JP2005298688A - Polyester-based film for coating metal sheet and its manufacturing method, polyester-based film-coated metal sheet and its manufacturing method, polyester-based film-coated metal can - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a polyester-based film for coating a metal sheet in which the part to be laminated to a metal sheet is broad, the material loss is little, and the film is hardly broken, and further to provide a polyester-based film-coated metal sheet capable of drawing and ironing processing under a high speed and a high processing degree and having an excellent can making properties. <P>SOLUTION: The polyester-based film for a coating metal sheet having a 0.1 μm or lower surface roughness (Ra) and a 1.360 g/cm<SP>3</SP>or lower density is obtained by solidifying a molten resin film of a polyester-based resin composition, obtained by mixing a crystalline polyester having a 180 °C or higher melting point and an olefinic polymer having functional groups in 200-2,000 equivalents/ton and having a 0.25-2.0 μm equivalent spherical diameter in a wt.% ratio of 70/30-99/1, on a cooling roll having a 0.2 μm or higher and lower than 4.0 μm surface roughness (Ra), and by uniaxially stretching it. And further the polyester-based film-coated metal sheet is obtained by coating the film on a metal sheet. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention is a polyester film used for the purpose of preventing corrosion of metal containers such as soft drinks, beer, canned foods and the like, a method for producing the same, a polyester film-coated metal plate obtained by laminating the film on a metal plate, and a method for producing the same. The present invention also relates to a polyester film-coated metal can obtained by molding from the polyester film-coated metal plate described above.

  More specifically, it is one of means for obtaining a metal can, for example, a polyester-based film excellent in can-making ability even in severe molding such as drawing and ironing, and a method for producing the same, and excellent in dent resistance. The present invention relates to a polyester film-coated metal plate from which a metal can can be obtained and a method for producing the same.

Conventionally, the inner surface and outer surface of a metal can have been widely coated with a solution in which various thermosetting resins such as epoxy and phenol are dissolved or dispersed in a solvent for the purpose of preventing corrosion. Has been done. However, this thermosetting resin coating method has a drawback in that it takes a long time to dry the paint, so that productivity is lowered and undesired problems such as environmental pollution due to a large amount of organic solvent often occur.

  In order to avoid such drawbacks, a method of coating a metal plate with a thermoplastic resin by a melt extrusion method is disclosed (for example, see Patent Document 1).

  However, in the above method, it is difficult to shorten the distance from the T die to the metal plate, and as a result, the thickness of both ends becomes very thick. Therefore, the central portion having a uniform thickness (substantially laminated to the metal plate). This is a laminating method in which the material loss is large and the both ends cut and removed cannot be reused.

  In order to avoid such drawbacks, a method is disclosed in which an unoriented film of polyethylene terephthalate and / or polybutylene terephthalate obtained by cooling and solidifying after melt extrusion is pressed onto a heated metal plate. In this method, the distance from the T die to the metal plate can be shortened. As a result, a central portion having a uniform thickness (a portion that can be substantially laminated on the metal plate) is wider than the above method and cut and removed. Thus, the both end portions can be recycled and used, so that the laminating method can reduce material loss (see, for example, Patent Document 2).

  However, in the above method, when the both ends are cut and removed, the film is easily broken, and when the film is formed at a high speed, a dent exceeding 50 μm is likely to be generated on the film surface. There was a drawback that the film was a laminated metal plate in which bubbles were present, and fine film tearing was liable to occur at the time of can making.

  In addition, “dent resistance” is an important characteristic that a metal can should have. “Dent resistance” refers to the susceptibility to film damage such as cracking or exfoliation of the coated film or film when a force such as impact or impact is applied. Good resistance to dent indicates that it is not easily damaged.

  As a specific situation example, for example, when a can filled and sealed with contents is dropped, a microcrack is generated in the coated film along with the deformation of the metal at the hit / impacted part. Depending on the degree of corrosiveness of the filled contents, there is a problem that it leads to metal corrosion.

  As a resin used for resin-coated metal plates for squeezing and ironing cans, including the purpose of improving dent resistance, dicarboxylic acid components are 50 to 95 mol% terephthalic acid and isophthalic acid and / or orthophthalic acid 50 to 5 mol%. A resin composition comprising 75 to 99% by weight of a crystalline saturated polyester resin comprising a compound whose main component is ethylene glycol as a hydroxy component and 25 to 1% by weight of an ionomer resin is disclosed (for example, see Patent Document 3). .

However, even when the resin composition is used, sufficient dent resistance cannot be obtained, and when an ionomer resin is used, foreign matter having a metal atom as a nucleus is easily generated in the molten resin film, and the coating for cans It was not yet satisfactory as a resin.
JP-A-57-203545 JP 2001-1447 A JP-A-7-195617

  The present invention aims to eliminate the drawbacks of the prior art. In other words, the central part with a uniform thickness (the part that can be laminated to a metal plate) is wide, and both ends that have been cut and removed can be recycled, so there is little material loss, and the film breaks when both ends are cut and removed. When the molten resin film is cooled and solidified at a higher speed, the film surface that comes into contact with the roll is less likely to have a dent exceeding 50 μm, so it can be drawn and ironed at a high speed and with a high degree of processing. It becomes possible to provide a polyester film-coated metal sheet having can properties. Further, the obtained metal can has a good dent resistance. Accordingly, the present invention provides a polyester film for metal plate coating having economical and excellent characteristics and a method for producing the same, a polyester film coated metal plate and a method for producing the same, and a polyester film coated metal can.

The first invention of the present application is a crystalline polyester having a melting point of 180 ° C. or higher, an olefin polymer having a functional group of 200 to 2000 equivalent / ton and an equivalent spherical equivalent diameter of 0.25 to 2.0 μm, Is a polyester film comprising a polyester resin composition mixed at a ratio of 70/30 to 99/1 wt%, and the polyester film satisfies the following formulas (I) to (III) After the molten resin film of the resin composition is solidified with a cooling roll having a surface roughness (Ra) of 0.2 μm or more and less than 4.0 μm, it is uniaxially stretched at least in the longitudinal direction, and the surface roughness (Ra) is It is a polyester film for metal plate coating, which is 0.1 μm or less and has a density of 1.360 g / cm ³ or less.
[Formula] (I) 1 ≦ m ≦ 30
(II) 0.15 ≦ (Mi−Mf) /m≦1.0
(III) 2 ≦ Mf ≦ 20
(In the formula, Mi represents the melt flow rate (MFR, g / 10 min) of the crystalline polyester measured at the melting point of the crystalline polyester + 30 ° C., and Mf represents the crystal measured at the melting point of the crystalline polyester + 30 ° C. MFR (g / 10 min) of a mixture of a functional polyester and an olefin polymer, and m represents the content (% by weight) of the olefin polymer in the mixture.

  2nd invention of this application is a manufacturing method of the polyester-type film for metal plate coating | coated as described above, Comprising: Surface roughness (Ra) is 0 for the molten film which extruded the polyester-type resin composition into the layer form from T-die. It is a method for producing a polyester film for coating a metal plate, characterized in that it is at least longitudinally uniaxially stretched after solidification with a cooling roll of 2 μm or more and less than 4.0 μm.

The third invention of the present application is a crystalline polyester having a melting point of 180 ° C. or higher, an olefin polymer having a functional group of 200 to 2000 equivalents / ton and an equivalent spherical equivalent diameter of 0.25 to 2.0 μm, Are mixed at a ratio of 70/30 to 99/1% by weight, and a molten resin film of a polyester resin composition satisfying the above formulas (I) to (III) has a surface roughness (Ra) of 0.2 μm. As described above, after solidifying with a cooling roll of less than 4.0 μm, at least uniaxially stretching in the longitudinal direction, the surface roughness (Ra) is 0.1 μm or less, and the density is 1.360 g / cm ³ or less. A polyester-based film-coated metal plate, wherein the film is coated on a surface corresponding to at least the inner surface side of the metal plate.

The fourth invention of the present application is a crystalline polyester having a melting point of 180 ° C. or higher, an olefin polymer having a functional group of 200 to 2000 equivalent / ton and an equivalent spherical equivalent diameter of 0.25 to 2.0 μm, Are coated at a ratio of 70/30 to 99/1% by weight and coated with a polyester film obtained from a polyester resin composition satisfying the above formulas (I) to (III). The molten resin film extruded in a layer form from the T die is solidified with a cooling roll having a surface roughness (Ra) of 0.2 μm or more and less than 4.0 μm, and at least both ends after being longitudinally uniaxially stretched Cutting and removing the polyester film, laminating the polyester film on a heated metal plate, and forming the film-coated metal plate into a crystalline polyester. By quenching after heating to above the melting point of Le is a method for producing a polyester film coated metal plate characterized by comprising the step of the density of the polyester film and 1.360g / cm ³ or less.

5th invention of this application is a can obtained by shape | molding from the said polyester film covering metal plate, Comprising: The density of the polyester film coat | covered at least on the inner surface side of a can is 1.360 g / cm < ³ > or less. A polyester film-coated metal can characterized by being.

  More specifically, the olefin-based polymer mainly contains at least one ethylene bond-forming α, β-unsaturated carboxylic acid or an ester-forming derivative thereof and at least one or more olefins having 2 to 6 carbon atoms. A copolymer comprising a constituent unit, or a mixture comprising the copolymer and a polymer comprising at least one of olefins having 2 to 6 carbon atoms as a main constituent unit, or having 2 to 6 carbon atoms A polymer (a) comprising at least one olefin as a main constituent unit and at least one of an ethylene bond-forming α, β-unsaturated carboxylic acid or an ester-forming derivative thereof and an olefin having 2 to 6 carbon atoms. It is characterized by comprising a mixture comprising a copolymer (b) having at least one or more main structural units.

  The method for producing a polyester film-coated metal sheet according to the present invention can reduce material loss, so that it is not only an economical production method but also a severe forming process such as drawing and ironing. Is a production method for obtaining a polyester film-coated metal plate having excellent canability.

  Furthermore, when a polyester film-coated metal sheet obtained by the present invention is canned, a metal can excellent in dent resistance can be obtained. Therefore, a very useful polyester film for coating a metal sheet, a method for producing the same, and a polyester film It can be said that it is a coated metal plate, a manufacturing method thereof, and a polyester film-coated metal can.

The polyester film for coating a metal plate of the present invention has a crystalline polyester having a melting point of 180 ° C. or higher, a functional group of 200 to 2000 equivalent / ton, and an equivalent spherical equivalent diameter of 0.25 to 2.0 μm. A polyester film comprising a polyester resin composition in which an olefin polymer is mixed at a ratio of 70/30 to 99/1% by weight, and the polyester film satisfies the formulas (I) to (III). The molten resin film of the polyester-based resin composition is solidified with a cooling roll having a surface roughness (Ra) of 0.2 μm or more and less than 4.0 μm, and is then uniaxially stretched at least in the longitudinal direction. It is necessary that Ra) is 0.1 μm or less and the density is 1.360 g / cm ³ or less.

  The crystalline polyester used in the present invention is a polymer comprising a dicarboxylic acid component and a glycol component.

  Dicarboxylic acid components include terephthalic acid, isophthalic acid, orthophthalic acid, naphthalenedicarboxylic acid, diphenylsulfone dicarboxylic acid, 5-sodium sulfoisophthalic acid and other aromatic dicarboxylic acids, oxalic acid, succinic acid, adipic acid, sebacic acid, decanedicarboxylic acid Aliphatic dicarboxylic acids such as acid, maleic acid, fumaric acid and dimer acid, oxycarboxylic acids such as p-oxybenzoic acid, and alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid can be used, preferably terephthalic acid, isophthalic acid It is preferable to mainly use dicarboxylic acids selected from the group consisting of naphthalenedicarboxylic acid and their ester derivatives, and more preferably 80 mol% or more of the above-mentioned dicarboxylic acids and their ester derivatives in total.

  When other dicarboxylic acids and their ester derivatives are used, the amount is preferably 20 mol% or less, more preferably 10 mol% or less. If the amount of other dicarboxylic acids and their ester derivatives used exceeds 20 mol%, the thermal stability of the polyester is deteriorated, which is not preferable.

  In addition, as glycol components, ethylene glycol, propanediol, butanediol, pentanediol, hexanediol, neopentylglycol and other alicyclic glycols such as cyclohexanedimethanol, bisphenol A ethylene oxide adduct, bisphenol An aromatic glycol such as an ethylene oxide adduct of S, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, or the like can be used. In addition, a small amount of a compound containing an amide bond, a urethane bond, an ether bond, a carbonate bond, or the like may be included.

  Here, it is preferable to mainly use ethylene glycol and 1,4-butanediol as the diol 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 used exceeds 20 mol%, the thermal stability of the polyester deteriorates, which is not preferable.

  In the present invention, the method for producing the polyester is not particularly limited. That is, it can be used even if it is produced by either the transesterification method or the direct polymerization method. Further, it may be produced by a solid phase polymerization method in order to increase the molecular weight. Furthermore, it was manufactured by a solid-state polymerization method under reduced pressure or in an inert gas atmosphere from the point of reducing the amount of oligomer from the polyester resin in the retort treatment etc. that is carried out after filling and sealing the contents in the can. It is preferred to use a polyester with a low oligomer content.

  In the present invention, antimony oxide, germanium oxide, a titanium compound or the like is used as a polymerization catalyst for polyester production.

  In the present invention, an antioxidant, a heat stabilizer, an ultraviolet absorber, a plasticizer, a pigment, an antistatic agent, a lubricant, a crystal nucleating agent, a lubricant composed of inorganic or organic particles, etc. may be added to the polyester as necessary. Good.

