JP2000154264A - Pre-colored resin film, metal plate coated with pre- colored resin and can prepared from metal plate coated with pre-colored resin - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a pre-colored resin film which has a thin film-thickness, exerts a high opacifying effect on the substrate to which it is applied, and produces various color tones through combinations of color pigments contained therein, a metal plate coated with this pre-colored resin film and a can coated with this pre-colored resin film. SOLUTION: A pre-colored resin film is prepared by adding two or more kinds of color pigments (pigment 4 and pigment 4') of different colors or materials to one layer of a resin layer comprising one or more layers (surface layer 1 and rear layer 2) mainly comprisin a polyester resin. Otherwise, a pre- colored resin film is prepared by adding one or more color pigments of different kinds to each of the two or more layers of a resin layer comprising two or more layers.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a colored resin film, and more particularly to a colored resin film having a small film thickness and excellent concealability of a base to be coated, a metal plate coated with the colored resin film, and The present invention relates to a can using a metal plate coated with the colored resin film.

[0002]

2. Description of the Related Art In recent years, a material obtained by laminating a thermoplastic resin film such as a polyester resin film on both sides of a metal plate has been used for food cans and beverage cans which are subjected to forming processing such as drawn cans and thinned drawn cans. Used in large quantities. Generally, the outer surface of food cans and beverage cans is printed to enhance its design, but it hides the underlying metal colors such as TFS, tinplate, and aluminum that are commonly used for can materials, and prints. For the purpose of sharpening, a laminate obtained by laminating a thermoplastic resin film containing a white pigment on a metal plate is used. In recent years, further design properties have been demanded for such cans, and simply laminating a thermoplastic resin film containing a white pigment on a metal plate and concealing the base of the metal plate has become unable to respond to user requirements. . The required base color is not only to conceal the metal plate base, but also to enhance the design of the outer surface of the can, such as brilliant metal colors such as gold and silver, or opaque primary colors and pale intermediate colors. Various types are used. In recent years, the thickness of cans has been reduced in order to reduce costs, and more severe processing has been performed such as squeezing, redrawing, or further ironing a metal plate on which a resin film is laminated. When such severe processing is performed, not only the metal substrate but also the coated resin film becomes thin. In addition, when severe processing is performed on the metal plate, irregularities are generated on the surface due to deformation of the crystal grains of the metal, and a dull gray color appearance is exhibited, and together with the thinning of the resin film by the processing described above, The color of the surface of the can after the molding process becomes dark. For this reason, a resin film having a sufficient hiding power even when the thickness is small is required, and at the same time, a resin film colored in various colors is required in order to further add designability. At present, in order to respond to such demands, after laminating a resin film containing a white pigment such as titanium dioxide on a metal plate, and before or after forming into a can, paint containing the pigment is applied several times. Overcoating increases concealment. Each time such paint is applied repeatedly, it is necessary to repeat painting and drying and baking each time.Therefore, a large number of facilities such as coating equipment, solvent treatment equipment, and drying and baking ovens must be added. And leads to a significant increase in manufacturing costs.

[0003]

SUMMARY OF THE INVENTION According to the present invention, a film thickness capable of responding to such a demand for designability without requiring large-scale capital investment and at a low manufacturing cost. Colored resin film that is thin and has excellent concealing properties of the base material to be coated, and can create various colors by combining color pigments to be contained, a metal plate coated with the colored resin film, and the colored resin It is an object to provide a can using a metal plate coated with a film.

[0004]

According to the present invention, there is provided a film made of a resin containing polyester as a main component comprising a single layer or two or more layers, wherein one layer contains two or more colored pigments having different colors or materials. In a colored resin film characterized by adding more than one kind, or a multilayer film made of a resin mainly composed of polyester composed of two or three or more layers, different kinds of pigments are added to two or more layers.
A colored resin film characterized by being added by kind or by two or more kinds, one kind of colored pigment added to one layer by two or more kinds is an inorganic pigment, and furthermore, one kind of colored pigment is Aluminum powder, wherein the thickness of the layer to which the aluminum powder is added is not more than 1/3 of the average particle size of the aluminum powder, and one type of coloring pigment is mica powder; The thickness of the added layer is not more than 1/3 of the average particle size of the mica powder, and one type of the coloring pigment is a titanium dioxide powder. Further, in the colored resin film of the present invention, the resin containing the polyester as a main component is ethylene terephthalate, ethylene isophthalate,
Butylene terephthalate, a modified bisphenol-terephthalic acid copolymer, and characterized by being mainly composed of at least one unit selected from cyclohexane dimethylene terephthalate, and the colored resin film is an unstretched film or a biaxially stretched film It is characterized by being. Further, the colored resin-coated metal plate of the present invention is a colored resin-coated metal plate obtained by laminating the above-mentioned colored resin film on at least one surface of the metal plate, wherein the metal plate is tinplate, tin-free steel ( TFS) or an aluminum alloy plate. Further, the present invention is also directed to a can using the above-mentioned colored resin-coated metal plate.

[0005]

BEST MODE FOR CARRYING OUT THE INVENTION The colored resin film of the present invention is mainly composed of a polyester resin composed of a single layer or two or more layers, and one layer contains two or more colored pigments having different colors or materials.
As a main component, a colored resin film to which at least one kind is added, or a polyester resin composed of two or three or more layers,
A colored resin characterized in that different types of pigments are added to two or more layers one by one or two or more types, and one or more of the colored pigments added to one layer is an inorganic pigment. It is a film that is excellent in concealing properties and design properties of the underlying metal, and is capable of producing various colors such as a metallic color having a brilliant color and a light intermediate color. In addition, the metal plate laminated with this colored resin film is excellent in concealment of the underlying metal plate, and when subjected to severe processing and molded into a can,
It does not peel off the resin film and has excellent can-making properties. Furthermore, a can formed by using a metal plate on which this colored resin film is laminated is excellent in concealing properties of a base metal,
In addition, it has a color excellent in design and can omit a part of the decorative printing process performed after the forming process, and can also omit some devices such as a printing machine and an oven.
Therefore, the cost can be reduced, and the generation of the organic solvent and carbon dioxide gas can be suppressed.

