JPH0449040A - Manufacture of coated metal sheet - Google Patents

Abstract

PURPOSE:To form an extremely strong adhesive structure and to improve remarkably processability and corrosion resistance accompanied therewith by distributing a surface treating agent-interlocating adhesive structure and surface treating agent-unexisting adhesive structure on the adhesive face between a metal sheet and a thermoplastic resin film. CONSTITUTION:A org. surface treating agent is provided on the surface of a metal sheet so as to make an effective coating area ratio to be 98% or less, especially 1-95%. In addition, the surface roughness of the metal sheet after coating with the surface treating agent is made to be 0.01-5 mum, especially 0.02-2mum. The surface treating agent- coated metal sheet 1 consists of a metal sheet 2 and a surface treating agent layer 3 provided on at least one surface thereof but this surface treating agent layer 3 is not continuous and always has an exposed face of the metal sheet of a covered face 4 thereof. On the adhesive face between the metal sheet 2 and the thermoplastic resin film 5, a part 6 of adhesive structure consisting of the metal sheet 2 the surface treating agent 3 and the thermoplastic resin film 5 and a part 7 of adhesive structure consisting of the metal sheet 2 and the thermoplastic resin film 5 are mixed so as to form both adhesive distribution structure. The adhesive structure is remarkably increased thereby.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a method for producing a coated metal plate, that is, a coated metal plate consisting of a metal plate and a thermoplastic resin film thermally bonded to at least one of its surfaces. especially adhesive strength,
Coated metal with improved workability and corrosion resistance 1 & 6: Related to manufacturing method of plate [Prior art] In the disassembly of metal containers, a so-called two-piece container in which the container body is formed by drawing a metal plate is used. There is no seam between the sides and the bottom, so it is generally preferred because it is aesthetically pleasing.

For metal containers, it is essential to apply an organic resin coating to the surface from the viewpoint of suppressing metal elution into the contents and preventing metal corrosion. The coating process is limited to spray painting, etc., which is extremely disadvantageous in terms of workability, number of steps, and environmental protection. is being carried out.

To apply the organic resin coating, there are two methods: using an organic resin solution or dispersion, using a thermoplastic resin film, etc.
Alternatively, a method of using both together is known, but the method of using a thermoplastic resin film does not require dry baking such as evaporation of a solvent, and can be coated with only thermal adhesion. It has become widely used because it has advantages such as continuity and completeness in the surface direction, small thickness and uniformity, etc., which can be used as is for forming a coating. However, directly thermally bonding a thermoplastic resin film to a metal plate generally results in a low adhesive strength, so it is necessary to apply a paint called adhesive brider to either the metal plate or the thermoplastic resin film, and then apply heat to the thermoplastic resin film. Adhesive systems are commonly employed.

For example, Japanese Patent Publication No. Sho 62-10188 discloses that a film-forming hardener resin component consisting of a specific epoxy resin component and a film-forming curing agent resin component reactive with the epoxy resin component is placed on a flexible metal foil substrate; It is described that a thermosetting brimer layer having a gel fraction within a certain range is provided, and a heat-sealable polyester film is thermally bonded through this layer.

In addition, Japanese Patent Publication No. 62-57672 describes a product in which an ultra-thin surface treatment layer is formed by applying hydroxymethyl-substituted phenols in the gas phase to the surface of a metal material maintained at a high temperature. It is described that it exhibits excellent adhesive properties.

Furthermore, in JP-A-1-154746, a thermosetting powder coating is applied to a metal plate, and polyethylene terephthalate (PET) is coated at a temperature that is above the melting point of the coating, below the curing start temperature, and below the melting point of polyethylene terephthalate. )
It is described that films are laminated and pressure-bonded, and then heated to a temperature above the curing start temperature of the paint and below the melting point of PET to produce a coated metal plate.

[Problems to be Solved by the Invention] In all of these proposals, a layer of thermosetting adhesive primer is provided on a metal plate, and a thermoplastic resin film is thermally bonded thereon. Thermosetting adhesive brimer has a laminated structure of thermoplastic resin film, but the most problematic part of this laminate structure in terms of adhesive failure is the adhesive brimer layer, which is the part between the metal plate and the adhesive brimer. It is recognized that adhesive failure occurs either by peeling at the interface or by cohesive failure of the adhesive brimer layer itself.