  In the present invention, it is necessary that the melting point of the crystalline polyester is 180 ° C. or more from the viewpoint of securing the punch releasability on the inner surface side of the can, particularly in drawing and ironing. Here, releasability refers to the ease with which the punch after molding is removed from the can body. If the releasability of the punch is poor, the can body is buckled near the opening of the can body. If the normal can height cannot be obtained, or if it is extremely inferior, the punch may not come off from the can body, resulting in a line stop.

  If it says further about melting | fusing point of crystalline polyester, when using as a film of the inner surface side of a can, melting | fusing point is preferable 200 degreeC or more, More preferably, 220 degreeC or more is good.

  In the present invention, it is necessary to use a functional group-containing polymer as the olefin polymer used in the polyester resin composition constituting the polyester film.

  Examples of the functional group-containing polymer include a copolymer of an olefin and a functional group-containing vinyl monomer, but the functional group has a polarity and a functional group having an effect of increasing the affinity with the polyester to be mixed is used. Are preferable, and examples thereof include a carboxyl group, a glycidyl group, and an acid anhydride group.

  Specifically, ethylene-α, β-unsaturated carboxylic acid copolymers such as ethylene- (meth) acrylate copolymers and ethylene- (meth) acrylic acid ester copolymers produced by various production methods and catalysts, ethylene -Vinyl acetate copolymer, ethylene-vinyl alcohol copolymer, ethylene-maleic anhydride copolymer, ionomer, etc. can be illustrated.

  The concentration of the functional group of the olefin polymer containing a functional group is in the range of 200 to 2000 equivalents / ton (the number of moles of functional groups present in 1 ton of the total weight of the olefin polymer). It is necessary to combine properties such as prevention of breakage, ensuring suitability for laminating on a metal plate, ensuring canability, and ensuring dent resistance of the can body. When the content of the functional group is within the above range, the affinity of the olefin polymer to the polyester resin is increased moderately, and the olefin polymer and polyester molecular chains chemically interact with each other, resulting in excellent impact resistance. It is presumed that sex will be exhibited.

  When the functional group concentration in the olefin polymer is less than 200 equivalents / ton, the effect of improving the dent resistance of the polyester film is insufficient, which is not preferable. On the contrary, when the functional group concentration of the olefin polymer exceeds 2000 equivalents / ton, it is necessary to increase the mixing amount of the olefin polymer in order to obtain the effect of the present invention, and the polyester system of the present invention increases as the mixing amount increases. This is not preferable because the thermal stability at the time of melt extrusion of the resin composition is lowered, and as a result, the mechanical properties and canability of the film may be lowered.

  Moreover, as a vinyl monomer copolymer having a functional group, some or all of the carboxylic acid groups of α, β-unsaturated carboxylic acid were neutralized with metal ions such as Na, K, Li, Zn, Mg, Ca, etc. In the case of using an ionomer, it is preferable that the total amount of metal ions does not exceed 200 ppm with respect to the total amount of the olefin-based polymer because foreign matters having metal particles as a core are easily generated in the melt extrusion process.

  Preferred examples of the olefin-based polymer used in the present invention include (1) a copolymer of an olefin having 2 to 6 carbon atoms and an ethylene bond-forming α, β-unsaturated carboxylic acid, and (2) 2 to 2 carbon atoms. A copolymer of an olefin of 6 and an ester-forming derivative of an ethylene bond-forming α, β-unsaturated carboxylic acid; (3) an olefin having 2 to 6 carbon atoms and an ethylene bond-forming α, β-unsaturated carboxylic acid; (4) Esters of α, β-unsaturated carboxylic acid having 2 to 6 carbon atoms and ethylene bond-forming α, β-unsaturated carboxylic acid And a mixture composed of a copolymer with a forming derivative and a polymer having a main structural unit of an olefin having 2 to 6 carbon atoms, and more preferably (5) a main structural unit having an olefin having 2 to 6 carbon atoms. Polymer (a) And a mixture of an olefin having 2 to 6 carbon atoms and a copolymer (b) of an ethylene bond-forming α, β-unsaturated carboxylic acid, and (6) an olefin having 2 to 6 carbon atoms as a main structural unit. Examples thereof include a mixture of the polymer (a) and a copolymer (b) of an olefin having 2 to 6 carbon atoms and an ester-forming derivative of an ethylene bond-forming α, β-unsaturated carboxylic acid.

  In the olefin polymer of the present invention, one of these olefin polymers can be used alone, but two or more of them can be used in combination.

  Examples of polymers having 2 to 6 carbon olefins or at least one olefin having 2 to 6 carbons as main structural units include low density polyethylene, medium density polyethylene, high density polyethylene, linear low Examples thereof include density polyethylene, ultra high molecular weight polyethylene, polypropylene, ethylene-propylene copolymer, and ethylene-butene copolymer.

  Examples of the copolymer of at least one or more olefins having 2 to 6 carbon atoms and at least one or more of α, β-unsaturated carboxylic acid or an ester-forming derivative thereof include ethylene-ethyl acrylate copolymer, ethylene -Methyl acrylate copolymer, ethylene-methyl methacrylate copolymer, ethylene-acrylic acid copolymer, ethylene-methacrylic acid copolymer, ethylene-butene-acrylic acid copolymer, and the like.

  Furthermore, in the present invention, as a further preferred example of the olefin polymer used in the polyester resin composition constituting the polyester film, a monomer component (crosslinkable monomer and / or graft) capable of forming a crosslinked structure and / or a branched structure is used. Examples thereof include polymers each containing a binding monomer) in the range of less than 5% by weight.

  Examples of such a monomer include unsaturated monomers having two or more addition polymerizable reactive groups.

  Examples of the crosslinkable monomer include butylene diacrylate, butylene dimethacrylate, trimethylolpropane trimethacrylate, divinylbenzene, trivinylbenzene, vinyl acrylate, vinyl methacrylate, and the like, preferably butylene diacrylate, 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, monoallyl itaconate, and the like. Preferably, allyl methacrylate and diallyl methacrylate are used.

  In the present invention, in order for the polyester resin composition constituting the polyester film to achieve its purpose, the mixing ratio of the crystalline polyester and the olefin polymer needs to be 70:30 to 99: 1 wt%. is there. When the olefin-based polymer is less than 1% by weight, the effect of improving the dent resistance of the obtained metal can is insufficient, which is not preferable. On the other hand, when the olefin-based polymer exceeds 30% by weight, the release property of the punch is deteriorated when used as a resin on the inner surface side of the can, which is not preferable.

  The mixing ratio of the crystalline polyester and the olefin polymer is more preferably in the range of 72:28 to 95: 5% by weight from the viewpoints of ensuring the release property of the punch and ensuring the dent resistance of the film.

  In the present invention, the polyester constituting the polyester film needs to contain olefin polymer fine particles having an average equivalent spherical equivalent diameter of 0.25 to 2.0 μm. For example, the olefinic polymer has a “sea”-“island” relationship with respect to the polyester, and the olefinic polymer is dispersed in the form of “islands” in the “sea” of the polyester.

  In this way, the olefin polymer is finely dispersed in the polyester, so that it exhibits the ability to absorb the impact energy applied to the film, and at the same time, since it has the above-mentioned functional group, molecules at the interface between the olefin polymer and the polyester. Interaction increases, and excellent impact resistance and adhesion are exhibited.

  When the equivalent sphere equivalent diameter of the olefin polymer exceeds 2.0 μm as an average value, the dispersion state in the polyester becomes coarse, so that the impact resistance is ensured unless the content is more than 30% by weight. As a result, the characteristics of the olefin polymer are more manifested, resulting in a decrease in heat resistance, leading to a decrease in punch releasability and a decrease in galling resistance, which is not preferable.

  On the other hand, when the thickness is less than 0.25 μm, the impact resistance is good, but the characteristics commensurate with the equivalent spherical equivalent diameter cannot be obtained, and the effect becomes saturated. Moreover, since it is difficult to stably produce fine particles having a size of less than 0.25 μm, it leads to a decrease in productivity and is not economical.

  The equivalent sphere equivalent diameter of the olefin-based polymer is preferably 0.3 to 1.8 μm, and more preferably 0.3 to 1.5 μm, from the viewpoint of impact resistance and productivity.

  Further, in order to control the dispersion diameter of the olefin polymer within the above range, as one example of selection of the olefin polymer, two or more types of olefins including a polyolefin having no functional group and a polyolefin containing a functional group The combined use of a polymer is mentioned.

  Specific examples include the combined use of polyethylene and ethylene- (meth) acrylic acid copolymer, and the combined use of ethylene-α-olefin copolymer and ethylene-α-olefin- (meth) acrylic acid copolymer. . Moreover, in order to make the dispersed particle diameter of an olefin polymer into said range, it can achieve by selecting the conditions of melt-mixing polyester and an olefin polymer arbitrarily.

In the present invention, in order for the polyester resin composition constituting the polyester film to achieve its purpose, it is necessary to satisfy the following formulas (I) to (III).
[Formula] (I) 1 ≦ m ≦ 30
(II) 0.15 ≦ (Mi−Mf) /m≦1.0
(III) 2 ≦ Mf ≦ 20
(In the formula, Mi represents the melt flow rate (MFR, g / 10 min) of the crystalline polyester measured at the melting point of the crystalline polyester + 30 ° C., and Mf represents the crystal measured at the melting point of the crystalline polyester + 30 ° C. MFR (g / 10 min) of a mixture of a functional polyester and an olefin polymer, and m represents the content (% by weight) of the olefin polymer in the mixture.

  The melt flow rate (MFR) here is a value indicating the melting characteristics of the resin composition measured by the method defined in JIS K7210, and the resin falls within a specific range indicated by the above formula. By setting the kind and amount, it is possible to satisfy the laminating property and can-making property to metal, and the impact resistance of the obtained metal can.

  In the above formula, when the value of (Mi−Mf) / m is less than 0.15, or when the value of Mf exceeds 20, the polyester film has a small ability to absorb impact energy and improves dent resistance. Since the effect is insufficient, it is not preferable.

  In the above formula, when the value of (Mi−Mf) / m exceeds 1.0, or the value of Mf is less than 2, the molten resin film is transferred to the chill roll as the mixing amount of the olefin polymer is increased. Since the melt tension at the time of casting becomes too large and stable film formation cannot be performed, it is not preferable.

  In the present invention, a polyester resin composition constituting a polyester film (a composition obtained by dry blending or melt mixing a polyester and an olefin polymer) is melted in a known single or twin screw extruder, and then T A layered molten resin film is obtained using a die.

  In the present invention, it is necessary to solidify the molten resin film with a cooling roll having a surface roughness (Ra) of 0.2 μm or more and less than 4.0 μm. In addition, the surface shape of the cooling roll can be a spiral groove, a diamond cut groove, a satin finish, etc. Of these, the surface has a satin finish A roll is particularly preferred.

  When the roll surface roughness (Ra) is less than 0.2 μm, when the molten resin film is cooled and solidified at high speed, countless dents exceeding 50 μm are generated on the film surface in contact with the cooling roll. When uniaxially stretched, the dent becomes large, and when this film is laminated, it becomes a coated metal plate in which bubbles due to the dent are present, and fine film breakage tends to occur starting from the bubbles during can making. Conversely, when the roll surface roughness (Ra) is 4.0 μm or more, the satin pattern is transferred to the film, and when this film is laminated to a metal plate, a patchy appearance defect occurs on the film. When used on the outer surface side, the commercial value decreases, which is not preferable.

  At this time, the roll surface roughness (Ra) is preferably 0.2 μm or more and 3.5 μm or less, and more preferably 0.2 μm or more and 2.5 μm or less.

  In the present invention, the average thickness of the central portion of the cooled solidified film is preferably 250 μm or less because stretchability is good.

  In this invention, when making molten resin contact a cooling roll, it is preferable to employ | adopt the method of spraying air forcibly or the method of making it closely_contact | adhere with static electricity. Moreover, both the forced air spraying method and the electrostatic contact method are more preferable to carry out the method in which both end portions and the central portion of the layered resin are made independent. Furthermore, when the molten resin contacts the cooling roll, it is more preferable to use a measure (for example, a device such as a vacuum chamber or a vacuum box) for reducing the accompanying flow by reducing the pressure on the opposite side.

  In the present invention, the molten resin film needs to be uniaxially stretched at least in the longitudinal direction after being cooled and solidified. Next, both ends are cut and removed to obtain a polyester film. As longitudinal stretching conditions, it is preferable to stretch 1.3 to 6.0 times in the longitudinal direction at a temperature equal to or higher than the glass transition temperature of the polyester constituting the film. When longitudinal stretching is carried out, when the both ends of the film are cut and removed, the film is hardly broken and productivity can be improved. Further, when both ends of the film are cut and removed and laminated on a metal plate, there is little material loss and it is economically preferable.

  Furthermore, in order to improve the uniformity of the thickness distribution of the polyester film and the productivity of the polyester film, transverse stretching may be performed after the longitudinal stretching. Moreover, it can heat-process for 1 to 20 seconds at the temperature of 50 degreeC or more under tension | tensile_strength and -20 degreeC of polyester as needed.

  In the present invention, when the resin obtained by cutting and removing both ends is reused, the reuse rate is not particularly limited, but is preferably 5 to 50% by weight.

  In the present invention, the thickness of the polyester film is not particularly limited, but when used as a film on the inner surface side of the can, it is 10 μm from the viewpoint of ensuring the releasability of the punch and ensuring the impact resistance. ˜50 μm is preferred.

