JP2004285343A - Metal plate laminating polyester-based film - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a polyester-based film excellent in resistance to breakage and adhesion of the film, when the film is stored for a specified period and then used for lamination, excellent in processability, when a metal plate laminated with the film is formed, and excellent in shock resistance of the formed product which is obtained by processing the laminated metal plate. <P>SOLUTION: This metal plate laminating polyester-based film is formed by subjecting a polyester-based resin composition given by blending a crystalline polyester in which a mol ratio of an amount of total phosphorus added to the polyester on the occasion of its production to an amount of total metal ions added thereto (phosphorus/metal ions) is in a range of 0.4-1.0 and which has a melting point of ≥ 180°C and an olefin-based polymer in a ratio of 70/30 to 99/1 (in wt%) to at least monoaxial drawing in the longitudinal direction and has a heat shrinkage percentage of 2-30% at 150°C in the direction in which the film is drawn, wherein the olefin-based polymer contains functional groups in a range of 200-2,000 eq/ton in the polymer. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a polyester film laminated on the surface of a metal plate used for containers, building materials, outer panels for home electric appliances and the like and used for the purpose of preventing corrosion. More specifically, a film-laminated metal plate with little embrittlement of the film during storage (decrease in longitudinal cut resistance) and good adhesion can be obtained. The present invention relates to a polyester-based film having good properties (for example, drawability, ironing, bending workability), and excellent impact resistance of the film-laminated metal plate and a formed body obtained by processing the metal plate.

  2. Description of the Related Art Conventionally, for the purpose of corrosion prevention, it has been widely practiced to coat a metal plate surface with a solution obtained by dissolving or dispersing various thermosetting resins such as epoxy-based and phenol-based resins in a solvent. However, this method of coating with a thermosetting resin has disadvantages in that it often takes a long time to dry the paint, resulting in a decrease in productivity and undesired problems such as environmental pollution due to a large amount of organic solvents.

  In order to solve such a drawback, for example, a method of coating a thermoplastic resin on a metal plate for a container by a melt extrusion method is known. (For example, see Patent Document 1). A method of coating a resin having a two-layer structure of a polyester layer containing ethylene terephthalate as a main component and a layer obtained by blending a polyester containing ethylene terephthalate and / or ethylene isophthalate as a main component with an olefin polymer by a melt extrusion method is also known. ing. (See Patent Document 2). However, in these coating methods, the thickness of both ends of the coating resin is large, and both ends of the obtained resin-coated metal plate can be trimmed to use only a central portion having a relatively uniform thickness as a material for can making. This was not a satisfactory method.

  In order to avoid such a drawback, a method of laminating a cast film of polyester having a melting point of 120 to 260 ° C. on a heated metal plate is disclosed. (See Patent Document 3). However, in this coating method, the film becomes brittle when the storage period until the obtained cast film is laminated to the metal plate becomes longer, and the film is easily cut off when tension is applied during lamination, which is not a substantially satisfactory method. Was.

  By the way, for example, a coating resin used for a metal plate for drawing and ironing can has a formability that can follow the drawing and ironing process, an adhesiveness that the resin does not peel off from the metal plate, and can withstand impact properties at the time of punching can. Impact resistance is required. However, the conventional coating resin for cans did not always satisfy such requirements.

As a method for improving the impact resistance of a polyester resin, for example, a biaxially stretched laminated film composed of a polyester layer containing polyethylene terephthalate and / or polyethylene isophthalate as a main component and a layer in which polyester and a thermoplastic elastomer are blended is used. Methods are known. (See Patent Document 4). However, according to the method described in the above publication, the adhesion when laminating the polyester film to the metal plate was not sufficient.
JP-A-57-203545 JP-A-7-276564 JP-A-7-207039 JP-A-8-156182

  SUMMARY OF THE INVENTION An object of the present invention is to solve the problems of the conventional technology. That is, when laminating after storing the polyester film for a certain period of time, it is difficult to cut the film, and a film-laminated metal plate having good adhesiveness is obtained. The present invention relates to a polyester-based film having good drawability, squeezing, ironing, and bending workability), and excellent impact resistance of the film-laminated metal plate and a formed body obtained by processing the metal plate.

  The inventors of the present invention have conducted intensive studies and found that the melting point is 180 ° C. or more when the molar ratio (phosphorus / metal ion) between the total amount of phosphorus and the total amount of metal ions added at the time of production is in the range of 0.4 to 1.0. Heat in the stretching direction at 150 ° C., obtained by uniaxially stretching a polyester resin composition obtained by blending a crystalline polyester and an olefin polymer in a ratio of 70/30 to 99/1 (% by weight) at least in the longitudinal direction. A polyester film having a shrinkage of 2 to 30%, wherein the olefin-based polymer is a polymer containing a functional group in a range of 200 to 2000 equivalents / ton in the polymer. The inventors have found that the problem can be solved, and have completed the present invention.

That is, the present invention is as follows.
[1] A crystalline polyester having a melting point of 180 ° C. or more and a melting ratio of 180 ° C. or more, in which the molar ratio (phosphorus / metal ion) of the total amount of phosphorus and the total amount of metal ions added during production is in the range of 0.4 to 1.0, The polyester resin composition blended at a ratio of 70/30 to 99/1 (% by weight) is uniaxially stretched at least in the machine direction. The heat shrinkage in the stretching direction at 150 ° C. is 2 to 30%. A polyester film for bonding a metal plate, wherein the olefin polymer is a polymer containing a functional group in a range of 200 to 2000 equivalents / ton in the polymer.
[2] A resin layer made of crystalline polyester A having a melting point of 180 ° C. or more with a molar ratio (phosphorus / metal ion) of 0.4 to 1.0 between the total amount of phosphorus and the total amount of metal ions added at the time of production. At least a resin sheet having a two-layer structure of (I) and a resin layer (II) composed of a polyester-based resin composition B in which polyester and an olefin-based polymer are blended in a ratio of 70/30 to 99/1 (% by weight) is used. A polyester film having a heat shrinkage of 2 to 30% in a stretching direction at 150 ° C., which is uniaxially stretched in a machine direction, wherein the olefin polymer has a polymer content of 200 to 2000 equivalents / ton in the polymer. A polyester film for bonding a metal plate, which is a polymer containing a functional group in a range.
[3] A resin layer made of crystalline polyester A having a melting point of 180 ° C. or more with a molar ratio (phosphorus / metal ion) of 0.4 to 1.0 between the total amount of phosphorus and the total amount of metal ions added during production. (I) and a resin layer (II) composed of a polyester-based resin composition B in which polyester and an olefin-based polymer are blended in a ratio of 70/30 to 99/1 (% by weight), wherein (I) layer / (II) A polyester film having a heat shrinkage of 2 to 30% in the stretching direction at 150 ° C. obtained by uniaxially stretching at least the longitudinal direction of a laminated resin sheet composed of three layers of layer / (I). A polyester film for bonding metal plates, wherein the olefin polymer is a polymer containing a functional group in the range of 200 to 2000 equivalents / ton in the polymer.
[4] The olefin polymer is
(1) a copolymer comprising as main constituent units at least one or more α-olefins having 2 to 6 carbon atoms and an ethylene bond-forming α, β-unsaturated carboxylic acid or an ester-forming derivative thereof;
Or
(2) The polyester film for bonding a metal plate according to any one of the above (1) to (3), which is a mixture of the copolymer of the above (1) and another polymer.
[5] The olefin-based polymer is a polymer (a) having at least one or more α-olefins having 2 to 6 carbon atoms as a main structural unit, and at least one or more α-olefins having 2 to 6 carbon atoms. And the copolymer (b) having an ethylene-bond-forming α, β-unsaturated carboxylic acid or an ester-forming derivative thereof as a main constituent unit, and for bonding a metal plate according to the above [4]. Polyester film.
[6] The polyester film for bonding a metal plate according to any one of [1] to [5], wherein the total amount of metal ions is the total amount of Mg ions, Ca ions, Mn ions, Zn ions, and Co ions. .

  The polyester-based film of the present invention is hardly cut when laminating after storing the film for a certain period of time, and has good workability (for example, drawing, ironing, bending workability) when molding the film-laminated metal plate. A film-laminated metal sheet which is good and has excellent adhesion and flavor properties is obtained, and the above-mentioned film-laminated metal sheet and the molded article obtained by molding the metal sheet have excellent impact resistance, which is extremely useful. It can be said that this is a polyester film.

Hereinafter, the present invention will be described in detail.
The polyester in the present invention is a polymer composed of a dicarboxylic acid component and a glycol component. Aliphatic dicarboxylic acids such as aliphatic dicarboxylic acids, oxalic acid, succinic acid, adipic acid, sebacic acid, decane dicarboxylic acid, maleic acid, fumaric acid, and dimer acid; oxycarboxylic acids such as p-oxybenzoic acid; and cyclohexanedicarboxylic acid Although alicyclic dicarboxylic acids of the above formula can be used, it is preferable to use mainly dicarboxylic acids selected from the group consisting of terephthalic acid, isophthalic acid and naphthalenedicarboxylic acid and ester derivatives thereof, It is more preferable to use 80 mol% or more of La ester derivatives in total. When other dicarboxylic acids and their ester derivatives are used, the amount is preferably at most 20 mol%, more preferably at most 10 mol%. If the amount of other dicarboxylic acids and their ester derivatives exceeds 20 mol%, the thermal stability of the polyester deteriorates, which is not preferable.

  As the glycol component, aliphatic glycols such as ethylene glycol, propanediol, butanediol (eg, 1,4-butanediol), pentanediol, hexanediol, and neopentyl glycol; and alicyclic rings such as cyclohexanedimethanyl. Aromatic glycols, such as aromatic glycols, ethylene oxide adducts of bisphenol A, and ethylene oxide adducts of bisphenol S, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, and the like can be used. In addition, it may contain a small amount of a compound containing an amide bond, urethane bond, ether bond, carbonate bond or the like. Here, it is preferable to mainly use ethylene glycol and 1,4-butanediol as the glycol component, and it is more preferable that the total amount of ethylene glycol and / or 1,4-butanediol is 80 mol% or more. If the amount of the other glycol component exceeds 20 mol%, the thermal stability of the polyester deteriorates, which is not preferable.

  Further, the polyester in the present invention can use one kind of resin selected from the above alone, but can also use two or more kinds of resins in combination, and in order to achieve the object of the present invention, And the amount of addition can be appropriately selected.

  The polyester of the present invention may contain, if necessary, an antioxidant, a heat stabilizer, an ultraviolet absorber, a plasticizer, a pigment, an antistatic agent, a lubricant, a nucleating agent, a lubricant comprising inorganic or organic particles, and the like. May be.

  The method for producing the polyester in the present invention is not particularly limited. That is, those produced by either the transesterification method or the direct polymerization method can be used. Further, those produced by a solid-phase polymerization method for increasing the molecular weight may be used. In particular, when used for containers, it is manufactured by a solid-state polymerization method under reduced pressure or an inert gas atmosphere in order to reduce the amount of oligomers from the polyester resin in retort treatment etc. performed after filling the contents. It is preferred to use polyesters having a low oligomer content.

