JP2010023440A - Polyester film laminated metal sheet - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a film for laminating metal, applicable as a laminate film for a two-piece can and excelling in moldability in manufacturing a can and in preserving the flavor of beverage, and to provide a film laminated metal sheet and a film laminated metal container. <P>SOLUTION: The metal sheet is laminated with a polyester film comprising a polyester base material layer and a coating layer. The polyester base material layer is mainly composed of copolymerized PET whose melting point is 230-245°C, and contains 2-20 mol% of alkylene oxide units with the carbon number of 2 or more derived from a polyoxyalkylene glycol component, to the total acid content in a polyester resin composition. The degree of orientation is 10% or less, and the weight average molecular weight (B) of the polyester resin composition is 40,000 or more when the film laminated on a metal substrate is remelted with heat at a temperature not lower than the melting point (subjected to so-called remelting treatment) and then quenched. The thickness of the coating layer is 0.002-0.5 g/m<SP>2</SP>, and a coefficient of dynamic friction of the surface of the coating layer using a steel ball loaded with 2 kg in an environment of 150°C, as a slider is 0.15 or less. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a polyester film laminated metal plate suitable for a resin-coated metal can. In particular, the present invention relates to a polyester film laminated metal plate suitably used for coating the outer surface of a drawn iron can. More specifically, the present invention relates to a polyester film laminated metal plate used for the outer surface of a drawn and ironed can excellent in canning processability such as drawing and ironing.

  As a method for preventing corrosion of the inner wall surface and the outer wall surface of a metal can, there is a method of laminating a thermoplastic resin film. A polyester film for laminating a metal material for food canning is disclosed (for example, see Patent Documents 1 and 2).

  This polyester film has excellent scratch resistance. For example, in a can manufacturing process in which a metal plate is formed into a cylinder and a lid is wound around the upper and lower openings of the cylinder, , "Film laminated metal plate"), or when the laminated metal plate is processed by winding or the like, there is no need to cause scratches and reduce the commercial value.

  In addition, this film has excellent resistance at the time of squeezing processing, and after being filled with food after canning, the amount of oligomer elution is small when heated hot water treatment such as retort treatment is performed, so it is laminated on the inner wall surface of a metal container. Excellent as a polyester film.

  However, these films have high haze, are inferior in transparency, and have problems in film properties such as touch resistance after canning.

  By the way, for food cans, in addition to the so-called three-piece cans, which are formed by cylindrically forming a metal plate, a lid is attached to the upper and lower openings of the metal cylinder, and a metal plate is deep-drawn to form a container part. In addition, there is a so-called two-piece can formed by winding a lid on the upper surface opening of the container.

  In the case of a three-piece can, the film-laminated metal plate is only formed into a cylindrical shape, but in the case of a two-piece can, the film-laminated metal plate is formed by drawing and ironing. Therefore, in order to be applicable to a two-piece can, it is necessary to have good formability of being formed following the formation of a metal plate and to have excellent adhesion to the metal plate. If the formability is insufficient or the film adheres poorly to the metal plate, a so-called delaminating phenomenon occurs in which the film peels off from the metal plate, or the film is produced during the production of the container part of a two-piece can. Because it will be torn.

  Furthermore, in the drawing process, the film laminated metal plate is processed into a container shape while repeatedly raising and lowering the punch. Therefore, in the case of a film laminated on the inner wall surface side of the container, releasability from the punch is required. The In the case of the outer wall surface of a container, the temperature at the time of canning tends to rise due to the friction temperature due to the material and thickness of the metal plate, and the heat resistance temperature of the film may be exceeded. Since there is a problem of deteriorating canability, it is necessary to have excellent releasability from the die. When molding is performed at a high temperature like a steel can, particularly high characteristics are required.

Up to now, it has been made of a polyester composition having a melting point of 220 to 250 ° C. mainly composed of a copolymer polyester composed of an ethylene terephthalate component and an ethylene isophthalate component, and has a density of less than 1.385 g / cm ³ and a plane orientation coefficient of 0.00. A biaxially oriented polyester film that is less than 130, wherein the polyester composition is derived from the polyoxyalkylene glycol component, wherein the polyoxyalkylene glycol component has 3 or more repeating alkylene oxide units having 3 or more carbon atoms. The alkylene oxide unit having 2 or more carbon atoms is contained in an amount of 2 to 20 mol% based on the total acid component of the polyester composition, and further 0.05 to 1.0 wt% of inert particles and wax. Metal plate bonding comprising a polyester composition containing 0.01 to 0.15% by weight A metal plate on which a laminated polyester film for laminating is bonded is known (for example, see Patent Document 2).

However, further improvement in can-making ability is required.
JP-A-7-227946 Japanese Patent No. 3248450 JP 2006-199915 A JP 2007-83709 A

  The object of the present invention has been made in view of such circumstances, and can be applied as a film laminated metal plate for so-called two-piece cans, and particularly used for the outer surface of a drawn iron can coated with excellent moldability in can manufacturing. An object of the present invention is to provide a film laminated metal plate and a film laminated metal container.

  The film-laminated metal plate of the present invention capable of achieving the above object is a metal plate obtained by laminating a polyester film comprising a polyester base layer and a coating layer, and the polyester base layer is a copolymer having a melting point of 230 to 245 ° C. 2 to 20 mol% of the alkylene oxide unit having 2 or more carbon atoms derived from the polyoxyalkylene glycol component and containing 2 to 20 mol% of the total acid amount of the polyester resin composition, and the degree of orientation is 10% or less And the weight average molecular weight (B) after the film existing on the metal substrate is remelted by heat above its melting point (so-called remelt treatment) and rapidly cooled is 40000 or more, The coating layer has a thickness of 0.002 to 0.5 g / m 2, contains a low molecular weight lubricant component, and loads 2 kg under a 150 ° C. environment. Dynamic friction coefficient of the surface of the coating layer the steel ball and sliding element multiplied by is characterized in that more than 0.15.

  In this case, it is preferable that the surface roughness of the center plane of the coating layer of the film-laminated metal plate is 0.02 μm or less.

  In this case, the thermoplastic polyester resin composition preferably contains 0.01 to 1.0% by weight of an antioxidant.

  Furthermore, in this case, a metal can characterized by forming the film-laminated metal plate is useful.

  When used as a film laminated metal plate for a two-piece can, the film-laminated metal plate of the present invention is excellent in moldability, particularly releasability from a die during can making. It is particularly useful in steel squeezed iron cans.

