JP5234311B2 - Laminate for drawing and ironing - Google Patents

Description

The present invention relates to a drawing and ironing laminates for obtaining the seamless can.

  Seamless cans used for food cans, etc., depending on the manufacturing method, squeezed iron cans (DI cans: Draw and Ironed Can), squeeze cans (DR cans: Draw Can) There are redrawn cans (DRD cans: Draw and Redrawn Can), bottle-type cans that form a drinking mouth by drawing (DR processing: Draw processing) after drawing and ironing (DI processing). Among these seamless cans, DI cans and bottle-type cans are widely used in beverage cans such as tea, beer, juice, carbonated drinks because of their cosmetics and thin and light weight.

  However, in DI processing, it is necessary to use a large amount of lubricating oil and coolant, degrease, wash, and surface treatment, then spray paint the inner surface and bake and dry. The load on the environment such as this problem was also large.

  Therefore, in order to perform DI processing without using a coolant, a laminated plate (hereinafter simply referred to as a laminated plate) in which a thermoplastic polyester resin film having high mechanical strength and high impact resistance is laminated on both sides of a metal plate is used. It has been proposed to use it for DI processing. In general, to produce seamless cans from laminates, drawing, ironing, and bottom processing are performed, and then, if necessary, predetermined heat treatment, opening trimming, printing, baking, neck flange processing, drinking The mouth is processed.

Here, when DI processing is performed on the above laminated plate, the frictional resistance between the laminated resin film and the processing tool is a major cause of molding defects such as breakage of the can body portion. A method of applying is used. Also, a method of dispersing wax in a resin film has been proposed in order to impart lubricity to the laminate itself (see, for example, Patent Document 1).
JP 2002-347170 A

  However, the wax applied to the surface of the polyester resin coating layer (resin film layer) of the laminate is reduced by the heat generated in DI processing, and gradually decreases as the molding process proceeds. Further, the lubricity of the surface of the polyester resin coating layer of the laminate is lowered, and there is a high possibility that molding defects such as breakage of the can body portion may occur. This problem was more prominent as the processing rate was higher.

  Moreover, the method of dispersing wax in the polyester resin coating layer (resin film layer) of the laminate as described in Patent Document 1 described above is obtained when the laminate is obtained by directly extruding the resin from the T-die to the metal plate. Is effective. However, such a method can be applied to the resin in the case where the heat treatment is performed at a temperature close to or higher than the melting point after the extrusion of the extruded polyester resin, the winding of the resin after heat setting, and the lamination of the resin to the metal plate. Thermal history may be more excessive than when the resin is extruded directly from the T-die to the metal plate, and some of the wax dispersed in the resin disappears, resulting in insufficient lubricity and poor molding. There was something to do. In addition, when the amount of wax added to the resin is increased, there is a problem that appearance defects such as precipitation of wax components and boiling (micro-foaming) of the film surface occur in a heating process such as an oven in the can manufacturing process. It was.

  In addition, when the adhesive layer is not provided between the resin film and the metal plate, the resin film in the portion near the opening edge of the can is peeled off from the metal plate due to a decrease in adhesion between the resin film and the metal plate. Further, if the can molding continues, the peeled resin film breaks, and the metal plate not coated with the resin film and the forming tool are in direct contact with each other, increasing the frictional resistance between them and opening the can end. There was also a problem that cracks and breaks occurred in the portion close to the edge, resulting in molding defects such as an ear-cut phenomenon.

Therefore, the present invention ensures DI workability by always providing lubricity to the laminate plate itself and the surface of the can during the can making process through the can making process while ensuring the adhesion between the metal plate and the resin film. It aims at providing the laminated board for drawing ironing which has the moldability excellent in the can manufacturing process.

The present invention is a drawn and ironed laminate including a metal plate and a thermoplastic polyester resin film laminated on both sides of the metal plate, the adhesive between the metal plate and at least one thermoplastic polyester resin film layer is formed, the adhesive layer includes a hydrocarbon compound wax and a binder resin, a hydrocarbon compound wax is present only in contact Chakusochu, incorporated into the thermoplastic polyester resin film by heat treatment This is a laminated board for drawing and ironing .

In the processing laminates according drawing and ironing the present invention, it is preferable crystallinity that will be calculated from the differential scanning calorimetry of the thermoplastic polyester resin film is 50% or less. Also, hydrocarbon compounds wax in the adhesive layer preferably comprises a polyolefin wax. Moreover, it is preferable that content of the hydrocarbon compound wax in an contact bonding layer is 0.1 to 5 mass%. The binder resin in the adhesive layer preferably contains at least one resin selected from the group consisting of epoxy resins, polyester resins, and polyurethane resins. Moreover, it is preferable that the dynamic friction coefficient in the surface of the said thermoplastic polyester resin film currently formed on the contact bonding layer is 0.2 or less.

  According to the present invention, in a laminate including a metal plate and a thermoplastic polyester resin film laminated on both sides thereof, an adhesive layer is formed between the metal plate and at least one side of the thermoplastic polyester resin. A laminated sheet containing a binder resin and a hydrocarbon compound wax is used for manufacturing a metal can. As a result, the wax bleed out from the binder resin of the adhesive layer gives lubricity to the surface of the laminate as a result of heat treatment at a temperature near or above the melting point of the polyester resin forming the film of the laminate. For this reason, it is possible to reduce the frictional resistance between the processing tool and the surface of the laminated plate during DI processing, and to obtain stable DI workability.

  In addition, the present invention has one feature in the location where the wax is present in the laminated plate after the lamination of the metal plate and the resin film and before the heat treatment. That is, in the conventional laminate in which the wax is dispersed in the polyester resin forming the film, the wax in the resin film is extremely reduced by the subsequent heat treatment. In addition, even if the wax content in the resin film is increased to 5% by mass or more in anticipation of a decrease in wax, the lubricity is not further improved, and if the wax content is increased to more than 5% by mass, heat treatment is performed. This causes poor appearance such as roughness after and after DI processing.

  On the other hand, in the laminated board of the present invention in which wax is dispersed in the binder resin of the adhesive layer between the film and the metal plate, the binder resin is obtained by heat treatment at a temperature near or higher than the melting point of the polyester resin thereafter. The wax inside bleeds out and enters the resin film. As a result, the content of the wax in the resin film after the heat treatment is higher in the laminate of the present invention than in the conventional laminate. For this reason, the laminated board of this invention can have DI processability more stable than the conventional laminated board.