Hereinafter, the present invention will be described in detail. FIGS. 1, 2, 3, 4, 5, 6, and 7 show examples of the cross-sectional structure of the colored resin film of the present invention. FIG. 1 is a sectional view of a colored resin film having two layers. The surface layer 1 is a layer containing no coloring pigment, and the back layer 2
Contains two kinds of coloring pigments A (4) and B (4 '). FIG. 2 is a sectional view of a colored resin film having two layers. Surface layer 1 contains coloring pigment B (4 ′),
The back layer 2 contains the coloring pigment A (4). FIG. 3 is a sectional view of a colored resin film having three layers. The surface layer 1 contains the color pigment B (4 ′), and the core layer 3 contains the color pigment A (4). FIG. 4 is a sectional view of a colored resin film having three layers. The surface layer 1 contains the coloring pigment B (4 ′) and the coloring pigment C (4 ″), and the core layer 3 contains the coloring pigment A (4). FIG. 5 is a sectional view of a colored resin film having two layers. Surface layer 1 is colored pigment A (4)
The back layer 2 further contains a coloring pigment B (4 ′). FIG. 6 is a sectional view of a colored resin film having three layers. The surface layer 1 contains the coloring pigment C (4 ″),
Further, the back layer 2 contains a coloring pigment A (4). Further, the core layer 3 contains the coloring pigment B (4 ′). FIG.
5 is a cross-sectional view in which the two-layered colored resin film shown in FIG. 5 is laminated on the metal plate 6 via the adhesive layer 5.

Although several examples of the colored resin film of the present invention have been described above, at least two or more different pigments are added to each colored resin film. By combining the type of the coloring pigment to be contained in the resin film and the position of the coloring resin film layer in the entire multilayer resin film, it is possible to develop various colors, but in order to develop a color rich in design properties. It is preferable to use at least two types of color pigments. And
It is preferable that one of the at least two types of coloring pigments is an inorganic pigment in order to cover the underlying metal. Further, if the total thickness of the resin film is 5 to 50 μm, it is possible to achieve both sufficient concealing properties and design properties.

Further, it is preferable to use a polyester resin as the resin film of the present invention. As the polyester resin, ethylene terephthalate, ethylene isophthalate, butylene terephthalate, butylene isophthalate, modified bisphenol-terephthalic acid copolymer,
And those having an ester unit such as cyclohexane dimethylene terephthalate are preferable, and further, it is preferable that the polyester is mainly composed of at least one ester unit selected from these. At this time, each of the ester units may be copolymerized, or two or more homopolymers or copolymers of the ester units may be blended and used. Other than the above, those using naphthalenedicarboxylic acid, adipic acid, sebacic acid, trimellitic acid, etc. for the acidic component of the ester unit, and propylene glycol, neopentyl glycol, diethylene glycol, pentaerythritol, etc. as the alcohol component May be used. Further, a mixture of a small amount of a polyester resin as a main component other than polyester, such as a polycarbonate resin, a polyamide resin, and a polyolefin resin, may be used. In doing so, it is necessary to have excellent adhesion to the metal plate so as not to peel or chip.

As the pigment used in the colored resin film of the present invention, various pigments described below can be used. As the white pigment, rutile-type or anatase-type titanium dioxide, zinc white, lead white, lead sulfate, lithobon, zinc sulfide, antimony oxide and the like can be used. Further, extenders which can provide a matting effect include barite, precipitated barium sulfate, barium carbonate, carbonated lime powder, precipitated calcium carbonate, gypsum, asbestos, clay (kaolin), silica powder, finely divided silica, diatomaceous earth, and base. Magnesium carbonate, alumina white, gloss white, satin white and the like can be used. As the black pigment, magnetite (iron black), carbon black, aniline black, cyanine black and the like can be used. Inorganic pigments such as yellow lead, zinc yellow, barium chromate, cadmium yellow, yellow iron oxide, loess, titanium yellow, lead cyanamide, and calcium lead oxide are included as yellow pigments, and azo pigments such as Hansa yellow are used as organic pigments. And nitro pigments such as naphthol yellow. As the orange pigment, in addition to inorganic pigments such as red lead graphite and chromium permillion, azo pigments such as permanent orange can be used as organic pigments. As the red pigment, besides inorganic pigments such as red iron red, lead red, silver vermilion, cadmium red, cadmium mercury red, antimony vermilion, etc., organic pigments such as azo pigments such as permanent red or quinacridone pigments can be used. As the purple pigment, cobalt purple [(Co3 (P
In addition to inorganic pigments such as O4) 2 or Co3 (AsO4) 2] or manganese violet, azo pigments such as fast violet B and basic dye lake pigments such as methyl violet lake can be used as organic pigments. As blue pigments, in addition to inorganic pigments such as ultramarine, navy blue, cobalt blue, cerulean blue, and Kuresu, organic pigments such as phthalocyanine pigments such as phthalocyanine blue and acidic dye lake pigments such as alkali blue lake can be used. As green pigments, in addition to inorganic pigments such as chrome green, zinc green, chromium oxide, pyridian, emerald green or cobalt green, nitroso pigments such as pigment green B and phthalocyanine pigments such as phthalocyanine green can be used as organic pigments. .

Among the above-mentioned pigments, inorganic pigments having a three-dimensional shape such as a spherical shape, a pseudo-spherical shape, a cylindrical shape, etc., preferably have a particle size in the range of 0.05 to 5 μm. When the diameter is smaller than 0.05 μm, the surface area per volume increases, the adsorption of moisture increases, the decrease in the intrinsic viscosity of the resin increases, and the color pigments easily aggregate. Conversely, if the particle size is larger than 5 μm, problems such as the film being easily cut occur, so the particle size is more preferably 0.1 to 1 μm.

Aluminum powder, bronze powder, copper powder, lead powder or zinc powder can be used as the metal powder pigment which gives a metallic luster. As a pigment other than the metal powder that produces a metallic luster color, surface-treated mica powder or the like can be used.
It is preferable that these pigments that produce a metallic glossy color have a plate shape, and the larger the particle size, the higher the glitter. In addition, a flat pigment has a particle diameter of 0.1 to 1000 μm in a wide range because the resin film is hard to be cut even when added to the resin film as compared with a three-dimensional pigment such as a sphere or a column. Can be used. However, if the particle size of the pigment becomes too large with respect to the thickness of the resin film, the resin film is easily broken in the film forming process, and therefore, the size should be several times or less with respect to the thickness of the resin film. Is preferable, and the particle size is more preferably in the range of 1 to 500 μm.

The mica powder is coated with titanium dioxide or iron oxide as a surface treatment, and by changing the coating amount, it is possible to obtain not only a metallic luster color such as gold or silver, but also a pearl or pastel color. Bright colors can be developed.