  The thermoplastic polyester resin composition used for the film-laminated metal plate of the present invention is not particularly limited, but a thermoplastic polyester resin is preferably used from the viewpoints of heat resistance and aroma retention. More specifically, it is preferable to use polyethylene isophthalate copolymerized PET.

  Moreover, in the said thermoplastic polyester, it is preferable that a melting peak exists in the range of 230 to 245 degreeC. If the melting peak is less than 230 ° C, the heat resistance and canability in the can making process are impaired, and if it exceeds 245 ° C, the temperature balance in the remelt treatment is lost and the yield is lowered, which is not preferable.

The polyethylene isophthalate copolymerized PET in the present invention is a polyester mainly composed of terephthalic acid and isophthalic acid as acid components.
Moreover, other copolymerization components can be included in the range which does not inhibit the purpose.
Among other copolymerizable components that can be used, dicarboxylic acid components include naphthalene dicarboxylic acid, diphenylsulfone dicarboxylic acid, aromatic dicarboxylic acids such as 5-sodium sulfoisophthalic acid, oxalic acid, succinic acid, adipic acid, sebacic acid, Aliphatic dicarboxylic acids such as decanedicarboxylic 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.
The amount of the above dicarboxylic acids and their ester derivatives that can be used is preferably 10 mol% or less, more preferably 6 mol% or less. When the usage-amount of other dicarboxylic acid and those ester derivatives exceeds 10 mol%, the thermal stability of polyester will worsen and it is unpreferable.

As the glycol component of the polyethylene isophthalate copolymer PET of the present invention, components other than the ethylene glycol component include aliphatic glycols such as propanediol, butanediol, pentanediol, hexanediol and neopentylglycol, cyclohexane Aromatic glycols such as dimethanol, aromatic glycols such as ethylene oxide adducts of bisphenol A, ethylene oxide adducts of bisphenol S, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, and 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, the amount of other glycol components that can be used is preferably 10 mol% or less, more preferably 5 mol% or less. If the amount of the other glycol component used exceeds 10 mol%, the thermal stability of the polyester deteriorates, which is not preferable.

  The method for producing the polyethylene isophthalate copolymer PET 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. In addition, the amount of oligomers from the polyester resin in the retort treatment etc. that is carried out after filling the can into the can is reduced, and from the standpoint of fragrance to prevent the content and flavor from deteriorating, From the viewpoint of preventing contamination, it is preferable to use a polyester having a low oligomer content produced by a solid phase polymerization method under reduced pressure or under an inert gas atmosphere.

  Here, for example, the content of the oligomeric cyclic trimer including ethylene terephthalate cyclic trimer is preferably 0.7% by weight or less.

  The intrinsic viscosity of the polyethylene isophthalate copolymerized PET of the present invention is preferably 0.6 to 1.2, more preferably 0.70 to 1.2. If the intrinsic viscosity is less than 0.6, the mechanical properties of the resulting film may be deteriorated, and even if the intrinsic viscosity exceeds 1.2, no further effect of improving the mechanical properties can be obtained. In addition, the productivity at the time of production of the polyester is lowered, which is not economical.

  In the production of polyethylene isophthalate copolymerized PET in the present invention, antimony oxide, germanium oxide, titanium compound and the like are used as a polymerization catalyst. In addition to the polymerization catalyst, a melt-extruded film using the polyester resin composition of the present invention. Mg salt such as magnesium acetate and magnesium chloride, Ca salt such as calcium acetate and calcium chloride, Mn salt such as manganese acetate and manganese chloride, zinc chloride and zinc acetate Zn salts such as cobalt chloride, cobalt salts such as cobalt acetate and the like, the total amount of each metal ion is 300 ppm or less, phosphoric acid or phosphoric acid ester derivatives such as phosphoric acid trimethyl ester and phosphoric acid triethyl ester as phosphorous atoms and 200 ppm or less It is also possible to add in a range. When the total amount of metal ions other than the above polymerization catalyst exceeds 300 ppm and the amount of phosphorus exceeds 200 ppm, not only is the resulting polyester colored significantly, but the heat resistance and hydrolysis resistance of the polyester may also decrease. Therefore, it is not preferable.

  At this time, when the molar ratio of the total phosphorus amount to be added and the total metal ion amount is 0.4 to 1.0, the polyester having the best balance of heat resistance, hydrolysis resistance, and electrostatic adhesion Is preferable. Here, molar ratio of addition amount = (total amount of phosphorus in phosphoric acid, phosphoric acid alkyl ester or derivative thereof (molar atom)) / (total amount of Mg ion, Ca ion, Mn ion, Zn ion, Co ion ( Mole atom)). When the molar ratio is less than 0.4, the composition of the present invention is markedly colored, and heat resistance and hydrolysis resistance are lowered. If it exceeds 1.0, sufficient electrostatic adhesion cannot be obtained.

The polyethylene isophthalate copolymerized PET synthesized as described above may be included in the polyester film only in one kind or in a mixture of two or more kinds.
Further, polyethylene isophthalate copolymer PET having a high isophthalic component and PET resin may be mixed.

  The thermoplastic polyester resin composition of the present invention preferably contains a polyoxyalkylene glycol component having 3 or more repeating alkylene oxide units having 2 or more carbon atoms.

In the present invention, the amount of the polyoxyalkylene glycol component contained in the thermoplastic polyester resin composition is such that the amount of the alkylene oxide unit having 2 or more carbon atoms derived from the polyoxyalkylene glycol component is the amount of the polyester composition. It is preferable that it is 2-20 mol% with respect to all the acid components.
By containing the said component in the said range, the elasticity at normal temperature and low temperature of a thermoplastic polyester film can be provided, and shaping | molding adhesiveness with another resin layer can be improved. In particular, it is effective in improving the formability during drawing and ironing cans that are subjected to shock deformation at high speed.
Moreover, the process abnormality at the time of continuous production by the accumulation | storage of the chip | tip (whisker) by the tearability defect of the film at the time of can making can be prevented by making the said component into 2 mol% or more.
Further, the amount of the polyoxyalkylene glycol component contained in the thermoplastic polyester resin composition is more preferably 2 to 10 mol%, and particularly preferably 2 to 5 mol%.
Examples of polyoxyalkylene glycols comprising alkylene oxide units having 2 carbon atoms include polyethylene glycol (2 carbon atoms), polytrimethylene glycol (3 carbon atoms), polytetramethylene glycol (4 carbon atoms), polyhexamethylene Glycol (6 carbon atoms) can be used, and one of these components may be used alone, or two or more components may be mixed and used. A polyoxyalkylene glycol having an average molecular weight in the range of 500 to 3000 can be suitably used, and an average molecular weight in the range of 800 to 2000 is more preferable.

