glycol or a derivative thereof, and terephthalic acid as a dicarboxylic acid or a derivative thereof. As long as the object of the present invention is not impaired, other glycols or derivatives thereof and dicarboxylic acids or derivatives thereof may be copolymerized. Specifically, ethylene glycol is 90 mol% or more, more preferably 95 mol% or more, and most preferably 98 mol% or more as a glycol component or a derivative thereof. Moreover, as a dicarboxylic acid component or its derivative (s), terephthalic acid is 90 mol% or more, More preferably, it is 95 mol% or more, Most preferably, it is 98 mol% or more.

Further, in any of the polyester films of the present invention, the plane orientation coefficient needs to be 0.161 or more and 0.178. By setting the plane orientation coefficient of the polyester film to 0.161 or more and 0.178 or less, followability to a deeper shape can be achieved. Here, the plane orientation coefficient refers to a refractive index (n _a ) in any one direction parallel to the film surface using an Abbe refractometer, and a refractive index (n _b ) in a direction perpendicular to the direction in the same plane. The refractive index (n _ZD ) in the thickness direction is measured and calculated from the following formula.
fn = (n _a + n _b ) / 2-n _ZD .

  When the plane orientation coefficient of the polyester film is less than 0.161, molding followability may be insufficient, and when it is attempted to make the plane orientation coefficient higher than 0.178, the film-forming property of the film is significantly reduced. Resulting in. The plane orientation coefficient of the polyester film provided on both sides of the laminate of the present invention is more preferably 0.162 or more and 0.176 or less, and 0.163 or more and 0.1. Most preferably, it is 174 or less.

  Unlike a thick metal plate, a metal foil having a thickness of 10 μm or more and 100 μm or less is broken when trying to be molded, and it is difficult for a single piece to be almost deformed. For this reason, by laminating a flexible layer such as a resin film, the shape may be deformed following the layer, but it is difficult to deform into a deep drawing shape. The laminate of the present invention has a polyester film laminated on both sides of a metal foil (A) having a thickness of 10 μm or more and 100 μm or less, and the plane orientation coefficient (fn) of any of the polyester films is 0.161 or more and 0.00. It has been found that by making it 178 or less, the moldability as a laminate is greatly improved. Moreover, the laminated body of this invention needs that the absolute value of the difference of the plane orientation coefficient of the polyester film laminated | stacked on both sides of metal foil (A) is 0.01 or less. By setting the absolute value of the difference in the plane orientation coefficient to 0.01 or less, molding followability to a deep drawing shape, shape retention that can suppress the occurrence of curling after molding, wrinkle generation by heating after molding, metal Delamination between the foil and the thermoplastic resin substrate layer and deformation over time can be achieved at the same time. From the viewpoint of forming followability to a deep drawing shape and curling resistance after forming, the absolute value of the difference in the plane orientation coefficient of the polyester film laminated on both sides of the metal foil (A) is 0.008 or less. Preferably, 0.005 or less is most preferable.

In any case, the polyester film in the present invention preferably has a thermal shrinkage ratio of 190% at 10 ° C. after 10 minutes of heat treatment in both the longitudinal direction and the width direction of 5% or more. The moldability as a laminated body further improves by making the thermal contraction rate after the heat treatment for 10 minutes at 190 ° C. of the polyester film 5% or more. Even if the plane orientation coefficient of the polyester film in the present invention is the same, the heat shrinkage ratio after heat treatment at 190 ° C. for 10 minutes is 5% or more, or less than 5%. There is a difference. The heat shrinkage ratio after heat treatment for 10 minutes at 190 ° C. of the polyester film indicates that the residual strain of the polyester film is large, and if the residual strain is large, the effect of suppressing the metal foil is effective. The present inventors speculate that the moldability of the laminate is improved by increasing the size. In a thick metal plate, it is unlikely that a large difference in formability occurs due to the slight stress caused by the residual strain of the laminated film, but in a metal foil having a thickness of 10 μm or more and 100 μm or less, the metal foil itself Since the strength is low, it is considered that the moldability is greatly affected due to the residual stress of the laminated film. The laminate of the present invention has a thermal shrinkage rate of 5% or more in both the longitudinal direction and the width direction after heat treatment at 190 ° C. for 10 minutes of the polyester film laminated on both sides of the metal foil (A) having a thickness of 10 μm to 100 μm. From the viewpoint of moldability, the thermal shrinkage after heat treatment at 190 ° C. for 10 minutes is preferably 5.5% or more in both the longitudinal direction and the width direction, and most preferably more than 6%. Further, from the viewpoint of dimensional stability, it is preferable that the thermal shrinkage rate after heat treatment at 190 ° C. for 10 minutes is 15% or less in both the longitudinal direction and the width direction.
The thickness of the polyester film used in the laminate of the present invention is preferably 9 μm or more and 40 μm or less from the viewpoint of molding followability and strength after molding. When the thickness is less than 9 μm, the film is too thin, and the molding followability and the strength after molding may be insufficient. On the other hand, if the thickness is greater than 40 μm, the film may be too thick and the molding followability may be reduced. The thickness of the polyester film is more preferably 12 μm or more and 35 μm or less, and most preferably 15 μm or more and 30 μm or less.