[0013] Tin-free steel (TFS), tinplate, or an aluminum alloy plate is generally used for food and beverage cans. A resin film-coated metal plate using such a metal plate is subjected to severe processing by a severe process. When formed, the surface of the body of the can becomes uneven, giving it a dark gray color. In view of the design, it is necessary to hide this color tone. In order to hide the color tone of the metal base, it is preferable that at least one film layer contains a colored inorganic pigment. Further, according to the present invention, it is possible to develop a required color by including two or more different pigments in the polyester resin film. For example, a white pigment and a red pigment can be mixed to produce a pink color, and a white pigment and a blue pigment can produce a light blue color. This is the same as mixing the primary colors to obtain an intermediate color, and can be adjusted to various colors by adjusting the type and amount of the pigment to be added. In this case, as in the two-layer film shown in FIG. 1, the color tone can be adjusted by including two types of pigment A (4) and pigment B (4 ′) in one layer. The pigment A (4) may be contained in the back layer 2 of the two-layer film and the pigment B (4 ') may be contained in the upper layer 1 as shown in FIG. However, in this case, in order to obtain the same effect as containing two kinds of coloring pigments in one layer shown in FIG. 1, an inorganic pigment having a large hiding effect is provided in the lower layer 2 and a hiding effect is provided in the upper layer 1. It is preferable to add an organic pigment having a small effect.

FIG. 3 shows a case where a three-layer film is used as a resin film to be coated. In this case, a layer containing a large amount of an inorganic pigment having a concealing property is applied to the core layer 3, and a layer containing an inorganic or organic pigment B (4 ′) for producing a desired color is formed on the upper layer (surface layer 1). It should be applied, even after shaping into a can, the dark color of the metal substrate was hidden,
It is possible to have an appearance excellent in design.
It is preferable to use titanium dioxide or carbon black as the inorganic pigment having a hiding property. In the case of titanium dioxide, a film layer having a thickness of 10 μm or more containing 10% by weight or more is contained. In the case of carbon black, 5% by weight or more is contained. If the film layer has a thickness of 10 μm or more, the underlying color can be hidden. The back layer 2 in FIG. 3 simply serves as an adhesive layer. The present invention is not limited to the number of layers of the resin film, and the resin film may have one or two or more layers containing a pigment, and may have one or more layers containing no pigment. It may or may not be necessary. However, when a large amount of inorganic pigment is added to conceal the underlying color, it is better to provide a layer containing no pigment as shown in FIG. 3 in order to improve the adhesion to the metal plate. preferable.

[0015] In recent years, it has been required that not only the dark color of the above-mentioned base metal substrate be concealed but also that it have a beautiful metallic luster as a design of the can. Alternatively, it can be obtained by incorporating a mica powder in the form of a plate whose surface has been treated into a resin film as a pigment. However, if these pigments are not aligned in parallel with the surface of the metal plate that covers the resin film, metallic luster is difficult to develop, and flat pigment particles must be aligned in parallel with the film surface. There is. In order to arrange the flat surface of the pigment in parallel with the film, the layer containing the aluminum powder or the mica powder is formed so that the layer containing the aluminum powder or the mica powder is 1/3 or less of the average particle size of the powder, preferably 1/3 of the average particle size of the powder.
The thickness may be 10 or less. If the layer to which the aluminum powder or mica powder is added is too thin, the resin film tends to break. For this reason, when adding a flat aluminum powder or mica powder, it is preferable to form a film having two or more layers also from the viewpoint of the strength of the resin film, instead of thinning the layer containing the aluminum powder or mica powder. It is necessary to increase the thickness of the other resin layer so that the film is hard to cut. In the example of FIG.
When aluminum powder having an average particle size of 20 μm is used for the pigment B (4 ′), the thickness of the surface layer is preferably 6 μm or less, and more preferably 2 μm or less, the flat surface of the aluminum powder is applied to the film surface. Line up in parallel. Also,
When forming a film, even if a pigment powder having a large particle size is used, the powder does not jump out of the surface layer of the film or move to another film layer, and the thinner the resin film layer, the thinner the resin film layer. The flat surface of the pigment powder tends to be parallel to the film surface. When the pigment is contained, the strength of the film is increased by setting the total thickness of the core layer 3 and the back layer 2 to 5 μm or more, preferably 10 μm, to increase the strength of the film in the film forming step and the laminating step. Breakage of the film can be prevented. When a resin film having such a metallic luster contains mica powder, a sufficient hiding effect cannot be obtained with mica powder alone, so that the film configuration shown in FIG. 2 or 3 is preferable. For example, in the case of FIG. 2, it is preferable that the surface layer 1 contains mica powder as the pigment B (4 ′), and the back layer 2 contains the inorganic pigment A (4) having a concealing property. In the case of FIG. 3, the pigment B
It is preferable that mica powder is contained as (4 ′), and the core layer 3 contains an inorganic pigment A (4) having a masking property.

When aluminum powder is contained, the aluminum powder itself has a concealing property. Therefore, as shown in FIG. 1 or FIG. 5, it is preferable to adopt a film configuration in which the back layer contains aluminum powder. In the case of 1, by adding aluminum powder to the back layer 2 as the pigment B (4 ′) and carbon black of the black pigment as the pigment A (4), a metallic black having a brilliant color can be obtained. By adding quinacridone as a red pigment, it is possible to develop a metallic red with a brilliant color. In the case of the film configuration shown in FIG. 5, by adding aluminum powder as the pigment B (4 ′) of the back layer 2 and containing a pigment having a desired color as the pigment A (4) of the surface layer 1, the metallic luster can be reduced. A colored film having the same can be obtained. In addition, by providing a layer containing a large amount of a coloring pigment having a concealing property under the layer containing the aluminum powder, the influence of blackening of the metal substrate after molding into a can is minimized, and a more metallic layer is formed. A metallic luster is obtained. For example, in the case of the film configuration shown in FIG.
Contains aluminum powder as a color pigment B (4 ′) and a color pigment having a desired color as another color pigment C (4 ″), and has a concealing property as a pigment A (4) of the core layer 3. By adding a large amount of a coloring pigment such as titanium dioxide, a more beautiful metallic glossy color can be obtained in which the influence of the dark color tone of the metal substrate formed into a can is reduced. In the case of the film configuration shown in FIG. 6, a coloring pigment having a desired color is contained as the coloring pigment C (4 ″) of the surface layer 1, and aluminum powder is contained as the pigment B (4 ′) of the core layer 3. Further, by incorporating a large amount of a coloring pigment such as titanium dioxide having concealing properties as the pigment A (4) of the back layer, the influence of the dark color tone of the metal substrate formed into a can was reduced. A more beautiful metallic gloss color can be obtained.

In the present invention, a lubricating material such as silica is applied to the resin film of the surface layer 1 or the back layer 2 as in a normal resin film in order to improve the winding shape when the resin film is wound. May be contained.

