JP4673754B2 - Colored laminated metal plate for containers and method for producing the same - Google Patents

Description

  The present invention relates to a colored laminated metal plate for containers and a method for producing the same, and more particularly to a colored laminated metal plate for containers having a smooth and bright appearance and excellent design properties and a method for producing the same.

  In conventional metal cans for containers, painted metal plates have been used, but the coating process is not only complicated and low in productivity, but also has a problem of discharging a large amount of solvent. A laminated metal plate obtained by thermocompression bonding to a heated metal plate is used. In particular, polyester resin film-laminated metal plates have been widely used because of their excellent economic efficiency, food hygiene, and heat fusion properties.

  By the way, conventional metal plates for containers such as cans using painted metal plates are disliked by the dark color tone of the base metal plate, and are painted with gold, white, etc. to give design. ing. However, when these are replaced with a laminated metal plate, there is a problem that it is difficult to add a colorant such as a pigment to the laminated film.

  The method of coloring the laminate film includes a method of producing a colored film by adding a colorant such as a pigment into the film resin, and a method of forming a colored layer by applying a colorant as a post-processing of the clear film. is there. However, in the former method in which a colorant is added to the film resin, the film production cost increases significantly due to an increase in the production cost of the colored raw resin and a production burden due to a color change loss in the film production process. Therefore, a method of forming a colored layer as a post-processing of the latter clear film is advantageous.

  Two methods can be considered as a method of forming a colored layer as a post-processing of the laminate film. The first method is a method of providing a colored layer on the outermost layer. In this case, problems such as pigment peeling and color fading occur. On the other hand, the second method is a method of providing a colored layer between the film and the metal plate. In the case of the second method, a colored adhesive layer is usually formed by containing a colorant in the adhesive layer. According to this method, by providing a colored layer that also serves as an adhesive layer between the film and the metal plate, a part of the manufacturing process can be omitted, the manufacturing cost can be reduced, and the productivity can be improved ( For example, see Patent Documents 1 to 5).

JP 2002-256247 A JP-A-4-266984 JP-A-8-199147 Japanese Patent Laid-Open No. 10-183095 JP 2002-206079 A

  However, when the adhesive layers and films described in Patent Documents 1 to 5 are used, there is a problem that retort brushing that causes discoloration of the adhesive or the polyester resin film occurs during retort heat sterilization after filling the can contents. was there. For this reason, the processed laminated metal sheet cannot obtain an appearance with excellent design.

  Accordingly, the present invention has been made in view of such problems, and the object of the present invention is to provide an external design that does not cause retort brushing of the film and coloring adhesive during retort heat sterilization after filling the can contents. It is an object of the present invention to provide a new and improved colored laminated metal sheet for containers and a method for producing the same that can maintain the properties.

  By the way, retort brushing of colored adhesives has a slow curing reaction rate of conventional adhesives, so that the adhesives are not sufficiently cured in the production of laminated metal sheets, and are bonded during retort heat sterilization after filling the can contents. It is thought to occur when an agent curing reaction occurs. Further, it is known that retort brushing of a polyester resin film is caused by a slow crystallization speed. Furthermore, the design of the appearance is also impaired by transferring irregularities due to dirt or scratches on the laminate roll to the film after lamination.

  Therefore, as a result of intensive studies to solve the above problems, the present inventors promoted the curing of the colored adhesive in the laminating process and used a polyester resin having a high crystallization speed as a film. It has been found that retort brushing of colored adhesives and films can be prevented.

  Furthermore, a hard skin layer is formed in the polyester resin film after lamination by allowing a region of many biaxially oriented polyester crystals having a birefringence of 0.04 or more to exist in a thickness direction of 5 μm or more from the outer surface of the film. It was found that the transfer resistance to dirt and scratches on the laminate roll on the film surface can be improved, and the design of the appearance can be remarkably improved.

The present invention has been completed based on the above findings, and the gist of the present invention is as follows.
(1) on one or both sides of a metal plate, a container colored laminated metal plate made by coating a multilayer resin film formed by laminating a colored adhesive layer and polyester resin film, the colored adhesive layer, the number average molecular weight of the main component epoxy resin of 2000 to 6000, further, a colorant, and a high-etherified amino resin from 1 to 10 parts by weight relative to the epoxy resin 100 parts by weight, relative to the epoxy resin 100 parts by weight wherein the blocked isocyanate compound of 1 to 10 parts by weight of Te, the polyester resin film is mainly composed of a polyester resin half-crystallization time is less than 100 seconds at 125 ° C., the said polyester resin film, double A region having a refraction of 0.04 or more exists in the thickness direction from the outer surface of the film to a thickness of 5 μm or more. A polyester resin having a main repeating unit of terephthalate and a polyester resin having a main repeating unit of butylene terephthalate, and a polyester resin having the main repeating unit of ethylene terephthalate and a polyester resin having the main repeating unit of butylene terephthalate the, 80: 20-30: is mixed at a mass ratio of 70, characterized in Rukoto, container colored laminated metal sheet.
( 2 ) The colored laminated metal plate for containers according to (1 ), wherein the polyester resin film has a thickness of 8 to 30 μm.
( 3 ) The colored laminated metal for containers according to (1) or (2) , wherein the colored adhesive layer further contains one or both of a phosphoric acid-modified compound and a block-free isocyanate compound Board.
(4) on one side or both sides of a metal plate, in the method for manufacturing a container for colored laminated metal plate with a resin film comprising a lamination step of thermally bonding using a lamination roll, the resin film contains (a) a colorant Painting and adhesive layer, a (b) a polyester resin containing ethylene terephthalate as the main repeating unit, multilayered resin was laminated a polyester resin and a polyester resin film Ru Tona that the butylene terephthalate as a main repeating unit a film, the colored The adhesive layer is mainly composed of an epoxy resin having a number average molecular weight of 2000 to 6000, and further includes a colorant, 1 to 10 parts by mass of a highly etherified amino resin with respect to 100 parts by mass of the epoxy resin, and the epoxy. 1 to 10 parts by mass of blocked isocyanate compound per 100 parts by mass of resin The polyester resin film is mainly composed of a polyester resin whose semi-crystallization time at 125 ° C. is 100 seconds or less, and the polyester resin film has a region having a birefringence of 0.04 or more outside the film. The polyester resin that is present in the thickness direction from the surface in a thickness direction of 5 μm or more and that has the ethylene terephthalate as the main repeating unit and the polyester resin that has the butylene terephthalate as the main repeating unit are mixed at a mass ratio of 80:20 to 30:70. In the laminating step, (A) the temperature of the adhesive surface of the multilayer resin film passing through the laminating roll with the metal plate is set to a temperature equal to or higher than the melting point of the polyester resin mainly composed of butylene terephthalate, And the thermocompression bonding time by the laminate roll is 10-80. In the condition that the re-sec, a step of thermocompression bonding the surface of the colored adhesive layer side to the metal plate of the multi-layer resin film, (B) the laminating temperature of the roll after passing the metal plate 0.99 ° C. or higher characterized in that it comprises a step of heat-treating 0.5-30 seconds, a method of manufacturing a container for colored laminated metal sheet according to (1).