  If the thickness is less than 10 μm, the impact strength of the film will be insufficient, so if the can filled with the contents is dropped, microcracks will occur in the impacted film, and the filled contents Depending on the case, metal corrosion may occur from the part, which is not preferable.

  On the other hand, when the thickness exceeds 50 μm, in particular, when the degree of processing of the can body part in the ironing process (plate thickness reduction rate) is high, the releasability of the punch is inferior, and the can body opening part is cramped, If it is intense, a phenomenon that the punch cannot be removed from the can may occur, which is not preferable.

  In the present invention, it is necessary for the surface roughness (Ra) of the polyester film to be 0.1 μm or less in order to ensure the can-making property and increase the commercial value of the resulting can. In order to ensure that the polyester film has a surface roughness (Ra) of 0.02 to 0.1 μm to ensure laminating properties with a metal plate (in order to suppress deterioration of unwinding property due to film blocking), preferable.

  In the present invention, the metal plate is not particularly limited, and a steel plate, an aluminum plate, and an aluminum alloy plate are used.

  The mechanical properties such as the plate thickness and tensile breaking strength are not particularly limited, and the steel plate is usually used as a steel plate for cans, specifically for drawn cans, drawn and ironed cans, lids The steel plate used for each application is used. The same applies to the surface treatment applied to the surface of the steel sheet, such as an electrolytic chromic acid-treated steel sheet commonly called TFS-CT, a steel sheet having an electrolytic chromic acid treatment applied to the upper layer of the Ni plating film, and the like.

  The same applies to aluminum plates and aluminum alloy plates, and mechanical properties such as plate thickness and tensile breaking strength are not particularly limited, and are usually used as aluminum plates for cans, specifically drawn and ironed cans. The aluminum plate used for each use for the lid and the lid is used. As for the surface treatment of the aluminum plate or the aluminum alloy plate, an aluminum plate or an aluminum alloy plate subjected to chromium phosphate treatment or other chemical conversion treatment is used.

  In the polyester film-coated metal plate of the present invention, it is essential to laminate the polyester film obtained in the present invention on at least the inner surface side of the metal plate, but the outer surface side of the can. For the surface, the polyester film obtained in the present invention may be used, or another polyester film may be used.

  As a method for obtaining a polyester film-coated metal plate, as an example, when the polyester film of the present invention is coated on both surfaces of the metal plate, the metal plate has a plate temperature of -20 ° C to the melting point of the polyester. After heating to + 150 ° C. or less, a polyester film is laminated simultaneously or sequentially on both surfaces of the metal plate using a laminating roll (primary adhesion). Then, after heating the plate | board temperature of a metal plate to the temperature of melting | fusing point +10 degreeC or more-melting | fusing point +60 degreeC of a polyester-type film continuously, the method etc. obtained by quenching etc. are employable.

  Further, when another polyester film is coated on the surface corresponding to the outer surface of the metal plate can, the plate temperature of the metal plate may be set based on the film having the higher melting point.

  The method of heating the metal plate when coating the metal plate with a film includes a method of heating in an electric furnace during the primary bonding, a method of heating by blowing hot air, a method of heating by contacting a heating roll, and a high frequency Although well-known means such as induction heating method can be employed, the polyester film is already coated (primary adhesion) when heating to a temperature of the melting point of the polyester + 10 ° C. to the melting point + 60 ° C. Therefore, a contact-type heating method such as a heating roll is not preferable, and a non-contact type heating method such as a method of heating in an electric furnace, a method of heating by blowing hot air, a method of induction heating at high frequency, etc. can be adopted. preferable.

  In addition, as a method of rapid cooling, compressed air (or compressed air), a method of cooling by cooling with pressurized air (or compressed air), a method of cooling by immersing in water or the like alone or a combination of them. It is possible to cool.

In the present invention, the density of the polyester film coated on the polyester film-covered metal plate needs to be 1.360 g / cm ³ or less as the density of the film before forming.

The density of 1.360 g / cm ³ or less indicates that the polyester film coated on the metal plate is in an amorphous state or a state very close to an amorphous state. The film can follow the drawing and ironing process sufficiently, the soundness of the inner film of the resulting can can be secured, and the forming of the drawing and ironing can having excellent corrosion resistance can be achieved.

In order to make the density 1.360 g / cm ³ or less, the heating condition and cooling condition of the metal plate after the primary bonding described above are important. That is, it is important to sufficiently melt the polyester film and to ensure a sufficient cooling rate. In particular, the cooling rate has a heat transfer coefficient of 0.0005 to 0.005 cal / cm ² · sec on the polyester film surface.・ It is important to cool at a temperature of ° C.

  Next, the polyester film-coated metal can of the present invention will be described.

  The metal can of the present invention uses a seamless can obtained by drawing and ironing as a basic can body.

  Specific examples of the can of the present invention include: (1) After drawing and ironing, the opening is trimmed to a normal can height, and then the opening is processed to a smaller diameter than the diameter of the can body (neck) In the case of a beer can size, for example, the outer diameter of the can body is designated as 211 (2 inches). A seamless can with a can body of +1 1/16 inch) drawn so that it can be wrapped with a can lid of 204 (2 inches + 4/16 inch). (2) Seamless by drawing and ironing. The can was created, and then the opening of the seamless can was further drawn, molded to a diameter that could be sealed with shoulder molding and a cap, and further threaded so that it could be closed with a cap, Refillable Seamless cans such as bottle-shaped cans, (3) Create a seamless can by drawing and ironing, then drawing the bottom of the can, forming it to a diameter that can be sealed with a shoulder or cap, and then closing with a cap For example, a seamless can such as a refillable bottle can that has been threaded so that it can be used.

The density of the polyester film coated on at least the inner surface side of the metal can in the present invention needs to be 1.360 g / cm ³ or less.

That the density is 1.360 g / cm ³ or less means that the material is substantially in an amorphous state or very close to an amorphous state.

The first reason why the density of the polyester film coated on at least the inner surface side of the polyester film-coated metal can in the present invention is 1.360 g / cm ³ or less is to secure the molding processability in the next step. Because.

  In other words, seamless cans made by drawing and ironing a polyester film-coated metal plate are further drawn on the opening as described above, and the opening is processed to a smaller diameter than the diameter of the can body (this process) Is called a neck-in process), and then the process of pulling out the flange to tighten the lid (this process is called flanging) is the easy-to-open aluminum lid (easy open end, This is generally used from the viewpoint of cost reduction.

  The neck-in process and the flange process are more severe as the diameter of the mouth is larger, and film peeling tends to occur at this part. The coated film of the can formed by drawing and ironing from the polyester film-coated metal plate may be crystallized again due to the thermal history of the processing, and this tends to cause problems. Of course, the can where the film has peeled is exposed to the contents of the peeled portion, which leads to corrosion of the base metal and cannot be used as a product.

In order to avoid such a problem, it is necessary that the stretch characteristics of the coated film and the adhesion with the base metal are good, and for that purpose, the coated polyester film is substantially amorphous. It is necessary to be in a state that is very close to the state or the amorphous state, and this can be achieved by setting the density to 1.360 g / cm ³ or less.

In addition, in the case of the above-described re-bottleable bottle-type cans, the polyester film is subjected to more severe processing such as shoulder molding processing and thread cutting processing than the processing of ordinary seamless cans. It is an absolute condition that the density of is 1.360 g / cm ³ or less.

The second reason why the density of the polyester film coated on at least the inner surface side of the polyester film-coated metal can in the present invention is 1.360 g / cm ³ or less is to ensure impact resistance.

  As in the present invention, in the case of cans made mainly by drawing and ironing, the coated polyester resin and the olefinic polymer dispersed therein are stretched violently in the can height direction. It has become. In such a state, molding distortion is accumulated in the olefin polymer, and the ability to absorb impact energy decreases.

Therefore, when the heat is applied again to restore the original spherical shape, the strain is released and the ability to absorb the impact energy is restored. However, at this time, it is important not to crystallize the polyester resin itself. By setting the density of the polyester film to 1.360 g / cm ³ or less, the strain that has entered during drawing and ironing is released, and good impact resistance is ensured.

In order to make the polyester film coated on the metal can obtained by drawing and ironing process substantially amorphous and to ensure the density of 1.360 g / cm ³ or less, the can is once again formed of the polyester film. This can be achieved by heating to the melting point or higher, remelting, and then rapidly cooling.

  The process for making the polyester film coated by heating the metal can amorphous is as follows: (1) Degreasing the lubricant with a degreasing agent before trimming the opening of the metal can obtained by drawing and ironing After that, at least the opening to be trimmed is made amorphous. (2) The metal can obtained by drawing and ironing is heated to volatilize the lubricant and at the same time become amorphous. (3) After trimming For seamless cans, before neck / flange processing, for bottle-type cans that can be re-plugged, before threading, make at least the relevant part amorphous, etc. It can be appropriately selected depending on the equipment.

In order to reduce the density of the polyester film coated on the polyester film-coated metal can to 1.360 g / cm ³ or less, the metal plate of the metal can can be formed in the same manner as the method for obtaining the polyester film-coated metal sheet. This can be achieved by heating the plate temperature to the melting point of the polyester + 10 ° C. or higher and the melting point + 60 ° C. or lower, followed by rapid cooling.

  As a method for heating the metal can, a heating method such as a method of heating in an electric furnace, a method of heating with hot air, a method of induction heating at high frequency, or the like can be adopted. Therefore, it is also possible to heat a metal can using the heat of the coating / printing process applied to the outer surface of the metal can.

  Further, as a method of rapid cooling, a method of cooling by blowing pressurized air (or compressed air) or cooled pressurized air (or compressed air) can be employed. Depending on the situation, a method of cooling by immersing in water or the like is also possible.

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

[Evaluation methods]
(1) Melting point of polyester Exothermic / endothermic curve (DSC curve) using a differential film calorimeter (DSC) with a differential scanning calorimeter (DSC) in a nitrogen stream using 10 mg of polyester film of film 01-25. The peak temperature of the endothermic peak that accompanies melting was measured as the melting point Tm (° C.).
(2) Intrinsic viscosity of polyester (IV)
It is a value (dl / g) measured at 25 ° C. by dissolving the polyester film of the films 01 to 25 in orthochlorophenol.
(3) Melt flow rate a. Polyester melt flow rate (Mi)
According to the method of JIS K7210, with a melt index measuring device (MELT INDEXER, manufactured by Toyo Seiki Co., Ltd.) with a temperature in the barrel set to 30 ° C. higher than the melting point of the polyester obtained by the method (1), an orifice diameter of 2.09 mm, weight The measured value when measured under the condition of 2.16 kgf was used.
b. Melt flow rate (Mf) of polyester resin composition
A polyester obtained by dry mixing a polyester and an olefin polymer in a pellet state into an extruder and melt-mixing the mixture at 270 ° C. according to the method of JIS K7210 by the method (1) Measured using a melt index measuring apparatus (MELT INDEXER, manufactured by Toyo Seiki Co., Ltd.) with the temperature in the barrel set to a temperature 30 ° C. higher than the melting point of the nozzle under the conditions of an orifice diameter of 2.09 mm and a load of 2.16 kgf. .
(4) Cooling roll surface roughness (Ra)
It measured according to JIS B0601 (1982).
(5) Polyester film surface roughness (Ra)
The polyester film of the films 01 to 25 cut out to 10 cm × 10 cm was visually observed, and the film surface in contact with the cooling roll at the time of casting was evaluated as having an evaluation value by the following method as having an evaluation value. In addition, it was set as the surface roughness (Ra) with the average value of 20 times measurement.
a. Measuring device: ET-30HK manufactured by Kosaka Laboratory
b. Palpation tip radius: 0.5 μm
c. Palpation load: 5mg
d. Measurement length: 1mm
e. Cut-off value: 0.08mm
(6) Functional group concentration in olefin polymer The olefin polymers of olefins A to G are dissolved in a mixed solvent of chloroform-d / trifluoroacetic acid, and the molecular structure and functional group concentration of the olefin polymer are analyzed by H-NMR spectrum analysis. (Mole%) was determined, and this was converted into a weight, and the content (molar equivalent) of the functional group per ton of olefin polymer was calculated.
(7) Average equivalent sphere equivalent diameter of olefin-based polymer After thin sections cut out with a microtome in the cross-sectional direction of the polyester-based films 01 to 25 before being subjected to molding, they are dyed with ruthenium oxide and held at room temperature for 10 minutes. Then, carbon was deposited and observed with a transmission electron microscope. The average equivalent sphere equivalent diameter of the dispersed particles was obtained by a weighted average using an image analyzer (manufactured by Toyobo, V10).
(8) Releasability of punch of can inner surface film The releasability of can inner surface film and processed punch is 500 randomly obtained from the continuously formed cans obtained in Examples 1 to 14 and Comparative Examples 1 to 6, 8, and 9. Cans were extracted and evaluated by observing the degree of buckling of the cans occurring at the opening of the molded can. The evaluation was performed by setting the following evaluation criteria.
◎: Can opening is good without cramping ○: Can opening is slightly cramped, but normal can height can be secured and there is no practical problem △: Can opening is cramped and normal can height It is difficult to secure the thickness and there is no practicality ×: The can body does not come out of the punch, or even if it falls out, the can opening portion is severely cramped and there is no practicality (9) Soundness evaluation of the can inner film (QTV test)
About the soundness of the inner surface film of the can used as a final product, using the continuous molding can obtained in Examples 1-14 and Comparative Examples 1-3, 6, 8, and 9, it is surface active in 1.0% saline. 350 ml of an electrolyte solution containing 0.1% of the agent was poured into the can, and a copper rod electrode was inserted into the poured electrolyte solution. After 3 seconds at an applied voltage of 6 V with the can body serving as an anode and the copper rod electrode serving as a cathode The current value (QTV value) was measured to evaluate the soundness of the inner film. (Hereinafter, this evaluation method is referred to as a QTV test.) Evaluation was performed by randomly extracting 50 cans, and the weighted average value of current values was used as the next evaluation standard.
◎: Less than 0 to 0.2 mA / can and good soundness ○: Less than 0.2 to 0.5 mA / can and practical level Δ: Less than 0.5 to 2 mA / can and not practical level ×: 2 mA / can (10) Dent resistance About the dent resistance of the inner film of the can used as a final product, continuous molding obtained in Examples 1 to 14 and Comparative Examples 3, 6, and 9 Using a can, 350 ml of tea is placed in the can, the can lid is wrapped and sealed, and after retort sterilization at 125 ° C. for 30 minutes, it is stored in a 4 ° C. cooler, and when the can body temperature reaches 4 ° C. Dent was caused by dropping from the bottom of the can at an angle of 60 ° from a position of 45 cm.
Subsequently, after opening the can and removing the tea content, 7% dilute hydrochloric acid was filled, and the corrosion state of the dent portion after 3 days at 38 ° C. was observed. Evaluation criteria were set as follows.
○: Corrosion in the dent portion is good and practical. ×: Corrosion occurs in the dent portion and there is no practicality.

