JP2001341257A - Resin film for metal plate laminate, laminate metal plate, and its manufacturing method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a resin film for a metal plate laminate and a laminate metal plate having excellent processability, impact resistance and flavor resistance, and a method for manufacturing the same. SOLUTION: The resin film for the metal plate laminate comprises a two- layer structure of a layer A/layer B of the layer A of an organic resin layer obtained by mixing a polyester resin having an ethylene terephthalate and/or an ethylene isophthalate as a basic skeleton, with a particulate resin having a glass transition point of 3 deg.C or lower and a mean particle size of 0.01 to 5 μm and dispersed in the polyester resin and mixed by a volumetric ratio of a range of 3 to 50 vol.% in the mixed resin and of the layer B of a polyester resin layer containing an ethylene terephthalate and/or an ethylene isophthalate as a basic skeleton. A thickness of the layer A is 10 to 50 μm and a thickness of the layer B is 5 to 30 μm and designed so that the layer B becomes an outermost layer in the case of laminating on the metal plate. At least one surface of the metal plate is covered with the resin film.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a resin film for laminating a metal plate, a laminated metal plate which is excellent in workability and impact resistance and can withstand severe molding, and a method for producing the same.

[0002]

2. Description of the Related Art Conventionally, as materials for metal cans that are required to be subjected to severe forming such as thin-walled deep-drawing cans, from the viewpoints of moldability, impact resistance, food hygiene, corrosion resistance, flavor and the like.
A metal plate coated with a polyethylene terephthalate resin is mainly used (JP-A-59-232852, etc.). Polyethylene terephthalate film originally has food hygiene and flavor resistance, and in addition, the crystal orientation of the film is controlled by laminating technology, etc., so that various performances can be designed to meet the required performance of the can. (JP-A-5-269920, JP-A-6-320
669). This technique is applicable at the current processing level.

However, in this field, gauge down of materials is progressing year by year, and this tendency is expected to continue in the future. This is nothing less than a stricter degree of work required in the future. However, with the current polyethylene terephthalate resin, it is difficult to achieve both workability and impact resistance when subjected to more severe processing. Specifically, workability and impact resistance are factors that greatly depend on the degree of crystal orientation (plane orientation) of the resin layer. That is, when the crystal orientation component increases in the resin layer, plastic deformation is inhibited in the crystal part, and the workability is deteriorated. Therefore, from the viewpoint of workability, the smaller the amount of crystal orientation, the better. On the other hand, when subjected to an impact, the crystal portion functions as a portion for stopping the progress of cracking. Therefore, from the viewpoint of impact resistance, the larger the amount of crystal orientation, the better. For this reason, the workability and the impact resistance are designed by adjusting the crystal orientation so as to be within the allowable range of both characteristics. The compatible region of both characteristics does not have a margin for a future increase in the working degree.

[0004]

Under such circumstances, the development of a laminated metal plate that can withstand a higher degree of processing is urgently desired. The present invention provides a solution to the problem, and provides a resin film for laminating a metal plate and a laminated metal plate having excellent workability, impact resistance, and flavor resistance, and a method for producing the same.

[0005]

Means for Solving the Problems The present inventors have studied the structure of a resin layer that can withstand more severe processing without losing the original good workability of a polyester resin (polyethylene terephthalate resin). As a result, they have found that by mixing a resin having a glass transition point lower than the lower limit of the practical temperature range (4 ° C.) into the polyester resin, the impact resistance can be improved without depending on the crystal orientation. Since the crystal orientation does not need to provide impact resistance, there is no need to increase the crystal orientation amount more than necessary, and high workability can be realized.

[0006] Impact resistance is a problem especially in the low temperature range. Metal cans such as beverage cans and food cans are sometimes refrigerated during the distribution process. In such an environment, when the can is impacted by dropping or the like, a specific problem is that the resin layer is damaged and the base is exposed. The fracture section of the resin layer of the polyester resin film-laminated metal plate that has been subjected to the impact has a brittle fracture appearance. This is because the glass transition point of the polyester resin is in a temperature range higher than the refrigeration temperature, and is so-called cracking.
If there is a site in the film that absorbs energy associated with sudden deformation due to impact, impact resistance should be significantly improved.

[0007] The inventors mixed various resins in the polyester resin and repeated the test. As a result, in a system in which a hard substance (eg, granular silica) that can simply prevent the propagation of cracks is mixed, the energy of the cracks cannot be completely absorbed, and the cracks propagate through the grain boundaries. I was not able to admit. On the other hand, in a system in which a resin having a glass transition point lower than the refrigeration temperature was mixed, a remarkable improvement in impact resistance was observed. This is considered to be because the resin whose glass transition point is lower than the refrigeration temperature absorbs cracking energy to some extent by elastic deformation. For this reason, the fracture cross section stopped cracking at many sites, and as a result, the fracture cross section exhibited a mode of ductile fracture.