  According to the present invention, the colored laminated metal for containers that can prevent retort brushing of the colored adhesive and the polyester resin film and maintain the design of the appearance during the retort heat sterilization treatment after filling the can contents. A board and a manufacturing method thereof can be provided.

  Further, according to the present invention, the unevenness of the laminating roll whose surface has been roughened due to contamination or scratches on the laminating roll is not transferred to the film surface after laminating, and can be maintained smooth. A laminated metal plate and a manufacturing method thereof can be provided.

  In addition, according to the coloring laminated metal plate for containers and the manufacturing method thereof according to the present invention, excellent film adhesion, heat resistance, water resistance and stability over time can be maintained as a can-making material.

  Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the accompanying drawings. In the present specification and drawings, components having substantially the same functional configuration are denoted by the same reference numerals, and redundant description is omitted.

  The colored laminated metal plate for containers according to the present invention is formed by coating a multilayer resin film in which a colored adhesive layer and a polyester resin film are laminated on one side or both sides of a metal plate. In this multilayer resin film, the colored adhesive layer is mainly composed of an epoxy resin, and further contains a colorant, a highly etherified amino resin, and a blocked isocyanate compound. The polyester resin film has a half-crystallization time at 125 ° C. The main component is a polyester resin that is 100 seconds or shorter.

As the metal plate used as the substrate, aluminum plates, mild steel plates, plated steel plates, etc. widely used as can materials can be used. In particular, surface-treated steel plates made of metal chromium and chromium hydrated oxide, so-called TFS (Tin Free Steel) is optimal. The amount of TFS metallic chromium and chromium hydrated oxide deposited is not particularly limited, but from the viewpoint of adhesion and corrosion resistance after processing, the metallic chromium is 40 to 500 mg / m ² in terms of chromium, chromium water. It is preferable to contain a sum oxide in the range of 8 to 20 mg / m ² .

(Configuration of colored adhesive)
Generally, in can applications, design properties are also an important required characteristic, and a bright color such as gold tends to be preferred as the color of the outer surface of the can. Bright colors such as gold can be obtained by laminating a transparent film colored with a yellow pigment and a red pigment on a glossy metal plate. Further, the glitter color such as gold is required not to change color after the retort sterilization treatment.

  However, as described above, the colored adhesive may cause a problem of retort brushing that changes color during retort processing. The present inventors believe that this is because the colored adhesive is not sufficiently cured by short-time heat treatment in the laminating process, and a curing reaction occurs even in retort heat treatment. In other words, retort brushing of gold-colored adhesive is a product in which the cured adhesive layer partially and non-uniformly expands and turns turbid brown because the adhesive is cured with residual solvent and moisture. I believe.

  Therefore, in the colored laminated steel sheet for containers according to the present invention, as a countermeasure against retort brushing of the colored adhesive, as an adhesive contained in the colored adhesive layer, an adhesive that can be cured by a short heat treatment in the laminating process. The composition is adopted.

  Hereinafter, the colored adhesive layer will be described. The composition of the colored adhesive layer according to the present invention is a heat treatment in a short time in the laminating process by adjusting an epoxy resin having a specific number average molecular weight, a high ether amino resin, and a blocked isocyanate compound at a specific blending ratio. Hardening is promoted, and adhesion, water resistance (retort brushing resistance), heat resistance, stability over time and durability are expressed. This will be described in detail below.

An epoxy resin having a number average molecular weight of 2000 to 6000 is used as the epoxy resin. As such an epoxy resin, for example, a bisphenol A type epoxy resin or a bisphenol F type epoxy resin having a number average molecular weight of 2000 to 6000 is preferably used. In particular, a bisphenol A type epoxy resin can be suitably used. Epoxy resins that meet the above conditions include trade name Epicoat 1007, Epicoat 1009, Epicoat 1010, EXA8435, and the like. It is possible to use several epoxy resins in combination so that the number average molecular weight is 2000 to 6000. More specifically, the epoxy resin used in the present invention is a bisphenol A-type diglycidyl ether resin, which is obtained by polymerization in the presence of an acid or alkali catalyst, such as a phosphoric acid catalyst or an amino catalyst, and is an epoxy having few branches. Resin is desirable. It is also possible to modify the bisphenol A type epoxy resin with dimer acid or the like.

  When the number average molecular weight of this epoxy resin is less than 2000, heat curing is insufficient only with heat at the time of lamination, adhesion strength is weak, and it peels easily at the adhesion interface upon contact with hot water. When the number average molecular weight exceeds 6000, physical properties as an adhesive are manifested, but there is a problem in the coating performance on the film because the viscosity of the adhesive is increased.

  As the highly etherified amino resin, a completely alkyl melamine resin and a completely alkyl benzoguanamine resin can be suitably used. Preferably, highly methylated hexamethoxymethylated melamine resin is used. Examples of commercially available products include Super Becamine L-105-60 (Dainippon Ink Chemical Co., Ltd.), Cymel 303 (Mitsui Cytec), Cymel 300 (Mitsui Cytec), and the like.

The amount of high-etherified amino resin per 100 parts by weight of the epoxy resin having a number average molecular weight of 2000 to 6000 is Ru 1-10 parts by der. When the amount of the highly etherified amino resin is less than 1 part by mass, the thermosetting reaction is slowed down. Thus, sufficient curing reaction does not proceed only by the heat treatment in the laminating process, and retort brushing of the adhesive may occur. When the amount is more than 10 parts by mass, the thermosetting reaction is sufficiently quick, but the stress inside the adhesive is increased and the adhesion during processing is lowered.