The polyester film of the present invention has a thickness ratio (H) between the polyester film (B) and the polyester film (C) when the polyester film (B) is a thin polyester film and the polyester film (C) is a large polyester film. However, it is preferable that the following formula I is satisfied.
0.5 ≦ H _B / H _C <1 (I)
When H B _/ H _C is less than 0.5 and the thickness difference is too large of a polyester film (B) and polyester film (C), there is a case where curling occurs after molding.

From the viewpoint of curling resistance after molding, the laminate of the present invention is more preferably satisfying the formula I ′, and most preferably satisfying the formula I ″.
0.6 ≦ H _B / H _C ≦ 1 (I ′)
0.7 ≦ H _B / H _C ≦ 1 (I ″).

In the laminate of the present invention, from the viewpoint of curling resistance, it is most preferable that the polyester films laminated on both sides of the metal foil (A) have the same thickness. That is, the form with the same thickness of a polyester film (B) and a polyester film (C) is the most preferable.
The laminate of the present invention is preferably formed by laminating the metal foil (A) and the polyester film via an adhesive layer having a thickness of 4 μm or less. If the adhesive layer is not provided between the metal foil (A) and the polyester film, the adhesive strength is insufficient and the laminate may not be used. On the other hand, when the thickness of the adhesive layer exceeds 4 μm, the long-term stability durability after molding may be deteriorated due to the influence of the adhesive layer, which is not preferable. The metal foil (A) and the polyester film are more preferably laminated through an adhesive layer having a thickness of 3 μm or less, more preferably laminated through an adhesive layer having a thickness of 2 μm or less. Then, it is most preferable if it is laminated via an adhesive layer having a thickness of 0.05 μm or more and 1 μm or less.

  The composition of the adhesive layer in the present invention is not particularly limited, and examples thereof include polyester adhesives, vinyl acetate adhesives, ethylene / vinyl acetate adhesives, urea adhesives, polyurethane adhesives, and the like. A polyurethane-based adhesive is preferably used from the viewpoints of handleability, curability, and adhesive strength.

  Moreover, an olefin resin containing a polar group is also preferably used. Examples of the polar group include a carboxyl group, an acid anhydride group, an epoxy group, an amide group, an ester group, a hydroxyl group, and the like. As a method for incorporating a polar group into an olefin-based resin, a polar group is included. Examples include a method of grafting and / or copolymerizing an unsaturated compound. As unsaturated compounds having a polar group, (meth) acrylic acid, maleic acid, maleic anhydride, itaconic anhydride, glycidyl (meth) acrylate, alkyl (meth) acrylate (1 to 10 carbon atoms) ester, maleic acid Alkyl (C1-C10) ester, (meth) acrylamide, (meth) acrylic acid-2-hydroxyethyl etc. can be mentioned. Here, as the olefin resin, various polyethylene resins such as low density polyethylene, medium density polyethylene, high density polyethylene, linear low density polyethylene, ethylene-α / olefin copolymer polymerized using a metallocene catalyst, polypropylene Polypropylene resins such as ethylene-propylene copolymer and ethylene-propylene-butene copolymer, and polyolefin resins such as methylpentene polymer can be used. Further, a polymer composed of an α-olefin monomer such as ethylene, propylene, butene-1, pentene-1, 4-methylpentene-1, hexene-1, octene-1, and a random copolymer composed of the α-olefin monomer. Also, a block copolymer comprising the α-olefin monomer can be used. Examples of such modified polyolefin resins using unsaturated compounds include “Yumex” manufactured by Sanyo Kasei, “Admer” manufactured by Mitsui Chemicals, “Modic” manufactured by Mitsubishi Chemical, “Orebak” manufactured by Arkema, “Rotada, manufactured by Toyo Kasei” Examples of the modified polyolefin resin modified by oxidative decomposition of the resin include “Viscol” and “Sunwax” manufactured by Sanyo Kasei Co., Ltd. Metal foil (A) In order to further improve the adhesiveness, an ionomer in which a crosslinked structure is formed with a metal ion such as sodium, potassium, zinc, or magnesium can also be preferably used.

  When applying the olefin resin which has a polar group as an adhesive layer of this invention, it is preferable to add a crosslinking agent from a viewpoint of adhesive strength. As the crosslinking agent, a thermally crosslinkable compound such as oxazoline, epoxy, melamine, isocyanate, carbodiimide is preferably used.