  Further, in the present invention, in the heat treatment during the can making process, the wax in the adhesive layer of the laminate is newly bleed out and replenished into the resin film. Even if various molding processes according to the can shape are provided, such as molding, the lubricity of the surface of the laminate is maintained, and good moldability is obtained.

That is, according to the present invention, it is possible to provide a drawn and ironed laminate having excellent formability in a can manufacturing process.

  The laminated board concerning this invention is the laminated board 10 containing the thermoplastic polyester resin film 12 laminated | stacked on both sides of the metal plate 11 and the metal plate 11 with reference to FIG. An adhesive layer 13 is formed between the thermoplastic polyester resin film 12 on one side, and the adhesive layer 13 includes a binder resin and a hydrocarbon compound wax.

  In the laminated plate according to the present invention, an adhesive layer 13 is formed between the metal plate 11 and at least one thermoplastic polyester resin film 12, and the adhesive layer 13 contains a binder resin and a hydrocarbon compound wax. Then, after the thermoplastic polyester resin film 12 is laminated on the metal plate 11 with the adhesive 13 interposed, the thermoplastic polyester resin film 12 is heated to a temperature equal to or higher than the melting point, whereby the adhesive layer 13 Since the hydrocarbon compound wax is bleed out into the molten thermoplastic polyester resin film 12, the coefficient of dynamic friction of the surface of the thermoplastic polyester resin film 12 on the adhesive layer 13 is reduced, and the laminate is subjected to DI processing. Therefore, good DI processability can be obtained.

  In the laminate according to the present invention, the degree of crystallinity calculated from the differential scanning calorimetry (DSC) measurement of the thermoplastic polyester resin film is preferably 50% or less. When the crystallinity of the thermoplastic polyester resin film exceeds 50%, the stretchability of the thermoplastic polyester resin film is remarkably inferior, and microcracks (microcracks) are generated in the resin film during DI processing. The reduction of the crystallinity of the resin film, that is, the amorphization of the resin film, is that the resin film laminated on the laminate is at a temperature higher than the melting point, preferably at a temperature of 5 ° C. or higher, more preferably from the melting point. It can be carried out by heating to a temperature of 25 ° C. or higher and then rapidly cooling.

The crystallinity of the resin film can be calculated by X-ray diffraction, heat of fusion measurement, density measurement, etc. The crystallinity of the thermoplastic polyester resin film of the laminate according to the present invention is measured by heat of fusion by DSC. The one calculated from Specifically, the crystallinity of the resin film in the present invention can be specifically determined by the following procedure.
[1] The laminate is immersed in a 7% by mass hydrochloric acid aqueous solution, and the resin film is peeled off from the metal plate.
[2] Wash the removed resin film thoroughly with pure water.
[3] After being placed in a room temperature (for example, 25 ° C.) place and dried for 1 day, 5 mg of a resin film is collected and subjected to thermal analysis (DSC 1st run).
[4] Thermal analysis (DSC 1st run) is performed by measuring the amount of heat generated by crystallization that occurs in the temperature rising process at a temperature rising rate of 25 ° C. to 10 ° C./min. This calorific value is A (unit: mJ / mg).
[5] The resin film subjected to the thermal analysis in [4] above is heated to a temperature equal to or higher than the melting point, and then rapidly submerged in water and placed in a place at room temperature (for example, 25 ° C.) and dried for one day.
[6] Thereafter, thermal analysis (DSC 2nd run) is performed under the same conditions as in [4] above, and the amount of heat generated by crystallization that occurs in the same temperature region as in the measurement of the 1st run is measured. This calorific value is defined as B (unit: mJ / mg).
[7] From the above calorific values A and B, the following equation (2)
Crystallinity (%) = 100 × (B−A) / B (2)
To calculate the degree of crystallinity (%).

  In the laminated plate according to the present invention, the metal plate 11 is not particularly limited as long as it is a metal plate used for a seamless can, but an aluminum plate, an aluminum alloy plate, a steel plate and the like are preferable from the viewpoint of excellent DI processability.

  In the laminated sheet according to the present invention, the thermoplastic polyester resin film 12 is not particularly limited, but from the viewpoint of mechanical strength, heat resistance, barrier properties, flavor retention (performance for maintaining the flavor of the contents), and the like. Polyester resin composed of homopolymers such as terephthalate (PET) resin, polybutylene terephthalate (PBT) resin, polyethylene naphthalate resin, etc., isophthalic acid copolymerized PET resin obtained by copolymerizing terephthalic acid with isophthalic acid (also referred to as I-PET resin) And a mixed polyester resin such as a PBT / PET blend resin (also referred to as PBT / PET resin) in which a polybutylene terephthalate resin and a polyethylene terephthalate resin are mixed. The resin film layer may be a single layer or a multilayer.

  In the laminated board according to the present invention, the hydrocarbon compound wax contained in the adhesive layer 13 refers to a wax formed of a hydrocarbon compound, such as a synthetic wax such as polyethylene wax and polyethylene oxide wax, paraffin wax, microwax. Examples include petroleum waxes such as crystallin wax, animal plant waxes such as lanolin wax, carnauba wax, and the like. Such a hydrocarbon compound wax preferably includes a polyolefin wax such as polyethylene wax or oxidized polyethylene wax, from the viewpoint of a large effect of reducing the dynamic friction coefficient of the surface of the thermoplastic polyester resin film 12, and includes polyethylene wax. It is more preferable.

  Further, the content of the hydrocarbon compound wax in the adhesive layer 13 is preferably 0.1% by mass or more and 5% by mass or less, and more preferably 0.5% by mass or more and 4% by mass or less. If the wax content is less than 0.1% by mass, the effect of reducing the dynamic friction coefficient of the surface of the thermoplastic polyester resin film 12 is small, and if it exceeds 5% by mass, the lubricity is not improved any more. If the amount is more than% by mass, it may cause appearance defects such as roughness after heat treatment and DI processing.

  Here, the kind and content of the hydrocarbon compound wax contained in the adhesive layer 13 can be measured by IR (infrared absorption) spectrum measurement. Specifically, the thermoplastic polyester resin film 12 of the laminated plate 10 is peeled off from the metal plate 11, the adhesive layer 13 attached to the thermoplastic polyester resin film 12 or the metal plate 11 is taken out, and an organic solvent such as hexane is removed. The hydrocarbon compound wax in the adhesive layer 13 is extracted and the IR spectrum of this hydrocarbon compound wax is measured.

  In the laminate according to the present invention, the binder resin contained in the adhesive layer 13 is not particularly limited, but from the viewpoint of enhancing the adhesion between the metal plate 11 and the thermoplastic polyester resin film 12, an epoxy resin, a polyester resin, and It is preferable to include at least one resin selected from the group consisting of polyurethane resins.