  An alkylene oxide unit having 2 or more carbon atoms derived from a polyoxyalkylene glycol component means a structural unit in which both ends of an alkylene chain form an ether bond with an adjacent alkylene chain with an oxygen atom interposed therebetween.

  The method for containing the polyoxyalkylene glycol component in the thermoplastic polyester resin composition of the present invention is not particularly limited. For example, a polyester composition obtained by adding a polyoxyalkylene glycol component at the stage of producing a polyester composition of a resin layer in the same manner as other raw materials and then terminating the polyester synthesis reaction may be used. Another copolymerized polyester copolymerized with oxyalkylene glycol may be melt-mixed with the thermoplastic polyester resin of the present invention. In the present invention, the latter method of melt mixing is preferable because the effect of improving the moldability and tearability of the can is exhibited more efficiently. In particular, the polyalkylene terephthalate-polytetramethylene oxide block copolymer is melt-mixed. The method is the most preferred form.

In particular, as a method for adding a polyoxyalkylene glycol composed of an alkylene oxide unit having 2 carbon atoms to a polyester composition, for example, a method of adding a polyalkylene terephthalate-polytetramethylene oxide block copolymer to polyethylene terephthalate. can give. Examples of the polyalkylene terephthalate include polybutylene terephthalate, and polybutylene terephthalate is preferable.
At this time, the ratio of the polyoxyalkylene glycol in the block copolymer is preferably 20 to 60% by weight, and more preferably 30 to 50% by weight.

In the present invention, the weight average molecular weight (A) of the thermoplastic polyester resin composition is 40,000 or more, so that the weight average molecular weight of the thermoplastic polyester resin composition after remelting can be maintained so as to be able to withstand can making. Therefore, it is preferable.
Also, at this time, the weight average molecular weight (B) after the film existing on the metal substrate is remelted by heat above its melting point (so-called remelt treatment), rapidly cooled, and canned, is 40000 or more. It is preferable as a specific numerical range in order to reduce galling after canning.
As described above, the weight average molecular weight (A) of the thermoplastic polyester resin composition used in the present invention and the film existing on the metal substrate are remelted by heat above its melting point (so-called It is preferable that the relationship of the weight average molecular weight (B) after remelting), rapidly cooling, and can-making processing satisfy the following formula (1), and a material whose molecular weight is rather increased by remelting is not suitable.
(B) / (A) ≦ 1 (1)

The film laminate metal plate of the present invention preferably contains 0.01 to 1% by weight of an antioxidant. This is because the film is bonded to a metal substrate, and the molecular weight of the film is prevented from lowering in the remelting process (so-called remelt treatment) and the can making process by heat higher than the melting point of the film. In particular, the polyalkylene glycol component is susceptible to thermal decomposition, and if the antioxidant is less than 0.01% by weight, the molecular weight is greatly reduced in the lamination / remelt treatment step. Moreover, even if it contains 1 weight% or more, an effect does not change and it becomes disadvantageous in cost.
This is because the thermal decomposition of the polyoxyalkylene glycol component contained in the thermoplastic polyester resin composition is linked to the entire thermoplastic polyester resin component.

  As the antioxidant used in the film laminate metal plate of the present invention, a primary antioxidant (which has a phenol-based or amine-based radical scavenging and chain termination action), and a secondary antioxidant (which is And phosphorous-based and sulfur-based peroxide decomposing actions), and any of these can be used. Specific examples include phenolic antioxidants (eg, phenol type, bisphenol type, thiobisphenol type, polyphenol type, etc.), amine antioxidants (eg, diphenylamine type, quinoline type, etc.), phosphorus antioxidants (eg, For example, phosphite type, phosphonite type, and the like) and sulfur-based antioxidants (for example, thiodipropionic acid ester type and the like). Specifically, n-octadecyl-β- (4′-hydroxy-3,5′-di-t-butylphenyl) propionate, tetrakis [methylene-3- (3 ′, 5′-di-t-butyl-) 4′-hydroxyphenyl) propionate] (which is commercially available as “Irganox 1010” (trade name)), 1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) ) Butane, 1,3,5-tris (3,5-di-t-butyl-4-hydroxybenzyl) -S-triazine-2,4,6 (1H, 3H, 5H) -trione, 1,3, 5-trimethyl-2,4,6-tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene (which is commercially available as "Irganox 1330" (trade name)), tris ( mix Mono and / or dinonylphenyl) phosphite, cyclic neopentanetetrayl bis (octadecyl phosphite), tris (2,4-di-t-butylphenyl phosphite), 2,2-methylene bis (4,6- And di-t-butylphenyl) octyl phosphite, di-lauryl-thiodipropionate, di-myristyl-thiodipropionate, and di-stearyl-thiodipropionate. These antioxidants may be used alone or in combination of two or more.

  In the film-laminated metal plate of the present invention, the lower the content of the low molecular weight compound is more preferable from the viewpoints of antifouling property of a can-making line and aroma retention in the case of the inner surface of the can. For example, the ethylene terephthalate cyclic trimer content in the thermoplastic resin after canning in the present invention is preferably 0.7% by weight or less. In the case of producing a two-piece can, after undergoing a remelt process for making the film non-oriented, after being drawn, the beverage is filled and subjected to a heat treatment such as a retort process. This is to prevent the oligomer from being eluted from the film in each step, and further transferring the oligomer to the beverage and adversely affecting the taste and flavor of the beverage.

The method for setting the content of the cyclic trimer including the ethylene terephthalate cyclic trimer in the polyester film to 0.7% by weight or less is not particularly limited. 1. a method of extracting and removing the cyclic trimer from the laminated film with water or an organic solvent after the laminated film is formed; Examples thereof include a method of forming a polyester film using a polyester having a small cyclic trimer. Of these, 2. This method is more economical and preferable.
2. In this method, the method for producing a polyester having a low cyclic trimer content is not limited, and the solid phase polymerization method: after polymerization, the cyclic trimer is extracted by heat treatment under reduced pressure or by extraction with water or an organic solvent. A removal method; and a combination of these methods. In particular, after producing a polyester having a low cyclic trimer content by solid phase polymerization, the method of extracting the obtained polyester with water to further reduce the cyclic trimer is the cyclic trimer in the film forming step. This is most preferable because the amount of body produced is suppressed.