When the colored resin film of the present invention is laminated on a metal plate 6, an adhesive layer 5 as shown in FIG. 7 may be used. It can be used as a lamination method when a tinplate that cannot be heated is used. As the adhesive, various commonly used adhesives such as an epoxy / phenol-based adhesive, an epoxy / urea-based adhesive, and a urethane-based adhesive can be used.

In the present invention, various surface-treated steel sheets and aluminum alloy sheets can be used as the metal plate on which the resin film is laminated. As the surface-treated steel sheet, an electrolytic chromic acid-treated steel sheet (tin-free steel (TFS)) or tinplate is preferable. In the case of TFS, 10 to 200 m
By forming a two-layer coating consisting of a lower layer composed of g / m 2 of metallic chromium and a surface layer composed of chromium hydrated oxide of 1 to 30 mg / m 2 in terms of chromium, the resin layer (A) of the resin film of the present invention is formed. ) And sufficient adhesion, and also have corrosion resistance.
In the case of tinplate, the surface of the steel sheet is plated with tin at 0 to 11.2 g / m2, and the tin-plated steel sheet is subjected to electrolytic treatment in an aqueous solution of chromate or chromate to obtain a tin equivalent of 1%.
It is preferable to form a layer composed of chromium metal hydrate and chromium hydrated oxide at ３０30 mg / m 2. In any case, the steel sheet serving as the substrate is preferably a low-carbon cold-rolled steel sheet generally used for can applications. Further, the thickness of the steel sheet is 0.1 to
Preferably it is between 0.32 mm.

The aluminum alloy plate is preferably a plate made of JIS 3000 or 5000 series aluminum alloy. The surface of the aluminum alloy plate is made of 0-200 mg / m 2 of metal chromium by electrolytic chromic acid treatment, To form a two-layer film of chromium hydrated oxide of 1 to 30 mg / m2, or 1 to 30 mg / m2 in terms of chromium by phosphoric acid chromate treatment.
It is preferable to form a chromium component of m2 and a phosphorus component of 0 to 30 mg / m2 in terms of phosphorus. In the case of an aluminum alloy plate, the thickness is preferably 0.15 to 0.4 mm.

[0021]

The present invention will be described in detail with reference to the following examples. Tables 1 and 2 show a list of resin films used in this example and the types of pigments contained in the resin films, respectively.
Shown in

Example 1 As a polyester resin, a copolymer resin consisting of 90 mol% of ethylene terephthalate and 10 mol% of ethylene isophthalate having an intrinsic viscosity of 1.0 was used, and a twin-screw extruder was used. The mixture was kneaded with rutile-type titanium dioxide having an average particle size of 0.2 μm at a temperature, and after extruding the resin, the resin was cut into pieces, and titanium dioxide was added to titanium dioxide.
A master batch in the form of a pellet having a size of 3 mm and containing 0% by weight was prepared. In the same manner, 280
Quinacridone was mixed with the same polyester resin as described above at a temperature of ° C. to a concentration of 5% by weight, and after extrusion, a master batch was formed into pellets having a size of 3 mm. Each masterbatch and ethylene terephthalate 90
Mol% / ethylene isophthalate 10 mol% copolymer resin is separately melt-kneaded at a temperature of 260 ° C. by two twin-screw extruders again to prepare a concentration of 30% by weight of titanium dioxide or 2% by weight of quinacridone, respectively. After that, the mixture was continuously sent to a two-layer co-extrusion die and extruded from a nozzle. The die has a nozzle width of 500 mm and a nozzle opening thickness of 0.8 mm
Was used. The extruded resin has the structure of the two-layer film shown in FIG. 2 and comprises a back layer (2) containing 20% by weight of titanium dioxide and a surface layer (1) containing 2% by weight of quinacridone. Next, the resin extruded from the die was immediately stretched to a thickness of about 150 μm in a molten state, heated to about 120 ° C. by an infrared heater, stretched three times in a longitudinal direction, and further heated in an oven at 120 ° C. The film was transversely stretched by a factor of 2, and then heat set at 170 ° C. The extruded resin was finally formed into a colored bilayer stretched film having a surface layer (1) of 5 μm, a back layer (2) of 10 μm, and a total thickness of 15 μm. The obtained resin film was trimmed at the edge and wound up, and then slit into a film having a width of 800 mm.

Example 2 50% by weight of polyethylene terephthalate having an intrinsic viscosity of 1.0 as a polyester resin
And a resin mixed with 50% by weight of polybutylene terephthalate having an intrinsic viscosity of 1.4, and in the same manner as in Example 1, a master batch containing 60% by weight of titanium dioxide and 5% by weight of quinacridone were contained. Each master batch was created. Each masterbatch and a mixed resin of 50% by weight of polyethylene terephthalate / 50% by weight of polybutylene terephthalate are melt-mixed at a temperature of 260 ° C. by a twin screw extruder to prepare a concentration containing 2% by weight of quinacridone and 20% by weight of titanium dioxide. After that, 50% by weight of polyethylene terephthalate / polybutylene terephthalate 5 melted by another twin screw extruder
The mixture was continuously fed into a two-layer co-extrudable die together with 0% by weight of the mixed resin, and extruded from a die nozzle so as to obtain the film configuration shown in FIG. The die has a nozzle width of 1000mm
The thickness of the nozzle opening was 0.8 mm. The extruded resin is then stretched in the molten state immediately after exiting the nozzle, containing a back layer (2) containing 20% by weight of titanium dioxide and 1% by weight of quinacridone and having a thickness of 15 μm, and a pigment-free, 2 μm thick layer. A colored two-layer unstretched film composed of a certain surface layer (1) was prepared. The created film is 8
It was trimmed to a width of 00 mm and wound up.

Example 3 As a polyester resin, 90 mol% of ethylene terephthalate and 10 mol% of an ethylene oxide-added bisphenol A-terephthalic acid copolymer which is a modified bisphenol-terephthalic acid copolymer having an intrinsic viscosity of 1.2 were used. Example 1 using a copolymer resin
A masterbatch containing 10% by weight of carbon black and a masterbatch containing 10% by weight of a flat aluminum powder having an average particle size of 25 μm were prepared in the same manner as described above. Each masterbatch was mixed with a copolymer resin of ethylene terephthalate 90 mol% / ethylene oxide-added bisphenol A-terephthalic acid copolymer 10 mol% at 260 ° C. by a twin screw extruder.
, And adjusted to a concentration containing 5% by weight of carbon black and 3% by weight of aluminum powder, and then melted by another twin screw extruder.
The resin was continuously fed into a two-layer co-extrudable die together with a resin of 0 mol% / ethylene isophthalate 10 mol%, and extruded from a die nozzle so as to obtain the film configuration of FIG. The same die as in Example 2 was used. The extruded resin is stretched in a molten state immediately after exiting the die and contains 5% by weight of carbon black and 3% by weight of aluminum powder.
A colored two-layer unstretched polyester film comprising a back layer (2) having a thickness of 15 μm and a surface layer (1) having a thickness of 2 μm containing no pigment was prepared. The film was trimmed to a width of 800 mm and wound up.