  In the laminated board according to the present invention, the coefficient of dynamic friction on the surface of the thermoplastic polyester resin film 12 formed on the adhesive layer 13 is 0.2 or less, which reduces the frictional resistance applied to the laminated board during DI processing. From the viewpoint of increasing the yield in DI processing, it is preferable.

  The laminated plate according to the present invention is a laminated plate 10 including a metal plate 11 and a thermoplastic polyester resin film 12 laminated on both sides of the metal plate 11, and the metal plate 11 and at least one side of the thermoplastic polyester resin film. Since the adhesive layer 13 is formed between the two layers, specifically, the adhesive layer 13 has one of the following three laminated structures.

(Embodiment A)
Referring to FIG. 1 (a), a laminated plate 10 of Embodiment A includes an adhesive layer 13 and a thermoplastic polyester resin film on an inner surface 11i of a metal plate 11 (referred to as a surface that becomes an inner surface of a can after molding, hereinafter the same). 12 are sequentially laminated, and a thermoplastic polyester resin film 12 is laminated on the outer surface 11e of the metal plate 11 (referred to as a surface that becomes the outer surface of the can after molding, hereinafter the same). That is, in the laminated plate 10 of Embodiment A, the thermoplastic polyester resin film 12, the adhesive layer 13, the metal plate 11, and the thermoplastic polyester resin film 12 are sequentially laminated from the inner surface 10i to the outer surface 10e of the laminated plate. Here, the adhesive layer 13 laminated on the inner surface 11i of the metal plate 11 contains a binder resin and a hydrocarbon compound wax.

  In the laminated board 10 of Embodiment A, it is as above-mentioned that it is preferable that the crystallinity degree of the thermoplastic polyester resin film 12 is 50% or less. Further, the hydrocarbon compound wax in the adhesive layer 13 preferably contains a polyolefin wax, and the content of the hydrocarbon compound wax is preferably 0.1% by mass or more and 5% by mass or less as described above. As described above, the binder resin in the adhesive layer 13 preferably includes at least one resin selected from the group consisting of epoxy resins, polyester resins, and polyurethane resins. Further, as described above, it is preferable that the dynamic friction coefficient on the surface of the thermoplastic polyester resin film 12 formed on the adhesive layer 13 is 0.2 or less.

(Embodiment B)
With reference to FIG. 1B, in the laminated plate 10 of Embodiment B, a thermoplastic polyester resin film 12 is laminated on the inner surface 11 i of the metal plate 11, and the adhesive layer 13 and the thermoplastic polyester are formed on the outer surface 11 e of the metal plate 11. Resin films 12 are sequentially laminated. That is, in the laminated plate 10 of Embodiment B, the thermoplastic polyester resin film 12, the metal plate 11, the adhesive layer 13, and the thermoplastic polyester resin film 12 are laminated in order from the inner surface 10i to the outer surface 10e of the laminated plate. Here, the adhesive layer 13 laminated on the outer surface 11e of the metal plate 11 contains a binder resin and a hydrocarbon compound wax.

  In the laminated board 10 of Embodiment B, it is as above-mentioned that it is preferable that the crystallinity degree of the thermoplastic polyester resin film 12 is 50% or less. Further, the hydrocarbon compound wax in the adhesive layer 13 preferably contains a polyolefin wax, and the content of the hydrocarbon compound wax is preferably 0.1% by mass or more and 5% by mass or less as described above. As described above, the binder resin in the adhesive layer 13 preferably includes at least one resin selected from the group consisting of epoxy resins, polyester resins, and polyurethane resins. Further, as described above, it is preferable that the dynamic friction coefficient on the surface of the thermoplastic polyester resin film 12 formed on the adhesive layer 13 is 0.2 or less.

(Embodiment C)
With reference to FIG. 1C, in the laminated plate 10 of Embodiment C, the adhesive layer 13 and the thermoplastic polyester resin film 12 are sequentially laminated on the inner surface 11 i of the metal plate 11, and the adhesive layer is formed on the outer surface 11 e of the metal plate 11. 13 and a thermoplastic polyester resin film 12 are sequentially laminated. That is, in the laminated plate 10 of Embodiment C, the thermoplastic polyester resin film 12, the adhesive layer 13, the metal plate 11, the adhesive layer 13, and the thermoplastic polyester resin film 12 are laminated in order from the inner surface 10i to the outer surface 10e of the laminated plate. ing. Here, the adhesive layer 13 laminated on the inner surface 11i and the outer surface 11e of the metal plate 11 contains a binder resin and a hydrocarbon compound wax.

  In the laminated board 10 of Embodiment C, it is as above-mentioned that it is preferable that the crystallinity degree of the thermoplastic polyester resin film 12 is 50% or less. Further, the hydrocarbon compound wax in the adhesive layer 13 preferably contains a polyolefin wax, and the content of the hydrocarbon compound wax is preferably 0.1% by mass or more and 5% by mass or less as described above. As described above, the binder resin in the adhesive layer 13 preferably includes at least one resin selected from the group consisting of epoxy resins, polyester resins, and polyurethane resins. Further, as described above, it is preferable that the dynamic friction coefficient on the surface of the thermoplastic polyester resin film 12 formed on the adhesive layer 13 is 0.2 or less.

  Based on the following examples and comparative examples, a laminated plate according to the present invention, a seamless can obtained by DI processing of the laminated plate, and a manufacturing method thereof will be specifically described. Here, the physical property of the produced laminated board was evaluated by the following test methods.

<Test method>
<Crystallinity of laminated resin film>
The laminated plate is heated to a temperature 15 ° C. higher than the melting point of the resin film laminated on the inner and outer surfaces of the laminated plate, and then forcedly cooled to 60 ° C. or less within 5 seconds by blowing air at about room temperature (25 ° C.). The resin film laminated on the inner and outer surfaces of the laminate was made amorphous. The crystallinity of the laminated resin film was calculated according to the following procedure.
[1] The laminate was immersed in a 7% by mass hydrochloric acid aqueous solution, and the resin film was peeled off from the metal plate.
[2] The peeled resin film was thoroughly washed with pure water.
[3] After being placed in a room temperature (25 ° C.) place and dried for 1 day, 5 mg of a resin film was collected and subjected to thermal analysis (DSC 1st run).
[4] In thermal analysis (DSC 1st run), the amount of heat generated by crystallization that occurred when the temperature was raised from 25 ° C. to 10 ° C./min was measured. The calorific value was A (unit: mJ / mg).
[5] The resin film subjected to the thermal analysis of [4] above was heated to a temperature equal to or higher than the melting point, quenched and submerged in water, placed in a room temperature (25 ° C.) state, and dried for 1 day.
[6] Thereafter, thermal analysis (DSC 2nd run) was performed under the same conditions as in [4] above, and the amount of heat generated by crystallization was measured. This calorific value was defined as B (unit: mJ / mg).
[7] From the above calorific values A and B, the following equation (2)
Crystallinity (%) = 100 × (B−A) / B (2)
Was used to calculate the degree of crystallinity (%).