  The intrinsic viscosity of the polyester film when the various components are mixed is preferably in the range of 0.6 to 1.2, more preferably in the range of 0.7 to 1.2. If the intrinsic viscosity of the polyester is less than 0.6, the mechanical properties of the resulting film may be lowered. If the polyester exceeds 1.2, the effect of the mechanical properties will not change, and the productivity of the raw material polyester will also be improved. It is not economical because it decreases.

  In addition to the additives mentioned so far, the film according to the present invention may be blended with an ultraviolet absorber, a plasticizer, a pigment, a crystal nucleating agent, a lubricant and the like as required.

As the lubricant, inorganic particles such as silica, titania, mica, talc, calcium carbonate, organic particles such as polymethyl methacrylate (PMMA), styrene-divinylbenzene, formaldehyde resin, silicone resin, polyamideimide, benzoguanamine, or these The slipperiness can be further improved by adding a surface-treated product.
The organic particles or inorganic particles may be added to the base film.
When added to the easy-sliding layer, those having an average particle size of 0.1 to 10.0 μm are preferably added within the range of 50 to 4000 ppm, and when added to the base film, the average particle size is 0.5 to It is preferable to add 30.0 μm in the range of 100 to 3000 ppm.

  The film may be a biaxially stretched film, a uniaxially stretched film, or an unstretched film. Here, the biaxial stretching method may be any of sequential biaxial stretching, simultaneous biaxial stretching, or a combination thereof. In the case of successive biaxial stretching, generally, a method of stretching in the longitudinal direction and then stretching in the transverse direction is adopted, but a method of stretching in the reverse order may be employed. In addition, it is preferable to fix the orientation of the polyester by heat treatment after biaxial stretching, but after biaxial stretching, re-stretching may be performed in the longitudinal direction and / or the width direction before the heat treatment step. Furthermore, the corona discharge treatment is not limited at all on one side or both sides of the film before or after the stretching step.

The film-laminated metal plate of the present invention is recommended to contain a resin and a low molecular weight pure lubricant or a resin, a low molecular weight lubricant and an antistatic agent in the coating layer.
Examples of the resin component include polyester resins, polyamide resins, polyurethane resins, epoxy resins, phenol resins, acrylic resins, polyvinyl acetate resins, polyolefin resins such as polyethylene and polypropylene, and their co-polymers. There are coalesced or modified resins, cellulosic resins, and others. In particular, polyester resins, polyurethane resins, or copolymers thereof exhibit good lubricity when combined with a lubricant, and do not inhibit adhesion with solvents. Use of a water-dispersible material is also preferable from the viewpoint of safety and environmental friendliness.

Low molecular weight lubricants include silicone components, paraffin wax, microwax, polypropylene wax, polyethylene wax, ethylene acrylic wax, stearic acid, behenic acid, 12-hydroxystearic acid, stearic acid amide, oleic acid amide, erucic acid amide, Methylenebisstearic acid amide, ethylene bisstearic acid amide, ethylene bis oleic acid amide, butyl stearate, monoglyceride stearate, pentaerythritol tetrastearate, hydrogenated castor oil, stearyl stearate, siloxane, higher alcohol polymer, stearyl alcohol , Calcium stearate, zinc stearate, magnesium stearate, lead stearate and the like. It is preferable to add at least one of these.
Among them, the addition of a silicone component or low molecular weight polyethylene wax is particularly preferable because it has a stick prevention effect by smoothing the surface of the layer and has a large effect of improving the slipperiness.

  Silicone components refer to organosiloxanes and have properties such as oil, rubber, and resin, which are called silicone oil, silicone rubber, and silicone resin, respectively. Since it has water repellent action, lubrication action, mold release action, etc., it is effective in reducing surface friction when laminated as a film surface layer. In particular, silicone resin is recommended. Silicone resin refers to organopolysiloxane having a three-dimensional network structure, and when it is laminated as a slippery layer on the polyester film surface and then wound up as a roll, transfer to the back surface of the film is less likely to occur. . Furthermore, those having a methyl group as the organic group are excellent in heat resistance and are particularly recommended. Of the silicone resins, polydimethylsiloxane compounds are particularly preferable.

  As content of a silicone component, 10 to 80 weight% is preferable as content in easy-slip layer solid content, Most preferably, it is 40 to 70%. If the content is less than 10% by weight, the effect of improving the slipping property is small, and if it exceeds 80% by weight, the transfer of the coating layer component is likely to occur.

  Further, the silicone component and other lubricants may be used in combination. As the lubricant used in combination, paraffin wax, microwax, polypropylene wax, polyethylene wax, ethylene acrylic wax, stearic acid, behenic acid, 12-hydroxystearic acid, Stearic acid amide, oleic acid amide, erucic acid amide, methylenebis stearic acid amide, ethylene bis stearic acid amide, ethylene bis oleic acid amide, butyl stearate, stearic acid monoglyceride, pentaerythritol tetrastearate, hydrogenated castor oil, stearic acid Examples include stearyl, siloxane, higher alcohol polymers, stearyl alcohol, calcium stearate, zinc stearate, magnesium stearate, lead stearate, etc. It is.

  As antistatic agents, surfactants such as quaternary ammonium salts, fatty acid polyhydric alcohol esters, polyoxyethylene adducts, betaine salts, alanine salts, phosphate salts, sulfonates, polyacrylic acid derivatives, etc. are effective. . In particular, sodium paraffinsulfonate is recommended because it has an antistatic effect and has little adverse effect on lubricity.

As mentioned above, polyester resin, polyurethane resin, or a copolymer thereof is used as a resin component, and a low molecular weight polyethylene wax or a combination of a silicone component and sodium paraffin sulfonate is used, and a squeezed iron can is coated by an in-line coating method. It is particularly recommended to form a slippery layer on the surface of the film.
Here, it is preferable that the coating layer does not contain lubricant particles, and so-called boiling is reduced.
The amount of the coating solution, as the amount present on the film after stretching is preferably 0.002~0.5g / ^{m 2,} more preferably from 0.005~0.2g / ^{m 2.} If it is 0.002 g / m ² or less, the slipperiness and the antistatic effect are reduced, and if it exceeds 0.5 g / m ² , the transparency of the film is lowered and the printability is also lowered.