  In the production of the polyester of the present invention, as a polymerization catalyst, antimony oxide, germanium oxide, a titanium compound and the like are used, and when a melt-extruded film is formed using the polyester resin composition of the present invention in addition to the polymerization catalyst. Magnesium salts such as magnesium acetate and magnesium chloride, Ca salts such as calcium acetate and calcium chloride, Mn salts such as manganese acetate and manganese chloride, and Zn salts such as zinc chloride and zinc acetate. And a metal compound such as a Co salt such as cobalt chloride and cobalt acetate in a total amount of not more than 300 ppm of each metal ion, and a phosphorus compound such as phosphoric acid or a phosphoric acid ester derivative such as phosphoric acid trimethyl ester and phosphoric acid triethyl ester. Can be added in the range of 200 ppm or less. When the total amount of metal ions other than the polymerization catalyst is 300 ppm and the phosphorus amount exceeds 200 ppm, not only coloring of the obtained polyester becomes remarkable, but also heat resistance and hydrolysis resistance of the polyester may be reduced. It is not preferred.

  The timing of adding the metal compound and the phosphorus compound is not particularly limited as long as it is during the production of the polyester (that is, from the time of polymerization of the polyester to before the melt extrusion step), but preferably both are added during the polymerization of the polyester.

  At this time, when the molar ratio between the total amount of phosphorus to be added and the total amount of metal ions is 0.4 to 1.0, a polyester having the best balance of heat resistance, hydrolysis resistance and electrostatic adhesion is obtained. It is preferable because it can be obtained. Here, the molar ratio of the added amount = (total amount of phosphorus (molar atom) in phosphoric acid, phosphoric acid alkyl ester, or derivative thereof) / (total amount of Mg ion, Ca ion, Mn ion, Zn ion, Co ion ( Molar atom)). When the above molar ratio is less than 0.4, coloring of the composition of the present invention becomes remarkable, and heat resistance and hydrolysis resistance decrease. If it exceeds 1.0, sufficient electrostatic adhesion cannot be obtained.

  The melting point of the polyester used in the present invention is 180 ° C. or higher, especially when used for containers. In the case of drawing and ironing, the resin on the inner side of the can secures the releasability of the punch, It is necessary for the resin on the outer surface side to prevent galling (restraining of vertical scratches on the resin film). Preferably, the melting point of the polyester is between 180C and 265C, more preferably between 215C and 250C.

In addition, when the polyester used in the present invention is particularly used for containers, it is a crystalline polyester and can be made into cans (in the case of drawing and ironing, the resin on the inner surface of the can secures the releasability of the punch, It is necessary for the resin on the outer surface side to prevent galling (restraining of vertical scratches on the resin film).
The term “crystalline polyester” as used herein means a polyester that shows a distinct melting peak when the temperature is raised from 20 ° C. to 300 ° C. at a rate of 10 ° C./min using a differential scanning calorimeter (DSC). .

Two-layer laminated film (layer constitution: (I) / (II)) and three-layer laminated film (layer constitution: (I) / (II)) composed of resin layer (I) and resin layer (II) of the present invention. For the resin layer (I) in / (I)), the above-mentioned crystalline polyester having a melting point of 180 ° C. or more is used. Further, for the resin layer (II) in the laminated film of the present invention, the polyester described above can be used as the polyester used for the resin layer (I). However, it is not necessary to use a crystalline polyester having a melting point of 180 ° C. or higher from the viewpoint of can-making properties. The polyester of the resin layer (I) and the polyester of the resin layer (II) may be the same or different.
Further, in the two-layer laminated film of the present invention, when the resin layer (II) is a layer on the side to be attached to the metal plate, the polyester of the resin layer (II) is formed from the resin layer ( It is preferred to select a polyester having a lower melting point than the polyester of I).

  In the present invention, the olefin polymer blended with the polyester is preferably polyethylene and / or an ethylene copolymer. For example, low density polyethylene, medium density polyethylene, high density polyethylene, linear low density polyethylene, ultra-high molecular weight polyethylene, polypropylene, ethylene-propylene copolymer, ethylene-butene copolymer, ethylene-vinyl acetate copolymer, Ethylene-ethyl acrylate copolymer, ethylene-methyl acrylate copolymer, ethylene-methyl methacrylate copolymer, ethylene-acrylic acid copolymer, ethylene-methacrylic acid copolymer, ethylene-ethyl acrylate-maleic anhydride copolymer Polymers, ethylene-maleic anhydride graft copolymers, ethylene-vinyl alcohol copolymers and the like can be used. The olefin-based polymer of the present invention can use one kind of resin selected from the above alone, or two or more kinds of resins can be used in combination. And the amount of addition can be appropriately selected.

  In the present invention, when the polyester and the olefin-based polymer are blended, the blend ratio needs to be 70:30 to 99: 1. When the content of the olefin-based polymer is less than 1%, the effect of improving the impact resistance of the obtained metal plate and the formed body obtained by processing the metal plate is insufficient, which is not preferable. Further, when the olefin-based polymer exceeds 30%, particularly when used for a container, it is not preferable because the can-making property and the flavor property of the obtained metal can are inferior.

  In the present invention, after a polymer obtained by dry blending or melt-mixing a polyester and an olefin-based polymer is melted in a known single-screw or twin-screw extruder, a layered molten resin film is obtained using a T-die.

  In the two-layer laminated film of the present invention, the polyester (resin layer (I)) and the polymer (polyester resin composition B) obtained by dry blending or melt mixing the polyester of the resin layer (II) and the olefin-based polymer are used. After melting in a known single-screw or twin-screw extruder, respectively, they are merged in the system to form two layers, and a layered molten resin film is obtained using a T-die, or the molten resin is fed from a separate channel. The resins are combined in a T-die to obtain a two-layered molten resin film.

  Furthermore, in the three-layer laminated film of the present invention, the polymer (polyester resin composition B) obtained by dry blending or melt mixing the polyester A of the resin layer (I) and the polyester and the olefin polymer of the resin layer (II). ) Are melted in a known single-screw or twin-screw extruder, respectively, and then merged in a melt line system to form three layers, using a T die to obtain a layered molten resin film, or from a separate flow path. The fed molten resins are combined in a T-die to obtain a three-layered molten resin film.

  In the present invention, as a method of cooling and solidifying the molten resin film obtained as described above, a known method of contacting the molten resin in a layer form from a T-die with a rotated cooling roll can be used. When the molten resin is brought into contact with the cooling roll, it is preferable to employ a method of forcibly blowing air, a method of bringing the molten resin into close contact with the cooling roll, or a method of setting the surrounding of the molten resin in contact with the cooling roll to a reduced pressure atmosphere. In both the forced air spraying method and the electrostatic adhesion method, a method in which both ends and the central portion of the layered resin are performed independently is more preferable.

  In the present invention, after cooling and solidifying, it is necessary to carry out 1.3 to 6.0 times longitudinal stretching of the cooled solidified product at a temperature equal to or higher than the glass transition point of the polyester. In order to further improve productivity, it is preferable to perform transverse stretching (for example, 3.0 to 5.0 times).

Then, the film is heat-treated under tension at a temperature of 50 ° C. or higher and a melting point of polyester of −20 ° C. for 1 to 20 seconds to obtain a film. In the polyester film of the present invention, it is particularly necessary to control the heat shrinkage in the stretching direction at 150 ° C. in the range of 2 to 30%. Preferably, the heat shrinkage is controlled in the range of 2 to 20%. By setting the heat shrinkage at 150 ° C. within the above range, oriented crystallization of the polyester film is appropriately suppressed, and both good handling properties after storage and good adhesion during thermal lamination with a metal plate are compatible. It becomes possible. If the heat shrinkage is less than 2%, the adhesion after lamination is undesirably reduced. On the other hand, when the heat shrinkage exceeds 30%, wrinkles and blocking occur due to temporal shrinkage in the longitudinal direction during storage until lamination, and talc occurs at both ends of the film due to shrinkage in the horizontal direction. It is not preferable because wrinkles and bubbles are easily generated on the laminated metal plate. As a suitable method for controlling the heat shrinkage in the above range, there is a method in which the heat treatment temperature after stretching the film is set to not less than the stretching temperature of the film and not more than 220 ° C, preferably not less than 150 ° C and not more than 210 ° C.
The heat shrinkage in the stretching direction at 150 ° C. here is a value measured according to JIS Z 1715.

  Next, after cutting and removing both ends of the film, the film is cut into a required width to obtain a roll-shaped polyester film. In the present invention, it is not possible to reuse a raw material obtained by a method of compacting or heating and melting the both ends of the cut and removed film and / or the remaining film obtained as a roll-shaped film. It is possible. In the case of the laminated film of the present invention, it is generally preferable to use the reusable raw material for the resin layer (II) from the viewpoint of maintaining the film properties. The reuse rate is not particularly limited, but is preferably 5 to 50%.

  The film of the present invention is, as described above, a polyester to which a metal compound and a phosphorus compound are added so that the molar ratio between the total phosphorus amount and the total metal ion amount during the production is in the range of 0.4 to 1.0, A film made from a polyester-based resin composition in which an olefin-based polymer is blended in a ratio of 70/30 to 99/1 (% by weight) as a raw material. Extremely good electrostatic adhesion, melting properties, workability of laminated metal sheet, impact resistance of molded products, etc. due to metal ions and olefin polymers can be obtained. The molten resin discharged from the T-die as the width of the molten resin film (neck-in) generated when extruding the molten resin increases and the film forming speed increases when the polyester resin is melt-extruded. The occurrence of the phenomenon (surging) in which the ears of the film fluctuates is suppressed, so that the film of the present invention not only can form a film stably and with good productivity, but also has excellent film uniformity, and has the above-described cutting and removing method. The amount of film at both ends can be greatly reduced.

In the polyester film of the present invention, the olefin-based polymer is a polymer containing a functional group, and the functional group concentration in the olefin-based polymer is 200 to 2000 equivalents / ton (existing in 1 ton of the total weight of the olefin-based polymer. (Molar equivalent of a functional group) is necessary in order to suppress the embrittlement of the film during storage, to combine the laminating property to metal, the can-making property, and the impact resistance of the can. When the content of the functional group is within the above range, the affinity of the olefin polymer to the polyester resin is appropriately increased, and the impact resistance is excellent due to the chemical interaction between the molecular chains of the olefin polymer and the polyester. Is exhibited. When the functional group concentration in the olefin polymer is less than 200 equivalents / ton, the effect of improving the impact resistance of the polyester film of the present invention is insufficient, and when the functional group concentration in the olefin polymer exceeds 2000 equivalents / ton. However, as the blending amount of the olefin-based polymer is increased to obtain the effects of the present invention, the flavor and thermal stability of the polyester-based film of the present invention may be undesirably reduced.
The “functional group concentration in the olefin polymer” as used herein means the molecular structure and the functional group concentration of the olefin polymer obtained by dissolving the olefin polymer in a mixed solvent of chloroform-d / trifluoroacetic acid and analyzing it by H-NMR spectrum analysis. (Mol%), and this is a value obtained by converting the weight into the content (molar equivalent) of the functional group per 1 ton of the olefin polymer.

  The functional group concentration in the olefin polymer is preferably from 250 to 1600 equivalents / ton, more preferably from 300 to 1400 equivalents / ton.