In thermally bonding a metal plate and a thermoplastic resin film, the present inventors have developed an approach based on the conventional technical concept of uniformly coating the metal plate with a surface treatment agent made of a thermosetting resin component in advance. On the contrary, on the adhesive surface, parts coated with the surface treatment agent and substantially uncoated parts are mixed on the metal plate,
When forming a surface-direction adhesive distribution structure in which a metal plate-surface treatment agent layer-thermoplastic resin film adhesive structure part and a metal plate-thermoplastic resin film adhesive structure part coexist, the coated metal It has been found that the contact S strength of the plate increases significantly.

That is, an object of the present invention is to provide a method for manufacturing a coated metal plate having a new and unique adhesive distribution structure in the plane direction and a combination of improved contact strength, workability, and corrosion resistance. .

[Means for Solving the Problems] According to the present invention, in the step of applying a surface treatment agent to the surface of a metal plate, the step of solidifying the surface treatment agent, and the step of laminating a thermoplastic resin film, An organic surface treatment agent is provided on at least one surface of the metal plate so that the effective coverage area ratio of the metal plate is 98% or less, and the surface roughness of the metal plate after applying the surface treatment agent is 06OI. A method for manufacturing a coated metal plate characterized in that the coated metal plate has a thickness of 5 gm to 5 gm is provided.

In the present invention, the surface treatment agent is preferably provided so that the effective coverage area ratio is 1 to 95%, and the metal plate before application of the surface treatment agent preferably has a surface roughness of 0.02 to 10 μm, Furthermore, add 0.01 to 10g/surface treatment agent.
It is preferable to provide the coating so that the average dry coating weight is 50 m''.

[Function] In this specification, the effective coverage area ratio refers to the ratio of the dyed area area per metal area after dyeing the surface treatment agent present on the surface of the metal plate after applying the surface treatment agent. This is a value determined by image processing analysis, which will be described in detail, and indicates the area ratio per metal surface of the surface treatment agent layer that exists as an effective coating on the surface of the metal plate. When the surface treatment agent is uniformly applied to the entire surface of the metal plate, this effective coverage area ratio is 100%, and when no surface treatment agent is applied to the metal plate surface at all, this effective coverage is 100%. The area ratio is 0%.

In the coated metal plate produced by the manufacturing method of the present invention, a layer of surface treatment agent is completely and uniformly provided on the surface of the metal plate (area ratio 100
%), the first feature is that an organic surface treatment agent is provided on the surface of the metal plate so that the effective coverage area ratio is 98% or less, and the patent is 1 to 95%.
Furthermore, in contrast to the conventional technique in which the surface of the metal plate after application is made as smooth as possible by applying the above-mentioned surface treatment agent, the surface roughness of the metal plate after application of the surface treatment agent is 0. Ol~5μ
(2) The second feature is to ensure that a specific roughness remains on the surface of the metal plate after application of the surface treatment agent, particularly to a roughness of 0.02 to 2 μm.

In FIG. 1 schematically showing the cross-sectional structure of the surface-treating agent-coated metal plate used for manufacturing the coated metal plate of the present invention and FIG. 2 schematically showing the top surface structure, this surface-treating agent-coated metal plate 1
consists of a metal plate 2 and nine layers 3 of a surface treatment agent provided on at least one surface of the metal plate 2, but this surface treatment agent layer 3 is not continuous and does not necessarily cover the exposed surface or coated surface 4 of the metal plate. have.

In FIG. 3, which schematically shows the cross-sectional structure of the coated metal plate produced by the manufacturing method of the present invention, this coated metal plate is related to the use of the surface treatment agent-coated metal plate l shown in FIGS. 1 and 2. Then, on the adhesive surface between the metal plate 2 and the thermoplastic resin film 5, there is a portion 6 of the adhesive structure of the metal plate 2-surface treatment agent layer 3-thermoplastic resin film 5, and a portion 6 of the adhesive structure of the metal plate 2-surface treatment agent layer 3-thermoplastic resin film 5. The adhesive distribution structure in the surface direction is formed such that the adhesive structure portions 7 and 7 are mixed.

In the coated metal plate produced by the manufacturing method of the present invention, the above-mentioned 6
Due to the coexistence of the surface treatment agent-mediated adhesive structure described in 7. and the surface treatment agent-free adhesive structure described in 7 above, a coated metal plate in which only a surface treatment agent-mediated adhesive structure exists or a coating in which only a surface treatment agent-absent adhesive structure exists. The fact that the adhesive strength is significantly increased compared to a metal plate was discovered as a phenomenon through many experiments and analyzes by the present inventors, and the reason for this has not yet been elucidated. However, although not necessarily limited to the following explanation, the present inventors estimate as follows.