The film laminated metal plate of the present invention can be produced by laminating a coating layer on the surface layer.
The method for forming the coating layer is not particularly limited as long as it can be uniformly formed on the surface. The method of laminating the resin on the surface layer by melt extrusion, coating of the coating solution during the film forming process (in-line coating), or film Application of a coating solution after film formation (off-line coating) is available. In-line coating is preferred because of the cost and the effect of improving the adhesion between the coating layer and the film because it is subjected to stretching heat treatment after coating, and examples include reverse roll method, air knife method, fountain method, etc. Is mentioned.

  In the film laminated metal plate of the present invention, static electricity causes troubles during processing, for example, wrapping around rolls in manufacturing processes, printing, other secondary processing processes, shocks to human bodies, work efficiency such as difficulty in handling, From the standpoint of preventing these problems, the surface specific resistance value of the surface on the side satisfying the defined μd, logΩ <14. 0 is preferred, more preferably logΩ ≦ 12.0.

  The method for laminating the film onto the metal plate is not particularly limited. For example, a dry lamination method or a thermal lamination method can be employed. Specifically, the metal plate is heated above the melting point of the laminate surface of the film, the film is brought into contact with the surface of the metal plate, and the nip roll is passed in this state. Subsequently, it laminates by making it cool and solidify in a 10-40 degreeC water tank.

  The film lamination may be performed on only one side of the metal plate or on both sides. In the case of double-sided lamination, it may be laminated at the same time or sequentially.

  When the present invention is applied to a two-piece can, in order to remove the orientation of the polyester after laminating, it is preferable to perform a remelt treatment in which it is heated above the melting point of the polyester constituting the film and then rapidly cooled. The degree of orientation by X-ray observation after the remelt treatment is 10% or less, which can be said to be substantially non-oriented. In other words, a biaxially stretched film in which the polyester is in an oriented state is difficult to be plastically deformed or stretched, making it difficult to perform a drawing process for forming the container portion. This is because the delaminating phenomenon of peeling off occurs, torn or torn. On the other hand, if it is substantially non-oriented, it can follow the deformation of the laminated metal plate, so that it can be molded with plastic deformation of the metal like a two-piece can without delaminating or tearing. Because it can.

  The film laminate metal container of the present invention is a metal container formed by appropriately forming the film laminate metal plate of the present invention, and the shape of the container and the method of forming the metal container are not particularly limited. Specifically, a so-called three-piece can in which the top cover is wound and filled with the contents, as well as a two-piece can that is formed by drawing a metal plate to form a container portion can be used.

  The film laminated metal plate of the present invention preferably has a dynamic friction coefficient of 0.150 or less, more preferably 0.120 or less, on the surface of the film having a steel ball loaded with a load of 2 kg in a 150 ° C. environment as a slider. Particularly preferred is 0.100 or less. This is for obtaining releasability from the die during can making. In a highly rigid metal plate such as a steel plate, the temperature at the time of canning tends to rise due to friction at the time of canning. Particularly in the case of an outer film, it is necessary to provide slipperiness at a high temperature to avoid this problem. Here, when the dynamic friction coefficient of the film surface using a steel ball loaded with a load of 2 kg in an environment of 150 ° C. exceeds 0.15, the releasability between the film and the die during can making decreases. As a result, the temperature of the can is raised, and as a result, the die is damaged.

  In the film laminated metal plate of the present invention, it is preferable that the surface roughness of the center plane of the coating layer is 0.03 μm or less.

  In the metal container of the present invention, the film-laminated metal plate of the present invention may be molded so as to be on the inner wall surface side of the metal container or may be molded so as to be on the outer wall surface side. It is a preferred embodiment to form so that

  In the present invention, the metal plate is not particularly limited, but a surface-treated steel plate such as tin free steel, an aluminum plate, an aluminum alloy plate, an aluminum plate or a surface-treated aluminum plate, or the like can be used.

In addition, when carrying out drawing ironing, you may apply | coat a lubricant to the film surface which a punch and die | dye contact as needed.
The film-laminated metal container of the present invention may be subjected to printing or the like as necessary, and may be subjected to a re-melt process after the can making process or the printing process.

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

Various evaluation methods in the present invention are shown below.
(1) Dynamic friction measurement using a steel ball as a slider in a 150 ° C environment (steel ball μ)
Three steel balls (according to JIS B1501 standard. Diameter 12.7 mmΦ) are arranged and fixed in a triangular shape at a measurement point of the remelt aluminum plate so that the distance between the vertices is 25 mm each, A slider (weight = 2.0 kg) was set so as to come into contact with the measurement point at three points (one point at each vertex of each steel ball), and the dynamic friction coefficient when sliding at 200 mm / min was measured.
(2) Molecular weight of film Aluminum was removed from the remelt plate or can product by hydrochloric acid treatment, and 2 mg of the film was sampled. Each was immersed in 0.4 ml of HFIP / chloroform = 2/3 (v / v), dissolved, and then adjusted to 8 ml with chloroform. It filtered with the 0.2 micrometer membrane filter, and used the filtrate for GPC.
Equipment: TOSOH HLC-8220GPC
Column: TSKgel SuperHM-H × 2 + TSKgel SuperH2000
(TOSOH)
Solvent: chloroform / HFIP = 98/2 (v / v),
Flow rate: 0.6 ml / min
Concentration: 0.025%
Temperature: 40 ° C
Detector: UV 254nm
The molecular weight was calculated in terms of standard polystyrene (PS).

(2) Center plane average roughness The remelt film of the remelt steel plate was measured using a surface roughness measuring instrument (Surfcorder ET-30HK, manufactured by Kosaka Laboratory).
Here, the central plane means a plane in which the sum of squares of the deviation between the plane and the cross-section curved surface is equal to the top and bottom and is the minimum.
The center plane average roughness is represented by SRa, the orthogonal coordinate axes X and Y axes are placed on the center plane of the roughness curve, the axis orthogonal to the center plane is the Z axis, and the roughness aspect is f (x, y). When the reference plane sizes Lx and Ly are used, the values given by the following formulas are meant.
_{SRa = 1 / (L x ×} L y) ∫ 0 Lx ∫ 0 Ly | f (x, y) | dx · dy
(3) Molecular weight of film 2 mg of the film was sampled. Each was immersed in 0.4 ml of HFIP / chloroform = 2/3 (v / v), dissolved, and then adjusted to 8 ml with chloroform. It filtered with the 0.2 micrometer membrane filter, and used the filtrate for GPC.
Equipment: TOSOH HLC-8220GPC
Column: TSKgel SuperHM-H × 2 + TSKgel SuperH2000
(TOSOH)
Solvent: chloroform / HFIP = 98/2 (v / v),
Flow rate: 0.6 ml / min
Concentration: 0.025%
Temperature: 40 ° C
Detector: UV 254nm
The molecular weight was calculated in terms of standard polystyrene (PS).
In the case of a remelt metal plate or a can-made product, the aluminum was removed by hydrochloric acid treatment, and only the film was separated to obtain a sample.
In Tables 1 and 2, the molecular weight of the film is expressed as molecular weight A, and the molecular weight of the can product film is expressed as molecular weight B.