  As an example of the resin composition having the above characteristics, a functional group-containing polymer can be used as the olefin-based polymer to be blended with the polyester resin. As the functional group-containing polymer, a copolymer of an olefin and a functional group-containing vinyl monomer can be used. Preferred functional groups include those having polarity and having an effect of increasing the affinity with the polyester resin to be blended, such as a carboxyl group, a glycidyl group, and an acid anhydride group. Specific examples of the functional group-containing polymer include ethylene-α, β-unsaturated carboxylic acids such as ethylene- (meth) acrylate copolymer and ethylene- (meth) acrylate copolymer produced by various production methods and catalysts. Examples thereof include an acid copolymer and an ethylene-methyl acrylate-glycidyl methacrylate copolymer.

  Further, as an example of a more preferable olefin-based polymer in order to obtain the object effect of the present invention, a polymer containing a monomer component capable of forming a crosslinked structure and / or a branched structure in an amount of less than 5% each is exemplified. can do. Examples of such a monomer include unsaturated monomers having two or more addition-polymerizable reactive groups. Examples of the crosslinking monomer include butylene diacrylate, butylene dimethacrylate, trimethylolpropane trimethacrylate, divinylbenzene, trivinylbenzene, vinyl acrylate, and vinyl methacrylate. Preferably, butylene diacrylate and butylene dimethacrylate can be used. Examples of the graft-bonding monomer include allyl acrylate, allyl methacrylate, diallyl maleate, diallyl fumarate, diallyl itaconate, monoallyl maleate, monoallyl fumarate, and monoallyl itaconate. Preferably, allyl methacrylate and diallyl methacrylate can be used.

  Further, in order to obtain the intended effect of the polyester film of the present invention, as an example of selection of a more preferable olefin polymer, the olefin polymer is dispersed in an island shape in a polyester resin, and the dispersion diameter of the olefin polymer is Is preferably in the range of 0.1 to 2.0 μm in terms of equivalent sphere. When the olefin-based polymer is finely dispersed in the polyester resin as described above, the intermolecular interaction at the interface between the olefin-based polymer and the polyester is increased, and excellent impact resistance is exhibited.

  In the selection of the preferred olefin-based polymer, the olefin-based polymer is dispersed in an island shape in the polyester resin, and the dispersion diameter of the olefin-based polymer is one of selection examples of the olefin-based polymer for finely dispersing in the above range. The use of an olefin-based polymer containing a polyolefin containing at least a functional group is mentioned. It is considered that the olefin-dispersed particles containing the functional group-containing polyolefin are finely dispersed more effectively than the olefin-dispersed particles made of the olefin-based polymer having no functional group.

  As one specific example of the olefin-based polymer, a main structural unit includes at least one or more α-olefins having 2 to 6 carbon atoms and an ethylene bond-forming α, β-unsaturated carboxylic acid or an ester-forming derivative thereof. Or a mixture of the copolymer and another polymer. In particular, an ethylene- (meth) acrylic acid copolymer and an ethylene-α-olefin- (meth) acrylic acid copolymer are preferred. No.

  Another selection example includes a combination of a polyolefin having no functional group and two or more olefin-based polymers including a polyolefin having a functional group. By blending the olefin group having the above structure with the polyester, it is considered that the olefin group is finely dispersed more effectively. Specific examples include a polymer (a) having at least one or more α-olefins having 2 to 6 carbon atoms as a main constituent unit, and at least one or more α-olefins having 2 to 6 carbon atoms and ethylene. Combination of a copolymer (b) having a bond-forming α, β-unsaturated carboxylic acid or an ester-forming derivative thereof as a main constituent unit, particularly, a combination of polyethylene and an ethylene- (meth) acrylic acid copolymer And a combination of an ethylene-α-olefin copolymer and an ethylene-α-olefin- (meth) acrylic acid copolymer.

  Further, the dispersion diameter of the olefin-based polymer can be controlled within the above range by arbitrarily selecting conditions for melt-kneading when blending the polyester and the olefin-based polymer. The conditions for melt-kneading depend on the type and amount of the selected polyester resin and olefin-based polymer, but when extruding a melt-blended resin directly from a T-die into a layer, a twin-screw extruder is better than a single-screw extruder. It is preferable to use an extruder.

  The metal sheet in the present invention is not particularly limited, but tin, thin tin-plated steel sheet, electrolytic chromium-oxidized steel sheet (tin-free steel), nickel-plated steel sheet, etc., hot-dip galvanized steel sheet, hot-dip zinc-iron alloy plating Hot-dip galvanized steel sheet such as steel sheet, hot-dip zinc-aluminum-magnesium alloy coated steel sheet, hot-dip zinc-aluminum-magnesium-silicon alloy coated steel sheet, hot-dip aluminum-silicon alloy coated steel sheet, hot-dip lead-tin alloy coated steel sheet Surface treated steel sheet such as electro-plated steel sheet such as electro-zinc-nickel plated steel sheet, electro-zinc-iron alloy plated steel sheet, electro-zinc-chromium alloy plated steel sheet, cold-rolled steel sheet and metals such as aluminum, copper, nickel, zinc, magnesium A plate or the like can be appropriately selected and used depending on the application. After heating these metal plates to a melting point of polyester of -20 ° C. or higher and a melting point of + 150 ° C., they are laminated on a metal plate using a laminating roll. Subsequently, the laminated metal plate is heated to a melting point of polyester of 10 ° C. or higher and a melting point of + 60 ° C. After heating below, water-cooled and / or air-cooled to obtain a film-laminated metal plate.

  In the present invention, the thickness of the film is not particularly limited, but is preferably from 10 to 150 μm from the viewpoint of covering effect (rust prevention) and economy.

  In the two-layer laminated film of the present invention, the processing conditions when forming through a processing such as drawing and ironing using a laminated metal plate by having a two-layer constitution of the resin layer (I) and the resin layer (II) are as follows. Even under severe conditions, both moldability and impact resistance can be achieved. The thickness ratio of the resin layer (I) / the resin layer (II) is preferably in the range of 30 to 70/70 to 30.

  In the three-layer laminated film of the present invention, the resin layer (I) and the resin layer (II) have a three-layer constitution of (I) / (II) / (I), so that drawing and ironing can be performed using a laminated metal plate. Satisfies the formability and impact resistance even when the processing conditions when forming through processing such as become severe, and the cutability of the film at the time of forming such as cupping when the metal plate to be laminated is made of a hard material Can be satisfied. The thickness ratio of the resin layer (I) / the resin layer (II) / the resin layer (I) is preferably in the range of 10 to 50/20 to 80/10 to 50 from the side to be the outer layer of the metal plate.

  Hereinafter, the present invention will be described in more detail based on examples.

[Evaluation method]
(1) Melting Point of Polyester A polyester composition was heated and melted at 300 ° C. for 5 minutes, and then quenched with liquid nitrogen, and 10 mg of a sample was used in a nitrogen stream at 10 ° C. using a differential scanning calorimeter (DSC). The peak temperature of the endothermic peak accompanying melting when the exothermic / endothermic curve (DSC curve) was measured at a heating rate of / min was defined as the melting point Tm (° C.).

(2) Functional group concentration in olefin polymer The olefin polymer is dissolved in a mixed solvent of chloroform-d / trifluoroacetic acid, and the molecular structure and the functional group concentration (mol%) of the olefin polymer are determined by H-NMR spectrum analysis. This was converted to a weight, and the content (molar equivalent) of the functional group per 1 ton of the olefin-based polymer was calculated.

(3) Appearance and cut resistance of roll film after storage The roll-like films obtained by the methods of Examples and Comparative Examples were stored at 40 ° C. for 30 days at a relative humidity of 80%. A tensile test according to JIS K 7127 (longitudinal direction n = 30, No. 1 test piece having a width of 15 mm, test speed: 200 mm / min) was performed. The evaluation criteria were set as follows, and ○ was evaluated as practical.
[appearance]
：: No wrinkle, blocking, and thinning ×: With wrinkle, blocking, and thinning [cutting resistance]
The evaluation was made with the number of samples having a breaking elongation of <5% or less. (2/30 or less were evaluated as practical.)

(4) Appearance of Film The appearance of films obtained by the methods of Examples and Comparative Examples was visually observed and evaluated as follows.
〇: No coarse unevenness or foreign matter observable visually on the film surface.
X: Many coarse irregularities exist on the film surface.

(5) Heat shrinkage rate Evaluated according to JIS Z 1715.

(6) Production method of laminated metal plate The films obtained by the methods of Examples and Comparative Examples were laminated on a metal plate heated to 250 ° C, heated at 275 ° C, and then rapidly cooled in water to produce a laminated metal plate. .

(7) Releasability between Can Inner Surface Resin and Processed Punch In Example 1 and Comparative Example 1, a laminated metal plate was made at a rate of 30 cans / min at a rate of n = 10, and buckling occurred at the top of the molded can. The degree was visually observed. In Examples 2 and 3 and Comparative Examples 2 and 3, after forming the laminated metal plate into a cup by drawing, n = 100 cans were formed by redrawing and ironing at a rate of 60 cans / min. The degree of buckling occurring at the top of the molded can was visually observed. The evaluation criteria were set as follows, and ○ was evaluated as practical.
○: No buckling occurred at the can opening. △: Buckling occurred at about 1/3 of the circumference of the can opening. ×: Buckling occurred at 1/3 or more of the circumference of the can opening.

(8) Galling resistance of the outer surface of the can (vertical scratches on resin on the outer surface of the can)
In Example 1 and Comparative Example 1, the laminated metal plate was canned at a rate of 30 cans / min at n = 10, and the formed resin on the outer wall of the body wall of the can was visually observed for the degree of scratch generation. In Examples 2 and 3 and Comparative Examples 2 and 3, after forming the laminated metal plate into a cup by drawing, n = 100 cans were formed by redrawing and ironing at a rate of 60 cans / min. The occurrence of scratches on the resin on the outer surface of the molded body wall was visually observed. The evaluation criteria were set as follows, and ○ was evaluated as practical.
：: No scratches Δ: Scratches occurred on about 1/3 of the outer surface ×: Severe scratches occurred on 1/3 or more of the outer surface

(9) Flavor property After immersing a 5 cm square laminated metal plate in d-limonene filled in a closed glass container, it is allowed to stand in a constant temperature room at 40 ° C. for 10 days to adsorb d-limonene. The d-limonene adhering to the surface was wiped off with a Kimwipe, and the weight W1 was measured. The laminated metal plate after the measurement of the weight W1 was vacuum-dried at 60 ° C. for 24 hours, and then the weight W2 was measured. The weight W3 of the film peeled from the laminated metal plate was measured. The amount of adsorbed d-limonene was determined by the following equation and expressed in weight%. Those having a d-limonene adsorption amount of 3% or less were evaluated as being practical.
d-limonene adsorption amount (% by weight) = (W1−W2) / W3 × 100

(10) Impact Resistance A 7 cm square sample was cut out from the center of the body wall of a can obtained by heating a can made of a laminated metal plate at 280 ° C. for 40 seconds and then rapidly cooling in water. A weight (600 g) having a tip diameter of 10 mm is dropped from a height of 10 cm on the surface corresponding to the outer surface of the can of this sample to give an impact. Then, the sample was placed on a glass container filled with 7% diluted hydrochloric acid (placed in a state where the convex portion of the sample was immersed), and after 3 days, the corrosion state of the convex portion was visually observed. The evaluation criteria were set as follows, and ○ was evaluated as practical.
：: No corrosion of the convex portions ×: Corrosion of the convex portions

(11) Intrinsic viscosity (IV)
It is a value (dl / g) measured at 25 ° C. in orthochlorophenol.