That is, as already pointed out, in a surface treatment agent-mediated adhesive structure, adhesive failure occurs due to interfacial peeling between the surface treatment agent and the metal plate and cohesive failure of the surface treatment agent, and in an adhesive structure without a surface treatment agent, adhesive failure occurs between the metal plate and the heat treatment agent. It is recognized that adhesive failure occurs due to interfacial peeling of the plastic resin film, but since the coated metal plate manufactured by the manufacturing method of the present invention has a surface treatment agent-mediated adhesive structure and a surface treatment agent-absent adhesive structure, neither of the above-mentioned Even if local adhesion failure starts for some reason, the propagation of adhesion failure is suppressed by encountering different adhesive structures in the plane direction, which leads to a remarkable increase in adhesive strength. Recognized as something. It is also conceivable that the anchoring effect of the surface treatment agent interposed in a discontinuous manner between the metal plate and the thermoplastic resin film improves the adhesive engagement between the two, thereby improving the adhesive strength.

In the coated metal plate of the present invention, the ratio of the surface treatment agent-mediated adhesive structure to the surface treatment agent-absent adhesive structure is defined by the effective coverage area ratio described above. It is said that the degree of fineness of the distribution with the structure is closely related to the surface roughness of the metal plate after the surface treatment agent is applied. Generally, as the continuity of the surface treatment agent layer increases, that is, as the dimension in the plane direction of this layer increases,
When the surface roughness of the coated metal plate becomes a small value, and on the other hand, the continuity of the surface treatment agent layer becomes small, that is, when the dimension in the planar direction of this layer becomes small, the surface roughness of the coated metal plate becomes a large value. In the present invention, by selecting the surface roughness of the surface treatment agent-coated metal plate in the range of 0.01 to 5 μm, particularly 0.02 to 2 μm, the surface treatment agent can be interposed in the surface treatment agent most suitable for increasing adhesive strength. It is recognized that the distribution size of the adhesive structure and the surface treatment agent-free adhesive structure is achieved.

In the coated metal plate manufactured by the manufacturing method of the present invention, the adhesion between the metal plate and the thermoplastic resin film is extremely strong, it follows various deformations of the metal plate well to generate plastic flow, and the adhesive structure in the plane direction concentrates stress. Because it has a stress dispersion type structure that is difficult to cause, it has excellent workability and can be used for drawing, drawing and ironing, various bead processing, dome processing, flange processing, rivet processing, and score processing without causing adhesive failure. The advantage is that various types of processing such as the following are possible. In addition, in this coated metal plate, the metal plate and the thermoplastic resin film are firmly adhered to each other, and the thermoplastic resin film is also maintained in a perfect film state without causing cracks, vinyl, delamination, etc. Therefore, metal corrosion such as under film corrosion does not occur, and when used as a material for various packaging containers, even when filled with highly corrosive contents, there is no possibility of metal leaching into the contents or metal corrosion. This also eliminates problems such as leakage or deterioration of appearance due to plate corrosion.

E Preferred Embodiments of the Invention] The metal plate used in the present invention may be a metal plate of any thickness, such as a foil or a sheet. The type of metal plate may be any iron or iron alloy such as a steel plate, a soft iron plate, or a stainless steel plate, or a light metal such as a pure aluminum plate, an aluminum alloy plate, or a brass plate. Plated plates whose surfaces are hot-dipped or electroplated with at least one metal such as tin, zinc, chromium, nickel, aluminum, etc., or chromic acid or its salts, phosphoric acid or A surface-treated plate obtained by chemical treatment or chemical conversion treatment with one or more of organic acids such as tannic acid, high-molecular acrylic acid, salts thereof, and fluorinated zirconium compounds can be used. In the case of aluminum plates, alumite treatment and boehmite treatment are also effective. The thickness of these metal plates is not particularly limited, but can generally be in the range of 0.005 to 1.0 mm. Among these, in the case of draw-formed containers, the thickness is 0. O
Electrolytic chromic acid treated steel plates, tin plated steel plates, aluminum plates, aluminum alloy plates, etc. with a thickness in the range of 0.1 to 0.5 ffim are used, and in the case of drawn and ironed containers, tin plated steel plates or aluminum with a thickness of 0.1 to 0.6 mrn are used. Boards etc. are used.

As the surface treatment agent consisting of a thermosetting resin component, thermosetting resins known per se, such as resol type phenol,
One or more types of aldehyde resin, xylene aldehyde resin, urea aldehyde resin, melamine aldehyde resin, benzoguanamine aldehyde resin, acetoguanamine aldehyde resin, epoxy resin, epoxy ester resin, bismaleimide resin, cyanate ester resin, urethane resin, etc. The thermosetting resin and the thermoplastic resin are used, and at least one component is thermosetting, and at least one component is reactive with the thermosetting resin. It is also possible to use a combination with

Examples of the surface treatment agent made of a thermoplastic resin component include, but are not limited to, the following.