  Examples of the blocked isocyanate compound include aliphatic isocyanate compounds such as hexamethylene diisocyanate, isopropylene diisocyanate, and methylene diisocyanate, alicyclic isocyanate compounds such as isophorone diisocyanate, methylcyclohexane diisocyanate, and lysine diisocyanate, tolylene diisocyanate, 1,5- And aromatic isocyanate compounds such as naphthylene diisocyanate.

  The isocyanate compound used in the present invention also includes compounds obtained from one or more of the above-mentioned isocyanates (dimers, trimers, adducts, burettes, prepolymers, etc.).

  Particularly, among these isocyanate compounds, aliphatic and / or alicyclic isocyanate compounds are suitable for use in the present invention, and hexamethylene diisocyanate and isophorone diisocyanate can be particularly preferably used. .

  Although the blocked isocyanate compound can contribute to the thermosetting reaction, it has the effect of reducing internal stress during curing when used in combination with a highly etherified amino resin.

The amount of blocked isocyanate compound per 100 parts by weight of the epoxy resin having a number average molecular weight of 2000 to 6000 is Ru 1-10 parts by der. When the amount of the blocked isocyanate compound is less than 1 part by mass, not only the thermosetting is slowed but also the processability tends to be lowered. When the amount is more than 10 parts by mass, the curing becomes excessive and the workability is lowered.

  In addition, various known catalysts can be used in combination to promote curing. Examples of the curing catalyst for the isocyanate compound include various organotin compounds such as dibutyltin dilaurate and dibutyltin dichloride, and various amines such as triethylenediamine and triethylamine. As a curing catalyst for the highly etherified amino resin, it is desirable to use an acid catalyst such as dodecylbenzenesulfonic acid or paratoluenesulfonic acid.

  The colored adhesive layer according to the present invention may further contain a phosphoric acid-modified compound. As such a phosphoric acid-modified compound, a compound obtained by modifying an epoxy resin with phosphoric acid or a compound obtained by modifying an ester compound with phosphoric acid can be used. Moreover, it is preferable that the compounding quantity of the phosphoric acid modification compound with respect to 100 mass parts of epoxy resins with a number average molecular weight 2000-6000 is 0.1-20 mass parts. By adding a phosphoric acid-modified compound, the adhesive strength to the metal plate is greatly improved, and the heat resistance, water resistance, curability and pigment dispersibility can be improved. When the addition amount is less than 0.1 parts by mass, the above performance is small. When the addition amount is more than 20 parts by mass, cohesive failure occurs inside the adhesive during lamination due to a decrease in the molecular weight of the entire adhesive, and the adhesion strength May not be obtained.

  In addition to the above composition, a block-free isocyanate compound can be added to the colored adhesive layer according to the present invention. Block-free isocyanate compounds include aliphatic isocyanate compounds such as hexamethylene diisocyanate, isopropylene diisocyanate, and methylene diisocyanate, alicyclic isocyanate compounds such as isophorone diisocyanate, methylcyclohexane diisocyanate, and lysine diisocyanate, tolylene diisocyanate, and 1,5-naphthyl. Examples thereof include aromatic isocyanate compounds such as range isocyanate. Of these, hexamethylene diisocyanate and isophorone diisocyanate can be particularly preferably used.

  Since the block-free isocyanate compound is cured at room temperature and the adhesive is pre-cured before lamination, it is possible to improve the adhesive curing at the time of lamination.

  The block-free isocyanate compound is 0.5 to 20 parts by mass with respect to 100 parts by mass of the colored adhesive composed of an epoxy resin having a number average molecular weight of 2000 to 6000, a high ether amino resin, a blocked isocyanate compound, and a phosphoric acid-modified compound. It is preferable to add in the range. If it is less than 0.5 parts by mass, the molecular weight does not increase due to insufficient room temperature curing, and cohesive failure may occur inside the adhesive during lamination, and adhesive strength may not be obtained. , It is not preferable because there is a concern about a decrease in adhesion strength due to poor adhesive flow during lamination.

  The colored adhesive layer according to the present invention is used for coloring a polyester resin film, and is used by adding and dispersing a pigment in the adhesive.

  There are inorganic pigments and organic pigments. In general, inorganic pigments are excellent in hiding power and weather resistance, but are poor in coloring power, while organic pigments are excellent in coloring power and clear color. , Hiding power and weather resistance tend to be relatively poor.

  Examples of inorganic pigments include, for example, white pigments such as titanium dioxide and zinc white, black pigments such as carbon black and graphite, yellow pigments such as yellow lead and iron oxide yellow, red pigments such as red lead and red bean paste, bitumen, and ultramarine blue. Blue pigments, green pigments such as chromium oxide green, and metallic pigments such as aluminum flakes and mica flakes.

  Examples of organic pigments include yellow and red azo organic pigments, quinacridone organic pigments, blue and green phthalocyanine organic pigments, and the like.

  For canned foods, gold or white that gives cleanliness is preferred because of the dark color of the base metal plate. Gold color is obtained by applying a colored adhesive with excellent transparency to which yellow and red azo organic pigments are added to a polyester resin film and overlaying it on the gloss of the underlying metal plate. For white, it is preferable to use a colored adhesive to which titanium dioxide having excellent coloring power and hiding power is added.

  Addition of the colorant is arbitrarily prescribed according to the coloration needs. However, in the present invention, the amount of adhesive applied to the polyester resin film is the minimum required for the purpose of resistance to retort brushing by curing the adhesive in the lamination process. Therefore, it is necessary to reduce the curing time. Therefore, in consideration of the dispersibility of the colorant and the coating performance on the film, the colorant addition concentration is adjusted to the maximum.

The coating amount of the coloring adhesives, range 0.5~20.0g / ^{m 2} is preferred. If it is less than 0.5 g / m ^2, it is difficult to uniformly apply the film surface. If it exceeds 20.0 g / m ² , it takes time to remove the solvent in the coating process, and the productivity is significantly reduced.

  It is preferable to add an inorganic lubricant such as silica or barium sulfate to the colored adhesive in order to improve the anti-blocking property and handling property of the film after coating.

(Configuration of polyester resin film)
Next, the polyester resin film according to the present invention that retains excellent surface gloss and high transparency even by retorting after filling the can contents will be described.

  A colored film laminated metal plate for containers coated with a polyester resin film may cause retort brushing in which the outer surface of the can changes color in a retort heat treatment performed after filling the contents of the can body. This phenomenon is that polyester molecules melted by lamination with a metal plate recrystallize non-uniformly and become cloudy.