  Next, the types and contents of the polyester and the olefin-based polymer used in Examples and Comparative Examples will be described.

(1) Polyester A: polyethylene terephthalate (IV = 0.73, phosphorus / metal ion ratio = 0.8)
In a reactor equipped with an inlet, a thermometer, a pressure gauge, a distilling tube with a rectification tower, and a stirring blade, 100 parts by weight of terephthalic acid and 82 parts by weight of ethylene glycol (the molar ratio of ethylene glycol / terephthalic acid = 2) .2), 0.05 mol% of germanium oxide as a Ge element, 0.05 mol% of magnesium acetate as a Mg element with respect to an acid component, and 0.23 weight of amorphous silica particles having an average particle diameter of 1.3 μm. Then, nitrogen was introduced while stirring, and the pressure in the system was kept at 0.3 MPa while stirring, and the esterification reaction was performed while distilling off water generated at a temperature of 230 ° C to 250 ° C outside the system. After the completion of the reaction, at 250 ° C., 0.04 mol% of trimethyl phosphate as a P amount was added, the pressure was gradually reduced while the temperature was raised, and the polycondensation reaction was performed at 275 ° C. under a vacuum of 1.0 hPa or less. The obtained polyester (polyester A, intrinsic viscosity 0.73, phosphorus / metal ion ratio = 0.8) resin was used.

(2) Polyester B: polyethylene terephthalate / isophthalate (8 mol% of repeating units of ethylene isophthalate, IV = 0.75, phosphorus / metal ion ratio = 0.8)
A polyester (polyester B, intrinsic viscosity 0.75, phosphorus / metal) was produced by the same method as that for producing polyethylene terephthalate (polyester A) except that 92 parts by weight of terephthalic acid and 8 parts by weight of isophthalic acid were used. (Ion ratio = 0.8) was used.

(3) Polyester C: polyethylene terephthalate / isophthalate (8 mol% of repeating units of ethylene isophthalate, IV = 0.75, phosphorus / metal ion ratio = 0)
The same method as that used for producing polyester A was used except that 92 parts by weight of terephthalic acid and 8 parts by weight of isophthalic acid were used without adding trimethyl phosphate. , Phosphorus / metal ion ratio = 0).

(4) Polyester D: polyethylene terephthalate / isophthalate (8 mol% of repeating units of ethylene isophthalate, IV = 0.75, phosphorus / metal ion ratio = 2.0)
The polyester obtained by the same method as the method of producing the polyester A except that 92 parts by weight of terephthalic acid and 8 parts by weight of isophthalic acid were used, and the trimethyl phosphate to be added was 0.1 mol% as a P element. Polyester D, intrinsic viscosity 0.75, phosphorus / metal ion ratio = 2.0) was used.

(5) Polyester E: A copolymerized polyester of terephthalic acid and ethylene glycol / cyclohexanedimethanol (70/30 mol%) was used.

(6) Olefin A: Low-density polyethylene (Sumikasen G401: trade name, manufactured by Sumitomo Chemical Co., Ltd.) was used.
(7) Olefin B: An ethylene-acrylic acid copolymer (Primacol 3440: trade name, manufactured by Dow Chemical Company) was used.
(8) Olefin C: Ethylene-methacrylic acid copolymer (manufactured by Du Pont-Mitsui Polychemicals, Nucrel N1108C: trade name) was used.
(9) Olefin D: Ethylene-ethyl acrylate copolymer (manufactured by DuPont-Mitsui Polychemicals Co., Ltd., Evaflex A712: trade name) was used.
(10) Olefin E: Ethylene-1-butene copolymer (manufactured by Nippon Synthetic Rubber Co., Ltd., EBM2041P: trade name) was used.
(11) Olefin F: Ethylene-methyl acrylate copolymer (EMAC2260 manufactured by Eastman Chemical Company) was used.

[Example 1-1]
Polyester B / Olefin A / Olefin B = 88/6/6 (% by weight) was pre-kneaded at 270 ° C. using a twin-screw vented extruder, and the raw material was dried at 100 ° C. for 24 hours. After being melted at 270 ° C. using an extruder, it was extruded in a layer form from a T-die into a cooling roll to obtain an unstretched sheet. The unstretched sheet is stretched 3.5 times in the longitudinal direction at a preheating temperature of 80 ° C. and a stretching temperature of 100 ° C., and further stretched 4.0 times in the transverse direction at a preheating temperature of 80 ° C. and a stretching temperature of 100 ° C. Heat treatment was performed at 8 ° C. for 8 seconds to obtain two types of polyester-based films (100-m roll-shaped film) having a thickness of 25 μm and 16 μm.

  After storing this film at 40 ° C. under the condition of a relative humidity of 80% for 30 days, the film was pressure-bonded to both sides of a 3004 aluminum alloy plate (0.26 mm thick) heated to 250 ° C., and heated to 275 ° C. Thereafter, the laminate was quenched in water to obtain a laminated aluminum plate.

  After applying a molding lubricant to the thus obtained laminated aluminum plate, the plate was heated and drawn at a plate temperature of 70 ° C. Next, the temperature of the obtained cup was set to 40 ° C., and ironing was performed at a mold temperature of 80 ° C. at a rate of 30 cans / min to obtain a 350 ml-sized seamless can.

  Melting point of polyester, concentration of functional group in olefin polymer, heat shrinkage, film appearance, appearance and cut resistance of roll film after storage, can-manufacturability (removability of can inner film and punch and outer film of can Tables 1 and 2 show the degree of scratching), flavor, and impact resistance. The film of this example is excellent in appearance, there is no decrease in appearance and cut resistance after storage, and the laminated plate of this example is excellent in can making properties and flavor properties, and the metal can of this example is impact resistant. It was excellent.

[Example 1-2]
Except that the transverse stretching was not performed, two types of polyester films (100 m roll-shaped film) having a thickness of 25 μm and 16 μm were obtained in the same manner as in Example 1-1.
Then, after storing in the same manner as in Example 1-1, a laminated aluminum plate was produced and canned to obtain a 350 ml-sized seamless can.

  Melting point of polyester, concentration of functional group in olefin polymer, heat shrinkage, film appearance, appearance and cut resistance of roll film after storage, can-manufacturability (removability of can inner film and punch and outer film of can Tables 1 and 2 show the degree of scratching), flavor, and impact resistance. The film of this example is excellent in appearance, there is no decrease in appearance and cut resistance after storage, and the laminated plate of this example is excellent in can making properties and flavor properties, and the metal can of this example is impact resistant. It was excellent.

[Example 1-3]
Except that the raw material was polyester B / olefin A / olefin C = 88/6/6 (% by weight), two kinds of polyester-based films having a thickness of 25 μm and 16 μm (a roll of 100 m) were prepared in the same manner as in Example 1-1. Film). Then, after storing in the same manner as in Example 1-1, a laminated aluminum plate was produced and canned to obtain a 350 ml-sized seamless can.

  Melting point of polyester, concentration of functional group in olefin polymer, heat shrinkage, film appearance, appearance and cut resistance of roll film after storage, can-making properties Tables 1 and 2 show the degree of scratching), flavor, and impact resistance. The film of this example is excellent in film appearance, there is no decrease in appearance and cut resistance after storage, and the laminated plate of this example is excellent in can making properties and flavor properties, and the metal can of this example is resistant to It had excellent impact properties.

[Example 1-4]
Except that the raw material was polyester B / olefin A / olefin D = 88/6/6 (% by weight), two kinds of polyester-based films having a thickness of 25 μm and 16 μm (a roll of 100 m) were prepared in the same manner as in Example 1-1. Film). Then, after storing in the same manner as in Example 1-1, a laminated aluminum plate was produced and canned to obtain a 350 ml-sized seamless can.

  Melting point of polyester, concentration of functional group in olefin polymer, heat shrinkage, film appearance, appearance and cut resistance of roll film after storage, can-manufacturability (removability of can inner film and punch and outer film of can Tables 1 and 2 show the degree of scratching), flavor, and impact resistance. The film of this example is excellent in appearance, there is no decrease in appearance and cut resistance after storage, and the laminated plate of this example is excellent in can making properties and flavor properties, and the metal can of this example is impact resistant. It was excellent.

[Example 1-5]
Except that the raw materials were polyester B / olefin B / olefin E = 88/6/6 (% by weight), two kinds of polyester-based films having a thickness of 25 μm and 16 μm (100 m roll-shaped) were used in the same manner as in Example 1-1. Film). Then, after storing in the same manner as in Example 1-1, a laminated aluminum plate was produced and canned to obtain a 350 ml-sized seamless can.

  Melting point of polyester, concentration of functional group in olefin polymer, heat shrinkage, film appearance, appearance and cut resistance of roll film after storage, can-making properties Tables 1 and 2 show the degree of scratching), flavor, and impact resistance. The film of this example is excellent in appearance, there is no decrease in appearance and cut resistance after storage, and the laminated plate of this example is excellent in can making properties and flavor properties, and the metal can of this example is impact resistant. It was excellent.

[Example 1-6]
Except that the raw material was changed to polyester B / olefin B = 80/20 (% by weight), two types of polyester films (100 m roll-shaped film) having a thickness of 25 μm and 16 μm were obtained in the same manner as in Example 1-1. . Then, after storing in the same manner as in Example 1-1, a laminated aluminum plate was produced and canned to obtain a 350 ml-sized seamless can.

  Melting point of polyester, concentration of functional group in olefin polymer, heat shrinkage, film appearance, appearance and cut resistance of roll film after storage, can-making properties Tables 1 and 2 show the degree of scratching), flavor, and impact resistance. The film of this example is excellent in appearance, there is no decrease in appearance and cut resistance after storage, and the laminated plate of this example is excellent in can making properties and flavor properties, and the metal can of this example is impact resistant. It was excellent.

[Example 1-7]
Except that the raw material was polyester A / polyester B / olefin A / olefin B = 34/54/6/6 (% by weight), two kinds of polyester-based films having a thickness of 25 μm and 16 μm in the same manner as in Example 1-1. (100 m roll-shaped film) was obtained.
Then, after storing in the same manner as in Example 1-1, a laminated aluminum plate was produced and canned to obtain a 350 ml-sized seamless can.

  Melting point of polyester, concentration of functional group in olefin polymer, heat shrinkage, film appearance, appearance and cut resistance of roll film after storage, can-manufacturability (removability of can inner film and punch and outer film of can Tables 1 and 2 show the degree of scratching), flavor, and impact resistance. The film of this example is excellent in appearance, there is no decrease in appearance and cut resistance after storage, and the laminated plate of this example is excellent in can making properties and flavor properties, and the metal can of this example is impact resistant. It was excellent.

[Example 1-8]
The film used in Example 1-1 was treated with electrolytic chromic acid-treated steel sheet (metallic chromium amount: 135 mg / m ² , chromium in hydrated chromium oxide: 15 mg / m ² , plate thickness: 0.23 mm, hardness T− 3) A laminated plate was prepared in the same manner as in Example 1-1 except for laminating on the top, and then a can was made to obtain a 350 ml-sized seamless can.

  Melting point of polyester, concentration of functional group in olefin polymer, heat shrinkage, film appearance, appearance and cut resistance of roll film after storage, can-manufacturability (removability of can inner film and punch and outer film of can Tables 1 and 2 show the degree of scratching), flavor, and impact resistance. The film of this example is excellent in appearance, there is no decrease in appearance and cut resistance after storage, and the laminated plate of this example is excellent in can making properties and flavor properties, and the metal can of this example is impact resistant. It was excellent.