(Example 4) The same polyester resin as in Example 1 was used except that the same copolymer resin consisting of 90 mol% of ethylene terephthalate / 10 mol% of ethylene oxide-added bisphebol A-terephthalic acid copolymer was used. In the same manner, a masterbatch containing 60% by weight of titanium dioxide having an average particle size of 0.2 μm and 10% by weight of a flat mica powder having an average particle size of 100 μm and having a surface coated with titanium dioxide were contained. Each master batch was created. Further, each of the master batches was mixed with ethylene terephthalate 90 using two twin-screw extruders.
Mol% / 10 mol% of ethylene oxide-added bisphenol A-terephthalic acid copolymer and mixed with 30% by weight of titanium dioxide or mica 3 respectively.
Ethylene terephthalate 90 having an intrinsic viscosity of 1.0, which was adjusted to a concentration of 100
Mol% / cyclohexane dimethylene terephthalate 10
It was fed into a three-layer co-extrudable die together with a copolymer resin consisting of mol%, and extruded from a die nozzle so as to obtain the film configuration of FIG. The die used had a nozzle width of 1000 mm and a nozzle opening thickness of 0.8 mm. The extruded resin is stretched in a molten state immediately after exiting the die, and the surface layer (1) and the core layer (3) are copolymerized by 90 mol% of ethylene terephthalate / 10 mol% of ethylene oxide-added bisphenol A-terephthalic acid copolymer. Resin, surface layer (1) contains mica 3% by weight and has a thickness of 5 μm
The core layer (3) is a 10 μm-thick colored layer containing 30% by weight of titanium dioxide, and the back layer (2) is a copolymer resin composed of 90 mol% of ethylene terephthalate / 10 mol% of cyclohexane dimethylene terephthalate. A colored three-layer unstretched polyester film composed of a layer having a thickness of 2 μm and containing no pigment was prepared. The film was trimmed to a width of 800 mm and wound up.

(Example 5) A copolymer resin composed of 90 mol% of ethylene terephthalate and 10 mol% of ethylene isophthalate as in Example 1 was used as the polyester resin, and the average particle diameter was calculated in the same manner as in Example 1. 25 μm
A masterbatch containing 10% by weight of a flat aluminum powder and a masterbatch containing 5% by weight of quinacridone were prepared. Furthermore, the same ethylene terephthalate 90 mol% / ethylene oxide-added bisphenol A-terephthalic acid copolymer 1 as in Example 3
A copolymer resin of 0 mol% is used, and the average particle size is 0.2
A masterbatch containing 60% by weight of μm 2 titanium dioxide was also prepared. Next, a colored three-layer unstretched film was prepared using the same extruder as in Example 4 so as to obtain the film configuration shown in FIG. The surface layer (1) and the core layer (3) are made of a copolymer resin composed of 90 mol% of ethylene terephthalate / 10 mol% of ethylene isophthalate, and the surface layer (1) is a colored layer having a thickness of 5 μm and containing 3% by weight of quinacridone. ,
The core layer (3) has a thickness of 2 containing 3% by weight of aluminum powder.
The colored layer of μm and the back layer (2) are made of a copolymer resin composed of 90 mol% of ethylene terephthalate / 10 mol% of ethylene oxide-added bisphenol A-terephthalic acid copolymer, and have a thickness of 10% containing 30% of titanium dioxide.
A colored three-layer unstretched polyester film as a μm colored layer was prepared. The film was trimmed to a width of 800 mm and wound up.

(Example 6) A copolymer resin comprising 90 mol% of ethylene terephthalate and 10 mol% of ethylene isophthalate as in Example 1 was used as the polyester resin, and the average particle diameter was determined in the same manner as in Example 1. 100μ
m and a masterbatch containing 10% by weight of flat mica powder coated with iron oxide and carbon black 1
A masterbatch containing 0% by weight was prepared. Further, a colored three-layer unstretched film was prepared using the same extruder as in Example 4 so as to obtain the film configuration shown in FIG. The surface layer (1), the core layer (2) and the back layer (3) are all 90 mol% ethylene terephthalate / ethylene isophthalate 1
A surface layer (1) containing 3% by weight of mica, a colored layer having a thickness of 5 μm, and a core layer (3).
Prepared a colored three-layer unstretched polyester film containing 3% by weight of carbon black and having a thickness of 10 μm and a backing layer (2) having a colorless layer having a thickness of 2 μm and containing no pigment. The film was trimmed to 800 mm and wound up.

Next, a comparative example will be described. Tables 1 and 2 show a list of the resin films used in the comparative examples and the types of pigments contained in the resin films together with the examples. Comparative Example 1 A masterbatch containing 60% by weight of titanium dioxide in a copolymer resin containing 90% by mole of ethylene terephthalate and 10% by mole of ethylene isophthalate as in Example 1, and 90% by mole of ethylene terephthalate /
A copolymer resin composed of 10 mol% of ethylene isophthalate was melt-mixed at a temperature of 260 ° C. by a twin-screw extruder, and was continuously extruded from a die nozzle. The die can extrude a single-layer resin, the nozzle width is 500 mm, and the thickness of the nozzle opening is 0.5 mm.
8 mm 2 was used. Then, the extruded resin was stretched in a molten state to a thickness of about 150 μm immediately after leaving the die, and the film was heated to about 120 ° C. by an infrared heater.
And stretched three times longitudinally, then heated in an oven at 120 ° C., further stretched three times transversely, and heat-set at 170 ° C. to obtain a 15 μm thick titanium dioxide containing 20% by weight of titanium dioxide. The layer was a colored biaxially stretched film.
The film was wound after trimming the edge to a width of 800 mm.

Comparative Example 2 A masterbatch containing 5% by weight of quinacridone as in Example 1 and 90 mol% of ethylene terephthalate / ethylene isophthalate 10
The copolymer resin consisting of mol% was melt-mixed at a temperature of 260 ° C. by a twin screw extruder, and was continuously extruded from a die nozzle.
Die can extrude single layer resin, nozzle width 1000m
m and the thickness of the nozzle opening was 0.8 mm. Next, the extruded resin was stretched in a molten state immediately after exiting from the nozzle to prepare a single-layer colored unstretched film having a thickness of 15 μm and containing 1% by weight of quinacridone. The film was wound after trimming the edge to a width of 800 mm.