Vinyl chloride resin, vinyl acetate resin and copolymer, vinylidene chloride resin and copolymer, acrylic resin and copolymer, polyester resin and copolymer, styrene resin and copolymer, polyamide resin and copolymer, urethane Thermoplastic resins consisting of one or more types of resins, copolymers, acid-modified polyolefin resins, etc. can be used.

A suitable surface treatment agent is one consisting of a combination of an epoxy resin component and a curing agent resin component that is reactive with the epoxy resin component.The epoxy resin component has an epoxy equivalent of 400 to 15,000, particularly 400 to 1
A bisphenol A type epoxy resin in the range of 0.000, ie an epoxy resin derived from bisphenol A and epichlorohydrin, is used. On the other hand, at least one functional group capable of reacting with the curing agent resin component, such as a hydroxyl group, a carboxyl group, an acid anhydride group, an amino group, an imino group, an amide group, or an imide group, is added to the terminal or side chain of the molecular chain. For example, as the hydroxyl group-containing resin, in addition to the methylol group- or etherified methylol group-containing resins such as the phenol resin, xylene resin, and amino resin listed above, , partially or completely saponified vinyl chloride/vinyl acetate copolymer,
A hydroxyalkyl ester type acrylic resin is used, and acid- or acid anhydride-containing resins include vinyl chloride/maleic anhydride copolymer, vinyl chloride/vinyl acetate/maleic anhydride copolymer, carboxylic acid-containing acrylic resin, etc. is used, and as the resin containing an amino group, an imino group, an amide group, or an imide group, a dimer acid-modified polyamide resin, an aminoalkyl ester type acrylic resin, etc. are used.

A combination of an etherified or unetherified methylol group-containing resin and an epoxy resin is particularly preferred.

The epoxy resin component and hardener resin component are generally 5:9.
Weight ratio of 5 to 99:1, especially 10:90 to 98:2
It is best to use them in combination at a weight ratio of

In the present invention, the method for forming a metal plate coated with a surface treatment agent whose effective coverage area ratio and surface roughness are within the above-mentioned ranges varies depending on the type of metal plate, the type of surface treatment agent, or a combination thereof. , select conditions based on the following criteria. Factors that affect the effective area ratio and surface roughness of a metal plate coated with a surface treatment agent include the surface roughness of the metal plate, the amount of treatment agent applied,
and a combination of both. In general, as the surface roughness of the metal plate increases, the effective coverage area rate tends to decrease, and the surface roughness of the coated metal plate also tends to increase; conversely, as the surface roughness of the metal plate decreases, the effective The coverage area ratio tends to increase and the surface roughness of the coated metal plate also tends to decrease. Thus, depending on the coating amount of the surface treatment agent, it is possible to select a metal plate with an appropriate surface roughness from the range of generally 0.02 to 10 μm, particularly 0.02 to 5 μm, depending on the dry coating weight of the surface treatment agent. Good.

On the other hand, when the dry coating weight of the surface treatment agent increases, the effective coverage area ratio increases and the surface roughness of the coated metal plate tends to decrease (on the contrary, when the dry coating weight of the surface treatment agent decreases) , the effective coverage area ratio tends to decrease and the surface roughness of the coated metal plate increases.Thus, depending on the surface roughness of the metal plate, generally 0.
It is advisable to select an appropriate dry coating weight of the surface treatment agent from the range of O1 to 10 g/m'', particularly 0.01 to 5 g/m2.

As a general tendency, if the surface roughness of the metal plate is small, the dry coating weight of the surface treatment agent should be reduced, and if the surface roughness of the metal plate is large, the dry coating weight should be increased. This relationship is expressed as an amount that satisfies the following formula % formula % (1), where the surface roughness of the gold 1&: plate and the dry coating weight of the R1 surface treatment agent are C.

FIG. 4 is a plot of the relationship between the surface roughness of the metal plate before coating and the dry coating weight for Examples and Comparative Examples to be described later.