  In the laminate of the present invention, a thermoplastic resin layer (D) formed by using a thermoplastic resin having a melting point lower than that of the polyester film formed from the polyester film (B) or (C). It is preferable to be laminated. The melting point is measured and analyzed in accordance with JIS K7121-1987 and JIS K7122-1987 using a differential scanning calorimeter (Seiko Denshi Kogyo's RDC220). Obtained from DSC curve when polyester film (B), polyester film (C), and thermoplastic resin layer (D) were each used in 5 mg samples, and the temperature was raised from 25 ° C to 300 ° C at 20 ° C / min as 1stRun. The temperature at the apex of the obtained endothermic peak was defined as the 1stRun crystal melting peak temperature (melting point). When there are a plurality of crystal melting peaks, the temperature at which the absolute value of the heat flow is the largest is taken as the crystal melting peak temperature, which is taken as the melting point. Here, when a clear melting point is not recognized in the thermoplastic resin layer (D) of the present invention, the glass transition is higher than the melting point of the thermoplastic resin comprising the polyester film (B) and the polyester film (C). Even when the temperature is low, it is included in the thermoplastic resin having a melting point lower than that of the polyester film. The glass transition temperature is measured in the same manner as the melting point, the specific heat change based on the transition from the glass state to the rubber state is read, and the glass transition temperature is determined based on JIS K7121-1987 (how to determine 9.3 glass transition temperature). When there are a plurality of glass transition temperatures, the glass transition temperature of the present invention is the one on the highest temperature side.

  The thermoplastic resin layer (D) is intended to be used as a sealant layer, and preferably has heat sealability. The thermoplastic resin (D) of the present invention preferably has a melting point of 80 ° C. or higher and lower than 220 ° C., more preferably 100 ° C. or higher and 200 ° C. or lower in order to achieve both excellent heat sealability and heat resistance. 120 ° C. or more and 190 ° C. or less is most preferable. Moreover, when a clear melting point is not recognized in the thermoplastic resin layer (D) of the present invention, the glass transition temperature is preferably 80 ° C. or higher and lower than 220 ° C., more preferably 100 ° C. or higher and 200 ° C. or lower. 120 ° C. or more and 190 ° C. or less is most preferable. Examples of the resin layer (D) that satisfies the above preferred melting point range include low density polyethylene, medium density polyethylene, high density polyethylene, linear low density polyethylene, ethylene-based resins such as ethylene-butene copolymer, homopolypropylene, Ethylene-propylene copolymer, propylene-based resin such as ethylene-propylene-butene copolymer, polyolefin resin such as methylpentene resin, cyclic olefin-based resin, polyvinyl chloride, ethylene copolymerizable with vinyl chloride monomer, Vinyl chloride resins such as copolymers of propylene, vinyl acetate, allyl chloride, allyl glycidyl ether, acrylic acid ester, methacrylic acid ester, vinyl ether and the like and vinyl chloride, and mixtures thereof are preferably used.

  The laminate of the present invention is preferably used for battery exterior applications. In order to maintain battery performance, the battery exterior has a water vapor barrier property that prevents the ingress of water vapor, an electrolyte solution property that does not swell with the electrolyte solution, a deep drawing property that meets the need for higher capacity, Long-term stability that maintains the shape is required.

  Since the laminate of the present invention has the metal foil (A), it is excellent in water vapor barrier properties, and is a laminate obtained by laminating polyester films on both sides of the metal foil (A). Because it is excellent in electrolyte solution resistance, deep-drawing moldability, and long-term stability of the laminate after molding, it is possible to obtain a very excellent battery exterior molded body by applying it to battery exterior applications. is there.

  Since the laminate of the present invention is excellent in water vapor barrier properties, electrolytic solution resistance, deep drawability, and long-term stability after molding as described above, it is particularly preferably used for automotive battery exterior applications where the usage environment is severe. be able to.

  Moreover, it is also preferable that the laminated body of this invention is used for a medical packaging use. Medical packaging requires gas barrier properties and water vapor barrier properties to prevent deterioration of the contents, deep-drawing formability to accommodate various shapes of contents, and long-term stability that stabilizes the shape even for long-term storage Needs are growing.

  Since the laminate of the present invention has the metal foil (A), it is excellent in gas barrier properties and water vapor barrier properties, and further a laminate obtained by laminating polyester films on both sides of the metal foil (A). Therefore, it can be used for deep-drawing molding, and also has excellent long-term stability. Therefore, it can be used for pharmaceutical packaging applications to obtain very good molded products for medical packaging. .

  As described above, the laminate of the present invention is excellent in water vapor barrier properties, deep-drawing properties, and long-term stability, and thus can be used particularly preferably for press-through package packaging applications for tablets that have a more strict shape and are stored for a long time. .

[Measurement method of characteristics]
The method for measuring the properties of the laminate and the like is as follows.

(1) The thickness laminate of each layer is embedded in an epoxy resin, and the laminate cross section is cut out with a microtome. The cross section is observed with a transmission electron microscope (TEM H7100 manufactured by Hitachi, Ltd.) at a magnification of 5000 times to determine the thickness of each layer.