[Abbreviations and contents of polyester and olefin polymer used in Examples and Comparative Examples]
(1) PET: Polyethylene terephthalate.
82 parts by weight of ethylene glycol (ethylene glycol / terephthalic acid molar ratio = 2) with respect to 100 parts by weight of terephthalic acid in a reactor equipped with an inlet, a thermometer, a pressure gauge, a distillation tube with a rectifying column, and a stirring blade .2) 0.05 mol% of germanium oxide as the Ge element, 0.05 mol% of magnesium acetate as the Mg element, and 0.23 weight of amorphous silica particles having an average particle diameter of 1.3 μm with respect to the acid component Part was charged, nitrogen was introduced with stirring, the pressure in the system was kept at 0.3 MPa, and the esterification reaction was carried out while distilling off the water produced at a temperature of 230 ° C. to 250 ° C. outside the system. After completion of the reaction, trimethyl phosphate was added at 0.04 mol% as P amount at 250 ° C, and the pressure was gradually reduced while raising the temperature, and a polycondensation reaction was carried out under a vacuum of 275 ° C and 1.0 hPa or less. Polyethylene terephthalate having an intrinsic viscosity of 0.73.
(2) PET-I: Polyethylene terephthalate / isophthalate (10 mol% repeating unit of ethylene isophthalate).
Polyethylene terephthalate / isophthalate having an intrinsic viscosity of 0.75 obtained by the same method as that for polyethylene terephthalate (PET) except that 90 parts by weight of terephthalic acid and 10 parts by weight of isophthalic acid were used.
(3) PET-II: Polyethylene terephthalate / isophthalate (8 mol% of repeating units of ethylene isophthalate).
Polyethylene terephthalate / isophthalate having an intrinsic viscosity of 0.75 obtained by the same method as that for polyethylene terephthalate (PET) except that 92 parts by weight of terephthalic acid and 8 parts by weight of isophthalic acid were used.
(4) CO-PES: Copolyester of terephthalic acid and ethylene glycol / cyclohexanedimethanol (70/30 mol%).
(5) Olefin A: Low density polyethylene (Sumitomo Chemical Co., Sumikasen G401: trade name).
(6) Olefin B: ethylene-acrylic acid copolymer (manufactured by Dow Chemical Company, Primacol 3440: trade name)
(7) Olefin C: ethylene-methacrylic acid copolymer (manufactured by Mitsui DuPont Polychemical Co., Ltd., Nucrel N1108C: trade name)
(8) Olefin D: Ethylene-ethyl acrylate copolymer (Mitsui DuPont Polychemical Co., Ltd., EVAFLEX A712: trade name)
(9) Olefin E: Ethylene-1-butene copolymer (manufactured by Nippon Synthetic Rubber Company, EBM2041P: trade name)
(10) Olefin F: Styrene-ethylene / butylene-styrene block copolymer (Asahi Kasei Corporation, Tuftec M1913: trade name)
(11) Olefin G: Ethylene-methyl acrylate copolymer (EMAC2260, manufactured by Eastman Chemical Co.)

[Example 1]
PET-I / olefin A / olefin B = 88/6/6 (% by weight) was premixed at 270 ° C. using a twin-screw vent type extruder to obtain a polyester resin composition.
Next, after drying the polyester-based resin composition at 100 ° C. for 24 hours, it was melted at 270 ° C. using a single screw extruder, and then using a T-die, the surface roughness (Ra) was 1.1 μm. Cast into a cooling roll (circumferential speed 80 m / min) in a layered manner, the distance between the T-die and the cooling roll is 2 cm, and the central part and both ends are electrostatically adhered by separate devices (central part: 4.5 kV, both ends Part: 6 kV DC power supply applied) After cooling and solidification, polyester film (film 01) having a thickness of 25 μm and polyester film having a thickness of 16 μm by stretching 4 times in the longitudinal direction at a preheating temperature of 80 ° C. and a stretching temperature of 100 ° C. A system film (film 02) was prepared.
Table 1 shows the MFR of the polyester resin composition and the like.
The obtained film 01 and film 02 were both good, with no film cracking or poor appearance at both ends.
In addition, although the surface roughness of the obtained film 01 and the film 02 was shown in Table 1, it turns out that the surface roughness of a film is small and smooth is obtained.
Next, a 3004 series aluminum alloy plate having a thickness of 0.28 mm subjected to chromic phosphate treatment with a chromium conversion amount of 15 mg / m ² on one side is heated to 245 ° C. with a heating roll, Film 01 is a polyester film having a melting point of 232 ° C. and a thickness of 16 μm on the other side (film A, a film necessary for molding a can described later, and is not subject to evaluation because it is irrelevant to Examples and Comparative Examples) Thereafter, the same is applied), and further heated to 245 ° C. as a plate temperature, and then immersed in water and rapidly cooled to obtain a polyester film-coated aluminum plate (Test 01).
Similarly, a polyester film-coated metal plate (Test 02) was obtained by combining the film 02 and the film A described above.
Table 1 shows the melting points of the film 01 and the film 02, the contents of the olefin polymer, etc., which are coated on the obtained polyester film-coated aluminum alloy plate.
After applying the processing lubricant to both sides of the polyester film-coated aluminum alloy plate thus obtained, Test 01 and Test 02, 80 can / so that the coated surface of Film 01 and the coated surface of Film 02 are the inner surface side of the can, respectively. Cup drawing, redrawing, and ironing were performed at a rate of minutes to produce a seamless can for a 350 ml can with a can wall portion processing degree of 62%.
About the obtained can, the mold release property of the inner surface side punch was investigated. The results are shown in Table 2.
Further, after trimming the opening of the can, the metal plate temperature is heated to 245 ° C., and then immediately cooled, and the polyester film is made amorphous, and then the 204 can lid is wound. Neck-in processing and flange processing were performed to produce a 350 ml can.
Both the film 01 and the film 02 coated on the inner surface of the obtained can were not peeled, and a good can was obtained. In addition, the measurement result of the density of the can inner surface side film is shown in Table 2.
The inner surface side of the can thus obtained was subjected to QTV test and evaluation of dent resistance.
The results are shown in Table 2.
As can be seen from Table 2, Test 01 and Test 02, which are the present examples, are methods for producing a polyester film-coated metal sheet having excellent can-making properties, and surface smoothness that provides a metal can having excellent dent resistance. It is a polyester film for metal plate coating excellent in properties, and can be said to be a method for producing a polyester film coated metal plate.

[Example 2]
Using the polyester resin composition used in Example 1, following the procedure of Example 1, the same procedure as in Example 1 was used except that a satin-like cooling roll having a surface roughness (Ra) of 0.5 μm was used. A polyester film (film 03) having a thickness of 25 μm and a polyester film (film 04) having a thickness of 16 μm were prepared.
Table 1 shows the MFR of the polyester resin composition and the like.
The obtained film 03 and film 04 were both good, with no film cracks or poor appearance at both ends.
In addition, although the surface roughness of the obtained film 03 and film 04 was shown in Table 1, it turns out that the surface roughness of a film is small and smooth.
After the film obtained in this manner was simultaneously press-bonded with the aluminum alloy plate used in Example 1 under the same conditions as in Example 1, film 03 on one side and film A used in Example 1 on the other side Further, after heating to 245 ° C. as a plate temperature, it was immersed in water and quenched to obtain a polyester film-coated aluminum alloy plate (Test 03).
Similarly, a polyester film-coated metal plate (Test 04) was obtained by combining the film 04 and the film A described above.
Table 1 shows the melting points of the film 03 and the film 04, the contents of the olefin polymer, and the like coated on the obtained polyester film-coated aluminum alloy plate.
After applying the processing lubricant to both sides of the polyester film-coated aluminum alloy plate thus obtained, Test 03 and Test 04, the film 03 coated surface and the film 04 coated surface were 80 cans / Cup drawing, redrawing, and ironing were performed at a rate of minutes to produce a seamless can for a 350 ml can with a can wall portion processing degree of 62%.
About the obtained can, the mold release property of the inner surface side punch was investigated. The results are shown in Table 2.
Further, after trimming the opening of the can, the metal plate temperature is heated to 245 ° C., and then immediately cooled, and the polyester film is made amorphous, and then the 204 can lid is wound. Neck-in processing and flange processing were performed to produce a 350 ml can.
Both the film 03 and the film 04 coated on the inner surface of the obtained can were not peeled, and a good can was obtained. In addition, the measurement result of the density of the can inner surface side film is shown in Table 2.
The inner surface side of the can thus obtained was subjected to QTV test and evaluation of dent resistance.
The results are shown in Table 2.
As can be seen from Table 2, Test 03 and Test 04 in this example are methods for producing a polyester film-coated metal sheet having excellent can-making properties, and surface smoothness to obtain a metal can having excellent dent resistance. It is an excellent polyester film for coating a metal plate, and can be said to be a method for producing a polyester film coated metal plate.

[Example 3]
Using the polyester resin composition used in Example 1, following the procedure of Example 1, the same procedure as in Example 1 was used except that a satin-like cooling roll having a surface roughness (Ra) of 3.3 μm was used. A polyester film (film 05) having a thickness of 25 μm was prepared.
Table 1 shows the MFR of the polyester resin composition and the like.
The obtained film 05 was good without film cracking at both ends and poor appearance.
In addition, although the surface roughness of the obtained film 05 was shown in Table 1, it turns out that the surface roughness of a film is small and smooth.
Using the aluminum alloy plate used in Example 1, the film thus obtained was simultaneously press-bonded with film 05 on one side and film A used in Example 1 on the other side under the same conditions as in Example 1. Then, after further heating to 245 ° C. as a plate temperature, it was immersed in water and quenched to obtain a polyester film-coated aluminum alloy plate (Test 05).
Table 1 shows the melting point of the film 05, the content of the olefin polymer, and the like coated on the obtained polyester film-coated aluminum alloy plate.
After applying the processing lubricant on both sides of the polyester film-coated aluminum alloy plate of Test 05 obtained in this way, cup drawing at a speed of 80 cans / min. By drawing and ironing, a seamless can for a 350 ml can having a can wall portion processing degree of 62% was prepared.
About the obtained can, the mold release property of the inner surface side punch was investigated. The results are shown in Table 2.
Further, after trimming the opening of the can, the metal plate temperature is heated to 245 ° C., and then immediately cooled, and the polyester film is made amorphous, and then the 204 can lid is wound. Neck-in processing and flange processing were performed to produce a 350 ml can.
There was no peeling of the film 05 coated on the inner surface of the resulting can, and a good can was obtained. In addition, the measurement result of the density of the can inner surface side film is shown in Table 2.
The inner surface side of the can thus obtained was subjected to QTV test and evaluation of dent resistance.
The results are shown in Table 2.
As can be seen from Table 2, test 05, which is this example, is a method for producing a polyester film-coated metal sheet having excellent canability, and is excellent in surface smoothness that provides a metal can with excellent dent resistance. It can be said that it is a polyester film for metal plate coating, and a method for producing a polyester film coated metal plate.

[Example 4]
The polyester resin composition used in Example 1 was cooled and solidified in the same manner as in Example 1 according to the procedure of Example 1, and then stretched three times in the longitudinal direction at a preheating temperature of 80 ° C. and a stretching temperature of 100 ° C. Then, the film was stretched 3 times in the transverse direction at a preheating temperature of 80 ° C. and a stretching temperature of 100 ° C. to produce a polyester film (film 06) having a thickness of 25 μm.
Table 1 shows the MFR of the polyester resin composition and the like.
The obtained film 06 was good without film cracking at both ends and poor appearance.
In addition, although the surface roughness of the obtained film 06 was shown in Table 1, it turns out that the surface roughness of a film is small and smooth.
Using the aluminum alloy plate used in Example 1, the film thus obtained was simultaneously pressure-bonded with film 06 on one side and film A used in Example 1 on the other side under the same conditions as in Example 1. Then, after further heating to 245 ° C. as a plate temperature, it was immersed in water and rapidly cooled to obtain a polyester film-coated aluminum alloy plate (Test 06).
Table 1 shows the melting point of the film 06, the content of the olefin polymer, and the like coated on the obtained polyester film-coated aluminum alloy plate.
After applying the processing lubricant on both sides of the polyester film-coated aluminum alloy plate of Test 06 obtained in this way, cup drawing at a speed of 80 cans / min. By drawing and ironing, a seamless can for a 350 ml can having a can wall portion processing degree of 62% was prepared.
About the obtained can, the mold release property of the inner surface side punch was investigated. The results are shown in Table 2.
Further, after trimming the opening of the can, the metal plate temperature is heated to 245 ° C., and then immediately cooled, and the polyester film is made amorphous, and then the 204 can lid is wound. Neck-in processing and flange processing were performed to produce a 350 ml can.
There was no peeling of the film 06 coated on the inner surface of the obtained can, and a good can was obtained. In addition, the measurement result of the density of the can inner surface side film is shown in Table 2.
The inner surface side of the can thus obtained was subjected to QTV test and evaluation of dent resistance.
The results are shown in Table 2.
As can be seen from Table 2, test 06 of this example is a method for producing a polyester film-coated metal sheet having excellent can-making properties and excellent surface smoothness to obtain a metal can having excellent dent resistance. It is a polyester film for metal plate coating, and can be said to be a method for producing a polyester film coated metal plate.