The surface treatment agent can be applied in the form of an organic solvent solution, an organic solvent dispersion, or an aqueous emulsified dispersion of the resin. Examples of organic solvents include alcohol solvents, ether solvents, ketone solvents, ester filters, and aliphatic to aromatic hydrocarbon solvents.
A species or a combination of two or more species may be used. The solid content concentration in these coating solutions is related to the dry coating weight of the formed film, but is generally preferably in the range of 1 to 80% by weight. The applied thermosetting resin surface treatment layer may be in a so-called half-cured state or in a fully cured state, but in the case of a dispersion type surface treatment agent, the surface treatment agent and the metal plate are in complete contact with each other. It is important that the When the surface treatment layer of thermosetting resin is half-cured, it may be used after being laminated and then post-cured. It is generally desirable to bake the metal plate coated with the surface treatment agent at a temperature of 100 to 400° C. for 0.1 seconds to 20 minutes.

As the thermoplastic resin film used in the present invention, any resin film can be used as long as it exhibits thermal adhesion to the metal plate, and various types may be used depending on the various properties required of the coated metal plate. A film with the following characteristics can be selected and used. Suitable examples of this resin film include, but are not limited to, the following.

Polyethylene terephthalate, polyethylene terephthalate/isophthalate, polyethylene terephthalate/
Various polyester films such as adipate, polybutylene terephthalate, polybutylene terephthalate/isophthalate, polyethylene naphthalate, polyethylene naphthalate/terephthalate, etc. Among them, ethylene terephthalate units account for 50 to 100 mol% of the total,
As the glycol component, glycols other than ethylene glycol, such as butylene glycol, propylene glycol, diethylene glycol, neopentane glycol, etc., or as the dicarboxylic acid, dicarboxylic acids other than terephthalic acid, such as isophthalic acid, phthalic acid, naphthalene dicarboxylic acid, adipic acid, and cepatic acid. A copolymerized polyester film containing , cyclohexanedicarboxylic acid, etc. as a copolymerization component.

Nylon 6, Nylon 11, Nylon 12, Nylon 6
6, nylon 6.10, nylon 6.12, nylon 6
/Nylon film such as nylon 66 copolymer.

Low-1 medium- or high-density polyethylene, linear low-density polyethylene, polypropylene, crystalline ethylene-propylene copolymers, polyethylene or polypropylene modified with maleic anhydride or acrylic acid, ionically crosslinked olefin copolymers (ionomers) ), polyolefin films such as ethylene-vinyl acetate copolymer, ethylene-acrylic acid ester copolymer, etc.

Other examples include various resin films such as polycarbonate, polyarylate, and polysulfone.

These resin films may be manufactured by a film-forming method known per se, such as the T-die method or the inflation IlI method, and the film may be unstretched or stretched or oriented in the -axis or biaxial direction. It can be anything. Further, the resin film used in the present invention may be a single layer film, or may be a multilayer film or a laminated film depending on requirements. In short, any material that can be thermally bonded to a metal plate is sufficient.

The thickness of the resin film is generally in the range of 5 to 1000 μm, particularly preferably in the range of 5 to 500 μm.

Thermal adhesion of a film to a metal plate coated with a surface treatment agent is achieved by heating the metal plate coated with a surface treatment agent using high frequency induction heating, other electric resistance heating, direct flame heating, infrared heating, ultrasonic vibration, etc. This is easily done by pressing the film.

At this time, thermal bonding can be carried out in two stages. For example, the film is temporarily bonded to a metal plate coated with a surface treatment agent at a relatively low temperature, and then this temporary bond is heated to a higher temperature to bond the wood. It's okay. Alternatively, the film may be thermally bonded to a metal plate coated with a surface treatment agent by a method called extrusion coating.

When thermally adhering a film to a metal plate coated with a surface treatment agent, it is at least necessary that the side of the film in contact with the metal plate be heated above the softening point temperature of the resin.
The other side of the film may or may not reach the softening point temperature of the resin.Also, after thermal bonding, the coated metal plate is rapidly cooled to supercool the resin film to suppress crystallization. Alternatively, the resin may be crystallized by cooling slowly.

The coated metal plate produced by the manufacturing method of the present invention can be used not only as a forming material for various packaging containers and their lids, but also for a wide range of applications such as various furniture, housings for various devices, and interior and exterior materials for houses. be able to. The coated metal sheet produced by the manufacturing method of the present invention is particularly useful as a material for forming drawn containers and drawn and ironed containers that require the most severe workability and corrosion resistance. In the production of draw-formed containers, the coated metal plate is sheared into discs, elliptical plates, or polygonal blanks, and the blanks are subjected to one-stage or multi-stage drawing between a drawing die and a punch, It is formed into a tapered or cylindrical container with a bottom and sides seamlessly connected. The drawing process can also be carried out by first drawing shallowly into a large-diameter cup and then deep-drawing into a small-diameter cup. The coated metal plate of the present invention can also be drawn with a drawing ratio of 1.3 to 4.0, particularly 1.5 to 3.5.