(2) Melting point, glass transition temperature Using a differential scanning calorimeter (Seiko Denshi Kogyo Co., Ltd., RDC220), measurement and analysis were performed according to JIS K7121-1987 and JIS K7122-1987. Polyester film (B), polyester film (C) 5 mg, used as a sample, 1stRun, the temperature at the top of the endothermic peak obtained from the DSC curve when the temperature was raised from 25 ° C to 300 ° C at 20 ° C / min. The crystal melting peak temperature (melting point) of 1stRun was used. When there were a plurality of crystal melting peaks, the temperature at which the absolute value of the heat flow was the largest was taken as the crystal melting peak temperature (melting point). Moreover, the specific heat change based on the transition from the glass state to the rubber state is read from the DSC curve obtained under the same conditions, and obtained based on JIS K7121-1987 (how to obtain the 9.3 glass transition temperature).

(3) Composition of polyester A polyester resin or a polyester film is dissolved in hexafluoroisopropanol (HFIP), and the content of each monomer residue and by-product diethylene glycol is quantified using ¹ H-NMR and ¹³ C-NMR.

(4) Refractive index (n _MD ) in the longitudinal direction of the film, refractive index in the width direction (n _TD ), refraction in the thickness direction using an Abbe refractometer with a plane orientation coefficient sodium D line (wavelength 589 nm) as a light source The ratio (n _ZD ) was measured, and the plane orientation coefficient (fn) was calculated from the following formula.
fn = ( _nMD + _nTD ) / 2- _nZD .

(5) Thermal shrinkage after heat treatment at 190 ° C. for 10 minutes The polyester film was cut into strips having a width of 10 mm and a length of 150 mm respectively in the longitudinal direction and the width direction, and parallel to the width direction 25 mm inside from both ends in the length direction. A line was drawn to accurately measure the distance L0 between two parallel lines. Subsequently, the strip-shaped sample was heat-treated in a hot air oven at 190 ° C. for 10 minutes, and after cooling, the distance L1 between two parallel lines was measured. A universal projector (V-16A (manufactured by Nikon)) was used for the measurement, and the measurement was made to a unit of 1 μm. The shrinkage percentage (%) was calculated from the dimensions before heat treatment and the dimensions after heat treatment by the following formula.

Thermal contraction rate (%) = ((L0−L1) / L0) × 100
In addition, 10 samples were measured for each of the longitudinal direction and the width direction, and the average value of each was used as the heat shrinkage rate in that direction.
(6) The moldable laminate is cut into a size of 150 mm × 80 mm, and a 40 mm × 60 mm rectangular male mold (R: 2 mm) and a female mold with a clearance of 0.5 mm between the male mold (R: 2 mm) The laminate was set in a mold made up of) and press-molded (pressurization: 0.1 MPa). The male press indentation height was increased from 5 mm by 1 mm, the test was conducted up to a height of 10 mm, and the evaluation was performed according to the following criteria.
When the laminate has a thermoplastic resin (D) layer, the laminate is set so that the thermoplastic resin (D) layer side is the male side, and the thermoplastic resin (D) layer is not provided. The laminate was set so that the polyester film surface side was the male side.
A: Molded at 7 mm (no damage)
○: Breakage occurred when 5 mm or more and less than 7 mm Δ: Breakage occurred when 3 mm or more and less than 5 mm x: Breakage occurred when 3 mm.

(7) Curling property after molding The laminate formed by the molding method described in (6) is evaluated according to the following criteria for curling property after placing on a horizontal glass table immediately after molding.
A: The lifting height is less than 10 mm.
○: Lifting height is 10 mm or more and less than 20 mm.
(Triangle | delta): The lift height is 20 mm or more and less than 30 mm.
X: The lifting height is 30 mm or more.

(8) Long-term stability After the laminate formed by the molding method described in (5) is evaluated for curl properties after being placed on a horizontal glass stand immediately after molding, the same laminate is stored for a long time ( The film is stored for 240 hours under conditions of a temperature of 23 ° C. and a humidity of 65%, and then the curl property after being placed on a horizontal glass table is evaluated, and evaluated according to the following criteria.
A: The difference between the raised height after long-term storage and the raised height immediately after molding is less than 5 mm.
○: The difference between the lifting height after long-term storage and the lifting height immediately after molding is 5 mm or more and less than 10 mm.
Δ: The difference between the lifting height after long-term storage and the lifting height immediately after molding is 10 mm or more and less than 15 mm.
X: The difference between the raised height after long-term storage and the raised height immediately after molding is 15 mm or more.

  The specific manufacture example of the laminated body of this invention is described below.

  The following were used as the metal foil (A), the polyester film (B), the polyester film (C), and the thermoplastic resin layer (D).

(1) Metal foil (A)
AL-I 40 μm Aluminum / iron alloy having an aluminum content of 99% by mass and an iron content of 1% by mass.