[Comparative Example 1-1]
Two types of polyester unstretched films (100 m roll-shaped film) having a thickness of 25 μm and 16 μm were obtained from the raw materials of Example 1-1. Then, it was stored in the same manner as in Example 1-1.

  Tables 1 and 2 show the melting point of the polyester, the functional group concentration in the olefin polymer, the heat shrinkage, the film appearance, the appearance and the cut resistance of the roll film after storage. Although the film of this comparative example was excellent in appearance, it was not preferable because, as a result of storage in the same manner as in Example 1-1, the cut resistance of the film was poor and wrinkles and wrinkles occurred.

[Comparative Example 1-2]
Except that the raw material was polyester B = 100 (% by weight) (raw material obtained by removing olefin from Example 1-1), two kinds of polyester-based films (100 m thick) having a thickness of 25 μm and 16 μm were prepared in the same manner as in Example 1-1. Roll-shaped film) was obtained. Then, after storing in the same manner as in Example 1-1, a laminated aluminum plate was produced and canned to obtain a 350 ml-sized seamless can.

  Melting point of polyester, concentration of functional group in olefin polymer, heat shrinkage, film appearance, appearance and cut resistance of roll film after storage, can-making properties Tables 1 and 2 show the degree of scratching), flavor, and impact resistance. The film of this comparative example was excellent in appearance, there was no decrease in appearance and cut resistance after storage, and the laminated plate of this comparative example was excellent in can making properties and flavor properties, but the impact resistance of metal cans was poor. Not good for bad.

[Comparative Example 1-3]
Except that the heat treatment temperature after the transverse stretching was set to 225 ° C, two types of polyester films (100 m roll-shaped film) having a thickness of 25 µm and 16 µm were obtained in the same manner as in Example 1-1. Then, after storing in the same manner as in Example 1-1, a laminated aluminum plate was produced and canned to obtain a 350 ml-sized seamless can.

  Melting point of polyester, concentration of functional group in olefin polymer, heat shrinkage, film appearance, appearance and cut resistance of roll film after storage, can-making properties Tables 1 and 2 show the degree of scratching. Although the film of this comparative example was excellent in appearance, and did not decrease in appearance and cut resistance after storage, it was not preferable because the film was peeled off when the laminated board was made.

[Comparative Example 1-4]
Two types of polyester films (100 m roll-shaped film) having a thickness of 25 μm and 16 μm were obtained in the same manner as in Example 1-1 except that the heat treatment was not performed after the transverse stretching.

  Tables 1 and 2 show the melting point of the polyester, the functional group concentration in the olefin polymer, the heat shrinkage, the film appearance, the appearance and the cut resistance of the roll film after storage. Although the film of this comparative example was excellent in appearance, it was unfavorable because the film was stored in the same manner as in Example 1-1, and as a result, wrinkles in the lateral direction of the film and bulges at both ends of the film were generated.

[Comparative Example 1-5]
Except that the raw material was polyester E / olefin A / olefin B = 88/6/6 (% by weight), two kinds of polyester-based films having a thickness of 25 μm and 16 μm (a roll of 100 m) were prepared in the same manner as in Example 1-1. Film). Then, after storing in the same manner as in Example 1-1, a laminated aluminum plate was produced and canned to obtain a 350 ml-sized seamless can.

Melting point of polyester, concentration of functional group in olefin polymer, heat shrinkage, film appearance, appearance and cut resistance of roll film after storage, can-manufacturability (removability of can inner film and punch and outer film of can Table 1 and Table 2 show the degree of scratching) and the flavor.
The film of this comparative example was excellent in appearance and did not decrease in appearance after storage, but the cut resistance of the film was poor, the flavor of the laminated aluminum plate was poor, and when the laminated aluminum plate was made, It is not preferable because the inner film adheres to the processing punch, buckling occurs over the entire circumference of the can opening, and further, the entire outer circumference of the can film is scratched.

[Comparative Example 1-6]
Except that the raw material was polyester B / olefin A / olefin B = 60/20/20 (% by weight), two kinds of polyester-based films having a thickness of 25 μm and 16 μm (100 m roll-shaped) were used in the same manner as in Example 1-1. Film). Then, after storing in the same manner as in Example 1-1, a laminated aluminum plate was produced and canned to obtain a 350 ml-sized seamless can.

  Melting point of polyester, concentration of functional group in olefin polymer, heat shrinkage, film appearance, appearance and cut resistance of roll film after storage, can-manufacturability (removability of can inner film and punch and outer film of can Tables 1 and 2 show the degree of scratching), flavor, and impact resistance. The film of this comparative example was excellent in appearance, did not deteriorate in appearance and cut resistance after storage, and the laminated plate of this comparative example was excellent in can-making properties, but was not preferred because of poor flavor properties.

[Comparative Example 1-7]
Polyester B / olefin A = 90/10 (% by weight) was melted at 270 ° C. using a single screw extruder, and extruded from a T-die into a layer on a cooling roll to obtain an unstretched sheet. The unstretched sheet is stretched longitudinally at a preheating temperature of 80 ° C. and a stretching temperature of 100 ° C., further stretched 4.0 times in a transverse direction at a preheating temperature of 80 ° C. and a stretching temperature of 100 ° C., and then heat-treated at 150 ° C. for 8 seconds. Thus, two types of polyester films (100 m roll film) having a thickness of 25 μm and 16 μm were obtained. Then, after storing in the same manner as in Example 1-1, a laminated aluminum plate was produced and canned to obtain a 350 ml-sized seamless can.

  Melting point of polyester, concentration of functional group in olefin polymer, heat shrinkage, film appearance, appearance and cut resistance of roll film after storage, can-making properties Tables 1 and 2 show the degree of scratching), flavor, and impact resistance. The film of this comparative example was excellent in appearance, there was no decrease in appearance and cut resistance after storage, and the laminated plate of this comparative example was excellent in can making properties and flavor properties, but the impact resistance of metal cans was poor. It was somewhat inferior.

[Comparative Example 1-8]
Except that the raw material was polyester B / olefin F = 80/20 (% by weight), two kinds of polyester films (100 m roll film) having a thickness of 25 μm and 16 μm were obtained in the same manner as in Example 1-1. . Then, after storing in the same manner as in Example 1-1, a laminated aluminum plate was produced and canned to obtain a 350 ml-sized seamless can.

  Melting point of polyester, concentration of functional group in olefin polymer, heat shrinkage, film appearance, appearance and cut resistance of roll film after storage, can-making properties Tables 1 and 2 show the degree of scratching), flavor, and impact resistance. The film of this comparative example was excellent in appearance, did not deteriorate in appearance and cut resistance after storage, and the laminated plate of this comparative example was excellent in can-making properties, but was not preferred because of poor flavor properties.

[Comparative Example 1-9]
Two types of polyester films having a thickness of 25 μm and 16 μm were obtained in the same manner as in Example 1-1 except that the raw materials were polyester C / olefin A / olefin B = 88/6/6 (% by weight).

  Tables 1 and 2 show the melting point of the polyester, the functional group concentration in the olefin-based polymer, the heat shrinkage, and the film appearance. The film of this comparative example is not preferable because a large number of visual foreign substances are present, and when the molten resin is extruded to obtain an unstretched sheet, the ear fluctuates.

[Comparative Example 1-10]
Two kinds of polyester films having a thickness of 25 μm and 16 μm were obtained in the same manner as in Example 1-1 except that the raw materials were polyester D / olefin A / olefin B = 88/6/6 (% by weight).

  Tables 1 and 2 show the melting point of the polyester, the functional group concentration in the olefin-based polymer, the heat shrinkage, and the film appearance. The film of this comparative example is not preferable because of poor adhesion to the cooling roll and a large number of visually uneven surface irregularities in the film.

[Example 2-1]
Polyester A / Polyester B = 40/60 (% by weight) as a raw material of the resin layer (I), and Polyester B / Olefin A / Olefin B = 88/6/6 (% by weight) as a raw material of the resin layer (II). The raw materials obtained by pre-kneading at 270 ° C. using a twin-screw vented extruder and dried at 100 ° C. for 24 hours are melted at 270 ° C. using a single-screw extruder, and then melted in a channel. They were merged and extruded in layers from a T die onto a cooling roll to obtain an unstretched sheet of the laminated resin. The unstretched sheet is stretched 3.5 times in the longitudinal direction at a preheating temperature of 80 ° C. and a stretching temperature of 100 ° C., and further stretched 4.0 times in the transverse direction at a preheating temperature of 80 ° C. and a stretching temperature of 100 ° C. Heat treatment was performed at 8 ° C. for 8 seconds to obtain two types of polyester films (200-m roll-shaped film) having a thickness of 25 μm and 16 μm. The ratio of the thickness of each layer of this film was (I) layer / (II) layer = 1/1.

  After storing this film at 40 ° C. under the condition of 80% relative humidity for 30 days, the film is pressed on both sides of a 3004 series aluminum alloy plate (0.26 mm thick) heated to 250 ° C., and heated to 275 ° C. And quenched in water to obtain a laminated metal plate.

  After applying a forming lubricant to the thus obtained laminated metal sheet, the sheet was heated and drawn at a sheet temperature of 70 ° C. Next, the temperature of the obtained cup was set to 40 ° C., and ironing was performed at a mold temperature of 80 ° C. at a rate of 60 cans / min to obtain a 350 ml-sized seamless can.

  Melting point of polyester, concentration of functional group in olefin polymer, heat shrinkage, film appearance, appearance and cut resistance of roll film after storage, can-making properties Tables 3 and 5 show the degree of scratching), flavor, and impact resistance. The film of this example is excellent in appearance, there is no decrease in appearance and cut resistance after storage, and the laminated plate of this example is excellent in can making properties and flavor properties, and the metal can of this example is impact resistant. It was excellent.

[Example 2-2]
Except that transverse stretching was not performed, two types of polyester films (200 m roll-shaped film) having a thickness of 25 μm and 16 μm were obtained in the same manner as in Example 2-1. The ratio of the thickness of each layer of this film was (I) layer / (II) layer = 1/1.
Then, after storing in the same manner as in Example 2-1, a laminated metal plate was prepared and made into a can to obtain a 350 ml-sized seamless can.

  Melting point of polyester, concentration of functional group in olefin polymer, heat shrinkage, film appearance, appearance and cut resistance of roll film after storage, can-manufacturability (removability of can inner film and punch and outer film of can Tables 3 and 5 show the degree of scratching), flavor, and impact resistance. The film of this example is excellent in appearance, there is no decrease in appearance and cut resistance after storage, and the laminated plate of this example is excellent in can making properties and flavor properties, and the metal can of this example is impact resistant. It was excellent.

[Example 2-3]
Except that the raw material of the resin layer (II) was polyester B / olefin A / olefin C = 88/6/6 (% by weight), two kinds of polyesters having a thickness of 25 μm and 16 μm were used in the same manner as in Example 2-1. A film (200 m roll film) was obtained. The ratio of the thickness of each layer of this film was (I) layer / (II) layer = 1/1.
Then, after storing in the same manner as in Example 2-1, a laminated metal plate was prepared and made into a can to obtain a 350 ml-sized seamless can.