(4) Inert particle amount of polyester Cut out as a sample. Using a fluorescent X-ray device (device name: ZSX100e) manufactured by Rigaku Corporation, each sample was measured from the upper and lower surfaces with an analysis diameter of 30 mmΦ, and converted to the amount of inert particles using a calibration curve for PET.

(5) Average particle diameter of inert particles The coating film sample dried overnight in a vacuum dryer is subjected to ion plasma etching, and the inert particles contained in the (I) and (II) layers of the base film. The particles were exposed. Subsequently, using a scanning electron microscope (SEM), the magnification was appropriately changed according to the size of the particles, and photography was performed. The equivalent circle diameter of at least 100 particles or more was obtained with an image processing apparatus, and divided by the number of particles to obtain a number-based average particle diameter (μm). When the contrast of the photographed particle was weak, the outline of the particle was traced on the OHP film with an ultra-fine magic pen, and the equivalent circle diameter of the particle was obtained with the image processing apparatus.
In addition, powder particles before adding particles to polyester are coated with a double-sided tape on a SEM sample table, and the powder is thinly deposited thereon. After carbon deposition, the particle size is measured using a scanning electron microscope (SEM). In accordance with this, the magnification was appropriately changed to take a picture. The equivalent circle diameter of at least 100 particles or more was obtained with an image processing apparatus, and divided by the number of particles to obtain a number-based average particle diameter (μm).

(6) Antistatic property The antistatic property was measured under the conditions of an applied voltage of 500 V, 23 ° C., and 65% RH with a surface resistor (a specific resistance measuring device manufactured by KAWAGUCHI ERECTRI WORKS).

(7) Can-making ability After forming a laminated metal plate into a cup by drawing, 300 cans can be continuously made by redrawing and ironing under the following forming conditions at a speed of 80 cans / minute, and the galling that occurs on the outer surface of the formed can The ratio of the number of generated cans was set as the following evaluation criteria, and ○ was evaluated as practical.
As used herein, galling occurs during can making, is caused by contact between the outer surface of the forming can and the forming jig, and is often linear.
○: Scratch generation rate of the outer surface of the can 5% or less Δ: Scratch generation rate of the outer surface of the can 30% to 6%
X: Scratch generation rate of outer surface of can 31% or more (molding conditions) Blank diameter: 152 mm, drawing ratio: 1.60, redrawing ratio: 1.44, ironing rate of can body side wall: 56% [however, ironing rate (T ₀ −t ₁ ) / t ₀ × 100, t ₀ : thickness before processing, t ₁ : calculated from the thickness of the can barrel side wall after processing]
It was drawn and ironed.

Next, the kind and content of polyester used for the Example and the comparative example are demonstrated.
A: Polyethylene terephthalate (IV = 0.73)
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 and 0.05 mol% of magnesium acetate as the Mg element are charged with respect to the acid component, and nitrogen is introduced while stirring to bring the pressure in the system to 0.3 MPa. The esterification reaction was carried out while distilling out the water produced at a temperature of 230 ° C. to 250 ° C. outside the system. After completion of the reaction, 0.04 mol% of trimethyl phosphate as P amount was added at 250 ° C., the pressure was gradually reduced while the temperature was raised, and a polycondensation reaction was performed under a vacuum of 275 ° C. and 1.0 hPa or less. The obtained intrinsic viscosity 0.73 polyester (PET) resin was used.
B: Polyethylene terephthalate / isophthalate (10 mol% of ethylene isophthalate repeating unit, IV = 0.74, 0.5% by weight of ethylene terephthalate cyclic trimer).
90 parts by weight of terephthalic acid, 10 parts by weight of isophthalic acid, 82 parts by weight of ethylene glycol (ethylene glycol / total acid component) were added to a reactor equipped with an inlet, a thermometer, a pressure gauge, a distillation tube with a rectifying column, and a stirring blade. Molar ratio = 2.2), 0.05 mol% of germanium oxide as the Ge element and 0.05 mol% of the magnesium acetate as the Mg element are charged with respect to the acid component, and nitrogen is introduced with stirring to introduce pressure in the system. Was maintained 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. out of the system. After completion of the reaction, at 250 ° C., 0.04 mol% of trimethyl phosphate is added as the P amount, the pressure is gradually reduced while the temperature is raised, and a polycondensation reaction is performed under a vacuum of 275 ° C. and 1.0 hPa or less. Obtained. Subsequently, this polyester was heat-treated at 200 ° C. under a vacuum of 1.0 hPa for 12 hours to obtain PET-I (10). The polyester obtained had an intrinsic viscosity of 0.74 (dl / g) and an ethylene terephthalate cyclic trimer of 0.5% by weight.
C: Polytetramethylene terephthalate-polytetramethylene oxide block copolymer polyester In a reactor equipped with an inlet, a thermometer, a pressure gauge, a distillation tube with a rectifying column, and a stirring blade, with respect to 100 parts by weight of dimethyl terephthalate , 75 parts by weight of 1,4-butanediol, 75 parts by weight of polytetramethylene glycol (average molecular weight 1000), and 0.05 parts by weight of normal butyl titanate were distilled out of the system at 190 ° C. to 230 ° C. The transesterification reaction was carried out. After completion of the reaction, 0.05 part by weight of tetranormal butyl titanate and 0.025 part by weight of phosphoric acid were added, and a polycondensation reaction was performed at 250 ° C. under reduced pressure (1.0 hPa or less). Polytetramethylene terephthalate-polytetramethylene oxide block copolymer, polytetramethylene oxide ratio 40% by weight, intrinsic viscosity 0.75). (Brand GP301, manufactured by Toyobo)
D: Polyester containing 5% by weight of antioxidant 5 parts by weight of phenolic antioxidant (Irganox 1010, manufactured by Ciba Geigy) is melt-kneaded with 95 parts by weight of polyester A, and oxidized. A polyester resin (D) containing 5% of an inhibitor was obtained.