[0008] In addition, a simple stack of a polyester resin layer and a resin layer having a glass transition point of 3 ° C or less causes problems in delamination, workability, and the like. Therefore, the resin having a glass transition point of 3 ° C. or lower needs to be dispersed in the polyester resin.

Further, it has been confirmed that by arranging a polyester resin layer having ethylene terephthalate and / or ethylene isophthalate as a basic skeleton on the outermost layer, flavor resistance due to adsorption of contents can be further improved.

[0010] The present invention has been made based on the above findings, and the gist thereof is as follows.

(1) A polyester resin having a basic skeleton of ethylene terephthalate and / or ethylene isophthalate has a glass transition point of 3 ° C. or less and an average particle size of 0.3.
It is composed of a mixed resin in which a granular resin having a particle size of 01 to 5 μm is dispersed, and the granular resin has a volume ratio of 3 to 50 v in the mixed resin.
When the organic resin layer mixed in the range of ol% is A layer and the polyester resin layer having ethylene terephthalate and / or ethylene isophthalate as a basic skeleton is B layer, it has a two-layer structure of A layer / B layer. A film,
The layer A has a thickness of 10 to 50 μm and the layer B has a thickness of 5 to 30 μm.
μm, and a resin film for laminating a metal plate (first invention), which is designed so that layer B is the outermost layer when laminating on a metal plate.

(2) The resin film for laminating a metal plate according to (1), wherein the resin having a glass transition point of the layer A of 3 ° C. or lower is a polyolefin.
invention).

(3) The resin film for laminating a metal plate according to the above (2), wherein the polyolefin is polypropylene.

(4) On at least one surface of the metal plate,
A laminated metal plate coated with the resin film according to any one of the above (1) to (3) (a fourth invention).

(5) The resin film contains 5 to 4 colored pigments.
The laminated metal plate according to the above (4), which is contained at 0 wt% (fifth invention).

(6) The laminated metal plate according to (4) or (5), wherein the plane orientation coefficient of the resin film in a direction parallel to the film surface is less than 0.01. .

(7) The metal plate has an adhesion amount of 50 to 20 on the surface.
And 0 mg / m ² of metallic chromium layer, the adhesion amount of metal chromium conversion is characterized in that an electrolysis chromate treated steel sheet having a chromium oxide layer of 3~30mg / m ² (4)
The laminated metal plate according to any one of (1) to (6) (a seventh invention).

(8) In producing the laminated metal plate according to any one of the above (4) to (7), the metal plate heated to the range of −70 ° C. to + 30 ° C. of the melting point of the polyester resin of the layer A is prepared. And a method of manufacturing a laminated metal plate, comprising laminating a resin film (eighth invention).

[0019]

BEST MODE FOR CARRYING OUT THE INVENTION The polyester resin having a basic skeleton of ethylene terephthalate and / or ethylene isophthalate according to the present invention means that the basic skeleton portion occupies 60 mol% or more in the polyester,
The acid component may optionally copolymerize various aromatic dicarboxylic acids and aliphatic dicarboxylic acids. Specifically, for example,
2,6-naphthalene dicarboxylic acid, 4,4'-biphenyl dicarboxylic acid, adipic acid, succinic acid, succinic acid,
Glutaric acid, pimelic acid, speric acid, azelaic acid,
Sepacic acid, dodecadionic acid, trans-1,4-cyclohexic acid dicarboxylic acid and the like. The glycol component may also copolymerize various aliphatic diols and aromatic diols. Specifically, for example, trimethylene glycol, tetramethylene glycol, pentamethylene glycol, trans-1,4-cyclohexanedimethanol, bisphenol A, p-xylene glycol,
cis-1,4-cyclohexanedimethyl, propylene glycol, butylene glycol and the like.

In the first invention, the resin having a glass transition point of 3 ° C. or less mixed with the layer A has an average particle diameter of 0.1 from the viewpoint of improving impact resistance and not adversely affecting other properties. 01-5 μmφ, volume ratio in mixed resin is 3
It needs to be in the range of 〜50 vol%. Also,
More preferably, the average particle size is 0.05 to 0.5 μm
It is preferable that φ and the volume ratio be in the range of 5 to 20 vol%. The lower limit of the average particle diameter and the volume ratio is defined from the viewpoint of effectively contributing to the improvement of impact resistance, and the upper limit is defined from the viewpoint of not adversely affecting workability. The glass transition point of 3 ° C. or less means that the metal can has a refrigeration temperature of 4 ° C. during the distribution process. This is because the property can be improved.