<Appearance of laminated resin film>
The laminated plate was heated to a temperature 15 ° C. higher than the melting point of the resin film laminated on the inner and outer surfaces of the laminated plate, and then forcedly cooled to 60 ° C. or less within 5 seconds by blowing air at about room temperature (25 ° C.). The resin film laminated on the inner and outer surfaces of the laminate was made amorphous. The appearance of the laminated resin film was visually observed and evaluated according to the following criteria. That is, it is good that there is no abnormality in the appearance such as surface roughness, the surface is rough, but the surface roughness can be eliminated by DI processing described later, and the surface roughness is also observed by DI processing described later. Those that did not eliminate the roughness were made unacceptable.

<Slidability of the surface of the laminated resin film>
The laminated plate is heated to a temperature 15 ° C. higher than the melting point of the resin film laminated on the inner and outer surfaces of the laminated plate, and then forcedly cooled to 60 ° C. or less within 5 seconds by blowing air at about room temperature (25 ° C.). The resin film laminated on the inner and outer surfaces of the laminate was made amorphous. The sliding property of the surface of the laminated resin film was evaluated by measuring the dynamic friction coefficient of the resin film surface using a three-point weight 30 shown in FIG. 3 in an environment of room temperature (25 ° C.) and a relative humidity of 60%. . 3-point weight 30, the height H at 60mm diameter D and cylindrical body 31 of 33 mm, part of the diameter D _B which is fixed by being incorporated into the main body 31 and three steel balls 33 of 16mm The weight M having a hook 35 that is partially incorporated and fixed in the main body 31 is a weight of 500 g. Three steel balls 33 are both a hard chrome plated stainless steel balls, the vertices of an equilateral triangle in which the center O _B of the steel ball 33 is a distance P from the center O of the lower surface of the circular body 31 is 14mm It is arranged to be located in. Referring to FIG. 4, the dynamic friction coefficient on the surface of the resin film is measured by using a hook 35 of a three-point weight 30 arranged so that three steel balls 33 are in contact with the surface of the resin film 10 at a constant speed v of 600 mm / min. When the load applied to the hook 35 is F (unit: gf) and the load of the three-point weight 30 is N (500 gf), the following formula (3)
μ = F / N (3)
Is used to calculate the dynamic friction coefficient μ. Here, the smaller the dynamic friction coefficient, the higher the slipperiness of the surface of the laminated resin film on the inner surface or outer surface of the laminated plate.

<Adhesion of laminated resin film>
The laminated plate is heated to a temperature 15 ° C. higher than the melting point of the resin film laminated on the inner and outer surfaces of the laminated plate, and then forcedly cooled to 60 ° C. or less within 5 seconds by blowing air at about room temperature (25 ° C.). The resin film laminated on the inner and outer surfaces of the laminate was made amorphous. The adhesion of the laminated resin film is made in a grid pattern using eleven cuts reaching the metal plate at an interval of about 2 mm using a knife on the laminated resin film, and a plastic film having a width of 24 mm is formed on the cut of the resin film. After the pressure-sensitive adhesive tape was brought into close contact, the state of the film at the cross section when the pressure-sensitive adhesive tape was peeled off was observed and evaluated according to the following criteria. That is, excellent peeling is not observed at all, good peeling is possible (peeling area is less than 5%), and good peeling is possible (peeling area is 5% or more and less than 30%). , And those where significant peeling (peeling area is 30% or more) are not allowed. Here, the peeled area means a value obtained by dividing the area of the film peeled off by the adhesive tape by the area of the entire film of the grid part and multiplying by 100 among the film of the grid part.

<DI processing success rate>
The laminated plate is heated to a temperature 15 ° C. higher than the melting point of the resin film laminated on the inner and outer surfaces of the laminated plate, and then forcedly cooled to 60 ° C. or less within 5 seconds by blowing air at about room temperature (25 ° C.). As a result, the resin film laminated on the metal plate was made amorphous. This is performed in order to prevent cracking or peeling of the laminated resin film during DI processing. Next, the laminated board in which the laminated resin film was made amorphous was DI processed so that the processing rates defined by the formula (1) were 50%, 60%, and 70% to form seamless cans. The DI processing success rate was evaluated by measuring the number of cans that could be processed without any trouble during the DI processing and the number of cans that failed to be processed. In other words, the success rate per 100 cans is 100%, the success rate is 95% or more and less than 100%, the success rate is 80% or more and less than 95%, the success rate is acceptable Of less than 80%.

(Comparative Example A-R1)
Referring to FIG. 2, a PBT / PET blend resin film having a thickness of 25 μm (blend mass ratio is PBT: PET = 6: 4, PBT) on an inner surface 11i of a 3004H19 aluminum alloy plate (metal plate 11) having a thickness of 0.3 mm. (Thermoplastic polyester resin film 12) is a PBT / PET blend resin film (thermoplastic polyester resin film 12) having a thickness of 15 μm on the outer surface 11e. ) Was heat-sealed at a temperature of the aluminum alloy plate of 200 ° C. using a heating roll to produce a laminated plate 10. Here, PBT means polybutylene terephthalate, and PET means polyethylene terephthalate. The obtained laminate 10 was tested by the above test method. The test results are summarized in Table 1, Table 3, and Table 9.

(Comparative Example AI-R1, Examples AI-1 to AI-7)
Referring to FIG. 1 (a), first, 100 parts by mass of an epoxy resin and 5 parts by mass of a phenol resin are included on one side of a PBT / PET blend resin film (thermoplastic polyester resin film 12) having a thickness of 25 μm ( That is, an adhesive (including an epoxy (Ep) resin as a binder resin), and an adhesive in which a wax having the type and content (mass%) shown in Table 1 was added to the entire adhesive (Examples AI-1 to AI-7) ) Or an adhesive to which no wax is added (Comparative Example AI-R1) was applied with a gravure roll so that the basis weight after drying was 15 mg / dm ^2, and dried with hot air at 100 ° C. for 5 seconds, A thermoplastic polyester resin film 12 with an inner surface adhesive layer 13 to be laminated on the inner surface 11i of the plate 11 was produced.