Example 1
[Preparation of coating solution]
Aqueous dispersion of polyester resin (TIE51 made by Takemoto Yushi) 26 wt%, polyethylene wax aqueous emulsion (HYTEC E-4BS made by Toho Chemical Co., Ltd.) 8 wt%, antistatic agent aqueous solution (TB214 made by Matsumoto Yushi) 2 wt%, water 34 wt% and IPA 30 wt% were mixed to prepare a coating solution.
[Production of polyester film]
Polyester A / B / C / D = 42/50/4/4 (wt%) as a raw material was dried at 100 ° C. for 24 hours, melted at 270 ° C. using a single screw extruder, and then layered from a T die. Then, the sheet was extruded on a cooling roll to obtain an unstretched sheet. After the unstretched sheet is stretched 3.3 times in the longitudinal direction at a preheating temperature of 80 ° C. and a stretching temperature of 100 ° C., the coating liquid prepared above is applied by an air knife method and heated until the film temperature reaches 70 ° C. Further, the film was stretched 3.7 times in the transverse direction at a stretching temperature of 100 ° C. with a tenter and then heat treated at 180 ° C. for 8 seconds to obtain a polyester film having a coating amount of 0.02 g / m ² and a thickness of 10 μm.

[Production of film-laminated metal plate]
After laminating and passing between the nip rolls so that the uncoated surface of the polyester film prepared above and the steel plate are in contact with both surfaces of the preheated steel plate, heat treatment is performed, and immediately in a 10-40 ° C. water tank. Then, the steel plate was quickly cooled to obtain a steel plate laminated on both sides. At the time of laminating, there was no initial adhesion, tension fluctuation, winding around a nip roll, etc., and the laminating suitability of the laminated film of this example was good.
Next, the film-laminated steel plate was subjected to 90 Sec heat treatment at 270 ° C. and then air-cooled and further quenched in water to prepare a remelt steel plate. In remelting, there was no reduction in molecular weight, and a remelting plate having a good dynamic friction coefficient using a steel ball as a slider under an environment of 150 ° C. was obtained.

[Production of film-laminated metal container]
The remelted steel plate produced above was drawn and ironed so that the thickness reduction rate was 30% to form a film laminated metal container. The obtained can product had no film molecular weight reduction, a good dynamic friction coefficient using a steel ball in a 150 ° C. environment as a slide, no galling or tearing on the outer surface, and excellent can manufacturing performance.

(Example 2)
A film for covering a squeezed iron can was obtained in the same manner as in Example 1 except that an aqueous dispersion of urethane resin (Hydran HW345 manufactured by Dainippon Ink Industries, Ltd.) was added instead of the aqueous dispersion of polyester resin.

(Example 3)
In Example 1, 6 parts by weight of an aqueous emulsion of microcrystalline wax (manufactured by Nopco 1245-M-SN San Nopco) was added in place of the aqueous emulsion of polyethylene wax, and squeezing was carried out in the same manner except that the amount of water was 36% by weight. A can coating film was obtained.

Example 4
A film for covering a squeezed iron can was obtained in the same manner as in Example 2 except that the antistatic agent was changed to Riquemar A (manufactured by Riken Vitamin).

(Comparative Example 1)
A film for squeezing and ironing can coating was obtained in the same manner as in Example 1 except that the coating solution was not applied.

(Comparative Example 2)
In Example 1, a squeezed and ironing can coating film was obtained in the same manner except that polyethylene wax was not added to the coating solution.

(Comparative Example 3)
A squeezed and ironing can coating film was obtained in the same manner as in Example 2 except that the coating amount was 0.6 g / m ² .

(Comparative Example 4)
A film for covering a squeezed iron can was obtained in the same manner as in Example 1, except that polyester A / B / C / D = 45.9 / 50/4 / 0.1 (% by weight) was used as a raw material.

(Comparative Example 5)
A film for covering a squeezed iron can was obtained in the same manner as in Example 1 except that A / B / C / D / E = 10/76/4/4 (% by weight) was used as a raw material.

Next, the kind and content of polyester used in further examples and comparative examples will be described.
A: Polyethylene terephthalate (IV = 0.73)
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 and 0.05 mol% of magnesium acetate as the Mg element are charged with respect to the acid component, and nitrogen is introduced while stirring to bring the pressure in the system to 0.3 MPa. The esterification reaction was carried out while distilling out the water produced at a temperature of 230 ° C. to 250 ° C. outside the system. After completion of the reaction, 0.04 mol% of trimethyl phosphate as P amount was added at 250 ° C., the pressure was gradually reduced while the temperature was raised, and a polycondensation reaction was performed under a vacuum of 275 ° C. and 1.0 hPa or less. The obtained intrinsic viscosity 0.73 polyester (PET) resin was used.
B: Polyethylene terephthalate / isophthalate (10 mol% of ethylene isophthalate repeating unit, IV = 0.74, 0.5% by weight of ethylene terephthalate cyclic trimer).
90 parts by weight of terephthalic acid, 10 parts by weight of isophthalic acid, 82 parts by weight of ethylene glycol (ethylene glycol / total acid component) were added to a reactor equipped with an inlet, a thermometer, a pressure gauge, a distillation tube with a rectifying column, and a stirring blade. Molar ratio = 2.2), 0.05 mol% of germanium oxide as the Ge element and 0.05 mol% of the magnesium acetate as the Mg element are charged with respect to the acid component, and nitrogen is introduced with stirring to introduce pressure in the system. Was maintained 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. out of the system. After completion of the reaction, at 250 ° C., 0.04 mol% of trimethyl phosphate is added as the P amount, the pressure is gradually reduced while the temperature is raised, and a polycondensation reaction is performed under a vacuum of 275 ° C. and 1.0 hPa or less. Obtained. Subsequently, this polyester was heat-treated at 200 ° C. under a vacuum of 1.0 hPa for 12 hours to obtain PET-I (10). The polyester obtained had an intrinsic viscosity of 0.74 (dl / g) and an ethylene terephthalate cyclic trimer of 0.5% by weight.
C: Polytetramethylene terephthalate-polytetramethylene oxide block copolymer polyester In a reactor equipped with an inlet, a thermometer, a pressure gauge, a distillation tube with a rectifying column, and a stirring blade, with respect to 100 parts by weight of dimethyl terephthalate , 75 parts by weight of 1,4-butanediol, 75 parts by weight of polytetramethylene glycol (average molecular weight 1000), and 0.05 parts by weight of normal butyl titanate were distilled out of the system at 190 ° C. to 230 ° C. The transesterification reaction was carried out. After completion of the reaction, 0.05 part by weight of tetranormal butyl titanate and 0.025 part by weight of phosphoric acid were added, and a polycondensation reaction was performed at 250 ° C. under reduced pressure (1.0 hPa or less). Polytetramethylene terephthalate-polytetramethylene oxide block copolymer, polytetramethylene oxide ratio 40% by weight, intrinsic viscosity 0.75). (Brand GP301 manufactured by Toyobo)
D: Polyester containing 5% by weight of antioxidant 5 parts by weight of phenolic antioxidant (Irganox 1010, manufactured by Ciba Geigy) is melt-kneaded with 95 parts by weight of polyester A, and oxidized. A polyester resin (D) containing 5% of an inhibitor was obtained.