Comparative Example 3 A masterbatch containing 10% by weight of carbon black as in Example 6 and a 90% by mole of ethylene terephthalate / 10% by mole of ethylene isophthalate as in Example 1 were used. Polymerized resin,
Using the same film forming apparatus as in Example 2, a colored two-layer unstretched film having the film configuration shown in FIG. 8 was prepared. The back layer (2) is a colorless layer having a thickness of 2 μm containing no pigment, and the surface layer (1) is a layer having a thickness of 10% containing 5% by weight of carbon black.
It was a colored layer of μm. The film was trimmed to 800 mm and wound up.

(Comparative Example 4) A flat mica powder having an average particle diameter of 40 μm smaller than the mica powder used in Example 3 and coated on the surface with titanium dioxide, and 90 mol% of ethylene terephthalate as in Example 1 A copolymer resin composed of 10 mol% of ethylene isophthalate was kneaded with a twin-screw extruder to prepare a master batch containing 10% by weight of mica powder. Further, using the same apparatus as in Example 2, a mixed resin containing 3% by weight of mica powder and a copolymer resin composed of 90 mol% of ethylene terephthalate and 10 mol% of ethylene isophthalate containing no pigment were heated and melted.
The molten resin was extruded from a two-layer co-extrusion die and stretched in a molten state to prepare a colored two-layer unstretched film shown in FIG. The back layer (2) was a colorless layer having a thickness of 2 μm containing no pigment, and the surface layer (1) was a colored layer having a thickness of 15 μm containing 3% by weight of mica powder. The film was trimmed to a width of 800 mm and wound up.

Comparative Example 5 A masterbatch containing 10% by weight of aluminum powder as in Example 5 and Example 1
Using a copolymer resin composed of 90 mol% of ethylene terephthalate / 10 mol% of ethylene isophthalate similar to that described above and using the same apparatus as in Comparative Example 3, a colored three-layer unstretched film having a film configuration shown in FIG. 9 was prepared. did. The surface layer (1) and the back layer (2) each are a colorless layer having a thickness of 2 μm containing no pigment, and the core layer (3) is a colored three-layer unstretched film consisting of a color layer having a thickness of 10 μm containing 3% by weight of aluminum powder. And The film was trimmed to a width of 800 mm and wound up.

(Comparative Example 6) A masterbatch containing 10% by weight of flat mica powder coated with iron oxide and having an average particle diameter of 30 μm smaller than the mica powder used in Example 6 was used as in Example 1. Created by the method of Further, using the masterbatch and a copolymer resin composed of 90 mol% of ethylene terephthalate and 10 mol% of ethylene isophthalate used in Example 1, using the same apparatus as in Comparative Example 5, the same film configuration as in FIG. Was prepared. The surface layer (1) and the back layer (2) were each a colorless layer having a thickness of 2 μm containing no pigment, and the core layer (3) was a colored layer having a thickness of 15 μm containing 3% by weight of mica powder. The film was trimmed to 800 mm and wound up.

Next, examples and comparative examples of the metal plate coated with the colored resin film will be described. (Example 1 and Comparative Example 1) 0.26 mm in thickness and 800 m in width
m, a resin film shown below was laminated on both surfaces of an aluminum alloy plate (JIS 5052 H39), both surfaces of which were subjected to phosphoric acid chromate treatment, by heat fusion using an apparatus shown in FIG. The aluminum alloy plate immediately before coming into contact with the pair of laminate rolls 8 was heated to 270 ° C. Further, as the resin film 9 laminated on one side of the aluminum alloy plate, the films prepared in Example 1 and Comparative Example 1 were used, and as the resin film 9 ′ laminated on the other side of the aluminum alloy plate, 90% ethylene terephthalate was used. % Of an unstretched resin film having an intrinsic viscosity of 1.0% / isophthalate and 10 mol% of an intrinsic viscosity of 1.0 μm and not containing a coloring pigment having a thickness of 25 μm.
It was used after slitting to m width. The laminating speed (advancing speed of the aluminum alloy plate) was 150 m / min, and a tension of 100 N was applied to the film.

(Examples 2 to 5 and Comparative Examples 2 to 5) Tin-free steel having a thickness of 0.18 mm and a width of 800 mm (metallic chromium content: 120 mg / m2, chromium hydrated oxide content: 15 mg / m2 as chromium) The resin films shown below were laminated on both sides by heat fusion using the apparatus shown in FIG. The tin-free steel immediately before contacting the pair of laminate rolls 8 was heated to 260 ° C. Furthermore, a resin film 9 laminated on one side of tin-free steel
The films prepared in Examples 2 to 5 and Comparative Examples 2 to 5 were respectively laminated. Another resin film 9 'to be laminated on the other side of the tin-free steel was 90 mol% of ethylene terephthalate having a thickness of 25 μm and isoform. Unstretched resin films having an intrinsic viscosity of 1.0 and consisting of 10 mol% of phthalate were slit into 800 mm widths, respectively. The laminating speed was 150 m / min and a tension of 100 N was applied to the film.

(Example 6 and Comparative Example 6) Thickness 0.18
A film having a thickness of 800 mm and a width of 800 mm (tin amount: 0.2 g / m 2, chromium hydrated oxide amount: 5 mg / m 2 as chromium) was laminated by heat fusion using the apparatus shown in FIG. Tinplate immediately before contact with the pair of laminate rolls 8 was heated to 200 ° C. Further, as the resin film 9 to be laminated on one side of the tinplate, the films prepared in Example 6 and Comparative Example 6 were used, and for the resin film 9 'to be laminated on the other side of the tinplate, 90 mol of ethylene terephthalate having a thickness of 25 μm was used. % And 10 mol% of isophthalate, an unstretched polyester resin film having an intrinsic viscosity of 1.0, slit each to a width of 800 mm, and apply a 1.0 μm-thick epoxyphenol-based film to both of the resin films 9 and 9 ′. The paint was applied to one side of the film in advance and dried, and laminated so that the tinplate substrate side and the applied surface were in contact with each other. The laminating speed was 150 m / min, and a tension of 100 N was applied to the film. Table 1 below shows a list of films used in this example and comparative examples.