  Next, the above thermoplastic polyester resin film with the inner surface adhesive layer 13 so that the adhesive layer 13 is in contact with the inner surface 11i of the aluminum alloy plate on the inner surface 11i of a 3004H19 aluminum alloy plate (metal plate 11) having a thickness of 0.3 mm. 12 was heat-sealed with a PBT / PET blend resin film (thermoplastic polyester resin film 12) having a thickness of 15 μm on the outer surface 11e at a temperature of an aluminum alloy plate of 200 ° C. using a heating roll to produce a laminate 10. The obtained laminate 10 was tested by the above test method. The test results are summarized in Table 1.

(Comparative Example AI-R2)
As the thermoplastic polyester resin film 12 laminated on the inner surface of the aluminum alloy plate (metal plate 11), except that a PBT / PET blend resin film having a thickness of 25 μm in which polyethylene wax was kneaded in advance by 0.5% by mass was used. A laminate 10 was produced and tested in the same manner as Comparative Example A-R1. The results are summarized in Table 1.

(Comparative Example AI-R3)
As the thermoplastic polyester resin film 12 laminated on the inner surface of the aluminum alloy plate (metal plate 11), except that a PBT / PET blend resin film having a thickness of 25 μm in which polyethylene wax was kneaded in advance by 0.5% by mass was used. A laminate 10 was produced and tested in the same manner as Comparative Example AI-R1. The results are summarized in Table 1.

(Comparative Example S-R1)
Referring to FIG. 2, an isophthalic acid copolymerized PET resin film (terephthalic acid (TPA) and isophthalic acid having a thickness of 25 μm is formed on an inner surface 11i of an electrolytic chromic acid treated steel plate (TFS) (metal plate 11) having a thickness of 0.24 mm. (Molecular ratio of copolymerization with (IPA) is TPA: IPA = 95: 5, melting point 245 ° C., hereinafter the same as in Comparative Examples and Examples) (thermoplastic polyester resin film 12) with 15 μm thick isophthalate on the outer surface 11e The acid-copolymerized PET resin film (thermoplastic polyester resin film 12) was heat-sealed at a steel plate temperature of 220 ° C. using a heating roll to produce a laminate 10. The obtained laminate 10 was tested by the above test method. The test results are summarized in Table 2, Table 6, and Table 11.

(Comparative Example SI-R1, Examples SI-1 to SI-7)
Referring to FIG. 1A, first, 100 parts by mass of an epoxy resin and 5 parts by mass of a phenol resin are provided on one surface of a 25 μm-thick isophthalic acid copolymerized PET resin film (thermoplastic polyester resin film 12). Containing (that is, containing epoxy (Ep) resin as a binder resin), and the adhesive (Examples SI-1 to SI) in which wax of the type and content (mass%) shown in Table 2 was added to the whole adhesive -7) or an adhesive to which no wax is added (Comparative Example SI-R1) was applied with a gravure roll so that the basis weight after drying was 15 mg / dm ^2, and dried with hot air at 100 ° C. for 5 seconds. The thermoplastic polyester resin film 12 with the adhesive layer 13 for laminating | stacking on the inner surface 11i of the metal plate 11 was produced. here,
Next, the thermoplastic polyester resin film 12 with the adhesive layer 13 is attached to the inner surface 11i of the electrolytic chromate-treated steel plate (metal plate 11) having a thickness of 0.24 mm so that the adhesive layer 13 is in contact with the inner surface 11i of the steel plate. A laminate 10 was produced by thermally fusing an isophthalic acid copolymerized PET resin film (thermoplastic polyester resin film 12) having a thickness of 15 μm on the outer surface 11e at a steel plate temperature of 220 ° C. using a heating roll. The obtained laminate 10 was tested by the above test method. The test results are summarized in Table 2.

(Comparative Example SI-R2)
As the thermoplastic polyester resin film 12 laminated on the inner surface of the electrolytic chromic acid-treated steel plate (metal plate 11), an isophthalic acid copolymerized PET resin film having a thickness of 25 μm in which 0.5% by mass of polyethylene wax was previously kneaded was used. Except for the above, a laminate 10 was produced and tested in the same manner as in Comparative Example S-R1. The results are summarized in Table 2.

(Comparative Example SI-R3)
As the thermoplastic polyester resin film 12 laminated on the inner surface of the electrolytic chromic acid-treated steel plate (metal plate 11), an isophthalic acid copolymerized PET resin film having a thickness of 25 μm in which 0.5% by mass of polyethylene wax was previously kneaded was used. Except for the above, a laminate 10 was produced and tested in the same manner as in Comparative Example SI-R1. The results are summarized in Table 2.

  From Table 1 and Table 2, the adhesive layer 13 and the thermoplastic polyester resin film 12 are sequentially laminated on the inner surface of the metal plate, regardless of whether the metal plate is an aluminum alloy plate or an electrolytic chromate-treated steel plate. It can be seen that the laminated plate in which the thermoplastic polyester resin film 12 is laminated on the outer surface and the binder resin and the hydrocarbon compound wax are contained in the adhesive layer has a high DI processing success rate. Moreover, the laminated board in which the hydrocarbon compound wax is contained in the thermoplastic polyester resin film 12 has a small dynamic friction coefficient and a high processing success rate, but the resin film appearance is remarkably deteriorated.

  Moreover, from the evaluation results of Tables 1 and 2, the content of the hydrocarbon compound wax in the adhesive layer is as follows: the comparison between Example AI-6 and AI-7 and the comparison between Example SI-6 and SI-7. Therefore, the upper limit is preferably 5.0 mass percent (that is, 5.0 mass% or less), and the comparison between Comparative Example AI-R1 and Example AI-5 and Comparative Example SI-R1 and Example SI-5 From this comparison, it can be seen that the lower limit is preferably 0.1% by mass (that is, 0.1% by mass or more).

(Comparative Example AE-R1, Examples AE-1 to AE-12)
Referring to FIG. 1B, first, 100 parts by mass of a polyester resin and 10 parts by mass of a blocked isocyanate resin are provided on one side of a PBT / PET blend resin film (thermoplastic polyester resin film 12) having a thickness of 15 μm. (Ie, including polyester (PEs) resin as a binder resin), and an adhesive in which a wax having the type and content (% by mass) shown in Table 3 or Table 4 was added to the entire adhesive (Example AE- 1 to AE-12) or an adhesive to which no wax is added (Comparative Example AE-R1) is applied with a gravure roll so that the basis weight after drying is 15 mg / dm ^2, and heated with hot air at 100 ° C. for 5 seconds. The thermoplastic polyester resin film 12 with the adhesive layer 13 for outer surfaces for making it dry and laminating | stack on the outer surface 11e of the metal plate 11 was produced.