  The colored laminated metal plate for containers according to the present invention solves both the retort brushing and the problem of transferring the irregularities of the laminating roll having a rough surface onto the laminated film surface to cause poor appearance.

  As the polyester resin, a polyester resin having a half crystallization time at 125 ° C. of 100 seconds or less is used as a main component. Thus, by setting the half crystallization time to 100 seconds or less, the polyester melt molecules in the film are finely crystallized at high speed during the retort heat treatment performed at a temperature near 125 ° C., and the color tone is made uniform. Partially cloudy retort brushing can be prevented. The semi-crystallization time of the polyester resin indicates the time required for recrystallization of the molten molecule, and indicates that the crystallization speed increases as the half-crystallization time decreases.

The crystallization rate fast polyester resin as described above, to use a polyester resin the d Ji terephthalate as the main repeating unit, the composite polyester resin comprising a polyester resin of butylene terephthalate as a main repeating unit as the main component .

  These polyester resins have good compatibility due to their similar chemical structure and have a melting point difference of about 30 ° C. Therefore, these polyester resins are melted at a temperature at which oxidative degradation does not become a problem, and polymer alloys that are mixed finely and uniformly. can do.

  The crystallization time of the polyester resin can be adjusted by changing the compounding ratio of a polyester resin having ethylene terephthalate as a main repeating unit and a polyester resin having butylene terephthalate as a main repeating unit. is there.

Specifically, although the crystallization time increases when the ratio of butylene terephthalate is increased, the blending ratio of the polyester resin having ethylene terephthalate as the main repeating unit and the polyester resin having butylene terephthalate as the main repeating unit is the mass ratio. in 80: 20-30: that be in the range of 70.

  The reason for this is that when the blending ratio of the polyester resin having butylene terephthalate as the main repeating unit is less than 80:20, retort brushing occurs because the crystallization speed is slow, and the blending ratio of the polyester resin having butylene terephthalate as the main repeating unit. If the ratio exceeds 30:70, it is difficult to form a biaxially stretched film.

  In addition, the colored laminated metal plate for containers according to the present invention has a region in which a polyester biaxial crystal having a birefringence of 0.04 or more is present in the thickness direction from the outer surface of the film to the polyester resin film after lamination. The presence of 5 μm or more makes it possible to form a hard skin layer, improve the transfer resistance against dirt and scratches on the laminate roll on the film surface, and remarkably improve the appearance design.

The region is birefringent 0.04 or more polyester resin film is less than 5μm after lamination, insufficient film surface hardness of the lamination, poor appearance that occur due to dirt or scratches Ramiroru is transferred to the film surface .

  On the other hand, as described above, the colored adhesive layer according to the present invention prevents retort brushing by promoting curing in the laminating process. However, a decrease in flexibility due to the curing of the colored adhesive layer causes a decrease in retort adhesion between the colored adhesive layer and the metal plate, which causes a problem of poor retort adhesion in can applications with a high processing rate. .

  Such poor retort adhesion occurs due to interface peeling between the adhesive and the metal surface. In other words, the processed strain remains in the film after lamination and after making the can, and the interface peeling between the adhesive layer having weak adhesion and the metal surface occurs due to the retort thermal shock.

  In order to prevent such a problem, it is preferable to improve the workability by increasing the film elongation by accelerating the melting of the polyester resin and breaking the polyester biaxial crystal to make it non-oriented. . Specifically, the region where the birefringence of the polyester resin film is less than 0.04 is preferably 4 μm or more from the contact interface with the metal plate.

  When the region where the birefringence of the polyester resin film is less than 0.04 is less than 4 μm from the contact interface with the metal plate, the polyester resin is not sufficiently melted, and many polyester biaxially oriented crystals remain. The film flexibility is poor, and in high-processing rate can applications, the residual film distortion becomes large, and the interface peeling between the adhesive layer and the metal surface occurs due to retort thermal shock.

  In addition, the thickness of the region having a birefringence of 0.04 or more and the region having a birefringence of less than 0.04 as described above can be controlled by the melting state of the multilayer resin film according to the heat lamination conditions. That is, when the melting of the film is increased, the region having a birefringence of less than 0.04 is thickened, and the region having a birefringence of 0.04 or more is thinned accordingly. Under normal heat laminating conditions, a birefringence of less than 0.04 is formed to be 4 μm or more near the contact interface between the colored adhesive layer and the polyester resin film.

  In general, a biaxially oriented polyester resin film is not optically isotropic and exhibits birefringence. The birefringence value in the thickness direction of the polyester resin film can be determined by measuring the retardation in the film thickness direction after removing the metal plate of the laminated metal plate using a polarizing microscope.

  When the linearly polarized light is incident on the biaxially oriented polyester resin film, it is decomposed into two linearly polarized light in the main refractive index direction, and the vibration of light in the high refractive index direction becomes slower than the vibration of light in the low refractive index direction: Causes retardation. The relationship between the retardation R generated when the film passes and the birefringence Δn is expressed by the following formula (1), where d is the thickness of the film.

  Δn = R / d (1)

  Next, a method for measuring retardation will be described. Monochromatic light passes through the polarizing plate to be linearly polarized light and is incident on the film. Linearly polarized light causes retardation in the film and becomes elliptically polarized light after passing through the film. The elliptically polarized light becomes linearly polarized light having an angle θ with respect to the vibration direction of the first linearly polarized light by passing through the Senarmont type compensator. This θ is measured by rotating the polarizing plate. The relationship between retardation R and θ is expressed by the following formula (2), where λ is the wavelength of monochromatic light.

  R = λ · θ / 180 (2)

  Therefore, the birefringence Δn is expressed by the following formula (3) from the above formulas (1) and (2).

  Δn = (θ · λ / 180) / d (3)

  In the above description, a single-layer polyester resin has been described. However, the polyester resin according to the present invention may be a multi-layer in which two or more polyester resin layers are laminated. For example, as a polyester resin to be laminated on a colored adhesive layer, a lower layer mainly composed of a polyester resin whose semi-crystallization time at 125 ° C. is 100 seconds or less and a high melting point (for example, a melting point of 245 ° C. or more). You may use the multilayer polyester resin which consists of a surface layer which has a polyester resin as a main component.

  Such a surface layer composed mainly of a high-melting polyester resin is hard to retain biaxially oriented crystals without melting during thermal lamination, and the irregularities on the surface of the laminate roll due to contamination and scratches on the laminate roll are transferred. Serves as a hard skin layer that will not be done. Therefore, by providing such a surface layer, a good appearance due to the smoothness after lamination can be obtained, and since it does not melt at the time of thermal lamination, stabilization of the lamination operation can be brought about.