[Example 5]
A polyester film (film 07) having a thickness of 25 μm was prepared in the same manner as in Example 1 except that PET-I / olefin A / olefin C = 88/6/6 (% by weight) was used as the polyester resin composition. did.
Table 1 shows the MFR of the polyester resin composition and the like.
The obtained film 07 was good with no film cracking at both ends and poor appearance.
In addition, although the surface roughness of the obtained film 07 was shown in Table 1, it turns out that the surface roughness of a film is small and smooth.
Using the aluminum alloy plate used in Example 1, the film 07 thus obtained was simultaneously pressure-bonded with the film 07 used on Example 1 and the film A used on Example 1 on the other side under the same conditions as Example 1. Then, after further heating to 245 ° C. as a plate temperature, it was immersed in water and quenched to obtain a polyester film coated aluminum alloy plate (Test 07).
Table 1 shows the melting point of the film coated on the obtained polyester film-coated aluminum alloy plate, the content of the olefin polymer, and the like.
After applying the processing lubricant on both sides of the polyester film-coated aluminum alloy plate of Test 07 obtained in this way, cup drawing at a speed of 80 cans / min. By drawing and ironing, a seamless can for a 350 ml can having a can wall portion processing degree of 62% was prepared.
About the obtained can, the inner surface side investigated the releasability of the punch. The results are shown in Table 2.
Further, after trimming the opening of the can, the metal plate temperature is heated to 245 ° C., and then immediately cooled, and the polyester film is made amorphous, and then the 204 can lid is wound. Neck-in processing and flange processing were performed to produce a 350 ml can.
There was no peeling of the film 07 coated on the inner surface of the obtained can, and a good can was obtained. In addition, the measurement result of the density of the can inner surface side film is shown in Table 2.
The inner surface side of the can thus obtained was subjected to QTV test and evaluation of dent resistance.
The results are shown in Table 2.
As can be seen from Table 2, Test 07, which is the present example, is a method for producing a polyester film-coated metal sheet having excellent canability, and is excellent in surface smoothness to obtain a metal can having excellent dent resistance. It can be said that it is a polyester film for metal plate coating, and a method for producing a polyester film coated metal plate.

[Example 6]
A polyester film (film 08) having a thickness of 25 μm was prepared in the same manner as in Example 1 except that PET-I / olefin A / olefin D = 88/6/6 (% by weight) was used as the polyester resin composition. did.
Table 1 shows the MFR of the polyester resin composition and the like.
The obtained film 08 was good with no film cracks at both ends and poor appearance.
In addition, although the surface roughness of the obtained film 08 was shown in Table 1, it turns out that the surface roughness of a film is small and smooth.
Using the aluminum alloy plate used in Example 1, the film obtained in this manner was simultaneously pressure-bonded with the film 08 on one side and the film A used in Example 1 on the other side under the same conditions as in Example 1. Then, after further heating to 245 ° C. as a plate temperature, it was immersed in water and quenched to obtain a polyester film-coated aluminum alloy plate (Test 08).
Table 1 shows the melting point of the film 08, the content of the olefin polymer, and the like, which are coated on the obtained polyester film-coated aluminum alloy plate.
After applying the processing lubricant on both sides of the polyester film-coated aluminum alloy plate thus obtained, cup drawing, redrawing and redrawing at a rate of 80 cans / minute so that the coated surface of the film 08 becomes the inner surface of the can. The ironing process was performed, and a seamless can for 350 ml cans with a can wall processing degree of 62% was prepared.
About the obtained can, the mold release property of the inner surface side punch was investigated. The results are shown in Table 2.
Furthermore, after trimming the opening of the can, after heating so that the metal plate temperature is 245 ° C., immediately quenching, after making the polyester film amorphous, perform neck-in processing and flange processing, A 350 ml can with a narrowed opening was produced. There was no peeling of the film 08 coated on the inner surface of the obtained can, and a good can was obtained. The measurement results of the density of the inner surface of the can are shown in Table 2.
The inner surface side of the can thus obtained was subjected to QTV test and evaluation of dent resistance.
The results are shown in Table 2.
As can be seen from Table 2, test 08, which is this example, is a method for producing a polyester film-coated metal sheet having excellent can-making properties, and is excellent in surface smoothness to obtain a metal can having excellent impact resistance. It can be said that it is a polyester film for metal plate coating, and a method for producing a polyester film coated metal plate.

[Example 7]
A polyester film (film 09) having a thickness of 25 μm was prepared in the same manner as in Example 1 except that PET-I / olefin B / olefin E = 88/6/6 (% by weight) was used as the polyester resin composition. did.
Table 1 shows the MFR of the polyester resin composition and the like.
The obtained film 09 was good without film cracks at both end portions and poor appearance.
In addition, although the surface roughness of the obtained film 09 was shown in Table 1, it turns out that the surface roughness of a film is small and smooth.
Using the aluminum alloy plate used in Example 1, the film thus obtained was simultaneously pressure-bonded with film 09 on one side and film A used in Example 1 on the other side under the same conditions as in Example 1. Thereafter, the plate was further heated to 245 ° C. and then quenched in water to obtain a polyester film-coated aluminum alloy plate (Test 09).
Table 1 shows the melting point of the film coated on the obtained polyester film-coated aluminum alloy plate, the content of the olefin polymer, and the like.
After applying the processing lubricant to both sides of the polyester film-coated aluminum alloy plate of Test 09 obtained in this way, cup drawing at a speed of 80 cans / min. By drawing and ironing, a seamless can for a 350 ml can having a can wall portion processing degree of 62% was prepared.
About the obtained can, the releasability of the punch inside the can was investigated. The results are shown in Table 2.
Further, after trimming the opening of the can, the metal plate temperature is heated to 245 ° C., and then immediately cooled, and the polyester film is made amorphous, and then the 204 can lid is wound. Neck-in processing and flange processing were performed to produce a 350 ml can.
There was no peeling of the film 09 coated on the inner surface of the obtained can, and a good can was obtained. In addition, the measurement result of the density of the can inner surface side film is shown in Table 2.
The inner surface side of the can thus obtained was subjected to QTV test and evaluation of dent resistance.
The results are shown in Table 2.
As can be seen from Table 2, test 09, which is this example, is a method for producing a polyester film-coated metal sheet having excellent can-making properties, and is excellent in surface smoothness to obtain a metal can having excellent dent resistance. It can be said that it is a polyester film for metal plate coating, and a method for producing a polyester film coated metal plate.

[Example 8]
PET-II / olefin A / olefin B = 94/3/3 (% by weight) was premixed at 270 ° C. using a twin-screw vent type extruder to obtain a polyester resin composition.
Next, after drying the polyester-based resin composition at 100 ° C. for 24 hours, it was melted at 270 ° C. using a single screw extruder, and then using a T-die, the surface roughness (Ra) was 1.1 μm. Cast into a cooling roll (circumferential speed 80 m / min) in a layered manner, the distance between the T-die and the cooling roll is 2 cm, and the central part and both ends are electrostatically adhered by separate devices (central part: 4.5 kV, both ends Part: DC power supply of 6 kV was applied), and after cooling and solidification, a polyester film (film 10) having a thickness of 30 μm was formed by stretching 4 times in the longitudinal direction at a preheating temperature of 80 ° C. and a stretching temperature of 100 ° C.
Table 1 shows the MFR of the polyester resin composition and the like.
The obtained film 10 was good without film cracking at both ends and poor appearance.
In addition, although the surface roughness of the obtained film 10 was shown in Table 1, it turns out that the surface roughness of a film is small and smooth.
Next, an electrolytic chromic acid-treated steel sheet heated to 250 ° C. and having a thickness of 0.19 mm (the amount of metal chromium adhesion on one side is 110 mg / m ² , and the amount of hydrated chromium oxide adhesion on the upper layer is 15 mg / m ^{2 in} terms of metal chromium) The film 10 on one side and the film A used in Example 1 on the other side are simultaneously pressure-bonded, and further heated to 255 ° C. as a plate temperature, then immersed in water and rapidly cooled, and a polyester film-coated steel sheet (Test 10) was obtained.
Table 1 shows the melting point of the film 10 coated on the obtained polyester film-coated steel sheet, the content of the olefin polymer, and the like.
After applying the processing lubricant to both sides of the polyester film coated steel sheet of Test 10 thus obtained, cup drawing and redrawing at a speed of 80 cans / minute so that the film 10 coated surface is on the inner surface side of the can. And the ironing process was performed and the seamless can for 350 ml cans in which the processing degree of the can wall part was 52% was created.
About the obtained can, the mold release property of the inner surface side punch was investigated. The results are shown in Table 2.
Further, after trimming the opening of the can, the metal plate temperature is heated to 255 ° C., and then immediately cooled, and after making the polyester film amorphous, the 204 can lid is wound. Neck-in processing and flange processing were performed to produce a 350 ml can.
There was no peeling of the film 10 coated on the inner surface of the obtained can, and a good can was obtained. In addition, the measurement result of the density of the can inner surface side film is shown in Table 2.
The inner surface side of the can thus obtained was subjected to QTV test and evaluation of dent resistance.
The results are shown in Table 2.
As can be seen from Table 2, Test 10, which is the present example, is a method for producing a polyester film-coated metal sheet having excellent can-making properties, and is excellent in surface smoothness to obtain a metal can having excellent dent resistance. It can be said that it is a polyester film for metal plate coating, and a method for producing a polyester film coated metal plate.

[Example 9]
PET-II / olefin A / olefin B = 72/14/14 (% by weight) was premixed at 270 ° C. using a biaxial vent type extruder to obtain a polyester resin composition.
Next, after drying the polyester-based resin composition at 100 ° C. for 24 hours, it was melted at 270 ° C. using a single screw extruder, and then using a T-die, the surface roughness (Ra) was 1.1 μm. Cast into a cooling roll (circumferential speed 80 m / min) in a layered manner, the distance between the T-die and the cooling roll is 2 cm, and the central part and both ends are electrostatically adhered by separate devices (central part: 4.5 kV, both ends Part: a 6 kV DC power supply was applied), and after cooling and solidification, a polyester film (film 11) having a thickness of 25 μm was prepared by stretching 4 times in the longitudinal direction at a preheating temperature of 80 ° C. and a stretching temperature of 100 ° C.
Table 1 shows the MFR of the polyester resin composition and the like.
The obtained film 11 was good without film cracking at both ends and poor appearance.
In addition, although the surface roughness of the obtained film 11 was shown in Table 1, it turns out that the thing whose surface roughness is small and smooth is obtained.
Next, the electrolytic chromium-treated steel plate used in Example 8 was heated to 250 ° C., and the film 11 used in Example 1 was simultaneously pressure-bonded on one side and the film A used in Example 1 on the other side. After heating, it was quenched in water to obtain a polyester film-coated steel sheet (Test 11).
Table 1 shows the melting point of the film coated on the obtained polyester film-coated steel sheet, the content of the olefin polymer, and the like.
After applying the processing lubricant to both sides of the polyester film-coated steel sheet of Test 11 obtained in this way, cup drawing and redrawing at a speed of 80 cans / minute so that the film 11 coating surface becomes the inner surface side of the can. And the ironing process was performed and the seamless can for 350 ml cans in which the processing degree of the can wall part was 52% was created.
About the obtained can, the mold release property of the inner surface side punch was investigated. The results are shown in Table 2.
Further, after trimming the opening of the can, the metal plate temperature is heated to 255 ° C., and then immediately cooled, and after making the polyester film amorphous, the 204 can lid is wound. Neck-in processing and flange processing were performed to produce a 350 ml can.
There was no peeling of the film 11 coated on the inner surface of the obtained can, and a good can was obtained. In addition, the measurement result of the density of the can inner surface side film is shown in Table 2.
The inner surface side of the can thus obtained was subjected to QTV test and evaluation of dent resistance.
The results are shown in Table 2.
As can be seen from Table 2, test 11, which is the present example, is a method for producing a polyester film-coated metal plate having excellent can-making properties, and is excellent in surface smoothness to obtain a metal can having excellent impact resistance. It can be said that it is a polyester film for metal plate coating, and is a method for producing a polyester film coated metal plate.