Table 1: Resin film -------------------------------------------------------------------------- Material category Number of layers Surface layer Core Layer Back layer Total thickness Stretched (thickness) (thickness) (thickness) (μm) −−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−− −−−− Example 1 2 PET / IA None PET / IA 15 Biaxial stretching (5 μm) (10 μm) −−−−−−−−−−−−−−−−−−−−−−−−−−− −−−−−−−−−−−− Example 2 2 PET 50% None PET 50% 17 Unstretched PBT 50% PBT 50% (2 μm) (15 μm) −−−−−−−−−−−−−− Example 3 2 PET / IA without PET / EP BisA 17 Unstretched (2 μm) (15 μm) −−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−− Example 4 3 PET / EP BisA PET / EP BisA PET / CHDM 17 Unstretched (5 μm ) (10μm) (2 μm) −−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−− Example 5 3 PET / IA PET / IA PET / EP BisA 17 Unstretched (5 μm) (2 μm) (10 μm) −−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−− − Example 6 3 PET / IA PET / IA PET / IA 17 Unstretched (5 μm) (10 μm) (2 μm) −−−−−−−−−−−−−−−−−−−−−−−−− −−−−−−−−−−−−− Comparative Example 1 1 PET / IA None None 15 Biaxial stretching (15 μm) −−−−−−−−−−−−−−−−−−−−−−−− −−−−−−−−−−−−−−− Comparative Example 2 1 PET / IA None None 15 Unstretched (15μm) −−−−−−−−−−−−−−−−−−−−−−− −−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−‐‐‐‐‐−−−−−−−−−−−−−−−−−−− possible possible possible −−−−−−−−−−−−−−−−− −−−−−− Comparative Example 4 2 PET / IA None PET / IA 17 Unstretched (15 μm) (2 μm) −−−−−−−−−−−−−−−−−−−−−−−−−− −−−−−−−−−−−−− Comparative Example 5 3 PET / IA PET / IA PET / IA 14 Unstretched (2 μm) (10 μm) (2 μm) −−−−−−−−−−−−−− −−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−− Comparative Example 6 3 PET / IA PET / IA PET / IA 19 Unstretched (2 μm) (15 μm) −−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−− Note) PET / IA: ethylene terephthalate / ethylene isophthalate copolymer polyester resin PET: Polyethylene terephthalate, PBT: Polyethylene terephthalate PET / EP BisA: Ethylene terephthalate / ethylene oxide / added bisphenol A-terephthalic acid copolymer PET / CHDM: Ethylene terephthalate / cyclohexane Dimethylene terephthalate copolymer resin

Next, the types of pigments contained in the film are shown in Table 2 below. Table 2: Pigments contained in the resin film -------------------------------------------------------------------------- Material category Surface layer Core Layer Back layer Laminate (Content weight%) (Content weight%) (Content weight%) Substrate −−−−−−−−−−−−−−−−−−−−−−−−−−−− −−−−−−−− Example 1 quinacridone (2) None Titanium dioxide (20) Aluminum alloy −−−−−−−−−−−−−−−−−−−−−−−−−−−− −−−−−−−−− Example 2 No additive None Quinacridone (1) Tin-free titanium dioxide (20) Steel −−−−−−−−−−−−−−−−−−−−−−−−− −−−−−−−−−−−− Example 3 No additive None Carbon black (5) Tin-free aluminum powder (3) Steel −−−−−−−−−−−−−−−−−−−− −−−−−−−− −−−−−−−− Example 4 Mica (3) Titanium dioxide (30) No addition Tin-free steel ---------------------------------------------------------- −−−−−−−−−−− Example 5 quinacridone (3) aluminum powder (3) titanium dioxide (30) tin-free steel −−−−−−−−−−−−−−−−−−−−− −−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−− / − // −−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−− −−−−−−−−−−−−−−−−−− Comparative Example 1 Titanium dioxide (20) None None Aluminum alloy −−−−−−−−−−−−−−−−−−−−−−−− −−−−−−−−−−−−−− Comparative Example 2 Quinacridone (1) None None Tin-free steel −−−−−−−−−−−−−−−−−−−−−−−−−− −−−−−−−−− -Comparative Example 3 Carbon black (5) None No addition Tin-free steel --------------------------------------------------------------- Comparative Example 4 Mica (3) None No additive Tin-free steel ----------------------------------------- Comparative Example 5 Additives Aluminum powder (3) Additives Tin-free steel -------------------------------------------------------------------------- Comparative example------------------------- 6 Additive mica (3) Additive tinplate ------------------------------------------------------------------------------------

Next, a method of forming a colored resin film-coated metal sheet into a can will be described. (Processing of Colored Resin Film-Coated Metal Sheet) After punching a colored resin film-coated metal sheet into a blank having a diameter of 160 mm, the colored resin film of the present invention was placed on the outer surface of the can, and a drawn can having a bottom diameter of 100 mm was prepared. did. Subsequently, a redrawing can having a bottom diameter of 80 mm was performed by redrawing. Further, the redrawn steel can was subjected to stretching and ironing at the same time as a stretched iron by composite processing to obtain a drawn ironed can having a can bottom diameter of 65 mm. In this combined machining, the distance between the redrawing part and the ironing part, which is the upper end of the can, is 20 mm, the shoulder radius of the redrawing die is 1.5 times the plate thickness, and the clearance between the redrawing die and the punch is the plate thickness. 1.0 times of the above, and the clearance of the ironed portion was set to 50% of the original plate thickness. Next, the upper portion of the can was trimmed by a known method, and neck-in processing and flange processing were performed.

Next, a method for evaluating a colored resin film and a metal plate coated with a colored resin film will be described. (Thickness of Each Layer of Multilayer Resin Film) The resin film was embedded in an epoxy-based embedding resin, sliced to a thickness of 5 μm, and measured by cross-sectional observation. (Intrinsic Viscosity) After dissolving the resin in a 1: 1 mixed solution of phenol / tetrachloroethane, the specific viscosity was measured with an Ubbelohde viscometer in a constant temperature bath at 30 ° C. to determine the intrinsic viscosity. (Pigment average particle size) It was measured by a light scattering method using laser light. (Designability of resin-coated metal plate) After applying the above-mentioned forming process to form a can, the outer surface of the obtained can is visually observed, and it is determined whether further undercoating is necessary to obtain sufficient design. It was judged. Table 3 below shows the observation results of the surface appearance.