  Next, a PBT / PET blend resin film (thermoplastic polyester resin film 12) having a thickness of 25 μm is formed on the inner surface 11i of a 3004H19 aluminum alloy plate (metal plate 11) having a thickness of 0.3 mm, and an adhesive layer 13 is formed on the outer surface 11e. Was laminated to the outer surface 11e of the aluminum alloy plate by heat-sealing the thermoplastic polyester resin film 12 with the outer surface adhesive layer 13 at a temperature of the aluminum alloy plate of 200 ° C. using a heating roll. . The obtained laminate 10 was tested by the above test method. The test results are summarized in Tables 3 and 4.

(Comparative Example AE-R2)
As the thermoplastic polyester resin film 12 laminated on the outer surface of the aluminum alloy plate (metal plate 11), except that a 15 μm thick PBT / PET blend resin film in which 0.5% by mass of polyethylene wax was previously kneaded was used. A laminate 10 was produced and tested in the same manner as Comparative Example A-R1. The results are summarized in Table 3.

(Comparative Example AE-R3)
As the thermoplastic polyester resin film 12 laminated on the outer surface of the aluminum alloy plate (metal plate 11), except that a 15 μm thick PBT / PET blend resin film in which 0.5% by mass of polyethylene wax was previously kneaded was used. A laminate 10 was produced and tested in the same manner as Comparative Example AE-R1. The results are summarized in Table 3.

(Comparative Example AE-R4, Examples AE-13 to AE-19)
As an adhesive for the outer surface adhesive layer 13, it contains 180 parts by mass of titanium oxide (TiO ₂ ), 100 parts by mass of a polyester resin and 10 parts by mass of a blocked isocyanate resin (that is, a polyester (PEs) resin as a binder resin. Including), an adhesive (Examples AE-13 to AE-19) to which a wax having the type and content (% by mass) shown in Table 5 is added to the entire adhesive, or an adhesive to which no wax is added (Examples AE-13 to AE-19) Using Comparative Example AE-R4), the basis weight after drying was set to 130 mg / dm ^2, and a laminate was produced in the same manner as Comparative Example AE-R1 except that it was dried with hot air at 130 ° C. for 8 seconds. A test was conducted. The test results are summarized in Table 5.

(Comparative Example AE-R5)
As the thermoplastic polyester resin film 12 laminated on the outer surface of the aluminum alloy plate (metal plate 11), except that a 15 μm thick PBT / PET blend resin film in which 0.5% by mass of polyethylene wax was previously kneaded was used. A laminate 10 was produced and tested in the same manner as Comparative Example AE-R4. The results are summarized in Table 5.

  From Tables 3 to 5, when the metal plate is an aluminum alloy plate, the thermoplastic polyester resin film 12 is laminated on the inner surface of the metal plate, and the adhesive layer and the thermoplastic polyester resin film are sequentially laminated on the outer surface of the metal plate, It can be seen that the laminate including the binder resin and the hydrocarbon compound wax in the adhesive layer has a high DI processing success rate. Moreover, the laminated board in which the hydrocarbon compound wax is contained in the thermoplastic polyester resin film 12 has a small dynamic friction coefficient and a high processing success rate, but the resin film appearance is remarkably deteriorated.

  Moreover, from the evaluation results of Table 3 and Table 5, the content of the hydrocarbon compound wax in the adhesive layer is the comparison between Example AE-6 and AE-7 and the comparison between Example AE-18 and AE-19. From the above, the upper limit is preferably 5.0% by mass (that is, 5.0% by mass or less), the comparison between Comparative Example AE-RI and Example AE-5, and Comparative Example AE-R4 and Example AE-17. From this comparison, it can be seen that the lower limit is preferably 0.1% by mass (that is, 0.1% by mass or less).

(Comparative Example SE-R1, Examples SE-1 to SE-12)
Referring to FIG. 1B, first, 100 parts by mass of a polyester resin and 10 parts by mass of a blocked isocyanate resin are formed on one side of a 15 μm-thick isophthalic acid copolymerized PET resin film (thermoplastic polyester resin film 12). (That is, polyester (PEs) resin is included as a binder resin), and an adhesive (Example SE) in which a wax having the type and content (% by mass) shown in Table 6 or Table 7 is added to the entire adhesive. -1 to SE-12) or an adhesive to which no wax is added (Comparative Example SE-R1) is applied with a gravure roll so that the weight per unit area after drying is 15 mg / dm ^2, and at 100 ° C. for 5 seconds. The thermoplastic polyester resin film 12 with the adhesive layer 13 for laminating on the outer surface 11e of the metal plate 11 was produced by drying with hot air.

  Next, a 25 μm-thick isophthalic acid copolymerized PET resin film (thermoplastic polyester resin film 12) is bonded to the outer surface 11e on the inner surface 11i of the electrolytic chromic acid-treated steel plate (metal plate 11) having a thickness of 0.24 mm. The above-mentioned thermoplastic polyester resin film 12 with the adhesive layer 13 was heat-sealed at a steel plate temperature of 220 ° C. using a heating roll so that the layer 13 was in contact with the outer surface 11e of the steel plate, thereby producing a laminate 10. The obtained laminate 10 was tested by the above test method. The test results are summarized in Tables 6 and 7.

(Comparative Example SE-R2)
As the thermoplastic polyester resin film 12 laminated on the outer surface of the electrolytic chromic acid-treated steel plate (metal plate 11), an isophthalic acid copolymerized PET resin film having a thickness of 15 μm in which 0.5% by mass of polyethylene wax was previously kneaded was used. Except for the above, a laminate 10 was produced and tested in the same manner as in Comparative Example S-R1. The results are summarized in Table 6.

(Comparative Example SE-R3)
As the thermoplastic polyester resin film 12 laminated on the outer surface of the electrolytic chromic acid-treated steel plate (metal plate 11), an isophthalic acid copolymerized PET resin film having a thickness of 15 μm in which 0.5% by mass of polyethylene wax was previously kneaded was used. Except for the above, a laminate 10 was produced and tested in the same manner as in Comparative Example SE-R1. The results are summarized in Table 6.