[Example 10]
PET-II / olefin A / olefin B = 85/5/10 (% by weight) was premixed at 270 ° C. using a twin-screw vent type extruder to obtain a polyester resin composition.
Next, after drying the polyester-based resin composition at 100 ° C. for 24 hours, it was melted at 270 ° C. using a single screw extruder, and then using a T-die, the surface roughness (Ra) was 1.1 μm. Cast into a cooling roll (circumferential speed 80 m / min) in a layered manner, the distance between the T-die and the cooling roll is 2 cm, and the central part and both ends are electrostatically adhered by separate devices (central part: 4.5 kV, both ends Part: DC power supply of 6 kV was applied), and after cooling and solidifying, a polyester film (film 12) having a thickness of 25 μm was formed by stretching it four times in the longitudinal direction at a preheating temperature of 80 ° C. and a stretching temperature of 100 ° C.
Table 1 shows the MFR of the polyester resin composition and the like.
The obtained film 12 was good without film cracking at both ends and poor appearance.
In addition, although the surface roughness of the obtained film 12 was shown in Table 1, it turns out that the thing whose surface roughness is small and smooth is obtained.
Next, the aluminum alloy plate used in Example 1 was heated to 250 ° C., film 12 on one side and film A used in Example 1 on the other side were simultaneously pressed, and further heated to 255 ° C. as the plate temperature. Then, it was immersed in water and rapidly cooled to obtain a polyester film-coated aluminum alloy plate (Test 12).
Table 1 shows the melting point of the film 12 covered with the obtained polyester film-coated aluminum alloy plate, the content of the olefin polymer, and the like.
After applying the processing lubricant on both sides of the polyester film-coated aluminum alloy plate of Test 12 obtained in this way, cup drawing at a speed of 80 cans / min. By drawing and ironing, a seamless can for a 350 ml can having a can wall portion processing degree of 62% was prepared.
About the obtained can, the mold release property of the inner surface side punch was investigated. The results are shown in Table 2.
Further, after trimming the opening of the can, the metal plate temperature is heated to 255 ° C., and then immediately cooled, and after making the polyester film amorphous, the 204 can lid is wound. Neck-in processing and flange processing were performed to produce a 350 ml can.
There was no peeling of the film 12 coated on the inner surface of the obtained can, and a good can was obtained. In addition, the measurement result of the density of the can inner surface side film is shown in Table 2.
The inner surface side of the can thus obtained was subjected to QTV test and evaluation of dent resistance.
The results are shown in Table 2.
As can be seen from Table 2, test 12, which is the present example, is a method for producing a polyester film-coated metal sheet having excellent canability, and is excellent in surface smoothness to obtain a metal can with excellent dent resistance. It can be said that it is a polyester film for metal plate coating, and a method for producing a polyester film coated metal plate.

[Example 11]
PET-II / olefin A / olefin B = 85/5/10 (% by weight) was premixed at 270 ° C. using a twin-screw vent type extruder to obtain a polyester resin composition.
Next, the polyester resin composition was dried at 100 ° C. for 24 hours, then melted at 270 ° C. using a single-screw extruder, and then surfaced with a surface roughness (Ra) of 2.4 μm using a T-die. Casted into a cooling roll (circumferential speed 80 m / min) in a layered manner, the distance between the T die and the cooling roll is 2 cm, and the center and both ends are electrostatically adhered by separate devices (center: 4.5 kV, both ends Part: a 6 kV DC power supply was applied), and after cooling and solidification, a polyester film (film 13) having a thickness of 25 μm was formed by stretching it four times in the longitudinal direction at a preheating temperature of 80 ° C. and a stretching temperature of 100 ° C.
Table 1 shows the MFR of the polyester resin composition and the like.
The obtained film 13 was good without film cracks at both ends and poor appearance.
In addition, although the surface roughness of the obtained film 13 was shown in Table 1, it turns out that the thing whose surface roughness is small and smooth is obtained.
Next, after heating the aluminum alloy plate used in Example 1 to 250 ° C., simultaneously pressing the film 13 on one side and the film A used in Example 1 on the other side, and further heating to 255 ° C. as the plate temperature Then, it was immersed in water and rapidly cooled to obtain a polyester film-coated aluminum alloy plate (Test 13).
Table 1 shows the melting point of the film 13, the content of the olefin polymer, and the like coated on the obtained polyester film-coated aluminum alloy plate.
After applying the processing lubricant to both sides of the polyester film-coated aluminum alloy plate of Test 13 obtained in this way, cup drawing at a speed of 80 cans / min. By drawing and ironing, a seamless can for a 350 ml can having a can wall portion processing degree of 62% was prepared.
About the obtained can, the mold release property of the inner surface side punch was investigated. The results are shown in Table 2.
Further, after trimming the opening of the can, the metal plate temperature is heated to 255 ° C., and then immediately cooled, and after making the polyester film amorphous, the 204 can lid is wound. Neck-in processing and flange processing were performed to produce a 350 ml can.
There was no peeling of the film 13 coated on the inner surface of the obtained can, and a good can was obtained. In addition, the measurement result of the density of the can inner surface side film is shown in Table 2.
The inner surface side of the can thus obtained was subjected to QTV test and evaluation of dent resistance.
The results are shown in Table 2.
As can be seen from Table 2, Test 13, which is this example, is a method for producing a polyester film-coated metal sheet having excellent can-making properties, and is excellent in surface smoothness to obtain a metal can having excellent dent resistance. It can be said that it is a polyester film for metal plate coating, and is a method for producing a polyester film coated metal plate.

[Example 12]
PET / PET-II / Olefin A / Olefin B = 34/54/6/6 (% by weight) was premixed at 270 ° C. using a biaxial vent type extruder to obtain a polyester resin composition.
Next, after drying the polyester-based resin composition at 100 ° C. for 24 hours, it was melted at 270 ° C. using a single screw extruder, and then using a T-die, the surface roughness (Ra) was 1.1 μm. Cast into a cooling roll (circumferential speed 80 m / min) in a layered manner, the distance between the T-die and the cooling roll is 2 cm, and the central part and both ends are electrostatically adhered by separate devices (central part: 4.5 kV, both ends Part: DC power supply of 6 kV was applied), and after cooling and solidifying, a polyester film (film 14) having a thickness of 20 μm was prepared by stretching 4 times in the longitudinal direction at a preheating temperature of 80 ° C. and a stretching temperature of 100 ° C.
Table 1 shows the MFR of the polyester resin composition and the like.
The obtained film 14 was good without film cracking at both ends and poor appearance.
In addition, although the surface roughness of the obtained film 14 was shown in Table 1, it turns out that the surface roughness of a film is small and smooth.
Next, the aluminum alloy plate used in Example 1 was heated to 260 ° C., the film 14 on one side, the polyester film having a melting point of 245 ° C. and a thickness of 16 μm on the other side (film B, when forming a can described later) Since this is a necessary film and is unrelated to the Examples and Comparative Examples, it is not subject to evaluation. The same applies hereinafter), and further heated to 265 ° C. as a plate temperature, and then rapidly cooled in water to be a polyester film-coated aluminum alloy A plate (Test 14) was obtained.
Table 1 shows the melting point of the film 14 and the contents of the olefin polymer coated on the obtained polyester film-coated aluminum alloy plate.
After applying the processing lubricant on both sides of the polyester film-coated aluminum alloy plate of Test 14 obtained in this way, cup drawing at a speed of 80 cans / min. By drawing and ironing, a seamless can for a 350 ml can having a can wall portion processing degree of 62% was prepared.
About the obtained can, the mold release property of the inner surface side punch was investigated. The results are shown in Table 2.
Further, after trimming the opening of the can, the metal plate temperature is heated to 255 ° C., and then immediately cooled, and after making the polyester film amorphous, the 204 can lid is wound. Neck-in processing and flange processing were performed to produce a 350 ml can.
There was no peeling of the film 14 coated on the inner surface of the obtained can, and a good can was obtained. In addition, the measurement result of the density of the can inner surface side film is shown in Table 2.
The inner surface side of the can thus obtained was subjected to QTV test and evaluation of dent resistance.
The results are shown in Table 2.
As can be seen from Table 2, test 14, which is the present example, is a method for producing a polyester film-coated metal sheet having excellent canability, and is excellent in surface smoothness to obtain a metal can having excellent dent resistance. It can be said that it is a polyester film for metal plate coating, and a method for producing a polyester film coated metal plate.

[Example 13]
PET-II / olefin A / olefin B = 88/10/2 (% by weight) was premixed at 270 ° C. using a twin-screw vent type extruder to obtain a polyester resin composition.
Next, after drying the polyester-based resin composition at 100 ° C. for 24 hours, it was melted at 270 ° C. using a single screw extruder, and then using a T-die, the surface roughness (Ra) was 1.1 μm. Cast into a cooling roll (circumferential speed 80 m / min) in a layered manner, the distance between the T-die and the cooling roll is 2 cm, and the central part and both ends are electrostatically adhered by separate devices (central part: 4.5 kV, both ends Part: DC power supply of 6 kV was applied), and after cooling and solidifying, a polyester film (film 15) having a thickness of 25 μm was prepared by stretching in the vertical direction at a preheating temperature of 80 ° C. and a stretching temperature of 100 ° C.
Table 1 shows the MFR of the polyester resin composition and the like.
The obtained film 15 was good without film cracking at both ends and poor appearance.
In addition, although the surface roughness of the obtained film 15 was shown in Table 1, it turns out that the surface roughness of a film is small and smooth.
Next, the aluminum alloy plate used in Example 1 was heated to 250 ° C., film 15 on one side and film A used in Example 1 on the other side were simultaneously pressure-bonded, and further heated to 255 ° C. as the plate temperature. Then, it was immersed in water and rapidly cooled to obtain a polyester film-coated aluminum alloy plate (Test 15).
Table 1 shows the melting point of the film 15, the content of the olefin polymer, and the like, which are coated on the obtained polyester film-coated aluminum alloy plate.
After applying the processing lubricant on both sides of the polyester film-coated aluminum alloy plate of test 15 obtained in this way, cup drawing at a speed of 80 cans / min. By drawing and ironing, a seamless can for a 350 ml can having a can wall portion processing degree of 62% was prepared.
About the obtained can, the mold release property of the inner surface side punch was investigated. The results are shown in Table 2.
Further, after trimming the opening of the can, the metal plate temperature is heated to 255 ° C., and then immediately cooled, and after making the polyester film amorphous, the 204 can lid is wound. Neck-in processing and flange processing were performed to produce a 350 ml can.
There was no peeling of the film 15 coated on the inner surface of the obtained can, and a good can was obtained. In addition, the measurement result of the density of the can inner surface side film is shown in Table 2.
The inner surface side of the can thus obtained was subjected to QTV test and evaluation of dent resistance.
The results are shown in Table 2.
As can be seen from Table 2, test 15 in this example is a method for producing a polyester film-coated metal plate having excellent canability, and is excellent in surface smoothness to obtain a metal can having excellent dent resistance. It can be said that it is a polyester film for metal plate coating, and a method for producing a polyester film coated metal plate.

[Example 14]
PET-II / olefin B = 80/12 (% by weight) was premixed at 270 ° C. using a twin-screw vent type extruder to obtain a polyester resin composition.
Next, after drying the polyester-based resin composition at 100 ° C. for 24 hours, the polyester resin composition was melted at 270 ° C. using a single screw extruder, and then using a T-die, the surface roughness (Ra) was 1.1 μm. Casted into a cooling roll (circumferential speed 80 m / min) in a layered manner, the distance between the T die and the cooling roll is 2 cm, and the center and both ends are electrostatically adhered by separate devices (center: 4.5 kV, both ends Part: DC power supply of 6 kV was applied), and after cooling and solidification, a polyester film (film 16) having a thickness of 25 μm was prepared by stretching 4 times in the longitudinal direction at a preheating temperature of 80 ° C. and a stretching temperature of 100 ° C.
Table 1 shows the MFR of the polyester resin composition and the like.
The obtained film 16 was good with no film cracking at both ends and poor appearance.
In addition, although the surface roughness of the obtained film 16 was shown in Table 1, it turns out that the surface roughness of a film is small and smooth.
Next, the aluminum alloy plate used in Example 1 was heated to 250 ° C., film 16 on one side and film A used in Example 1 on the other side were simultaneously pressed, and further heated to 255 ° C. as the plate temperature. Then, it was immersed in water and rapidly cooled to obtain a polyester film-coated aluminum alloy plate (Test 16).
Table 1 shows the melting point of the film 16, the content of the olefin polymer, and the like, which are coated on the obtained polyester film-coated aluminum alloy plate.
After applying the processing lubricant to both sides of the polyester film-coated aluminum alloy plate of test 16 obtained in this way, cup drawing at a speed of 80 cans / min. By drawing and ironing, a seamless can for a 350 ml can having a can wall portion processing degree of 62% was prepared.
About the obtained can, the mold release property of the inner surface side punch was investigated. The results are shown in Table 2.
Further, after trimming the opening of the can, the metal plate temperature is heated to 255 ° C., and then immediately cooled, and after making the polyester film amorphous, the 204 can lid is wound. Neck-in processing and flange processing were performed to produce a 350 ml can.
There was no peeling of the film 16 coated on the inner surface of the obtained can, and a good can was obtained. In addition, the measurement result of the density of the can inner surface side film is shown in Table 2.
The inner surface side of the can thus obtained was subjected to QTV test and evaluation of dent resistance.
The results are shown in Table 2.
As can be seen from Table 2, test 16, which is the present example, is a method for producing a polyester film-coated metal plate having excellent canability, and is excellent in surface smoothness to obtain a metal can having excellent dent resistance. It can be said that it is a polyester film for metal plate coating, and a method for producing a polyester film coated metal plate.