(2) Polyester film (B), (C)
Polyester film-I 10 μm, melting point: 255 ° C., plane orientation coefficient: 0.165
190 ° C. heat shrinkage (MD / TD): 8.3% / 6.5%
Glycol: EG (98 mol%), DEG (2 mol%)
Dicarboxylic acid: TPA (100 mol%).
Polyester film-II 12 μm, melting point: 255 ° C., plane orientation coefficient: 0.168
190 ° C. heat shrinkage (MD / TD): 8.5% / 6.2%
Glycol: EG (98 mol%), DEG (2 mol%)
Dicarboxylic acid: TPA (100 mol%).
Polyester film-III 12 μm, melting point: 255 ° C., plane orientation coefficient: 0.160
190 ° C. heat shrinkage (MD / TD): 7.9% / 6.4%
Glycol: EG (98 mol%), DEG (2 mol%)
Dicarboxylic acid: TPA (97 mol%), IPA: (3 mol%).
Polyester film-IV 16 μm Melting point: 255 ° C., plane orientation coefficient: 0.162
190 ° C. heat shrinkage (MD / TD): 8.3% / 6.7%
Glycol: EG (98 mol%), DEG (2 mol%)
Dicarboxylic acid: TPA (100 mol%).
Polyester film-V 16 μm, melting point: 255 ° C., plane orientation coefficient: 0.173
190 ° C. heat shrinkage (MD / TD): 9.2% / 6.6%
Glycol: EG (98.5 mol%), DEG (1.5 mol%)
Dicarboxylic acid: TPA (100 mol%).
Polyester film-VI 16 μm, melting point: 255 ° C., plane orientation coefficient: 0.168
190 ° C. heat shrinkage (MD / TD): 8.9% / 6.5%
Glycol: EG (98 mol%), DEG (2 mol%)
Dicarboxylic acid: TPA (100 mol%).
Polyester film-VII 25 μm, melting point: 255 ° C., plane orientation coefficient: 0.165
190 ° C. heat shrinkage (MD / TD): 8.3% / 6.4%
Glycol: EG (98 mol%), DEG (2 mol%)
Dicarboxylic acid: TPA (100 mol%).
Polyester film-VIII 25 μm, melting point: 255 ° C., plane orientation coefficient: 0.171
190 ° C. heat shrinkage (MD / TD): 8.5% / 6.3%
Glycol: EG (98 mol%), DEG (2 mol%)
Dicarboxylic acid: TPA (100 mol%).
Polyester film-IX 25 μm, melting point: 255 ° C., plane orientation coefficient: 0.159
190 ° C. heat shrinkage (MD / TD): 7.2% / 6.1%
Glycol: EG (98 mol%), DEG (2 mol%)
Dicarboxylic acid: TPA (95 mol%), IPA: (5 mol%).
Polyester film-X 38 μm, melting point: 255 ° C., plane orientation coefficient: 0.165.
190 ° C. heat shrinkage (MD / TD): 7.5% / 6.2%
Glycol: EG (98 mol%), DEG (2 mol%)
Dicarboxylic acid: TPA (95 mol%), IPA: (5 mol%)
Polyester film-XI 16 μm, melting point: 255 ° C., plane orientation coefficient: 0.168
190 ° C. heat shrinkage (MD / TD): 6.7% / 5.8%
Glycol: EG (98 mol%), DEG (2 mol%)
Dicarboxylic acid: TPA (100 mol%).
Polyester film-XII 16 μm, melting point: 255 ° C., plane orientation coefficient: 0.168
190 ° C. heat shrinkage (MD / TD): 6.1% / 5.4%
Glycol: EG (98 mol%), DEG (2 mol%)
Dicarboxylic acid: TPA (100 mol%).
Polyester film-XIII 16 μm, melting point: 255 ° C., plane orientation coefficient: 0.168
190 ° C. heat shrinkage (MD / TD): 5.3% / 4.4%
Glycol: EG (98 mol%), DEG (2 mol%)
Dicarboxylic acid: TPA (100 mol%).
* EG: Ethylene glycol, DEG: Diethylene glycol TPA: Terephthalic acid, IPA: Isophthalic acid (3) Thermoplastic resin layer (D)
PP-I 40 μm, melting point: 175 ° C. Polypropylene film PP-II 60 μm, melting point: 175 ° C. Polypropylene film PP-III 80 μm, melting point: 175 ° C. Polypropylene film PVC-I 40 μm, melting point: not observed, glass transition temperature: 82 ° C. Polyvinyl chloride film In addition, the laminates obtained in Examples and Comparative Examples described below were evaluated by the following methods.

Example 1
Using AL-I as the metal foil (A), polyester film-I as the polyester film (B), polyester film-I as the polyester film (C), and PP-I as the thermoplastic resin layer (D), A laminate having a laminated structure of polyester film (C) / adhesive layer / metal foil (A) / adhesive layer / polyester film (B) / adhesive layer / thermoplastic resin layer (D) was obtained by the method described below.

First, phosphoric acid chromate treatment was performed as a chemical conversion treatment on both sides of AL-I. Next, a corona discharge treatment (E value = 40 W · min / m ² ) is performed on one surface of the polyester film-I, and a urethane-based adhesive is applied to the corona-treated surface so as to have a dry thickness of 3 μm. The treated AL-I was laminated on both surfaces by dry lamination. Furthermore, a corona discharge treatment (E value = 40 W · min / m ² ) was performed on one side of the PP-I film, and a urethane-based adhesive similar to the above was applied to the corona-treated surface so as to have a dry thickness of 3 μm. The corona-treated surface was positioned on the polyester film-I side to obtain a laminate having the structure of polyester film-I / adhesive layer / AL-II / adhesive layer / polyester film-I / adhesive layer / PP-I.