  However, when a surface layer composed mainly of a high-melting polyester resin is provided in this way, the retort adhesion is significantly reduced by the residual stress of the high-melting polyester resin on the surface layer. , It is preferable that a region having a birefringence of less than 0.04 exists in the thickness direction of 4 μm or more from the interface between the lower layer and the colored adhesive layer.

(Explanation of film thickness of polyester resin)
Although the thickness of a polyester resin film is suitably set according to the application environment of a container outer surface, it is preferable that it is 8-30 micrometers. If the thickness of the polyester resin film is less than 8 μm, the productivity of the film is reduced, and it becomes difficult to secure a surface area of 5 μm of birefringence of 0.04 or more after lamination, and appearance defects due to lamiroll transfer occur. Absent. If the film thickness exceeds 30 μm, the raw material cost increases, which is not economical, and bending workability with a small curvature deteriorates, which is not preferable.

  Moreover, you may mix | blend a lubricant, antioxidant, a heat stabilizer, a ultraviolet absorber, a plasticizer, an antistatic agent, a crystallizing agent etc. with a polyester resin as needed.

(Method for producing polyester resin film)
Next, the manufacturing method of the polyester resin film which concerns on this invention is demonstrated. The polyester resin film is manufactured as a biaxially stretched film. For example, when using a polyester resin in which PET (polyethylene terephthalate) having a resin melting point of 226 to 256 ° C. and PBT (polybutylene terephthalate) having a temperature of 220 ° C. is used, these resins are melted and kneaded by an extruder and used in a T die. A cast film is formed, biaxially stretched, and then heat-treated at a heat setting temperature of 150 to 210 ° C. for molecular crystallization to produce a raw film.

  In the raw film according to the present invention, it is essential that the heat setting temperature is lower than the melting point of the polyester resin. If heat treatment is performed at a heat setting temperature equal to or higher than the melting point of the polyester resin, the polyester resin as the base material melts, and the film may not be manufactured.

  The polyester resin film can maintain surface smoothness, excellent surface gloss, and high transparency even in retort processing after filling the can contents. The laminated metal plate having a bright color such as gold of the present invention is obtained by applying a colored adhesive to the polyester resin film surface to form a highly transparent colored film and superimposing it on the gloss of the underlying metal plate. That is, it is preferable to use a highly transparent film in order to produce a colored laminated metal plate for containers having excellent design properties.

(Manufacturing method of multilayer resin film)
The colored adhesive layer having the above-described configuration is prepared by diluting and preparing an adhesive containing a colorant with a diluting solvent, and using a roll coater method, a die coater method, a gravure method, a gravure offset method, a spray coating method, or the like. It can form by apply | coating to the polyester resin film surface by. Then, in order to volatilize and remove the diluting solvent, it is dried at a temperature of 50 to 180 ° C. and wound up in a coil shape. In this way, the multilayer resin film according to the present invention is formed.

  As the diluting solvent, for example, ester solvents such as methyl acetate and butyl acetate, ketone solvents such as acetone, methyl ethyl ketone, and methyl isobutyl ketone, aromatic hydrocarbon solvents such as toluene and xylene can be used.

  Compared to a plastic film coater, the steel sheet coater has a higher equipment cost. Therefore, it is more advantageous to apply the adhesive layer to the film than to apply it to the steel sheet. The raw film coated with the colored adhesive of the present invention is manufactured to be tack-free by the molecular weight of the epoxy resin, the formulation of the block-free isocyanate compound, and the coating / drying conditions described above.

(Configuration of film on the inner surface of the can)
The multilayer resin film produced as described above is used on the outer surface side of the can, but the configuration of the film used on the inner surface side of the can can be arbitrarily selected. For example, polyester or polyolefin films may be used, and these films may be blended with lubricants, antioxidants, heat stabilizers, UV absorbers, pigments, plasticizers, antistatic agents, crystallizing agents, etc. as necessary. good.

  The inner film can be a multilayer film of two or more layers, and an adhesive can be applied to the surface of the film that contacts the metal. The thickness of the inner film is desirably 6 to 100 μm, the lower limit of the thickness is restricted by the corrosion resistance to the can contents, and the upper limit is economically restricted. It is also possible to apply a non-laminated surface of a metal plate obtained by laminating the multilayer resin film of the present invention on one side and apply it to a container such as a can.

(Method for producing colored laminated metal plate for containers)
Next, based on FIG. 1, the manufacturing method of the colored laminated metal plate for containers which concerns on this invention is demonstrated in detail. In addition, FIG. 1 is explanatory drawing which shows schematic structure of an example of the manufacturing apparatus of the coloring laminated metal plate for containers which concerns on this invention.

  The method for producing a colored laminated metal plate for containers according to the present invention includes a laminating step in which a resin film is thermocompression bonded to one or both surfaces of a metal plate heated to a temperature exceeding the melting point of the polyester resin film using a laminating roll. .

  Here, the resin film includes a colored adhesive layer 22 containing a colorant, a polyester resin having ethylene terephthalate as a main repeating unit, and a polyester resin having butylene terephthalate as a main repeating unit, as shown in FIG. Is a multilayer resin film 20 in which a polyester resin film 24 mainly composed of the above mixture is laminated.

  In the laminating step, as shown in FIG. 1, the metal plate 10 is heated to a temperature exceeding the melting point of the polyester resin 24, and a laminate roll 42 is used to laminate the metal plate 10 from one side (the outer surface of the can). The layer resin film 20 is laminated by thermocompression bonding the can inner surface film 30 from the other surface of the metal plate 10 (the side that becomes the inner surface of the can) using a laminating roll 44. Moreover, the nip width d at the time of thermocompression bonding is, for example, 70 mm, and the metal plate 10 passes through this in, for example, 0.03 seconds. Further, the laminated metal plate that has passed through the laminate rolls 42 and 44 is cooled in the water quench 50.

  In addition, the laminating process of laminating the surface of the multilayer resin film 20 on the colored adhesive layer 22 side by thermocompression bonding to the metal plate 10 includes (A) the metal plate of the multilayer resin film 20 passing through the laminate rolls 42 and 44. The temperature of the adhesive surface with 10 is a temperature equal to or higher than the melting point of the polyester resin whose main repeating unit is butylene terephthalate, and the thermocompression bonding time by the laminate rolls 42 and 44 is 10 to 80 milliseconds. A step of thermocompression bonding the surface of the resin film 20 on the colored adhesive layer 22 side to the metal plate 10, and (B) a heat treatment at a temperature of 150 ° C. or higher for the metal plate 10 after passing through the laminate rolls 42 and 44 for 0.5 to 30 seconds. And a process of performing. Hereinafter, the conditions (A) and (B) will be described in more detail.