  Melting point of polyester, concentration of functional group in olefin polymer, heat shrinkage, film appearance, appearance and cut resistance of roll film after storage, can-making properties Tables 3 and 5 show the degree of scratching), flavor, and impact resistance. The film of this example is excellent in appearance, there is no decrease in appearance and cut resistance after storage, and the laminated plate of this example is excellent in can making properties and flavor properties, and the metal can of this example is impact resistant. It was excellent.

[Example 2-4]
Except that the raw material for the resin layer (II) was polyester B / olefin A / olefin D = 88/6/6 (% by weight), two kinds of polyesters having a thickness of 25 μm and 16 μm were used in the same manner as in Example 2-1. A film (200 m roll film) was obtained. The ratio of the thickness of each layer of this film was (I) layer / (II) layer = 1/1.
Then, after storing in the same manner as in Example 2-1, a laminated metal plate was prepared,
A seamless can of 50 ml size was obtained.

  Melting point of polyester, concentration of functional group in olefin polymer, heat shrinkage, film appearance, appearance and cut resistance of roll film after storage, can-making properties Tables 3 and 5 show the degree of scratching), flavor, and impact resistance. The film of this example is excellent in appearance, there is no decrease in appearance and cut resistance after storage, and the laminated plate of this example is excellent in can making properties and flavor properties, and the metal can of this example is impact resistant. It was excellent.

[Example 2-5]
Except that the raw material of the resin layer (II) was polyester B / olefin B / olefin E = 88/6/6 (% by weight), two kinds of polyesters having a thickness of 25 μm and 16 μm were used in the same manner as in Example 2-1. A film (200 m roll film) was obtained. The ratio of the thickness of each layer of this film was (I) layer / (II) layer = 1/1.
Then, after storing in the same manner as in Example 2-1, a laminated metal plate was prepared and made into a can to obtain a 350 ml-sized seamless can.

  Melting point of polyester, concentration of functional group in olefin polymer, heat shrinkage, film appearance, appearance and cut resistance of roll film after storage, can-making properties Tables 3 and 5 show the degree of scratching), flavor, and impact resistance. The film of this example is excellent in appearance, there is no decrease in appearance and cut resistance after storage, and the laminated plate of this example is excellent in can making properties and flavor properties, and the metal can of this example is impact resistant. It was excellent.

[Example 2-6]
Except that the raw material of the resin layer (II) was polyester B / olefin B = 80/20 (% by weight), two kinds of polyester-based films (thickness of 25 m and 16 m) (200 m roll) were prepared in the same manner as in Example 2-1. Film). The ratio of the thickness of each layer of this film was (I) layer / (II) layer = 1/1. Then, after storing in the same manner as in Example 2-1, a laminated metal plate was prepared and made into a can to obtain a 350 ml-sized seamless can.

  Melting point of polyester, concentration of functional group in olefin polymer, heat shrinkage, film appearance, appearance and cut resistance of roll film after storage, can-making properties Tables 3 and 5 show the degree of scratching), flavor, and impact resistance. The film of this example is excellent in appearance, there is no decrease in appearance and cut resistance after storage, and the laminated plate of this example is excellent in can making properties and flavor properties, and the metal can of this example is impact resistant. It was excellent.

[Example 2-7]
Except that the raw material of the resin layer (II) was polyester A / polyester B / olefin A / olefin B = 34/54/6/6 (% by weight), the thickness was 25 μm and 16 μm as in Example 2-1. Two types of polyester films (200 m roll film) were obtained. The ratio of the thickness of each layer of this film was (I) layer / (II) layer = 1/1. Then, after storing in the same manner as in Example 2-1, a laminated metal plate was prepared and made into a can to obtain a 350 ml-sized seamless can.

  Melting point of polyester, concentration of functional group in olefin polymer, heat shrinkage, film appearance, appearance and cut resistance of roll film after storage, can-making properties Tables 3 and 5 show the degree of scratching), flavor, and impact resistance. The film of this example is excellent in appearance, there is no decrease in appearance and cut resistance after storage, and the laminated plate of this example is excellent in can making properties and flavor properties, and the metal can of this example is impact resistant. It was excellent.

[Example 2-8]
The film used in Example 2-1 was treated with electrolytic chromic acid-treated steel sheet (metallic chromium amount: 135 mg / m ² , chromium in chromium hydrated oxide: 15 mg / m ² , plate thickness: 0.23 mm, hardness T− 3) A laminated plate was prepared in the same manner as in Example 2-1 except that the laminate was laminated on the top, and a can was made to obtain a 350 ml-sized seamless can.

  Melting point of polyester, concentration of functional group in olefin polymer, heat shrinkage, film appearance, appearance and cut resistance of roll film after storage, can-making properties Tables 3 and 5 show the degree of scratching), flavor, and impact resistance. The film of this example is excellent in appearance, there is no decrease in appearance and cut resistance after storage, and the laminated plate of this example is excellent in can making properties and flavor properties, and the metal can of this example is impact resistant. It was excellent.

[Comparative Example 2-1]
Two types of polyester unstretched films (200 m roll-shaped film) having a thickness of 25 μm and 16 μm were obtained from the raw materials of Example 2-1. The ratio of the thickness of each layer of this film was (I) layer / (II) layer = 1/1. Then, it stored like Example 2-1.

  Tables 4 and 5 show the melting point of the polyester, the functional group concentration in the olefin-based polymer, the heat shrinkage, the appearance and the cut resistance of the roll film after storage. Although the film of this comparative example was excellent in appearance, it was not preferable because, as a result of storage in the same manner as in Example 2-1, the cut resistance of the film was poor and wrinkles and wrinkles occurred.

[Comparative Example 2-2]
Except that the raw material of the resin layer (II) was polyester B = 100 (% by weight) (raw material obtained by removing the olefin from Example 2-1), two types having a thickness of 25 μm and 16 μm were performed in the same manner as in Example 2-1. (200 m roll-shaped film) was obtained. The ratio of the thickness of each layer of this film was (I) layer / (II) layer = 1/1. Then, after storing in the same manner as in Example 2-1, a laminated metal plate was prepared and made into a can to obtain a 350 ml-sized seamless can.

  Melting point of polyester, concentration of functional group in olefin polymer, heat shrinkage, film appearance, appearance and cut resistance of roll film after storage, can-making properties Tables 4 and 5 show the degree of flaws), flavor, and impact resistance. The film of this comparative example was excellent in appearance, there was no decrease in appearance and cut resistance after storage, and the laminated plate of this comparative example was excellent in can making properties and flavor properties, but the impact resistance of metal cans was poor. Not good for bad.

[Comparative Example 2-3]
Except that the heat treatment temperature after the transverse stretching was set to 225 ° C, two types of polyester films (200 m roll-shaped film) having a thickness of 25 µm and 16 µm were obtained in the same manner as in Example 2-1. The ratio of the thickness of each layer of this film was (I) layer / (II) layer = 1/1. Then, after storing in the same manner as in Example 2-1, a laminated metal plate was prepared and made into a can to obtain a 350 ml-sized seamless can.

  Melting point of polyester, concentration of functional group in olefin polymer, heat shrinkage, film appearance, appearance and cut resistance of roll film after storage, can-making properties Tables 4 and 5 show the degree of scratching. Although the film of this comparative example was excellent in appearance, and did not decrease in appearance and cut resistance after storage, it was not preferable because the film was peeled off when the laminated board was made.

[Comparative Example 2-4]
Two types of polyester films (200 m roll-shaped film) having a thickness of 25 μm and 16 μm were obtained in the same manner as in Example 2-1 except that the heat treatment was not performed after the transverse stretching. The ratio of the thickness of each layer of this film was (I) layer / (II) layer = 1/1.

  Tables 4 and 5 show the melting point of the polyester, the functional group concentration in the olefin-based polymer, the heat shrinkage, the film appearance, the appearance and the cut resistance of the roll film after storage. Although the film of this comparative example was excellent in appearance, it was not preferable because the film was stored in the same manner as in Example 2-1.

[Comparative Example 2-5]
Except that the raw material of the resin layer (I) was polyester E = 100 (% by weight), two types of polyester films (200-m roll-shaped film) having a thickness of 25 μm and 16 μm were obtained in the same manner as in Example 2-1. Was. The ratio of the thickness of each layer of this film was (I) layer / (II) layer = 1/1. Then, after storing in the same manner as in Example 2-1, a laminated metal plate was prepared and made into a can to obtain a 350 ml-sized seamless can.

  Melting point of polyester, concentration of functional group in olefin polymer, heat shrinkage, film appearance, appearance and cut resistance of roll film after storage, can-making properties Table 4 and Table 5 show the degree of flaws) and flavor. The film of this comparative example was excellent in appearance, and there was no appearance defect after storage, but the cut resistance of the film was poor, the flavor of the laminated metal plate was poor, and when the laminated metal plate was made, the inner surface of the can It is not preferable because the film and the processing punch adhere to each other, buckling occurs over the entire periphery of the opening of the can, and furthermore, scratches occur over the entire periphery of the film on the outer surface of the can.

[Comparative Example 2-6]
Except that the raw material of the resin layer (II) was polyester B / olefin A / olefin B = 60/20/20 (% by weight), two kinds of polyesters having a thickness of 25 μm and 16 μm were used in the same manner as in Example 2-1. A film (200 m roll film) was obtained. The ratio of the thickness of each layer of this film was (I) layer / (II) layer = 1/1. Then, after storing in the same manner as in Example 2-1, a laminated metal plate was prepared and made into a can to obtain a 350 ml-sized seamless can.

  Melting point of polyester, concentration of functional group in olefin polymer, heat shrinkage, film appearance, appearance and cut resistance of roll film after storage, can-making properties Tables 4 and 5 show the degree of flaws), flavor, and impact resistance. The film of this comparative example was excellent in appearance, and did not have a decrease in appearance and cut resistance after storage. Was partially deformed, and a part of the film on the outer surface of the can was scratched.

[Comparative Example 2-7]
Polyester A / Polyester B = 40/60 (% by weight) as a raw material for the resin layer (I), and Polyester B / Olefin A = 90/10 (% by weight) as a raw material for the resin layer (II). After being melted at 270 ° C. using a machine, they were merged in a flow path and extruded in a layer form from a T-die onto a cooling roll to obtain an unstretched sheet of a laminated resin. The unstretched sheet is stretched longitudinally at a preheating temperature of 80 ° C. and a stretching temperature of 100 ° C., further stretched 4.0 times in a transverse direction at a preheating temperature of 80 ° C. and a stretching temperature of 100 ° C., and then heat-treated at 150 ° C. for 8 seconds. Thus, two types of polyester films (200 m roll-shaped film) having a thickness of 25 μm and 16 μm were obtained. The ratio of the thickness of each layer of this film was (I) layer / (II) layer = 1/1. Then, after storing in the same manner as in Example 2-1, a laminated metal plate was prepared and made into a can to obtain a 350 ml-sized seamless can.

  Melting point of polyester, concentration of functional group in olefin polymer, heat shrinkage, film appearance, appearance and cut resistance of roll film after storage, can-making properties Tables 4 and 5 show the degree of scratching), flavor, and impact resistance. The film of this comparative example was excellent in appearance, there was no decrease in appearance and cut resistance after storage, and the laminated plate of this comparative example was excellent in can making properties and flavor properties, but the impact resistance of metal cans was poor. It was somewhat inferior.