(Example 2)
Polyester film-II / adhesive layer / AL-II / adhesive layer / polyester film-I / adhesive layer / PP-I in the same manner as in Example 1 except that polyester film-II was used as the polyester film (C). A laminate with the following structure was obtained.

(Example 3)
Polyester film-IV / adhesive layer / AL-I / adhesive layer in the same manner as in Example 2 except that polyester film-II was used as the polyester film (B) and polyester film-IV was used as the polyester film (C). A laminate having a structure of / polyester film-II / adhesive layer / PP-I was obtained.

Example 4
Polyester film-V / adhesive layer / AL-I / adhesive layer / In the same manner as in Example 3 except that polyester film-V was used as the polyester film (B) and polyester film-V was used as the polyester film (C). A laminate having the structure of polyester film-V / adhesive layer / PP-I was obtained.

(Example 5)
Polyester film-VI / adhesive layer / AL-I / adhesive layer / polyester film-V / adhesive layer / PP-I in the same manner as in Example 4 except that polyester film-VI was used as the polyester film (C). A laminate with the following structure was obtained.

(Example 6)
Polyester film-VII / adhesive layer / AL-I / adhesive layer / In the same manner as in Example 5 except that polyester film-VI was used as the polyester film (B) and polyester film-VII was used as the polyester film (C). A laminate having the structure of polyester film-VI / adhesive layer / PP-I was obtained.

(Example 7)
Polyester film-VIII / adhesive layer / AL-I / adhesive layer / In the same manner as in Example 6 except that polyester film-VII was used as the polyester film (B) and polyester film-VIII was used as the polyester film (C). A laminate having the structure of polyester film-VII / adhesive layer / PP-I was obtained.

(Example 8)
Polyester film-X / adhesive layer / AL-I / adhesive layer / In the same manner as in Example 7, except that polyester film-VIII was used as the polyester film (B) and polyester film-X was used as the polyester film (C). A laminate having the structure of polyester film-VIII / adhesive layer / PP-I was obtained.

Example 9
Polyester film-X / adhesive layer / AL-I / adhesive layer / polyester film-X / adhesive layer / PP-I in the same manner as in Example 8 except that polyester film-X was used as the polyester film (B). A laminate with the following structure was obtained.

(Example 10)
Polyester film-II / adhesive layer / AL-I / adhesive layer / polyester film-I / adhesive layer / PP-I in the same manner as in Example 2 except that the surface treatment of AL-I was changed to boehmite treatment. A laminated body having a structure was obtained.

(Example 11)
Using AL-I as the metal foil (A), polyester film-V as the polyester film (B), polyester film-VI as the polyester film (C), and PP-I as the thermoplastic resin layer (D), A laminate having a laminated structure of polyester film (C) / adhesive layer / metal foil (A) / adhesive layer / polyester film (C) / adhesive layer / thermoplastic resin layer (D) was obtained by the method described below.

First, phosphoric acid chromate treatment was performed as a chemical conversion treatment on both sides of AL-I. Next, a film in which an acid-modified olefin + melamine adhesive (dry thickness 1.5 μm) is applied to one side of each of the polyester film-V and the polyester film-VI is converted into a chemical conversion treatment surface of AL-I, Lamination was performed using a laminator so that the adhesive surface was in contact (180 ° C., 0.3 MPa, 2 m / min) to obtain a laminate of polyester film-VI / adhesive layer / polyester film V. Further, a corona discharge treatment (E value = 40 W · min / m ² ) is performed on one side of the PP-I film, and a urethane-based adhesive is applied to the corona treatment surface so as to have a dry thickness of 3 μm. A laminate having a structure of PET-VI / adhesive layer / AL-I / adhesive layer / polyester film-V / adhesive layer / PP-I was obtained so as to be positioned on the polyester film-V side.

(Example 12)
Using AL-I as the metal foil (A), polyester film-V as the polyester film (B), polyester film-VI as the polyester film (C), and PP-I as the thermoplastic resin layer (D), A laminate having a laminated structure of polyester film (C) / adhesive layer / metal foil (A) / adhesive layer / polyester film (B) / adhesive layer / thermoplastic resin layer (D) was obtained by the method described below.