[Comparative Example 1]
Using the polyester resin composition used in Example 1, following the procedure of Example 1, the same procedure as in Example 1 was used except that a mirror-like cooling roll having a surface roughness (Ra) of 0.05 μm was used. A polyester film (film 17) having a thickness of 25 μm was prepared.
Table 1 shows the MFR of the polyester resin composition and the like.
Although the film 17 obtained did not show film cracks at both ends, the film surface showed a dent of 50 μm or more due to entrainment of bubbles when solidified with a cooling roll, and the appearance was not good. Therefore, the surface roughness of the obtained film 17 was not measured.
Next, the aluminum alloy plate used in Example 1 was heated to 245 ° C., film 17 on one side and film A used in Example 1 on the other side were simultaneously pressed, and further heated to 245 ° C. as the plate temperature. Then, it was immersed in water and rapidly cooled to obtain a polyester film-coated aluminum alloy plate (Test 17).
Table 1 shows the melting point of the film 17, the content of the olefin polymer, and the like, which are coated on the obtained polyester film-coated aluminum alloy plate.
After applying the processing lubricant on both sides of the polyester film-coated aluminum alloy plate of Test 17 thus obtained, cup drawing at a speed of 80 cans / min. By drawing and ironing, a seamless can for a 350 ml can having a can wall portion processing degree of 62% was prepared.
About the obtained can, the mold release property of the inner surface side punch was investigated. The results are shown in Table 2.
Further, after trimming the opening of the can, the metal plate temperature is heated to 255 ° C., and then immediately cooled, and after making the polyester film amorphous, the 204 can lid is wound. Neck-in processing and flange processing were performed to produce a 350 ml can.
There was no peeling of the film 17 coated on the inner surface of the obtained can, and a good can was obtained. In addition, the measurement result of the density of the can inner surface side film is shown in Table 2.
A QTV test was performed on the inner surface side of the can thus obtained. The results are shown in Table 2.
As can be seen from Table 2, dent resistance was not evaluated because the results of the QTV test were extremely inferior and not at a practical level.
As can be seen from Table 2 and the above description, Test 17 which is Comparative Example 1 has a poor appearance of the film-coated metal plate (bubbles are generated), and when canned, bubbles are formed on the inner surface side and the outer surface side. Since the film tearing as the starting point occurred, it is not preferable as a polyester film for covering a metal plate, a method for producing a polyester film for covering a metal plate, or a method for producing a polyester film covered metal plate.

[Comparative Example 2]
The polyester resin composition used in Example 1 was used in the same manner as in Example 1 except that a satin-like cooling roll having a surface roughness (Ra) of 4.3 μm was used according to the procedure of Example 1. A polyester film (film 18) having a thickness of 25 μm was prepared.
Table 1 shows the MFR of the polyester resin composition and the like.
Although the obtained film 18 had no film cracks at both ends, the roll pattern when solidified with a cooling roll was transferred to the film surface, and the appearance was not good. Therefore, the surface roughness of the obtained film 18 was not measured.
Next, the aluminum alloy plate used in Example 1 was heated to 245 ° C., film 18 on one side and film A used in Example 1 on the other side were simultaneously pressed, and further heated to 245 ° C. as the plate temperature. Then, it was immersed in water and rapidly cooled to obtain a polyester film-coated aluminum alloy plate (Test 16).
Table 1 shows the melting point of the film 18, the content of the olefin polymer, etc., which are coated on the obtained polyester film-coated aluminum alloy plate.
After applying the processing lubricant to both sides of the polyester film-coated aluminum alloy plate of Test 18 obtained in this way, cup drawing at a speed of 80 cans / min. By drawing and ironing, a seamless can for a 350 ml can having a can wall portion processing degree of 62% was prepared.
About the obtained can, the mold release property of the inner surface side punch was investigated. The results are shown in Table 2.
Further, after trimming the opening of the can, the metal plate temperature is heated to 245 ° C., and then immediately cooled, and the polyester film is made amorphous, and then the 204 can lid is wound. Neck-in processing and flange processing were performed to produce a 350 ml can.
There was no peeling of the film 18 coated on the inner surface of the obtained can, and a good can was obtained. In addition, the measurement result of the density of the can inner surface side film is shown in Table 2.
A QTV test was performed on the inner surface side of the can thus obtained. The results are shown in Table 2.
As can be seen from Table 2, dent resistance was not evaluated because the results of the QTV test were extremely inferior and not at a practical level.
As can be seen from Table 2 and the above description, Test 18, which is Comparative Example 2, was poor in appearance, such as a pear-like trace spread on the film-coated metal plate. In addition, elephant-like spots caused by the textured pattern on the inner surface of the resulting metal can, which not only reduces the commercial value of the metal can, but also deteriorates the soundness of the inner film. It is not preferable as a polyester film for metal plate coating, a method for producing a polyester film for metal plate coating, or a method for producing a polyester film coated metal plate.

[Comparative Example 3]
A polyester film (film 19) having a thickness of 25 μm was prepared according to the procedure of Example 1 using PET-I alone (no olefin polymer added) as the polyester resin composition.
Similarly, using polyester / PET-II = 39/61 (wt%) as the polyester resin composition (no addition of olefin polymer), a polyester film (film 20) having a thickness of 25 μm according to the procedure of Example 1 It was created.
Table 1 shows the MFR of the polyester resin composition and the like.
The obtained films 19 and 20 did not show film cracks at both ends, and had good appearance.
In addition, although the surface roughness of the obtained film 16 and the film 20 was shown in Table 1, it turns out that the surface roughness of a film is small and smooth is obtained.
Next, the aluminum alloy plate used in Example 1 was heated to 245 ° C., film 19 on one side and film A used in Example 1 on the other side were simultaneously pressure-bonded, and further heated to 245 ° C. as the plate temperature. Then, it was immersed in water and rapidly cooled to obtain a polyester film-coated aluminum alloy plate (Test 19).
Similarly, the electrolytic chromic acid-treated steel plate used in Example 8 was heated to 260 ° C., and the film 20 on one side and the film B used in Example 12 on the other side were simultaneously pressure-bonded. After heating to 265 ° C. as a temperature, it was immersed in water and rapidly cooled to obtain a polyester film-coated steel sheet (Test 20).
Table 1 shows the melting points of the film 19 and the film 20 coated on the obtained polyester film-coated aluminum alloy plate and the polyester film-coated steel sheet, the content of the olefin polymer, and the like.
After applying the processing lubricant to both surfaces of the polyester film-coated aluminum alloy plate of Test 19 and the polyester film-coated steel plate of Test 20 thus obtained, the film 19-coated surface and the film 20-coated surface become the inner surface side of the can, respectively. As described above, cup drawing, redrawing, and ironing are performed at a speed of 80 cans / minute, respectively, and the polyester film-coated aluminum alloy sheet is a seamless can for 350 ml cans with a can wall processing degree of 62%. The polyester film-coated steel sheet was a seamless can for a 350 ml can having a working degree of 52%.
About the obtained can, the mold release property of the inner surface side punch was investigated. The results are shown in Table 2.
Further, after trimming the opening of the can, the can obtained from Test 17 has a metal plate temperature of 245 ° C., and the can obtained from Test 18 has a metal plate temperature of 265 ° C. Immediately after the heating, the polyester-based film was made amorphous, and then a neck-in process and a flange process were performed so that the 204 can lid was wound up to produce a 350 ml size can.
Both the film 19 and the film 20 coated on the inner surface of the obtained can were not peeled, and a good can was obtained. In addition, the measurement result of the density of the can inner surface side film is shown in Table 2.
The inner surface side of the can thus obtained was subjected to QTV test and evaluation of dent resistance.
The results are shown in Table 2.
As can be seen from Table 2, since both the test 19 and the test 20 of Comparative Example 3 are inferior in the dent resistance of the obtained metal can, it is not preferable as a polyester film for covering a metal plate or a polyester film-covered metal can.

[Comparative Example 4]
A polyester film (film 21) having a thickness of 25 μm is prepared according to the procedure of Example 1 using CO-PES / olefin A / olefin B = 88/6/6 (wt%) as a polyester resin composition. did.
Table 1 shows the MFR of the polyester resin composition and the like.
The obtained film 21 did not show film cracks at both ends, and had a good appearance.
In addition, although the surface roughness of the obtained film 21 was shown in Table 1, it turns out that the surface roughness of a film is small and smooth.
Next, the aluminum alloy plate used in Example 1 was heated to 250 ° C., film 22 on one side and film A used in Example 1 on the other side were simultaneously pressed, and further heated to 245 ° C. as the plate temperature. Then, it was immersed in water and rapidly cooled to obtain a laminated polyester film-coated aluminum alloy plate (Test 21).
Table 1 shows the melting point of the film 21, the content of the olefin polymer, and the like, which are coated on the obtained laminated polyester film-coated aluminum alloy plate.
After applying the processing lubricant on both sides of the laminated polyester film-coated aluminum alloy plate of Test 21 thus obtained, cup drawing is performed at a speed of 100 cans / minute so that the film 21-coated surface is the inner surface side of the can. Redrawing and ironing were performed to produce a 350 ml seamless can having a can wall portion processing degree of 62%.
About the obtained can, the mold release property of the inner surface side punch was investigated. The results are shown in Table 2.
As shown in Table 2, the can molded from the test 21 was inferior in the punch releasability of the inner surface film, and the punch did not come off from the can body frequently. Therefore, subsequent evaluation was not performed.
As can be seen from Table 2 and the above description, the test 21 which is Comparative Example 4 has a defect in punch releasability on the inner surface of the can during can making. It is not preferable as a method for producing a film or a method for producing a polyester film-coated metal sheet.

[Comparative Example 5]
A polyester film (film 22) having a thickness of 25 μm was prepared according to the procedure of Example 1 using PET-II / olefin A / olefin B = 65/15/20 (wt%) as the polyester resin composition.
Table 1 shows the MFR of the polyester resin composition and the like.
The obtained film 22 did not show film cracks at both ends, and had a good appearance.
In addition, although the surface roughness of the obtained film 22 was shown in Table 1, it turns out that the surface roughness of a film is small and smooth.
Next, the aluminum alloy plate used in Example 1 is heated to 250 ° C., the film 22 on one side and the film A used in Example 1 on the other side are simultaneously pressure-bonded, and further heated to 255 ° C. as the plate temperature. Then, it was quenched in water to obtain a polyester film-coated aluminum alloy plate (Test 22).
Table 1 shows the melting point of the film 22, the content of the olefin polymer, and the like coated on the obtained polyester film-coated aluminum alloy plate.
After applying a processing lubricant on both sides of the polyester film-coated aluminum alloy plate of Test 22 thus obtained, cup drawing at a rate of 80 cans / minute each so that the film 22 coated surface becomes the inner surface side of the can, Redrawing and ironing were performed to produce a 350 ml seamless can having a can wall portion processing degree of 62%.
About the obtained can, the mold release property of the inner surface side punch was investigated. The results are shown in Table 2.
As shown in Table 2, the can molded from the test 22 was remarkably inferior in punch releasability of the inner surface film, and the state where the punch did not come off from the can body sporadically was not at a practical level. Therefore, subsequent evaluation was not performed.
As can be seen from Table 2, Test 22 which is Comparative Example 5 is not preferable as a polyester film for covering a metal plate or a polyester film-covered metal plate because a punch releasability failure occurred on the inner surface of the can during can making.

[Comparative Example 6]
A polyester-based resin composition was obtained by premixing PET-II / olefin A = 88/12 (% by weight) as a polyester-based resin composition at 270 ° C. using a biaxial vent type extruder.
Next, after drying the polyester-based resin composition at 100 ° C. for 24 hours, it was melted at 270 ° C. using a single screw extruder, and then using a T-die, the surface roughness (Ra) was 1.1 μm. Cast into a cooling roll (circumferential speed 80 m / min) in a layered manner, the distance between the T-die and the cooling roll is 2 cm, and the central part and both ends are electrostatically adhered by separate devices (central part: 4.5 kV, both ends Part: DC power supply of 6 kV was applied), and after cooling and solidification, a polyester film (film 23) having a thickness of 25 μm was formed by stretching in the longitudinal direction 4 times at a preheating temperature of 80 ° C. and a stretching temperature of 100 ° C.
Table 1 shows the MFR of the polyester resin composition and the like.
The obtained film 23 was good without film cracking at both ends and poor appearance.
In addition, although the surface roughness of the obtained film 23 was shown in Table 1, it turns out that the surface roughness of the film is small and smooth.
Next, the electrolytic chromic acid-treated steel plate used in Example 8 was heated to 250 ° C., the film 23 on one side and the film A used in Example 1 on the other side were simultaneously pressure-bonded, and further the plate temperature was 255 ° C. After being heated, the film was immersed in water and quenched to obtain a polyester film-coated steel sheet (Test 23).
Table 1 shows the melting point of the film 23 covered with the obtained polyester film-coated steel sheet, the content of the olefin polymer, and the like.
After applying the processing lubricant on both sides of the polyester film-coated steel sheet of Test 23 obtained in this way, cup drawing and redrawing at a speed of 80 cans / minute so that the film 23 coating surface becomes the inner surface side of the can. And the ironing process was performed and the seamless can for 350 ml cans in which the processing degree of the can wall part was 52% was created.
About the obtained can, the inner surface side investigated the releasability of the punch. The results are shown in Table 2.
Further, after trimming the opening of the can, the metal plate temperature is heated to 255 ° C., and then immediately cooled, and after making the polyester film amorphous, the 204 can lid is wound. Neck-in processing and flange processing were performed to produce a 350 ml can.
There was no peeling of the film 23 coated on the inner surface of the obtained can, and a good can was obtained. In addition, the measurement result of the density of the can inner surface side film is shown in Table 2.
The inner surface side of the can thus obtained was subjected to QTV test and evaluation of dent resistance.
The results are shown in Table 2.
As can be seen from Table 2, the test 23 of Comparative Example 6 is inferior in the release property of the punch on the inner surface of the can at the time of can making, and also inferior in the soundness of the inner surface film (QTV test result). . Moreover, the dent resistance of the inner film of the obtained can is also inferior, and it is not preferable as a polyester film for metal plate coating, a method for producing a polyester film for metal plate coating, or a polyester film coated metal plate.