(Example 5)
[Preparation of coating solution]
Solid content of dimethyl silicone resin (SE4005 manufactured by Nissin Chemical Laboratory) is 70% by weight in the total solid content in the coating liquid, and solid content of aqueous dispersion of copolymer polyester resin (AGN709 manufactured by Toyobo) is 20% in solid content. An IPA-water solution containing 10% by weight of a solid content of acetylene glycol derivative (Surfinol 485 manufactured by Shin-Etsu Chemical Co., Ltd.) by weight was used as a coating solution (coating solution-1).
[Production of polyester film]
Polyester A / B / C / D = 42/50/4/4 (wt%) as a raw material was dried at 100 ° C. for 24 hours, melted at 270 ° C. using a single screw extruder, and then layered from a T die. Then, the sheet was extruded on a cooling roll to obtain an unstretched sheet. After the unstretched sheet is stretched 3.3 times in the longitudinal direction at a preheating temperature of 80 ° C. and a stretching temperature of 100 ° C., the coating liquid prepared above is applied by an air knife method and heated until the film temperature reaches 70 ° C. Further, the film was stretched 3.7 times in the transverse direction at a stretching temperature of 100 ° C. with a tenter and then heat-treated at 180 ° C. for 8 seconds to obtain a polyester film having a coating amount of 0.01 g / m ² and a thickness of 10 μm.

[Production of film-laminated metal plate]
After laminating and passing between nip rolls so that the uncoated surface of the polyester film prepared above and the steel plate are in contact with both surfaces of the preheated aluminum plate, heat treatment is performed, and immediately in a 10-40 ° C. water tank. Then, the steel plate was quickly cooled to obtain a steel plate laminated on both sides. At the time of laminating, there was no initial adhesion, tension fluctuation, winding around a nip roll, etc., and the laminating suitability of the laminated film of this example was good.
Next, the film-laminated steel plate was subjected to 90 Sec heat treatment at 270 ° C. and then air-cooled and further quenched in water to prepare a remelt steel plate. In remelting, there was no reduction in molecular weight, and a remelting plate having a good dynamic friction coefficient using a steel ball as a slider under an environment of 150 ° C. was obtained.

[Production of film-laminated metal container]
The remelted steel plate produced above was drawn and ironed so that the thickness reduction rate was 30% to form a film laminated metal container. The obtained can product had no film molecular weight reduction, had a good coefficient of dynamic friction using a steel ball in a 150 ° C. environment as a slider, had no outer surface tearing or galling, and was excellent in can manufacturing performance.

(Example 6)
In Example 5, the solid content of the dimethyl silicone resin (SE4005 manufactured by Nissin Chemical Laboratory) was 70% by weight of the total solid content in the coating solution, and the solid content of the aqueous dispersion of copolymerized polyester resin (Vylonal MD1500, manufactured by Toyobo). 10% by weight of a solid content of 10% by weight of a solid content of a polyoxyalkylene type surfactant (Surf SN Wet 980 manufactured by San Nopco), and an IPA-water solution as a coating solution (coating solution-2) By the same method as in Example 5, a squeezed and ironing can coating film was obtained.

(Comparative Example 6)
A film for squeezing and ironing can coating was obtained in the same manner as in Example 5 except that the coating solution was not applied.

(Comparative Example 7)
A squeezed and ironing can coating film was obtained in the same manner as in Example 6 except that the coating amount was 0.6 g / m ² .

(Comparative Example 8)
A film for covering a squeezed iron can was obtained in the same manner as in Example 5 except that polyester A / B / C / D = 45.9 / 50/4 / 0.1 (% by weight) was used as a raw material.

(Comparative Example 9)
A film for covering a squeezed iron can was obtained in the same manner as in Example 5 except that A / B / C / D / E = 10/76/4/4 (% by weight) was used as a raw material.

  The results are shown in Tables 1 and 2.

  The metal laminating film of the present invention is excellent in moldability in can manufacturing and can be used as a laminate film for two-piece cans, and contributes to the industry.

Claims (5)

A metal plate obtained by laminating a polyester film composed of a polyester base layer and a coating layer, wherein the polyester base layer is mainly composed of copolymerized PET having a melting point of 230 to 245 ° C. and derived from a polyoxyalkylene glycol component. 2 to 20 mol% of alkylene oxide units having a number of 2 or more are contained with respect to the total acid amount of the polyester resin composition, the degree of orientation is 10% or less, and the film is present on a metal substrate. The polyester resin composition has a weight average molecular weight (B) of 40,000 or more after the film is re-melted by heat above its melting point (so-called remelt treatment) and rapidly cooled, and the thickness of the coating layer is 0.002 to 0.002 0.5 g / m ² , containing a low molecular weight lubricant component, and a steel ball loaded with a load of 2 kg in a 150 ° C. environment. A film-laminated metal plate, wherein the surface layer has a dynamic friction coefficient of 0.15 or less.   2. The film-laminated metal plate according to claim 1, wherein the coating layer of the film-laminated metal plate has a center surface roughness of 0.02 μm or less.   The film-laminated metal plate according to claim 1, wherein the thermoplastic polyester resin composition contains 0.01 to 1.0% by weight of an antioxidant.   2. The film laminated metal plate according to claim 1, wherein the low molecular weight lubricant is a low molecular weight polyethylene wax or a silicone component.   A metal can obtained by making the film-laminated metal plate according to claim 4.