First, phosphoric acid chromate treatment was performed as a chemical conversion treatment on both sides of AL-I. Next, a film in which acid-modified olefin + melamine adhesive (dry thickness: 0.8 μm) is applied to one side of each of polyester film-V and polyester film-VI is converted to a chemical conversion treatment surface of AL-I, Lamination was performed using a laminator so that the adhesive surface was in contact (180 ° C., 0.3 MPa, 2 m / min) to obtain a laminate of polyester film-VI / adhesive layer / polyester film V. Further, a corona discharge treatment (E value = 40 W · min / m ² ) is performed on one side of the PP-I film, and a urethane-based adhesive is applied to the corona treatment surface so as to have a dry thickness of 3 μm. A laminate having a structure of PET-VI / adhesive layer / AL-I / adhesive layer / polyester film-V / adhesive layer / PP-I was obtained so as to be positioned on the polyester film-V side.

(Example 13)
Using AL-I as the metal foil (A), polyester film-V as the polyester film (B), polyester film-VI as the polyester film (C), and PP-I as the thermoplastic resin layer (D), A laminate having a laminated structure of polyester film (C) / adhesive layer / metal foil (A) / adhesive layer / polyester film (B) / adhesive layer / thermoplastic resin layer (D) was obtained by the method described below.

First, phosphoric acid chromate treatment was performed as a chemical conversion treatment on both sides of AL-I. Next, a corona discharge treatment (E value = 40 W · min / m ² ) is performed on one side of each of the polyester film-V and the polyester film-VI, and a urethane-based adhesive is applied to the corona-treated surface with a dry thickness of 4.5 μm. Polyester film-V and polyester film-VI were laminated by dry lamination on both sides of AL-I which had been coated as described above and subjected to phosphoric acid chromate treatment. Further, a corona discharge treatment (E value = 40 W · min / m ² ) is performed on one side of the PP-I film, and a urethane-based adhesive is applied to the corona treatment surface so as to have a dry thickness of 3 μm. A laminate having a configuration of polyester film-IV / adhesive layer / AL-II / adhesive layer / polyester film-V / adhesive layer / PP-I was obtained so as to be positioned on the polyester film-I side.

(Example 14)
Polyester film-IV / adhesive layer / AL-I / adhesive layer / polyester film-II / adhesive layer / PP-II in the same manner as in Example 3 except that PP-II was used as the thermoplastic resin (D). A laminate with the following structure was obtained.

(Example 15)
Polyester film-IV / adhesive layer / AL-I / adhesive layer / polyester film-II / adhesive layer / PP-III in the same manner as in Example 3 except that PP-III was used as the thermoplastic resin (D). A laminate with the following structure was obtained.

(Example 16)
Polyester film-IV / adhesive layer / AL-I / adhesive layer / polyester film-II / adhesive layer / PVC-II in the same manner as in Example 3 except that PVC-I was used as the thermoplastic resin (D). A laminate with the following structure was obtained.

(Example 17)
A laminate was obtained in the same manner as in Example 7 except that the laminated structure was changed to polyester film-VIII / adhesive layer / AL-I / adhesive layer / polyester film-VII / adhesive layer / PP-I.

(Example 18)
Example except that acid-modified olefin + melamine adhesive was used as an adhesive layer between the polyester film (C) and the metal foil (A) and an adhesive layer between the polyester film (B) and the metal foil (A). In the same manner as in Example 4, a laminate having the structure of polyester film-V / adhesive layer / AL-I / adhesive layer / polyester film-V / adhesive layer / PP-I was obtained.

(Example 19)
The same as in Example 4 except that a vinyl acetate adhesive was used as the adhesive layer between the polyester film (C) and the metal foil (A) and the adhesive layer between the polyester film (B) and the metal foil (A). Thus, a laminate having the structure of polyester film-V / adhesive layer / AL-I / adhesive layer / polyester film-V / adhesive layer / PP-I was obtained.

(Example 20)
Except having used the polyester-type adhesive agent as an adhesive layer between a polyester film (C) and metal foil (A), and an adhesive layer between a polyester film (B) and metal foil (A), it is the same as that of Example 4. A laminate having the structure of polyester film-V / adhesive layer / AL-I / adhesive layer / polyester film-V / adhesive layer / PP-I was obtained.

(Example 21)
Polyester film-VI / adhesive layer / AL-I / adhesive layer in the same manner as in Example 1 except that polyester film-VI was used as the polyester film (B) and polyester film-VI was used as the polyester film (C). A laminate having a structure of / polyester film-VI / adhesive layer / PP-I was obtained.

(Example 22)
Polyester film-XI / adhesive layer / AL-I / adhesive layer in the same manner as in Example 1 except that polyester film-XI was used as the polyester film (B) and polyester film-XI was used as the polyester film (C). A laminate having a structure of / polyester film-XI / adhesive layer / PP-I was obtained.

(Example 23)
Polyester film-XII / adhesive layer / AL-I / adhesive layer in the same manner as in Example 1 except that polyester film-XII was used as the polyester film (B) and polyester film-XII was used as the polyester film (C). A laminate having a structure of / polyester film-XII / adhesive layer / PP-I was obtained.

(Example 24)
Polyester film-XIII / adhesive layer / AL-I / adhesive layer in the same manner as in Example 1 except that polyester film-XIII was used as the polyester film (B) and polyester film-XIII was used as the polyester film (C). A laminate having a structure of / polyester film-XIII / adhesive layer / PP-I was obtained.