  First, in the condition (A), the conditions regarding the heating temperature of the metal plate 10 are conditions necessary for thermocompression bonding the multilayer resin film 20 according to the present invention to the metal plate 10. By heating the metal plate 10 to a melting point or higher of the polyester resin having butylene terephthalate as a main repeating unit, the film melts and increases the fluidity at the time of lamination, so that the colored adhesive layer 22 softened through the film is formed on the metal plate 10. A sufficient adhesion can be obtained by increasing the contact area with the metal plate 10 by wetting the surface.

  A composite polyester resin in which a polyester resin containing ethylene terephthalate as the main repeating unit and a polyester resin containing butylene terephthalate as the main repeating unit forms a polymer alloy that is finely and uniformly mixed, and has a low melting point composition. When the polyester resin having butylene terephthalate as the main repeating unit melts, the resin becomes fluid, so that a good adhesion can be obtained.

  On the other hand, when the temperature of the metal plate 10 passing through the laminating rolls 42 and 44 is lower than the melting point of the polyester resin whose main repeating unit is butylene terephthalate, the melting of the film becomes insufficient. The film cannot be sufficiently wetted on the surface, resulting in insufficient adhesion.

  In addition, the heating method of the metal plate 10 is not specifically limited, For example, well-known methods, such as a hot air circulation heat transfer system, a resistance heating system, a heat roll heat transfer system, an induction heating system, can be used.

  The laminate rolls 42 and 44 are cooled, and the surface (outer surface) of the polyester resin film is in contact with the surface of the laminate rolls 42 and 44 to prevent overmelting to the outer surface of the film.

  Next, in the condition (A), the condition relating to the thermocompression bonding time is a necessary condition for obtaining a sufficient adhesion force of the multilayer polyester resin film 20 according to the present invention to the metal plate 10. The pressure bonding time is set to 10 to 80 msec. When the pressure bonding time is less than 10 msec, it is difficult to obtain sufficient adhesion because the time is too short even if the temperature of the bonding surface is equal to or higher than the melting point of the polyester resin 24. This is because if the pressure bonding time exceeds 80 msec, the productivity decreases due to a decrease in the laminating plate speed, which is not preferable.

Moreover, it is preferable that the surface pressure in the said thermocompression bonding is 1-30 kgf / cm < ² >. If the surface pressure is 1 kgf / cm ² , the pressure bonding time is short as described above, and it is difficult to obtain a sufficient adhesion force. On the other hand, when the surface pressure exceeds 30 kgf / cm ² , there is no inconvenience in the performance of the colored laminated metal plate for containers, but the force applied to the laminating rolls 42 and 44 is large, and equipment strength is required, so that the size of the manufacturing apparatus is large. This is not preferable because it is uneconomical.

  Thus, the thermocompression bonding conditions (crimping time and surface pressure) are comprehensively determined for the purpose of achieving both the quality and economical efficiency of the colored laminated metal sheet for containers.

  In the laminating step, it is preferable that the cleanness of the atmosphere is class 10,000 or less. This is because if there are many foreign substances in the atmosphere at the time of lamination, foreign substances are mixed into the interface between the multilayer resin film 20 or the can inner surface film 30 and the metal plate 10 and cause film defects during can manufacturing.

  In addition, as the laminate rolls 42 and 44, various rolls such as a chrome plating roll, a ceramic coating roll, and a rubber lining roll can be selected. Although not particularly limited, a heat crown in the roll nip, It is preferable to use a rubber lining roll from the viewpoint of avoiding a defective shape of the metal plate caused by variations.

  In addition, the colored laminated metal plate for containers after passing through the laminating rolls 42 and 44 has a high temperature of about 200 ° C., and if it is wound as a coil as it is, film fusion or blocking between coil wraps occurs. It is necessary to cool by water cooling etc. using 50 grade | etc.,.

  Further, under the condition (B), heat treatment for 0.5 to 30 seconds at a laminate metal plate temperature of 150 ° C. or higher after passing through the laminate roll is necessary for curing the colored adhesive. Specifically, this heat treatment is performed after passing through the laminate nip and before cooling by water quench. In this way, by proceeding with the curing reaction of the colored adhesive after passing through the laminate nip and before cooling with water quench, the colored adhesive is prevented from curing during retort heat treatment. Retort brushing can be prevented more effectively.

  According to the method for producing a colored laminated metal sheet for containers according to the present invention as described above, retort brushing is prevented, and the colored appearance such as gold / brilliant color having excellent smoothness and severe processing applications are used. A laminated metal plate having film adhesion can be provided.

  EXAMPLES Hereinafter, although an Example demonstrates this invention more concretely, this invention is not limited only to the following Example.

(Manufacture of colored laminated steel sheets for containers)
A loaf plate having a thickness of 0.21 mm is degreased and pickled, then chrome-plated in a chromium plating bath containing chromic anhydride and fluoride, and after an intermediate rinse, electrolytic conversion treatment is performed with a chemical conversion treatment solution containing chromic anhydride and fluoride. The obtained metal plate was used as a base material. The chromium plating amount of the base material was adjusted so that the metal chromium adhesion amount was 100 mg / m ² and the chromium hydrated oxide amount was 12 mg / m ² .

  A mixed polyester resin of PET / IA3 and PBT is melted and mixed with an extruder to form a cast film with a T-die, biaxially stretched, and then heat-treated at a heat setting temperature of 170 ° C. for biaxially oriented crystallization. A polyester resin film was produced. The composition of the sample polyester resin film is as shown in Table 1 below. PET / IA3 indicates a copolymerized polyester of 97 mol% polyethylene terephthalate / 3 mol% polyethylene isophthalate.

  About the manufactured polyester resin film for samples, melting | fusing point and semi-crystallization time were measured. The measurement results are shown in Table 1 below. Here, the melting point of the polyester resin was measured by increasing the temperature at a rate of 20 ° C./min using a Dupont Instrument 910 DSC and determining the melting peak. The semi-crystallization time of the polyester resin was measured by a depolarization method using a polymer crystallization rate measuring apparatus MK-701 manufactured by Kotaki Corporation.