(Comparative Example SE-R4, Examples SE-13 to SE-19)
As an adhesive for the outer surface adhesive layer 13, it contains 180 parts by mass of titanium oxide (TiO ₂ ), 100 parts by mass of a polyester resin and 10 parts by mass of a blocked isocyanate resin (that is, a polyester (PEs) resin as a binder resin. Including), an adhesive to which the wax of the type and content (% by mass) shown in Table 8 is added to the entire adhesive (Example SE-13 to SE-19) or an adhesive to which no wax is added ( Using Comparative Example SE-R4), the weight per unit area after drying was 130 mg / dm ^2, and the laminate was prepared in the same manner as Comparative Example SE-R1 except that it was dried with hot air at 130 ° C. for 8 seconds. A test was conducted. The test results are summarized in Table 8.

(Comparative Example SE-R5)
As the thermoplastic polyester resin film 12 laminated on the outer surface of the electrolytic chromic acid-treated steel plate (metal plate 11), an isophthalic acid copolymerized PET resin film having a thickness of 15 μm in which 0.5% by mass of polyethylene wax was previously kneaded was used. Except for the above, a laminate 10 was produced and tested in the same manner as in Comparative Example SE-R4. The results are summarized in Table 8.

  From Table 6 to Table 8, even when the metal plate is an electrolytic chromate-treated steel plate, the thermoplastic polyester resin film 12 is laminated on the inner surface of the metal plate, and the adhesive layer and the thermoplastic polyester resin film are sequentially formed on the outer surface of the metal plate. It can be seen that the laminated sheet laminated and containing the binder resin and the hydrocarbon compound wax in the adhesive layer has a high DI processing success rate. Moreover, the laminated board in which the hydrocarbon compound wax is contained in the thermoplastic polyester resin film 12 has a small dynamic friction coefficient and a high processing success rate, but the resin film appearance is remarkably deteriorated.

  Moreover, from the evaluation results of Table 6 and Table 8, the content of the hydrocarbon compound wax in the adhesive layer was compared with Example SE-6 and SE-7 and Example SE-18 and SE-19. From the above, the upper limit is preferably 5.0% by mass (that is, 5.0% by mass or less), the comparison between Comparative Example SE-RI and Example SE-5, and Comparative Example SE-R4 and Example SE-17. From the comparison, it can be seen that the lower limit is preferably 0.1% by mass (that is, 0.1% by mass or less).

(Comparative Example AB-R1, Examples AB-1 to AB-13)
Referring to FIG. 1C, first, 100 parts by mass of an epoxy resin and 5 parts by mass of a phenol resin are included on one side of a 25 μm-thick PBT / PET blend resin film (thermoplastic polyester resin film 12) ( That is, an epoxy (including epoxy (Ep) resin as a binder resin), an adhesive in which the wax of the type and content (mass%) shown in Table 9 or Table 10 is added to the entire adhesive (Example AB-1). AB-13) or an adhesive to which no wax is added (Comparative Example AB-R1) is applied with a gravure roll so that the basis weight after drying is 15 mg / dm ² and dried with hot air at 100 ° C. for 5 seconds. Thus, a thermoplastic polyester resin film 12 with an inner surface adhesive layer 13 to be laminated on the inner surface 11i of the metal plate 11 was produced.

Further, on one side of a PBT / PET blend resin film (thermoplastic polyester resin film 12) having a thickness of 15 μm, 100 parts by mass of a polyester resin and 10 parts by mass of a blocked isocyanate resin (that is, polyester (PEs ) Including resin), and adhesives (Examples AB-1 to AB-13) or wax added with waxes of the types and contents (mass%) shown in Table 9 or Table 10 with respect to the entire adhesive A non-adhesive adhesive (Comparative Example AB-R1) was applied with a gravure roll so that the basis weight after drying was 15 mg / dm ² , dried with hot air at 100 ° C. for 5 seconds, and the outer surface 11e of the metal plate 11 A thermoplastic polyester resin film 12 with an outer surface adhesive layer 13 for lamination was prepared.

  Next, the above thermoplastic polyester resin film with the inner surface adhesive layer 13 so that the adhesive layer 13 is in contact with the inner surface 11i of the aluminum alloy plate on the inner surface 11i of a 3004H19 aluminum alloy plate (metal plate 11) having a thickness of 0.3 mm. 12 is heated at an aluminum alloy plate temperature of 200 ° C. using a heating roll so that the outer surface 11e is in contact with the outer surface 11e of the aluminum alloy plate and the thermoplastic polyester resin film 12 with the outer surface adhesive layer 13 is heated. The laminated board 10 was produced by fusing. The obtained laminate 10 was tested by the above test method. The test results are summarized in Table 9 and Table 10.

(Comparative Example AB-R2)
As thermoplastic polyester resin film 12 laminated on the inner and outer surfaces of an aluminum alloy plate (metal plate 11), a PBT / PET blend resin having a thickness of 25 μm and a thickness of 15 μm each containing 0.5% by mass of polyethylene wax in advance. A laminate 10 was produced and tested in the same manner as Comparative Example A-R1 except that a film was used. The results are summarized in Table 9.

(Comparative Example AB-R3)
As thermoplastic polyester resin film 12 laminated on the inner and outer surfaces of an aluminum alloy plate (metal plate 11), a PBT / PET blend resin having a thickness of 25 μm and a thickness of 15 μm each containing 0.5% by mass of polyethylene wax in advance. A laminate 10 was prepared and tested in the same manner as Comparative Example AB-R1 except that a film was used. The results are summarized in Table 9.

(Examples AB-14 to AB-16)
As an adhesive for the outer surface adhesive layer 13, it contains 180 parts by mass of titanium oxide (TiO ₂ ), 100 parts by mass of a polyester resin and 10 parts by mass of a blocked isocyanate resin (that is, a polyester (PEs) resin as a binder resin. Using an adhesive to which the wax of the type and content (% by mass) shown in Table 10 is added to the whole adhesive, and the basis weight after drying is set to 130 mg / dm ^2, and hot air at 130 ° C. for 8 seconds. A laminate was prepared and tested in the same manner as Example AB-2 except that it was dried. The test results are summarized in Table 10.

(Comparative Example SB-R1, Examples SB-1 to SB-13)
Referring to FIG. 1C, first, 100 parts by mass of an epoxy resin and 5 parts by mass of a phenol resin are provided on one side of a 25 μm-thick isophthalic acid copolymerized PET resin film (thermoplastic polyester resin film 12). Including an adhesive (that is, including an epoxy (Ep) resin as a binder resin) and a wax having the type and content (mass%) shown in Table 11 or Table 12 added to the entire adhesive (Example SB- 1 to SB-13) or an adhesive to which no wax is added (Comparative Example SB-R1) was applied with a gravure roll so that the basis weight after drying was 15 mg / dm ^2, and hot air was applied at 100 ° C. for 5 seconds. The thermoplastic polyester resin film 12 with the inner surface adhesive layer 13 for drying and laminating on the inner surface 11i of the metal plate 11 was produced.