Further, it is also possible to thin the side wall portion by ironing by supplying the cup obtained by the drawing process described above between an ironing die and an ironing punch. In the coated metal plate manufactured by the manufacturing method of the present invention, the ironing rate is 2
Even after processing from 0 to 80%, especially from 25 to 75%, the adhesion between the film and the metal plate is perfect.

[Effects of the Invention] In the coated metal plate produced by the manufacturing method of the present invention, a surface treatment agent-mediated adhesive structure and a surface treatment agent-absent adhesive structure are mixedly distributed on the adhesive surface between the metal plate and the thermoplastic resin film. This provides the advantage that an extremely strong adhesive structure is formed, and that processability and corrosion resistance are also significantly improved.

[Example] Example 1 Dry! ? ! Membrane weight is 0.
Epoxy/phenol paint was applied as a surface treatment agent using a gravure coater to give a coating weight of 8 g/cm2, and baked in a hot air oven at 230°C for 30 seconds to obtain a TFS plate coated with the surface treatment agent.

A part of this steel plate was taken out and its surface roughness was determined according to JISBO60.
Measured according to 1. In addition, a part of this steel plate was subjected to effective coverage area ratio measurement. The measurement was performed by first immersing the sample in a staining solution containing 1% by weight of methyl violet in dimethylformamide for 10 minutes, washing thoroughly with distilled water, drying, and performing image analysis. For image analysis, this sample was magnified 100 times using a metallurgical microscope.
This image was imported into a computer, contrast processing was performed on the stained area and non-stained area, and then binarization processing was performed. The number of pixels in the stained area of the processed image was measured, and the effective coverage area ratio was determined by dividing the number of pixels in the stained area by the number of pixels on the entire observation surface. Changing the measurement site for effective coverage area rate 5
Measurements were performed twice, and the average was taken as the effective coverage area ratio of this steel plate. These measurement results are summarized in Table 1.

Next, a 25L thick coating was applied to both sides of this surface-treated TFS plate.
II11 biaxially oriented polyethylene terephthalate (PE
T) Heat lamination of the film at 255°C, which is the same as the melting point,
By immediately cooling with water, an organic coated metal plate was obtained.

This organic coated metal plate was coated with a lubricant and subjected to a four-stage drawing process, with a cup diameter of 66m+a and a cup height of 140++m.
A deep drawn can with a total drawing ratio of 2.7 was obtained. In the process of producing this metal can, the workability of this organic coated metal plate was evaluated by observing the presence or absence of delamination and the presence or absence of cracks in the coating resin layer. Additionally, 100 2mm square goblets were made by making scratches in the vertical and horizontal directions on the organic coating layer on the inner side wall of the can, 120mm from the bottom of the can, reaching the metal surface, and completely covered with 600" Scotch tape. The adhesion of the organic coating layer was evaluated by pasting it in a similar manner and then rapidly peeling it off, and counting the number of goblets remaining in the organic coating layer.In addition, cola (carbonated drink) was poured into the deep-drawn can. Filled, sealed, and stored for 6 months at 37°C, the state of corrosion on the inside of the can,
Observed leak. These results are shown in Table 1.

From the above results, it was found that an organic coated metal plate with excellent adhesion, workability, and corrosion resistance could be obtained.

Example 2 Base plate thickness 0.26+++m, surface roughness Ra O, 271
℃m AI-Mn-based aluminum alloy was treated with a surface treatment agent in the same manner as in Example 1 so that the dry coating weight was 2.4 g/ra'',
ET) film was laminated to obtain an organic coated metal plate. The surface roughness and effective coverage area ratio of this organic coated metal plate after application of the surface treatment agent are shown in Table 1.

Further, a deep drawn can was produced in the same manner as in Example 1, and the workability, adhesion, and corrosion resistance of the organic coated metal plate were evaluated. These results are summarized in Table 1.

From the above results, it was found that an organic coated metal plate with excellent adhesion, workability, and corrosion resistance could be obtained.

Comparative Example 1 A tin plate with a base plate thickness of 0.18■■ and a surface roughness Ra (1,012 μm) was coated in the same manner as in Example 1, with a dry coating weight of 0.
．． A surface treatment agent was applied to the product at a concentration of 6 g/kg, and a polyethylene terephthalate/isophthalate (PET/I) film was laminated at 255°C to obtain an organic coated metal plate. The surface roughness and effective coverage area ratio of this metal plate after application of the surface treatment agent are shown in Table 1.