[Comparative Example 2-8]
Except that the raw material of the resin layer (I) was the same as that of the resin layer (II), two kinds of polyester films (200 m roll-shaped film) having a thickness of 25 μm and 16 μm were prepared in the same manner as in Example 2-1. Obtained. The ratio of the thickness of each layer of this film was (I) layer / (II) layer = 1/1. Then, after storing in the same manner as in Example 2-1, a laminated metal plate was prepared and made into a can to obtain a 350 ml-sized seamless can.

  Melting point of polyester, concentration of functional group in olefin polymer, heat shrinkage, film appearance, appearance and cut resistance of roll film after storage, can-making properties Tables 4 and 5 show the degree of flaws), flavor, and impact resistance. The film of this comparative example was excellent in appearance, without deterioration in appearance and cut resistance after storage, and the flavor of the laminated metal plate was also good. The punch was stuck, a part of the bottom of the can was deformed, and a part of the film on the outer surface of the can was scratched. However, when the can-making speed was set to 30 cans / min, there was no problem in can-making properties.

[Comparative Example 2-9]
Except that the raw material of the resin layer (II) was polyester B / olefin F = 80/20 (% by weight), two types of polyester films (thickness of 25 m and 16 m) were prepared in the same manner as in Example 2-1. Film). The ratio of the thickness of each layer of this film was (I) layer / (II) layer = 1/1. Then, after storing in the same manner as in Example 2-1, a laminated metal plate was prepared and made into a can to obtain a 350 ml-sized seamless can.

  Melting point of polyester, concentration of functional group in olefin polymer, heat shrinkage, film appearance, appearance and cut resistance of roll film after storage, can-making properties Tables 4 and 5 show the degree of flaws), flavor, and impact resistance. The film of this comparative example was excellent in appearance, and did not decrease in appearance and cut resistance after storage. Was partially deformed, and a part of the film on the outer surface of the can was scratched. Further, when the film of the present comparative example obtains an unstretched resin sheet, due to a decrease in the thermal characteristics of the resin, film deformation occurs in the molten resin film, or a stable film cannot be formed, such as unevenness in the obtained film. Not preferred.

[Example 3-1]
Polyester A / Polyester B = 40/60 (% by weight) as a raw material of the resin layer (I), and Polyester B / Olefin A / Olefin B = 88/6/6 (% by weight) as a raw material of the resin layer (II). The raw materials obtained by pre-kneading at 270 ° C. using a twin-screw vented extruder and dried at 100 ° C. for 24 hours are melted at 270 ° C. using a single-screw extruder, and then melted in a channel. They were merged and extruded in layers from a T die onto a cooling roll to obtain an unstretched sheet of the laminated resin. The unstretched sheet is stretched 3.5 times in the longitudinal direction at a preheating temperature of 80 ° C. and a stretching temperature of 100 ° C., and further stretched 4.0 times in the transverse direction at a preheating temperature of 80 ° C. and a stretching temperature of 100 ° C. Heat treatment was performed at 8 ° C. for 8 seconds to obtain two types of polyester films (200-m roll-shaped film) having a thickness of 25 μm and 16 μm. The ratio of the thickness of each layer of the film was (I) layer / (II) layer / (I) layer = 1/2/1.

  After storing this film at 40 ° C. under the condition of 80% relative humidity for 30 days, the film is pressed on both sides of a 3004 series aluminum alloy plate (0.26 mm thick) heated to 250 ° C., and heated to 275 ° C. And quenched in water to obtain a laminated aluminum plate.

  After applying a molding lubricant to the thus obtained laminated aluminum plate, the plate was heated and drawn at a plate temperature of 70 ° C. Next, the temperature of the obtained cup was set to 40 ° C., and ironing was performed at a mold temperature of 80 ° C. at a rate of 60 cans / min to obtain a 350 ml-sized seamless can.

  Melting point of polyester, concentration of functional group in olefin polymer, heat shrinkage, film appearance, appearance and cut resistance of roll film after storage, can-manufacturability (removability of can inner film and punch and outer film of can Tables 6 and 8 show the degree of scratching), flavor, and impact resistance. The film of this example is excellent in appearance, there is no decrease in appearance and cut resistance after storage, and the laminated plate of this example is excellent in can making properties and flavor properties, and the metal can of this example is impact resistant. It was excellent.

[Example 3-2]
Except that transverse stretching was not performed, two kinds of polyester films (200-m roll-shaped film) having a thickness of 25 μm and 16 μm were obtained in the same manner as in Example 3-1. The ratio of the thickness of each layer of the film was (I) layer / (II) layer / (I) layer = 1/2/1. Then, after storing in the same manner as in Example 3-1, a laminated metal plate was prepared and made into a can to obtain a seamless can of 350 ml size.

  Melting point of polyester, concentration of functional group in olefin polymer, heat shrinkage, film appearance, appearance and cut resistance of roll film after storage, can-manufacturability (removability of can inner film and punch and outer film of can Tables 6 and 8 show the degree of scratching), flavor, and impact resistance. The film of this example is excellent in appearance, there is no decrease in appearance and cut resistance after storage, and the laminated plate of this example is excellent in can making properties and flavor properties, and the metal can of this example is impact resistant. It was excellent.

[Example 3-3]
Except that the raw material of the resin layer (II) was polyester B / olefin A / olefin C = 88/6/6 (% by weight), two kinds of polyesters having a thickness of 25 μm and 16 μm were used in the same manner as in Example 3-1. A film (200 m roll film) was obtained. The ratio of the thickness of each layer of the film was (I) layer / (II) layer / (I) layer = 1/2/1. Then, after storing in the same manner as in Example 3-1, a laminated metal plate was prepared and made into a can to obtain a seamless can of 350 ml size.

  Melting point of polyester, concentration of functional group in olefin polymer, heat shrinkage, film appearance, appearance and cut resistance of roll film after storage, can-manufacturability (release properties of can inner film and punch and outer film of can Tables 6 and 8 show the degree of scratching), flavor, and impact resistance. The film of this example is excellent in appearance, there is no decrease in appearance and cut resistance after storage, and the laminated plate of this example is excellent in can making properties and flavor properties, and the metal can of this example is impact resistant. It was excellent.

[Example 3-4]
Except that the raw material of the resin layer (II) was polyester B / olefin A / olefin D = 88/6/6 (% by weight), two kinds of polyesters having a thickness of 25 μm and 16 μm were used in the same manner as in Example 3-1. A film (200 m roll film) was obtained. The ratio of the thickness of each layer of the film was (I) layer / (II) layer / (I) layer = 1/2/1. Then, after storing in the same manner as in Example 3-1, a laminated metal plate was prepared and made into a can to obtain a seamless can of 350 ml size.

  Melting point of polyester, concentration of functional group in olefin polymer, heat shrinkage, film appearance, appearance and cut resistance of roll film after storage, can-making properties Tables 6 and 8 show the degree of scratching), flavor, and impact resistance. The film of this example is excellent in appearance, there is no decrease in appearance and cut resistance after storage, and the laminated plate of this example is excellent in can making properties and flavor properties, and the metal can of this example is impact resistant. It was excellent.

[Example 3-5]
Except that the raw material of the resin layer (II) was polyester B / olefin B / olefin E = 88/6/6 (% by weight), two kinds of polyesters having a thickness of 25 μm and 16 μm were used in the same manner as in Example 3-1. A film (200 m roll film) was obtained. The ratio of the thickness of each layer of the film was (I) layer / (II) layer / (I) layer = 1/2/1. Then, after storing in the same manner as in Example 3-1, a laminated metal plate was prepared and made into a can to obtain a seamless can of 350 ml size.

  Melting point of polyester, concentration of functional group in olefin polymer, heat shrinkage, film appearance, appearance and cut resistance of roll film after storage, can-making properties Tables 6 and 8 show the degree of scratching), flavor, and impact resistance. The film of this example is excellent in appearance, there is no decrease in appearance and cut resistance after storage, and the laminated plate of this example is excellent in can making properties and flavor properties, and the metal can of this example is impact resistant. It was excellent.

[Example 3-6]
Except that the raw material of the resin layer (II) was changed to polyester B / olefin B = 80/20 (% by weight), two kinds of polyester-based films having a thickness of 25 μm and 16 μm (roll of 200 m) were prepared in the same manner as in Example 3-1. Film). The ratio of the thickness of each layer of the film was (I) layer / (II) layer / (I) layer = 1/2/1. Then, after storing in the same manner as in Example 3-1, a laminated metal plate was prepared and made into a can to obtain a seamless can of 350 ml size.

  Melting point of polyester, concentration of functional group in olefin polymer, heat shrinkage, film appearance, appearance and cut resistance of roll film after storage, can-making properties Tables 6 and 8 show the degree of scratching), flavor, and impact resistance. The film of this example is excellent in appearance, there is no decrease in appearance and cut resistance after storage, and the laminated plate of this example is excellent in can making properties and flavor properties, and the metal can of this example is impact resistant. It was excellent.

[Example 3-7]
Except that the raw material of the resin layer (II) was polyester A / polyester B / olefin A / olefin B = 34/54/6/6 (% by weight), the thickness was 25 μm and 16 μm as in Example 3-1. Two types of polyester films (200 m roll film) were obtained. The ratio of the thickness of each layer of the film was (I) layer / (II) layer / (I) layer = 1/2/1. Then, after storing in the same manner as in Example 3-1, a laminated metal plate was prepared and made into a can to obtain a seamless can of 350 ml size.

  Melting point of polyester, concentration of functional group in olefin polymer, heat shrinkage, film appearance, appearance and cut resistance of roll film after storage, can-making properties Tables 6 and 8 show the degree of scratching), flavor, and impact resistance. The film of this example is excellent in appearance, there is no decrease in appearance and cut resistance after storage, and the laminated plate of this example is excellent in can making properties and flavor properties, and the metal can of this example is impact resistant. It was excellent.

[Example 3-8]
The film used in Example 3-1 was treated with electrolytic chromic acid-treated steel sheet (metallic chromium amount: 135 mg / m ² , chromium in hydrated chromium oxide: 15 mg / m ² , plate thickness: 0.23 mm, hardness T− 3) A laminated plate was prepared in the same manner as in Example 3-1 except for laminating on the top, and a can was prepared to obtain a 350 ml-sized seamless can.

  Melting point of polyester, concentration of functional group in olefin polymer, heat shrinkage, film appearance, appearance and cut resistance of roll film after storage, can-making properties Tables 6 and 8 show the degree of scratching), flavor, and impact resistance. The film of this example is excellent in appearance, there is no decrease in appearance and cut resistance after storage, and the laminated plate of this example is excellent in can making properties and flavor properties, and the metal can of this example is impact resistant. It was excellent.

[Comparative Example 3-1]
Two types of polyester-based unstretched films (200 m roll-shaped film) having a thickness of 25 μm and 16 μm were obtained from the raw materials of Example 3-1. The ratio of the thickness of each layer of the film was (I) layer / (II) layer / (I) layer = 1/2/1. Then, it stored like Example 3-1.

  Tables 7 and 8 show the melting point of the polyester, the functional group concentration in the olefin-based polymer, the heat shrinkage, the film appearance, the appearance and the cut resistance of the roll film after storage. Although the film of this comparative example was excellent in appearance, it was not preferable because, as a result of storage in the same manner as in Example 3-1, the cut resistance of the film was poor and wrinkles and thickening occurred.