  Next, a multi-layer resin film for a sample was produced by coating a color adhesive having the composition shown in Table 1 below on the polyester resin film surface for the sample with a roll coater to a coating thickness of 1.6 μm.

  Here, as the colored adhesive, epoxy resin Epicoat 1004 (number average molecular weight 1650, made by Japan Epoxy Resin), Epicoat 1007 (number average molecular weight 2900, made by Japan Epoxy Resin), Epicoat 1009 (number average molecular weight 3800, Japan Epoxy Resin) Manufactured), Epicoat 1010 (number average molecular weight 5500, manufactured by Japan Epoxy Resin) was used.

  Further, Cymel 300 (manufactured by Mitsui Cytec) was used as the highly etherified amino resin, and Desmodur BL3475 (manufactured by Sumitomo Bayer Urethane) was used as the blocked isocyanate compound. Neostan U-200 (manufactured by Nitto Kasei) was used as the tin catalyst, and Neicure 5225 (manufactured by KING INDUSTRIES) was used as the acid catalyst. As the phosphoric acid-modified compound, Epicoat 1007 was modified with phosphoric acid to have an acid value of 3 to 6 (mgKOH / g). As the block-free isocyanate compound, Vernock DN980 (manufactured by Dainippon Ink & Chemicals, Inc.) was used. In addition, yellow and red azo organic pigments were used as pigments. In addition, polyester resin Aron Melt PES-360 (number average molecular weight 20000, manufactured by Toagosei Co., Ltd.) was used as a main agent comparison.

  Further, using the apparatus as shown in FIG. 1, the chrome-plated steel sheet as the base material is heated to the temperature shown in Table 1, and one of the surfaces (the surface on the can outer surface side) By laminating the resin film on the other surface (the surface on the inner surface side of the can) with a copolymer polyester resin film of PET / IA12: polyethylene terephthalate 88 mol% / polyethylene isophthalate 12 mol% as a film for the inner surface of the can A colored laminated steel sheet for containers was manufactured.

(Evaluation of colored laminated steel sheet for containers)
About the colored laminated steel sheet for containers manufactured as mentioned above, the film outer surface orientation thickness, the surface property after lamination, the appearance after retort heat treatment, and the results of evaluating the DRD can retort adhesion will be described.

Evaluation of the colored laminated steel sheet for containers was performed as follows.
(1) Film outer surface orientation thickness The film outer surface orientation thickness refers to the thickness of a region where a lot of polyester biaxially oriented crystals in the film after lamination exist and which function as a hard skin layer even while passing through the laminate roll. The thickness was measured from the outer surface of the film with a refraction of 0.04 or more as a region where a lot of biaxially oriented crystals remained. Specifically, it was measured by obtaining a phase angle θ and birefringence distribution with a polarizing microscope using a sample obtained by slicing a film into a thin film in the thickness direction.
(2) Surface properties after laminating The transfer resistance that suppresses the appearance defects caused by the unevenness due to dirt and scratches on the laminating roll being transferred to the film after laminating was evaluated. Specifically, the surface roughness of the artificial roll scratched with the sandpaper count # 600 on the fluororubber surface of the laminate roll and the transfer scratch Ra of the film after lamination of the scratch were measured, and the transfer rate was evaluated to evaluate the transfer resistance. .
The center line average roughness Ra was measured at a 0.8 mm pitch using a contact type three-dimensional roughness meter. The transfer rate is obtained as a ratio of the scratches Ra on the surface of the laminate roll and the transfer scratch Ra on the film after lamination. Taking practical characteristics into consideration, the transfer rate of 60% or more is large, and the transfer rate of less than 60% is small. The thing was made into (circle).
(3) Appearance after Retort Heat Treatment A Φ160 mm disk was punched from the laminated metal plate, and a DRD can (drawn can) having an inner diameter of 87 mm was obtained by two-stage drawing. After trimming the flange part of this DRD can to a width of 2.5 mm, filling with water, tightening the lid, and performing a retort heat treatment at 125 ° C for 90 minutes, the change in the appearance of the can after the retort heat treatment Judgment was made visually. Specifically, ◯ indicates that there was no change in appearance, △ indicates that there was a slight retort brushing, and X indicates that there was a significant retort brushing. In addition, retort brushing was performed by the following appearance evaluation for both the film and the colored adhesive.
In film retort brushing, steam is sprayed unevenly on the surface of the can in the retort treatment tank, resulting in non-uniform recrystallization of the polyester melt molecules and appearing as film turbidity. In this case, the appearance of the metallic plate covered with a cloudy film becomes poor.
In retort brushing of colored adhesive, the adhesive hardens with residual solvent and moisture during retorting, so that the cured adhesive layer expands partially and non-uniformly, and the gold color becomes partially cloudy brown. Discolor. In this case, the appearance is poor because the transparent film covers the discolored metal plate.
(4) DRD can retort adhesion As in (3), the can and flange trimmed DRD can were subjected to retort heat treatment at 125 ° C. for 90 minutes, and film peeling of the flange portion of the can after retort heat treatment was visually observed. . Specifically, the case where there was no peeling of the film was marked with ◯, and the case where there was peeling of the film was marked with ×.

  The evaluation results of the colored laminated steel sheet for containers performed as described above are shown in Table 1 below.

  In Examples 1 to 3 and Comparative Example 1, the mixing ratio of PET and PBT of the polyester resin film was changed. The ratio of PBT is 15%, and the semi-crystallization time of the polyester resin film is 200 seconds. Comparative Example 1 outside the scope of the present invention, as shown in Table 1, shows that retort brushing of the film is remarkable. I understood. That is, it was suggested that the retort brushing of the film can be prevented by setting the semi-crystallization time of the polyester resin film at 125 ° C. to 100 seconds or less.

  In Examples 4 and 5 and Comparative Example 2, the film outer surface orientation thickness after lamination, that is, the thickness of the region where the birefringence is 0.04 or more is changed. In Comparative Example 2 in which the region thickness of the birefringence of 0.04 or more was less than 5 μm (3 μm), it was confirmed that the transfer of the scratches on the surface of the laminate roll was large and poor in the surface properties of the film after lamination. That is, by setting the thickness of the region where the birefringence is 0.04 or more to 5 μm or more, the unevenness of the laminate roll whose surface is rough due to contamination or scratches on the laminate roll is smoothed without being transferred to the film surface after lamination. It was suggested that gender can be maintained.