In addition, although four stages of drawing were performed in the same manner as in Example 1, delamination of the coating resin layer occurred during the processing.
This example, in which the surface roughness after application of the surface treatment agent was outside the scope of the present invention, was inferior in workability.

Comparative Example 2 Tin-free steel (TFS) with a base plate thickness of 0.18 m+m, a heat treatment degree of DR-9, and a surface roughness (center line average roughness) of Ra O, 07 μl was treated as in Example 1 without applying a surface treatment agent. A polyethylene terephthalate (PET) film was laminated in the same manner to obtain an organic coated metal plate. The surface roughness and effective coverage area ratio of this metal plate after application of the surface treatment agent are shown in Table 1.

Further, a deep drawn can was produced in the same manner as in Example 1, and the workability, adhesion, and corrosion resistance of the organic coated metal plate were evaluated. This example, in which no surface treatment agent was applied and was outside the scope of the present invention, was inferior in terms of adhesion and corrosion resistance.

Comparative Example 3 Dry coating weight with a reverse roll coater on tin-free steel (TFS) with a base plate thickness of 0.18 am, heat treatment degree DR-9, surface roughness (center line average roughness) Ra O, 07μ layer A surface treatment agent was applied so that the weight was 12.0g7m'', and polyethylene terephthalate (
RET) film was laminated to obtain a state-covered metal plate. The surface roughness and effective coverage area ratio of this metal plate after application of the surface treatment agent are shown in Table 1.

Further, a deep drawn can was produced in the same manner as in Example 1, and the workability, adhesion, and corrosion resistance of the organic coated metal plate were evaluated. This example, in which the effective coverage area ratio after application of the surface treatment agent was outside the scope of the present invention, was inferior in terms of adhesion and corrosion resistance.

Comparative Example 4 Dry coating was applied to tin-free steel (TFS) with a base plate thickness of 0.18 mm, a heat treatment degree of DR-9, and a surface roughness (center line average roughness) of Ra 5.30 am in the same manner as in Example 1. A surface treatment agent was applied so that the film weight was 0.6 g/m'', and a polyethylene terephthalate (PET) film was laminated to obtain an organic coated metal plate.Surface roughness of this metal plate after application of the surface treatment agent The effective coverage area ratios are shown in Table 1.

Further, a deep drawn can was produced in the same manner as in Example 1, and the workability, adhesion, and corrosion resistance of the organic coated metal plate were evaluated. This example, in which the surface roughness after application of the surface treatment agent was outside the scope of the present invention, was inferior in terms of corrosion resistance.

Example 3 Both sides of tin-free steel (TFS) with a base plate thickness of 0.10 mm, a heat treatment degree of DR-9, and a surface roughness (center line average roughness) Ra O of 06 μm were coated with a dry m coating weight of 0. 1g/m
Apply epoxy/melamine paint as a surface treatment agent using a gravure coater so that
Baking was performed at 0° C. for 2 seconds to obtain a TFS plate coated on the surface-treated side.

The surface roughness and effective coverage area ratio of this organic coated metal plate after application of the surface treatment agent were measured in the same manner as in the example work, and are shown in Table 1.

Furthermore, a polyethylene terephthalate (PET) film was laminated to obtain an organic coated metal plate.

Further, a deep drawn can was produced in the same manner as in Example 1, and the workability, adhesion, and corrosion resistance of the organic coated metal plate were evaluated. These results are summarized in Table 1.

From the above results, it was found that an organic coated metal plate with excellent adhesion, workability, and corrosion resistance could be obtained.

Example 4 A tin-free steel (TFS) with a base plate thickness of 0.20 mm, a heat treatment degree of T-2.5, and a surface roughness (center line average roughness) Ra of 4.13μ was prepared in the same manner as in Example 1. A surface treatment agent was applied so that the dry coating weight was 1.2 g/a'', and
0 uI 11 biaxially oriented polyethylene terephthalate/isophthalate (PET/1), copolymer film 170
An organic coated metal plate was obtained by laminating at a temperature of 0.degree. C., then heating to 250.degree. C. to completely melt, and then immediately cooling with water. The surface roughness and effective coverage area ratio of this metal plate after application of the surface treatment agent are shown in Table 1.

This organic coated metal plate was subjected to two stages of drawing and ironing to create a cup diameter of 52.64mm and a cup height of 140w+m.
A drawn ironing can with a total ironing rate of 48.0% was prepared, and the workability, adhesion, and corrosion resistance of the organic coated metal plate were evaluated. These results are summarized in Table 1.

From the above results, it was found that an organic coated metal plate with excellent adhesion, workability, and corrosion resistance could be obtained.