Table 3: Results of Visual Evaluation of Can Appearance-------------------------------------------------------------------------------------------------- Properties --------------------------------------------------------------------------------------------------------- Example 1 Vermilion Unnecessary Example 2 Pink Unnecessary Example 3 Luminous black Unnecessary Implement Example 4 Bright silver Not required Example 5 Bright red Not required Example 6 Gold Not required Comparative example 1 White Not required if required Comparative example 2 Dark red Repainting required Comparative example 3 Black Not required if required Comparative example 4 Dull pale yellow Repainting required Comparative Example 5 Dull mouse color Repainting required Comparative Example 6 Dull rattle color Repainting required ------------------------------------------------------

Next, the evaluation results of each of the examples and comparative examples will be described. As a result of laminating all the colored resin films on a metal plate and molding and processing into cans, Examples 1 and 2 exhibited a vermilion and pink color appearance and a neutral color by using a combination of a red pigment and a white pigment, respectively. I was able to. Further, Example 3 was able to develop a brilliant tone, that is, metallic black, and Example 4 was able to develop a metallic silver color. Similarly, in Example 5, a metallic red color is used.
In Example 6, metallic gold could be developed. In each case, a color that cannot be formed by a single pigment is developed by a combination of the pigments, and at the same time, since all the colored resin films contain an inorganic pigment, a dull gray color caused by the metal substrate is concealed. Example 3,
4, 5, and 6 are all because the thickness of the resin layer containing the aluminum powder and the mica powder is smaller than the average particle diameter of the aluminum powder and the mica powder, and the powder particles are arranged in parallel to the metal substrate surface. , And it is considered that the film further exhibits glitter. As described above, in each of the examples, it was possible to omit further undercoating.

In contrast, Comparative Examples 1 and 3 simply exhibited white and black colors, and it was necessary to further apply a base coat in order to develop the required color. In Comparative Example 2, the color of the underlying metal substrate could not be concealed and the color was dark red. In Comparative Example 4, the color of the underlying metal substrate could not be concealed, and at the same time, the layer containing mica powder had a thickness of 1 mm.
Since the ratio was larger than / 3, the mica powder did not line up parallel to the substrate surface, and was black, pale yellow, and far from gold. Comparative Examples 5 and 6 also have aluminum powder,
Since the thickness of the layer containing the mica powder was larger than 1/3 of the average particle size, the layer did not exhibit a brilliant color and did not cover the black base metal. For this reason, it was necessary to further apply a base coat for all of the comparative examples.

[0044]

According to the present invention, a multi-layer film made of a polyester resin contains two or more kinds of coloring pigments, and furthermore, an inorganic coloring pigment is used for one kind of the can to provide a can having a good design. At the same time, the color tone of the underlying metal substrate can be hidden. Therefore, it is not necessary to apply the undercoating, and the undercoating and baking steps can be omitted. In addition, by selecting aluminum powder or mica powder as one of the coloring pigments, a brilliant color, that is, a metallic color can be developed in the can, and a variety of colors can be developed. Further, by setting the thickness of the layer containing the aluminum powder and the mica powder to 1/3 or less of the average particle diameter, the powder particles of the pigment are arranged in parallel to the substrate surface, and it is possible to further increase the glitter. It can sufficiently cope with the design required in recent years. By using the colored resin film of the present invention, it is possible to provide a can having excellent design properties and capable of reducing the production cost.

[Brief description of the drawings]

FIG. 1 is a diagram showing an example of a cross-sectional structure of a colored resin film of the present invention.

FIG. 2 is a diagram showing another example of the cross-sectional structure of the colored resin film of the present invention.

FIG. 3 is a view showing another example of the cross-sectional structure of the colored resin film of the present invention.

FIG. 4 is a diagram showing another example of the cross-sectional structure of the colored resin film of the present invention.

FIG. 5 is a diagram showing another example of the cross-sectional structure of the colored resin film of the present invention.

FIG. 6 is a view showing another example of the cross-sectional structure of the colored resin film of the present invention.

FIG. 7 is a diagram showing an example of a cross-sectional structure of a metal plate on which a colored resin film of the present invention is laminated.

FIG. 8 is a diagram illustrating an example of a cross-sectional structure of a colored resin film of a comparative example.

FIG. 9 is a diagram showing another example of the cross-sectional structure of the colored resin film of the comparative example.

FIG. 10 is a schematic view of an apparatus for manufacturing a resin film-coated metal plate.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Surface layer 2 Back layer 3 Core layer 4, 4 ', 4' 'Pigment 5 Adhesive layer 6 Metal plate 7 Resin film (for inner surface of can) 8 Laminating roll 9, 9' Resin film 10 Heating roll 11 Roll 12 Quench part

Continued on the front page (51) Int.Cl. ⁷ Identification FI FI Theme Court II (Reference) B65D 1/16 B65D 1/16 1/28 1/28 (72) Inventor Yasuo Ohashi 1296-1296 Higashitoyoi, Kudamatsu City, Yamaguchi Prefecture F-term in Toyo Kohan Co., Ltd. Technical Research Institute (Reference) BA02 BA03 BA04 BA06 BA10A BA10C BA13 BA15 CA13 EH71D EJ38 GB16 HB00 JA20H JN24

Claims (14)

[Claims] 1. A film made of a resin containing polyester as a main component comprising a single layer or two or more layers, wherein two or more kinds of coloring pigments having different colors or materials are added to one layer. Colored resin film. 2. A multi-layer film composed of a resin mainly composed of two or three or more layers of polyester and containing two or more layers, one or two or more pigments of different types are added to two or more layers. A colored resin film, characterized in that: 3. The colored resin film according to claim 1, wherein one or more of the coloring pigments added to one layer is an inorganic pigment. 4. The colored resin film according to claim 1, wherein one of the coloring pigments is aluminum powder. 5. The colored resin film according to claim 4, wherein the thickness of the layer to which the aluminum powder is added is 1/3 or less of the average particle size of the aluminum powder. 6. The colored resin film according to claim 1, wherein one of the coloring pigments is mica powder. 7. The colored resin film according to claim 5, wherein the thickness of the layer to which the mica powder is added is 1/3 or less of the average particle size of the mica powder. 8. The colored resin film according to claim 1, wherein one of the coloring pigments is titanium dioxide powder. 9. A resin comprising a polyester as a main component according to claim 1 or 2, selected from ethylene terephthalate, ethylene isophthalate, butylene terephthalate, modified bisphenol-terephthalic acid copolymer, and cyclohexane dimethylene terephthalate. The colored resin film according to any one of claims 1 to 7, wherein one or more units are mainly used. 10. The colored resin film according to claim 1, wherein the colored resin film is an unstretched film. 11. The colored resin film according to claim 1, wherein the colored resin film is a biaxially stretched film. 12. The method according to claim 1, wherein at least one surface of the metal plate is provided.
A colored resin-coated metal plate, wherein the colored resin film according to any one of Items 1 to 11 is laminated. 13. The colored resin-coated metal plate according to claim 12, wherein the metal plate is tinplate, tin-free steel (TFS), or an aluminum alloy plate. 14. A can using the colored resin-coated metal plate according to claim 12 or 13.