(Comparative Example 1)
Polyester film-V / adhesive layer / AL-I / adhesive layer / In the same manner as in Example 1 except that polyester film-IV was used as the polyester film (B) and polyester film-V was used as the polyester film (C). A laminate having the structure of polyester film-IV / adhesive layer / PP-I was obtained.

(Comparative Example 2)
Polyester film-III / adhesive layer / AL-I / adhesive layer / In the same manner as in Example 1 except that polyester film-III was used as the polyester film (B) and polyester film-III was used as the polyester film (C). A laminate having the structure of polyester film-III / adhesive layer / PP-I was obtained.

(Comparative Example 3)
Polyester film-IV / adhesive layer / AL-I / adhesive layer / polyester film-III / adhesive layer / PP-I in the same manner as in Comparative Example 2 except that polyester film-IV was used as the polyester film (C). A laminate with the following structure was obtained.

(Comparative Example 4)
Polyester film-IX / adhesive layer / AL-I / adhesive layer / In the same manner as in Example 1 except that polyester film-VIII was used as the polyester film (B) and polyester film-IX was used as the polyester film (C). A laminate having the structure of polyester film-VIII / adhesive layer / PP-I was obtained.

(Comparative Example 5)
Using AL-I as the metal foil (A), polyester film-VIII as the polyester film (C) and PP-I as the thermoplastic resin layer (D), the polyester film (C) / A laminate having an adhesive layer / metal foil (A) / adhesive layer / thermoplastic resin layer (D) laminate structure was obtained.

First, phosphoric acid chromate treatment was performed as a chemical conversion treatment on both sides of AL-I. Next, a corona discharge treatment (E value = 40 W · min / m ² ) is performed on one surface of the polyester film-VIII, and a urethane-based adhesive is applied to the corona-treated surface so as to have a dry thickness of 3 μm. Lamination was performed on one side of the treated AL-I by dry lamination. Further, corona discharge treatment (E value = 40 W · min / m ² ) was performed on one side of the PP-I film, and urethane adhesive (AD-502, CAT10L, ethyl acetate manufactured by Toyo Morton Co., Ltd.) was applied to the corona treatment surface. (Mass ratio 15: 1.5: 25, dry thickness 3 μm) is applied so that the corona-treated surface is positioned on the phosphoric acid chromate-treated surface side of AL-I, and polyester film-VIII / adhesive layer / AL-II / A laminate having the structure of adhesive layer / PP-I was obtained.

  In the table, “ad” represents an adhesive layer.

  The laminate of the present invention is a laminate obtained by laminating a polyester film on both sides of the metal foil (A), and has a plane orientation coefficient (fn) and a plane orientation of the polyester film. By setting the absolute value of the coefficient difference within a specific range, battery exterior applications and pharmaceuticals can be used to achieve molding conformability to deep drawing shapes, pinhole resistance during molding, and curl resistance after molding. It can be preferably used for packaging applications.

Claims (12)

A laminate formed by laminating a polyester film on both sides of a metal foil (A) having a thickness of 10 μm or more and 100 μm or less,
In any of the polyester films, the plane orientation coefficient (fn) is 0.161 or more and 0.178 or less,
The laminated body whose absolute value of the difference of the plane orientation coefficient of the said polyester film laminated | stacked on both sides is 0.01 or less. 2. The laminate according to claim 1, wherein in any of the polyester films, the heat shrinkage ratio after heat treatment at 190 ° C. for 10 minutes is 5% or more in both the longitudinal direction and the width direction. In any of the polyester films, the heat shrinkage ratio after heat treatment at 190 ° C. for 10 minutes exceeds 6% in both the longitudinal direction and the width direction. When the thickness of the polyester film is 9 μm or more and 40 μm or less, respectively, the polyester film (B) having a small thickness and the polyester film (C) having a large polyester film,
The laminate according to claim 1, wherein a thickness ratio (H) of the polyester film (B) and the polyester film (C) satisfies the following formula.
0.5 ≦ H _B / H _C <1 (I) 2. The laminate according to claim 1, wherein the thickness of each polyester film is 9 μm or more and 40 μm or less, and the thickness is the same. The laminate according to any one of claims 1 to 5, wherein the metal foil (A) and the polyester film are each laminated through an adhesive layer having a thickness of 4 µm or less. The thermoplastic resin which uses the thermoplastic resin whose melting | fusing point is lower than the resin which comprises the said polyester film for the polyester film (B) or polyester film (C) of the laminated body in any one of Claims 1-6. A laminate formed by laminating layers (D). The laminate according to any one of claims 1 to 7, wherein the metal foil (A) is a foil containing aluminum. The laminate according to any one of claims 1 to 8, which is used for battery exterior applications. The laminated body of Claim 9 used for the battery exterior use for motor vehicles. The laminate according to any one of claims 1 to 8, which is used for medical packaging. The laminate according to any one of claims 1 to 8 or 11, which is used for press-through packaging for tablets.