[Comparative Example 3-2]
Except that the raw material of the resin layer (II) was polyester B = 100 (% by weight) (raw material obtained by removing the olefin from Example 3-1), two types having a thickness of 25 μm and 16 μm were performed in the same manner as in Example 3-1. (200 m roll-shaped film) was obtained. The ratio of the thickness of each layer of the film was (I) layer / (II) layer / (I) layer = 1/2/1. Then, after storing in the same manner as in Example 3-1, a laminated metal plate was prepared and made into a can to obtain a seamless can of 350 ml size.

  Melting point of polyester, heat shrinkage, film appearance, appearance and cut resistance of roll film after storage, can-making properties (release of inner film and punch and degree of scratching on outer film of can), flavor, resistance The impact properties are shown in Tables 7 and 8. The film of this comparative example was excellent in appearance, there was no decrease in appearance and cut resistance after storage, and the laminated plate of this comparative example was excellent in can making properties and flavor properties, but the impact resistance of metal cans was poor. Not good for bad.

[Comparative Example 3-3]
Except that the heat treatment temperature after the transverse stretching was 225 ° C., two kinds of polyester films (200 μm roll-shaped film) having a thickness of 25 μm and 16 μm were obtained in the same manner as in Example 3-1. The ratio of the thickness of each layer of the film was (I) layer / (II) layer / (I) layer = 1/2/1. Then, after storing in the same manner as in Example 3-1, a laminated metal plate was prepared and made into a can to obtain a seamless can of 350 ml size.

  Melting point of polyester, concentration of functional group in olefin polymer, heat shrinkage, film appearance, appearance and cut resistance of roll film after storage, can-manufacturability (removability of can inner film and punch and outer film of can Tables 7 and 8 show the degree of scratching. Although the film of this comparative example was excellent in appearance, and did not decrease in appearance and cut resistance after storage, it was not preferable because the film was peeled off when the laminated board was made.

[Comparative Example 3-4]
Except that the heat treatment was not performed after the transverse stretching, two types of polyester films (200 m roll-shaped film) having a thickness of 25 μm and 16 μm were obtained in the same manner as in Example 3-1. The ratio of the thickness of each layer of the film was (I) layer / (II) layer / (I) layer = 1/2/1.

  Tables 7 and 8 show the melting point of the polyester, the functional group concentration in the olefin-based polymer, the heat shrinkage, the film appearance, the appearance and the cut resistance of the roll film after storage. Although the film of this comparative example was excellent in appearance, it was not preferable because the film was stored in the same manner as in Example 3-1 and as a result, wrinkles in the lateral direction of the film and bulges at both ends of the film were generated.

[Comparative Example 3-5]
Except that the raw material of the resin layer (I) was changed to polyester E = 100 (% by weight), two kinds of polyester films (roll films of 200 m) having a thickness of 25 μm and 16 μm were obtained in the same manner as in Example 3-1. Was. The ratio of the thickness of each layer of the film was (I) layer / (II) layer / (I) layer = 1/2/1. Then, after storing in the same manner as in Example 3-1, a laminated metal plate was prepared and made into a can to obtain a seamless can of 350 ml size.

Melting point of polyester, concentration of functional group in olefin polymer, heat shrinkage, film appearance, appearance and cut resistance of roll film after storage, can-manufacturability (removability of can inner film and punch and outer film of can Table 7 and Table 8 show the degree of flaws) and flavor.
The film of this comparative example was excellent in appearance, and there was no appearance defect after storage, but the cut resistance of the film was poor, and the flavor of the laminated metal plate was poor, and when the laminated aluminum plate was made, the inner surface of the can It is not preferable because the film and the processing punch adhere to each other, buckling occurs over the entire periphery of the opening of the can, and furthermore, scratches occur over the entire periphery of the film on the outer surface of the can.

[Comparative Example 3-6]
Except that the raw material of the resin layer (II) was polyester B / olefin A / olefin B = 60/20/20 (% by weight), two kinds of polyesters having a thickness of 25 μm and 16 μm were used in the same manner as in Example 3-1. A film (200 m roll film) was obtained. The ratio of the thickness of each layer of the film was (I) layer / (II) layer / (I) layer = 1/2/1. Then, after storing in the same manner as in Example 3-1, a laminated metal plate was prepared and made into a can to obtain a seamless can of 350 ml size.

  Melting point of polyester, concentration of functional group in olefin polymer, heat shrinkage, film appearance, appearance and cut resistance of roll film after storage, can-manufacturability (removability of can inner film and punch and outer film of can Table 7 and Table 8 show the degree of scratching), flavor, and impact resistance. The film of this comparative example was excellent in appearance, and did not have a decrease in appearance and cut resistance after storage. Was partially deformed, and a part of the film on the outer surface of the can was scratched.

[Comparative Example 3-7]
Polyester A / Polyester B = 40/60 (% by weight) as a raw material for the resin layer (I), and Polyester B / Olefin A = 90/10 (% by weight) as a raw material for the resin layer (II). After being melted at 270 ° C. using a machine, they were merged in a flow path and extruded in a layer form from a T-die onto a cooling roll to obtain an unstretched sheet of a laminated resin. The unstretched sheet is stretched longitudinally at a preheating temperature of 80 ° C. and a stretching temperature of 100 ° C., further stretched 4.0 times in a transverse direction at a preheating temperature of 80 ° C. and a stretching temperature of 100 ° C., and then heat-treated at 150 ° C. for 8 seconds. Thus, two types of polyester films (200 m roll-shaped film) having a thickness of 25 μm and 16 μm were obtained. The ratio of the thickness of each layer of the film was (I) layer / (II) layer / (I) layer = 1/2/1. Then, after storing in the same manner as in Example 3-1, a laminated metal plate was prepared and made into a can to obtain a seamless can of 350 ml size.

  Melting point of polyester, concentration of functional group in olefin polymer, heat shrinkage, film appearance, appearance and cut resistance of roll film after storage, can-making properties Tables 7 and 8 show the degree of scratching), flavor, and impact resistance. The film of this comparative example was excellent in appearance, there was no decrease in appearance and cut resistance after storage, and the laminated plate of this comparative example was excellent in can making properties and flavor properties, but the impact resistance of metal cans was poor. It was somewhat inferior.

[Comparative Example 3-8]
Except that the raw material of the resin layer (I) was the same as the raw material of the resin layer (II), two kinds of polyester-based films having a thickness of 25 μm and 16 μm (a roll film of 200 m) were used in the same manner as in Example 3-1. Got. The ratio of the thickness of each layer of the film was resin layer (I) / resin layer (II) / resin layer (I) = 1/2/1. Then, after storing in the same manner as in Example 3-1, a laminated metal plate was prepared and made into a can to obtain a seamless can of 350 ml size.

  Melting point of polyester, concentration of functional group in olefin polymer, heat shrinkage, film appearance, appearance and cut resistance of roll film after storage, can-making properties Table 7 and Table 8 show the degree of scratching), flavor, and impact resistance. The film of this comparative example is excellent in appearance, there is no decrease in appearance and cut resistance after storage, and the laminated metal plate of this comparative example has good flavor properties, but when the laminated metal plate is made, As a result, the releasability of the film on the inner surface of the can and the punch was poor, a part of the bottom of the can was deformed, and a part of the film on the outer surface of the can was damaged. However, when the can-making speed was set to 30 cans / min, there was no problem in can-making properties.

[Comparative Example 3-9]
Except that the raw material of the resin layer (II) was changed to polyester B / olefin F = 80/20 (% by weight), two kinds of polyester-based films having a thickness of 25 μm and 16 μm (roll of 200 m) were used in the same manner as in Example 3-1. Film). The ratio of the thickness of each layer of the film was (I) layer / (II) layer / (I) layer = 1/2/1. Then, after storing in the same manner as in Example 3-1, a laminated metal plate was prepared and made into a can to obtain a seamless can of 350 ml size.

  Melting point of polyester, concentration of functional group in olefin polymer, heat shrinkage, film appearance, appearance and cut resistance of roll film after storage, can-manufacturability (removability of can inner film and punch and outer film of can Table 7 and Table 8 show the degree of scratching), flavor, and impact resistance. The film of this comparative example was excellent in appearance, and did not decrease in appearance and cut resistance after storage. Was partially deformed, and a part of the film on the outer surface of the can was scratched. Further, when the film of the present comparative example obtains an unstretched resin sheet, due to a decrease in the thermal characteristics of the resin, film deformation occurs in the molten resin film, or a stable film cannot be formed, such as unevenness in the obtained film. Not preferred.

Claims (6)

  The molar ratio (phosphorus / metal ion) between the total amount of phosphorus and the total amount of metal ions to be added at the time of production is in the range of 0.4 to 1.0. Polyester resin having a heat shrinkage in the stretching direction at 150 ° C. of 2 to 30%, obtained by stretching the polyester resin composition blended at a ratio of 30 to 99/1 (% by weight) at least in the longitudinal direction. A polyester film for bonding metal plates, wherein the olefin polymer is a polymer having a functional group in the range of 200 to 2000 equivalents / ton in the polymer.   Resin layer (I) composed of crystalline polyester A having a melting point of 180 ° C. or more with a molar ratio (phosphorus / metal ion) of 0.4 to 1.0 between the total amount of phosphorus and the total amount of metal ions to be added during production. And a resin sheet having a two-layer structure of a resin layer (II) composed of a polyester-based resin composition B in which polyester and an olefin-based polymer are blended in a ratio of 70/30 to 99/1 (% by weight) at least in a longitudinal direction. A polyester film having a heat shrinkage of 2 to 30% in a stretching direction at 150 ° C. obtained by uniaxial stretching, wherein the olefin polymer is functionalized in the polymer in the range of 200 to 2000 equivalents / ton. A polyester film for bonding a metal plate, which is a polymer containing a group.   Resin layer (I) made of crystalline polyester A having a melting point in the range of 0.4 to 1.0 and a melting point of 180 ° C. or more in the molar ratio (phosphorus / metal ion) between the total phosphorus amount and the total metal ion amount added at the time of production. And a resin layer (II) composed of a polyester resin composition B obtained by blending a polyester and an olefin-based polymer in a ratio of 70/30 to 99/1 (% by weight), wherein (I) layer / (II) layer / ( I) A polyester film having a heat shrinkage in the stretching direction at 150 ° C. of 2 to 30%, which is obtained by stretching a laminated resin sheet composed of three layers at least uniaxially in the longitudinal direction, A polyester film for laminating a metal plate, wherein the olefin polymer is a polymer having a functional group in a range of 200 to 2000 equivalents / ton in the polymer. Olefin polymer is
(1) a copolymer comprising as main constituent units at least one or more α-olefins having 2 to 6 carbon atoms and an ethylene bond-forming α, β-unsaturated carboxylic acid or an ester-forming derivative thereof;
Or
(2) The polyester film for bonding metal plates according to any one of claims 1 to 3, which is a mixture of the copolymer (1) and another polymer.   An olefin-based polymer comprising at least one or more α-olefins having 2 to 6 carbon atoms as a main constituent unit, and at least one or more α-olefins having 2 to 6 carbon atoms and an ethylene bond The polyester film for laminating metal plates according to claim 4, comprising a copolymer (b) having a main constituent unit of a formable α, β-unsaturated carboxylic acid or an ester-forming derivative thereof.   The polyester film for bonding metal plates according to any one of claims 1 to 5, wherein the total amount of metal ions is the total amount of Mg ions, Ca ions, Mn ions, Zn ions, and Co ions.