  In Examples 6 and 7, and Comparative Example 3, the number average molecular weight of the epoxy resin of the colored adhesive was changed. It was recognized that Comparative Example 3 having an epoxy resin molecular weight of 1650, which is outside the scope of the present invention, is inferior in DRD can retort adhesion. That is, it was suggested that the retort adhesion at the interface between the metal plate and the colored adhesive layer can be improved by setting the molecular weight of the epoxy resin as the main component of the colored adhesive layer to 2000 to 6000. .

  In Example 8 and Comparative Examples 4 and 5, the composition amount of the highly etherified amino resin was changed. In Comparative Example 4 containing no highly etherified amino resin, the thermosetting reaction rate of the colored adhesive was slow, so that the curing reaction did not proceed sufficiently in the laminate heat treatment, and retort brushing of the colored adhesive occurred. In Comparative Example 5 in which the addition amount of the highly etherified amino resin was 20 parts by mass, it was confirmed that the thermosetting in the laminate was sufficient, but the DRD can retort adhesion was inferior.

  In Example 9 and Comparative Examples 6 and 7, the composition amount of the block-free isocyanate compound was changed. It was found that Comparative Example 6 containing no block-free isocyanate compound did not cause retort brushing of the colored adhesive, but was inferior in DRD can retort adhesion. Moreover, also in the comparative example 7 whose addition amount of a block free isocyanate compound is 20 mass parts, the fall of DRD can retort adhesiveness was recognized.

  From the results of Examples 8 and 9 and Comparative Examples 4 to 7, it was suggested that the highly etherified amino resin greatly contributed to the acceleration of the curing of the adhesive during the lamination process. Moreover, it was suggested that the blocked isocyanate compound has the effect of reducing the internal stress during curing of the colored adhesive when used in combination with a highly etherified amino resin.

Example 1 0 is obtained by changing the heat treatment time after passing through laminating rolls until cooled in a water quench.

In Comparative Example 8 using a polyester resin as the main component of the colored adhesive, retort brushing occurred due to insufficient curing of the colored adhesive in the laminating process. This suggests that epoxy resin contributes greatly to the acceleration of adhesive curing during the lamination process.

  As mentioned above, although preferred embodiment of this invention was described referring an accompanying drawing, it cannot be overemphasized that this invention is not limited to this example. It will be apparent to those skilled in the art that various changes and modifications can be made within the scope of the claims, and these are naturally within the technical scope of the present invention. Understood.

  The present invention is applicable to a colored laminated metal plate for containers and a method for producing the same, and particularly applicable to a colored laminated metal plate for containers having a smooth and bright appearance and excellent design properties and a method for producing the same. is there.

It is explanatory drawing which shows schematic structure of the manufacturing apparatus of the coloring laminated metal plate for containers which concerns on one Embodiment of this invention.

Explanation of symbols

10 Metal plate 20 Multi-layer resin film (film for can outer surface)
22 Colored Adhesive Layer 24 Polyester Resin Film 30 Can Inner Film 42,44 Laminate Roll 50 Water Quench

Claims (4)

A colored laminated metal plate for containers formed by coating a multilayer resin film in which a colored adhesive layer and a polyester resin film are laminated on one side or both sides of a metal plate ,
The colored adhesive layer is mainly composed of an epoxy resin having a number average molecular weight of 2000 to 6000, and further, a colorant and 1 to 10 parts by mass of a highly etherified amino resin with respect to 100 parts by mass of the epoxy resin , wherein the blocked isocyanate compound of 1 to 10 parts by weight with respect to the epoxy resin 100 parts by weight,
The polyester resin film is mainly composed of a polyester resin having a semi-crystallization time at 125 ° C. of 100 seconds or less ,
In the polyester resin film, a region having a birefringence of 0.04 or more exists in a thickness direction of 5 μm or more from the outer surface of the film,
The polyester resin comprises a polyester resin having ethylene terephthalate as a main repeating unit and a polyester resin having butylene terephthalate as a main repeating unit, the polyester resin having ethylene terephthalate as a main repeating unit, and the repeating unit having butylene terephthalate as a main repeating unit. the polyester resin to be a unit, 80: 20-30: is mixed at a mass ratio of 70, characterized in Rukoto, container colored laminated metal sheet. The colored laminated metal sheet for containers according to claim 1, wherein the polyester resin film has a thickness of 8 to 30 µm. The colored laminated metal sheet for containers according to claim 1 or 2 , wherein the colored adhesive layer further contains one or both of a phosphoric acid-modified compound and a block-free isocyanate compound. In a method for producing a colored laminated metal plate for containers, including a laminating process in which a resin film is thermocompression bonded to one side or both sides of a metal plate using a laminating roll ,
The resin film is, (a) a coloring adhesive layer containing a colorant, (b) a polyester resin containing ethylene terephthalate as the main repeating unit, a polyester resin and Tona Ru polyester resin of butylene terephthalate as the main repeating unit A multi-layer resin film in which films are laminated,
The colored adhesive layer is mainly composed of an epoxy resin having a number average molecular weight of 2000 to 6000, and further, a colorant and 1 to 10 parts by mass of a highly etherified amino resin with respect to 100 parts by mass of the epoxy resin, 1 to 10 parts by weight of a blocked isocyanate compound with respect to 100 parts by weight of the epoxy resin,
The polyester resin film is mainly composed of a polyester resin having a semi-crystallization time at 125 ° C. of 100 seconds or less,
In the polyester resin film, a region having a birefringence of 0.04 or more exists in a thickness direction of 5 μm or more from the outer surface of the film,
The polyester resin having ethylene terephthalate as a main repeating unit and the polyester resin having butylene terephthalate as a main repeating unit are mixed at a mass ratio of 80:20 to 30:70,
The laminating process includes:
(A) The temperature of the adhesive surface with the metal plate of the multilayer resin film passing through the laminating roll is set to a temperature equal to or higher than the melting point of the polyester resin mainly composed of butylene terephthalate, and depending on the laminating roll. Under the condition that the thermocompression bonding time is 10 to 80 milliseconds , the step of thermocompression bonding the surface on the colored adhesive layer side of the multilayer resin film to the metal plate ;
(B) a step of heat-treating the metal plate after passing through the laminate roll at a temperature of 150 ° C. or higher for 0.5 to 30 seconds ;
The manufacturing method of the coloring laminated metal plate for containers of Claim 1 characterized by the above-mentioned .