Moreover, 180 mass parts titanium oxide, 100 mass parts polyester resin, and 10 mass parts block isocyanate resin are included in the single side | surface of 15-micrometer-thick isophthalic acid copolymerization PET resin film (thermoplastic polyester resin film 12). That is, a polyester (PEs) resin is included as a binder resin), and an adhesive (Example SB-1 to 1) in which a wax having the type and content (% by mass) shown in Table 11 or Table 12 is added to the entire adhesive. SB-13) or an adhesive to which no wax was added (Comparative Example SB-R1) was applied with a gravure roll so that the basis weight after drying was 130 mg / dm ² and dried with hot air at 130 ° C. for 8 seconds. A thermoplastic polyester resin film 12 with an outer surface adhesive layer 13 to be laminated on the outer surface 11e of the metal plate 11. Made.

  Next, the thermoplastic polyester resin film 12 with the inner surface adhesive layer 13 is attached to the inner surface 11i of the 0.24 mm thick electrolytic chromate-treated steel plate (metal plate 11) so that the adhesive layer 13 is in contact with the inner surface 11i of the steel plate. The thermoplastic polyester resin film 12 with the outer surface adhesive layer 13 is heat-sealed at a steel plate temperature of 220 ° C. using a heating roll so that the adhesive layer 13 is in contact with the outer surface 11e of the steel plate. A plate 10 was produced. The obtained laminate 10 was tested by the above test method. The test results are summarized in Tables 11 and 12.

(Comparative Example SB-R2)
As the thermoplastic polyester resin film 12 laminated on the inner and outer surfaces of the electrolytic chromic acid-treated steel plate (metal plate 11), each of isophthalic acid co-polymers having a thickness of 25 μm and a thickness of 15 μm in which 0.5% by mass of polyethylene wax has been previously kneaded. A laminate 10 was produced and tested in the same manner as Comparative Example S-R1, except that a polymerized PET resin film was used. The results are summarized in Table 11.

(Comparative Example SB-R3)
As the thermoplastic polyester resin film 12 laminated on the inner and outer surfaces of the electrolytic chromic acid-treated steel plate (metal plate 11), each of isophthalic acid co-polymers having a thickness of 25 μm and a thickness of 15 μm in which 0.5% by mass of polyethylene wax has been previously kneaded. A laminate 10 was produced and tested in the same manner as Comparative Example SB-R1 except that a polymerized PET resin film was used. The results are summarized in Table 11.

(Examples SB-14 to SB-16)
As an adhesive for the outer surface adhesive layer 13, it contains 180 parts by mass of titanium oxide (TiO ₂ ), 100 parts by mass of a polyester resin and 10 parts by mass of a blocked isocyanate resin (that is, a polyester (PEs) resin as a binder resin. Using an adhesive to which the wax of the type and content (% by mass) shown in Table 12 was added to the entire adhesive, and the basis weight after drying was 130 mg / dm ^2, and hot air at 130 ° C. for 8 seconds. A laminate was prepared and tested in the same manner as Example SB-2 except that it was dried. The test results are summarized in Table 12.

  From Tables 9 to 12, even if the metal plate is an aluminum alloy plate or an electrolytic chromate-treated steel plate, an adhesive layer and a thermoplastic polyester resin film are sequentially laminated on the inner surface of the metal plate, and on the outer surface of the metal plate. It can be seen that the laminate in which the adhesive layer and the thermoplastic polyester resin film are sequentially laminated and the adhesive layer contains the binder resin and the hydrocarbon compound wax have a high DI processing success rate. Moreover, the laminated board in which the hydrocarbon compound wax is contained in the thermoplastic polyester resin film 12 has a small dynamic friction coefficient and a high processing success rate, but the resin film appearance is remarkably deteriorated.

  It should be understood that the embodiments and examples disclosed herein are illustrative and non-restrictive in every respect. The scope of the present invention is defined by the terms of the claims, rather than the description above, and is intended to include any modifications within the scope and meaning equivalent to the terms of the claims.

It is a schematic sectional drawing which shows the laminated board concerning this invention. Here, (a) shows one embodiment, (b) shows another embodiment, and (c) shows still another embodiment. It is a schematic sectional drawing which shows a typical laminated board. It is the schematic which shows the 3 point | piece weight for measuring the dynamic friction coefficient of the surface of a laminated resin film in this invention. Here, (a) is a schematic side view, and (b) is a schematic bottom view. It is the schematic which shows the method of measuring the dynamic friction coefficient of the surface of a laminated resin film in this invention.

Explanation of symbols

  10 Laminated plate, 10e, 11e outer surface, 10i, 11i inner surface, 11 metal plate, 12 thermoplastic polyester resin film, 13 adhesive layer, 30 3-point weight, 31 body, 33 steel ball, 35 hook.

Claims (6)

It is a laminated plate for drawing and ironing processing comprising a metal plate and a thermoplastic polyester resin film laminated on both sides of the metal plate,
An adhesive layer is formed between the metal plate and at least one side of the thermoplastic polyester resin film,
The adhesive layer contains a binder resin and a hydrocarbon compound wax,
The hydrocarbon compound wax, prior SL exists only in the adhesive layer, said thermoplastic polyester resin film drawing and ironing laminates, characterized in that can be incorporated into the heat treatment. The laminate for drawing and ironing processing according to claim 1, wherein the degree of crystallinity calculated from differential scanning calorimetry of the thermoplastic polyester resin film is 50% or less. 3. The drawn ironing laminate according to claim 1, wherein the hydrocarbon compound wax in the adhesive layer includes a polyolefin-based wax. 4. The laminated sheet for drawing ironing according to any one of claims 1 to 3 , wherein a content of the hydrocarbon compound wax in the adhesive layer is 0.1 mass% or more and 5 mass% or less. The laminate for drawing and ironing according to any one of claims 1 to 4, wherein the binder resin in the adhesive layer includes at least one resin selected from the group consisting of an epoxy resin, a polyester resin, and a polyurethane resin. . For drawing and ironing according to any of claims 1 to kinetic friction coefficient at the surface of the thermoplastic polyester resin film which is formed on the adhesive layer, characterized in that more than 0.2 to claim 5 Laminated board.

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