[Comparative Example 7]
A polyester-based resin composition was obtained by premixing PET-II / olefin F = 90/10 (% by weight) as a polyester-based resin composition at 270 ° C. using a twin-screw vent type extruder.
Next, after drying the polyester-based resin composition at 100 ° C. for 24 hours, the polyester resin composition was melted at 270 ° C. using a single screw extruder, and then using a T-die, the surface roughness (Ra) was 1.1 μm. Casted into a cooling roll (circumferential speed 80 m / min) in a layered manner, the distance between the T die and the cooling roll is 2 cm, and the center and both ends are electrostatically adhered by separate devices (center: 4.5 kV, both ends Part: 6 kV DC power applied) After cooling and solidification, an attempt was made to create a polyester film (film 24) by stretching in the longitudinal direction at a preheating temperature of 80 ° C. and a stretching temperature of 100 ° C. The film 24 could not be obtained because the ejection became unstable at the stage of obtaining and the film could not be stably formed.
Therefore, a film-coated metal plate cannot be obtained and the test 24 is not performed.
Table 1 shows the MFR of the polyester resin composition and the like.
As can be seen from the above description, Comparative Example 7 is not preferable as a method for producing a metal film-covering polyester film and a metal sheet-covering polyester film because there is a problem in film forming properties.

[Comparative Example 8]
A polyester-based resin composition was obtained by premixing PET-II / olefin G = 90/10 (% by weight) as a polyester-based resin composition at 270 ° C. using a biaxial vent-type extruder.
Next, after drying the polyester-based resin composition at 100 ° C. for 24 hours, it was melted at 270 ° C. using a single screw extruder, and then using a T-die, the surface roughness (Ra) was 1.1 μm. Cast into a cooling roll (circumferential speed 80 m / min) in a layered manner, the distance between the T-die and the cooling roll is 2 cm, and the central part and both ends are electrostatically adhered by separate devices (central part: 4.5 kV, both ends Part: a 6 kV DC power supply was applied), and after cooling and solidification, a polyester film (film 25) having a thickness of 25 μm was prepared by stretching it four times in the longitudinal direction at a preheating temperature of 80 ° C. and a stretching temperature of 100 ° C.
Table 1 shows the MFR of the polyester resin composition and the like.
Although the film 25 was obtained, when obtaining an unstretched resin sheet, a phenomenon in which the molten resin film was swayed due to a decrease in the thermal characteristics of the resin, and the resulting film had spots such as spots was obtained. Was not obtained.
In addition, although the surface roughness of the obtained film 25 was shown in Table 1, it turns out that the surface roughness of a film is small and smooth.
Next, the aluminum alloy plate used in Example 1 is heated to 250 ° C., the film 25 on one side and the film A used in Example 1 on the other side are simultaneously pressed, and further heated to 255 ° C. as the plate temperature. Then, it was immersed in water and rapidly cooled to obtain a polyester film-coated aluminum alloy plate (Test 25).
Table 1 shows the melting point of the film 25, the content of the olefin polymer, and the like, which are coated on the obtained polyester film-coated aluminum alloy plate.
After applying the processing lubricant to both sides of the polyester film-coated aluminum alloy plate of Test 25 thus obtained, cup drawing at a speed of 80 cans / min. By drawing and ironing, a seamless can for a 350 ml can having a can wall portion processing degree of 62% was prepared.
About the obtained can, the mold release property of the inner surface side punch was investigated. The results are shown in Table 2.
Further, after trimming the opening of the can, the metal plate temperature is heated to 255 ° C., and then immediately cooled, and after making the polyester film amorphous, the 204 can lid is wound. Neck-in processing and flange processing were performed to produce a 350 ml can.
There was no peeling of the film 25 coated on the inner surface of the obtained can, and a good can was obtained. In addition, the measurement result of the density of the can inner surface side film is shown in Table 2.
The QTV test was evaluated on the inner surface side of the can thus obtained. The results are shown in Table 2. As can be seen from Table 2, dent resistance was not evaluated because the results of the QTV test were extremely inferior and not at a practical level.
As can be seen from Table 2, in the method of Test 25 which is Comparative Example 8, the inner surface of the can is inferior in punch releasability during can making, and the soundness of the inner film is also inferior due to the influence. Therefore, it is not preferable as a polyester film for metal plate coating, a method for producing a polyester film for metal plate coating, a polyester film coated metal plate, or a polyester film coated metal can.

[Comparative Example 9]
After trimming the opening using a 350 ml-size seamless can obtained from Test 14 of Example 12 and having a working degree of the can wall of 62%, the can was heated so that the metal plate temperature was 240 ° C. And then cooled rapidly. Next, a neck-in process and a flange process were performed so that the 204 can lid was wound, and a 350 ml size can (test 26) with a narrowed opening was manufactured.
The inner film of the obtained can was slightly peeled off, and it was inferior as a can.
In addition, the measurement result of the density of the can inner surface side film is shown in Table 2.
The inner surface side of the can thus obtained was subjected to QTV test and evaluation of dent resistance.
The results are shown in Table 2.
As can be seen from Table 2, the test 26, which is Comparative Example 9, is inferior in the results of the QTV test (the reaction part is a neck-in processed part), and is also inferior in dent resistance. It is not preferable.

＊１ 無延伸フィルム表面に５０μｍ以上の凹み発生
＊２ 無延伸フィルム表面に梨地跡発生
＊３ 非晶質のため融点ピークなし

* 1 50 μm or more dents are generated on the surface of the unstretched film.
* 2 Sashimi remains on the unstretched film surface
* 3 No melting point due to amorphous

  The method for producing a polyester film-coated metal sheet according to the present invention can reduce material loss, so that it is not only an economically superior production method but also can manufacturing properties (in particular, can inner film and processing punch). This is a production method for obtaining a polyester film-coated metal plate excellent in releasability and flavor. When the polyester film-coated metal plate obtained by the present invention can be made, since the dent resistance of the metal can is good, the polyester film for metal coating and its production method, the polyester film-coated metal plate and its It can be said that it is a manufacturing method and a polyester film-coated metal can.

Claims (11)

A crystalline polyester having a melting point of 180 ° C. or higher, and an olefin polymer having a functional group of 200 to 2000 equivalent / ton and an equivalent spherical equivalent diameter of 0.25 to 2.0 μm, 70/30 to 99 / A polyester-based film comprising a polyester-based resin composition mixed at a ratio of 1% by weight, wherein the polyester-based film is a molten resin film of the polyester-based resin composition satisfying the following formulas (I) to (III): , After solidifying with a cooling roll having a surface roughness (Ra) of 0.2 μm or more and less than 4.0 μm, the surface roughness (Ra) is at least 0.1 μm, and is uniaxially stretched in the longitudinal direction, and A polyester film for covering a metal plate, having a density of 1.360 g / cm ³ or less.
[Formula] (I) 1 ≦ m ≦ 30
(II) 0.15 ≦ (Mi−Mf) /m≦1.0
(III) 2 ≦ Mf ≦ 20
In the formula, Mi represents the melt flow rate (MFR, g / 10 min) of the crystalline polyester measured at a temperature of the melting point of the crystalline polyester + 30 ° C., and Mf represents the crystallinity measured at the temperature of the melting point of the crystalline polyester + 30 ° C. The MFR (g / 10 min) of the mixture of polyester and olefin polymer is shown, and m shows the content (% by weight) of the olefin polymer in the mixture.   The olefin-based polymer according to claim 1 is mainly composed of at least one of an ethylene bond-forming α, β-unsaturated carboxylic acid or an ester-forming derivative thereof and at least one of olefins having 2 to 6 carbon atoms. A metal plate coating comprising: a copolymer comprising a structural unit, or a mixture comprising the copolymer and a polymer mainly comprising at least one kind of olefin having 2 to 6 carbon atoms. Polyester film.   The polymer (a) in which the olefin polymer according to claim 1 is mainly composed of at least one olefin having 2 to 6 carbon atoms and an ethylene bond-forming α, β-unsaturated carboxylic acid or ester thereof For coating a metal plate, comprising a mixture comprising at least one type-forming derivative and at least one type of olefin having 2 to 6 carbon atoms as a main structural unit (b) Polyester film.   It is a manufacturing method of the polyester-type film for metal plate coating in any one of Claim 1 thru | or 3, Comprising: The surface roughness (Ra) of the molten film which extruded the polyester-type resin composition into the layer form from T die | dye Is at least longitudinally uniaxially stretched after being solidified by a cooling roll having a thickness of 0.2 μm or more and less than 4.0 μm. A crystalline polyester having a melting point of 180 ° C. or higher, and an olefin polymer having a functional group of 200 to 2000 equivalent / ton and an equivalent spherical equivalent diameter of 0.25 to 2.0 μm, 70/30 to 99 / A molten resin film of a polyester resin composition satisfying the following formulas (I) to (III) mixed at a ratio of 1% by weight is cooled with a surface roughness (Ra) of 0.2 μm or more and less than 4.0 μm. After solidifying with a roll, a polyester film having a surface roughness (Ra) of 0.1 μm or less and a density of 1.360 g / cm ³ or less, which is uniaxially stretched at least in the longitudinal direction, is at least a can of a metal plate A polyester film-coated metal plate, characterized in that it is coated on a surface corresponding to the inner surface side of the polyester film.
[Formula] (I) 1 ≦ m ≦ 30
(II) 0.15 ≦ (Mi−Mf) /m≦1.0
(III) 2 ≦ Mf ≦ 20
In the formula, Mi represents the melt flow rate (MFR, g / 10 min) of the crystalline polyester measured at a temperature of the melting point of the crystalline polyester + 30 ° C., and Mf represents the crystallinity measured at the temperature of the melting point of the crystalline polyester + 30 ° C. The MFR (g / 10 min) of the mixture of polyester and olefin polymer is shown, and m shows the content (% by weight) of the olefin polymer in the mixture.   The olefin polymer according to claim 5 is mainly composed of at least one or more of ethylene bond-forming α, β-unsaturated carboxylic acid or an ester-forming derivative thereof and at least one or more of olefins having 2 to 6 carbon atoms. Polyester film coating characterized by comprising a copolymer comprising a constituent unit, or a mixture comprising the copolymer and a polymer mainly comprising at least one kind of olefin having 2 to 6 carbon atoms. Metal plate.   The olefin polymer according to claim 5, wherein the polymer (a) comprising at least one olefin having 2 to 6 carbon atoms as a main constituent unit and an ethylene bond-forming α, β-unsaturated carboxylic acid or ester thereof A polyester film coating comprising a mixture comprising a copolymer (b) having at least one or more formable derivatives and at least one or more olefins having 2 to 6 carbon atoms as main structural units. Metal plate. A crystalline polyester having a melting point of 180 ° C. or higher, and an olefin polymer having a functional group of 200 to 2000 equivalent / ton and an equivalent spherical equivalent diameter of 0.25 to 2.0 μm, 70/30 to 99 / A method for producing a polyester film-coated metal sheet coated with a polyester film obtained from a polyester resin composition satisfying the following formulas (I) to (III) mixed at a ratio of 1% by weight: The molten resin film extruded in a layer form from a die is solidified with a cooling roll having a surface roughness (Ra) of 0.2 μm or more and less than 4.0 μm, and at least longitudinally uniaxially stretched, and then both ends are cut and removed. Laminating the polyester film on a heated metal plate, and adding the film-coated metal plate to the melting point of the crystalline polyester or higher. Method for producing a polyester film coated metal sheet, characterized in that the rear quenched to become the step of the density of the polyester film and 1.360g / cm ³ or less.
[Formula] (I) 1 ≦ m ≦ 30
(II) 0.15 ≦ (Mi−Mf) /m≦1.0
(III) 2 ≦ Mf ≦ 20
In the formula, Mi represents the melt flow rate (MFR, g / 10 min) of the crystalline polyester measured at a temperature of the melting point of the crystalline polyester + 30 ° C., and Mf represents the crystallinity measured at the temperature of the melting point of the crystalline polyester + 30 ° C. The MFR (g / 10 min) of the mixture of polyester and olefin polymer is shown, and m shows the content (% by weight) of the olefin polymer in the mixture.   The olefin polymer according to claim 8 is mainly composed of at least one of an ethylene bond-forming α, β-unsaturated carboxylic acid or an ester-forming derivative thereof and at least one of olefins having 2 to 6 carbon atoms. Polyester film coating characterized by comprising a copolymer comprising a constituent unit, or a mixture comprising the copolymer and a polymer mainly comprising at least one kind of olefin having 2 to 6 carbon atoms. A method for producing a metal plate.   The olefin polymer according to claim 8, wherein the polymer (a) comprising at least one olefin having 2 to 6 carbon atoms as a main constituent unit and an ethylene bond-forming α, β-unsaturated carboxylic acid or ester thereof A polyester film coating comprising a mixture comprising a copolymer (b) having at least one or more formable derivatives and at least one or more olefins having 2 to 6 carbon atoms as main structural units. A method for producing a metal plate. A can obtained by molding from the polyester film-coated metal sheet according to any one of claims 5 to 7, wherein the density of the polyester film coated on at least the inner surface side of the can is 1.360 g / A polyester film-coated metal can characterized by having a cm ³ or less.