Example 5 A reverse coater was used to coat tin-free steel (TFS) with a base plate thickness of 0.20 m+■, a heat treatment degree of T-4, and a surface roughness (center line average roughness) Ra O of 07 μ■, with a dry coating weight of Polyethylene terephthalate (PET) was treated in the same manner as in Example 1 by applying a surface treatment agent so that the
The films were laminated to obtain an organic coated metal plate. The surface roughness and effective coverage area ratio of this metal plate after application of the surface treatment agent are shown in Table 2.

This organic coated metal plate was punched into a lid with a diameter of 82 mm.
This is then processed into a fully open (full oven) type score from the outside of the lid (diameter 79+a+i, remaining score thickness 95μm).
), rivets and opening tabs are installed.
I made an easy-open lid.

Using 1% saline as an electrolyte, the inner surface of the lid was used as an anode, and a stainless steel plate was used as the counter electrode, a voltage of 6.3 V was applied between the lids, and the degree of metal exposure was evaluated based on the current flowing after 4 seconds. did. The measurement was performed on 50 sheets and the average was taken. In addition, the contents were filled with boiled salmon and trout in a welded can body for general food cans, and the easy-open lid was tightened according to the usual method.
Sterilization was performed at 5°C for 90 minutes.

After storage at 50° C. for 3 months, the seamed portion was cut and the lid was separated from the can body, and the corrosion state of the inner surface of the lid and the opening of the pitting portion were observed and evaluated using a microscope. These results are shown in Table 2.

From the above results, it was found that an organic coated metal plate with excellent adhesion, workability, and corrosion resistance could be obtained.

Example 6 Base plate thickness 0.32 mm, heat treatment degree T-2.5, surface roughness Ra
A thermoplastic maleic modified vinyl chloride vinyl acetate copolymer was coated on both sides of a 7.4 μm tin-free steel (TFS) coil using a reverse roll coater so that the dry coating weight was 7.0 g/m1. After applying a surface treatment agent and making it tack-free at 150℃ for 3 minutes,
of polyethylene terephthalate/isophthalate (PE
T/l) copolymer film was laminated at 220°C to obtain an organic coated metal. The surface roughness and effective coverage area ratio of this organic coated metal plate after application of the surface treatment agent are shown in Table 5. Here, a 0.4% by weight xylene solution of Sudan Red 7B was used as the staining agent, and staining was performed for 1 minute. Image processing was performed as described in Example 1.

Next, a lubricant is applied to this coated metal plate, and the drawing ratio is set to 1.
32, cup diameter 100a++a, cup height 26mm,
A tray was formed. The observation results of the contact layers on the inner and outer surfaces of this tray and the metal exposure on the inner surface were measured using enamel rate values, and the evaluation results are shown in Table 5.

Example 7 Base plate thickness 0.32 mm, heat treatment degree T-1, surface roughness Ra15
Other than applying it to both sides of GM tin-free steel (TFS) so that the dry coating weight was 20 "gets",
Molding was performed in the same manner as in Example 6 to produce a tray,
The evaluation results are shown in Table 5.

[Brief explanation of the drawing]

FIG. 1 is a sectional view showing the cross-sectional structure of a metal plate coated with a surface treatment agent used in the present invention, FIG. 2 is a top view showing the top structure of the metal plate coated with a surface treatment agent in FIG. FIG. 4 is a graph plotting the relationship between the surface roughness of the metal plate before coating and the dry coating weight in Examples and Comparative Examples of the present invention. 1 is a metal plate coated with a surface treatment agent, 2 is a metal plate, 3 is a surface treatment agent layer, 4 is a surface not coated with metal, and 5 is a thermoplastic resin film. Patent Applicant: Yasushi Kuwahara

Claims (1)

[Claims] 1. In the step of applying a surface treatment agent to the surface of a metal plate, the step of solidifying the surface treatment agent, and the step of laminating a thermoplastic resin film, at least one surface of the metal plate is treated with an organic material. The surface treatment agent is applied to the metal plate so that the effective coverage area ratio is 98% or less, and the surface roughness of the metal plate after applying the surface treatment agent is 0.01 to 5 μm. A method for manufacturing a coated metal plate. 2. The method for producing a coated metal plate according to claim 1, wherein the surface treatment agent is provided so that the effective coverage area ratio is 1 to 95%. 3. The metal plate before applying the surface treatment agent is 0.02 to 10 μm
The method for producing a coated metal plate according to claim 1, having a surface roughness of . 4. Claim 1, characterized in that the surface treatment agent is provided so that the average dry coating weight is 0.1 to 10 g/m^2.
The method for manufacturing the coated metal plate described above.