The resin having a glass transition point of 3 ° C. or lower according to the present invention is not particularly limited. Examples thereof include low-density polyethylene, medium-density polyethylene, high-density polyethylene, polypropylene, polyvinylidene chloride, and polyethyl acrylate. N-propyl polyacrylate, isobutyl polyacrylate, n-butyl polyacrylate, polychlorotrifluoroethylene, polyvinylidene fluoride, polybutadiene, polyacetal and the like. Further, the resin having a glass transition point of 3 ° C. or lower may be one kind or a mixture of two or more kinds.

Further, a compatibilizer, a lubricant, a plasticizer, an antistatic agent and a weathering agent may be added as long as the effects of the present invention are not hindered. By adding each additive, each known effect can be obtained, and more preferable ones can be provided depending on the application.

The reason why the thickness of the layer A is set in the range of 10 to 50 μm is that the upper limit is determined from the viewpoint of economy and the lower limit is determined from the viewpoint of impact resistance and workability. The reason why the thickness of the B layer is 5 to 30 μm is an economic reason for both the upper limit and the lower limit. The upper limit is simply because a larger amount of resin is required, and the lower limit is economically disadvantageous from the viewpoint of the cost of forming an ultra-thin film.

In the second invention, the reason why the resin having a glass transition point of 3 ° C. or lower is defined as a polyolefin is that it is a more preferable type of resin from the viewpoint of workability. This is because it is the most preferred type of resin.

Since the above-mentioned film having a two-layer structure of layer A / layer B is based on polyester, there is no inconvenience in terms of delamination and workability. When this two-layer film is laminated on a metal plate such that the layer B is the outermost layer, a laminated metal plate having excellent workability, impact resistance and flavor resistance can be obtained.

In the fifth invention, the pigment is 5 to 40% by weight.
The lower limit is the lower limit of the effect of the pigment, and the upper limit is the upper limit of a range that does not affect processing. The pigment may be contained in one or both of the A layer and the B layer, but it is more effective to contain the pigment in the B layer which is the outermost layer.

[0027] The type of pigment is not particularly limited, but as long as the effects of the present invention are not hindered, calcium carbonate, barium carbonate, aerosil, titanium dioxide, zinc white, gloss white, alumina white, magnesium carbonate, carbon black , Magnetite, cobalt blue, red iron, etc. can be used as appropriate to finish the metal laminate plate or metal can in a preferable color tone.

In the sixth invention, the plane orientation coefficient in the direction parallel to the film surface of the resin film is specified to be less than 0.01 because those in this range have particularly good workability. As the plane orientation coefficient increases, the degree of processing becomes inferior. This is because the oriented crystals hinder plastic deformation as described above, but within the range of the plane orientation coefficient of the present invention, it is a level that does not substantially affect the workability.

In the area of the plane orientation coefficient according to the sixth invention,
Compared to the prior art, it has sufficiently excellent impact resistance,
Depending on the required performance, it is possible to intentionally increase the plane orientation coefficient to more than 0.01 to obtain more excellent impact resistance.

The metal plate of the present invention is not particularly limited, but is preferably a metal plate made of iron, aluminum, or the like in view of formability. In the case of a metal plate made of iron, an inorganic oxide coating layer, for example, a chromic acid treatment, a phosphoric acid treatment, a chromic acid / phosphoric acid treatment, in order to improve adhesion and corrosion resistance on the surface thereof,
A chemical conversion coating layer represented by electrolytic chromic acid treatment, chromate treatment, chromium chromate treatment, or the like may be provided.
Further, a spreadable metal plating layer, for example, a plating layer of nickel, tin, zinc, aluminum, gunmetal, brass, or the like may be provided. 0.5 to 15mg / for tin plating
m ² , 1.8 to ²⁰ for nickel or aluminum
Those having a plating amount of g / m ² are preferred.

In the case of a metal plate made of iron, the electrolytic chromate-treated steel sheet specified in the seventh invention is particularly preferable from the viewpoints of adhesion to a film, corrosion resistance, and production cost. Seventh
In the invention, the lower limit of the amount of metallic chromium in the metallic chromium layer is 5
Was defined as 0 mg / m ² is because corrosion resistance becomes 50 mg / m ² or more, the post-process adhesion more excellent, the defined upper limit to 200 mg / m ² is 200 mg / m ² than in corrosion resistance, This is because the effect of improving the adhesion after processing saturates, and conversely increases the manufacturing cost. (The lower limit of the amount of chromium in the chromium oxide in terms of metal chromium is specified as 3 mg / m ² , because when the amount is less than 3 mg / m ² , the adhesion is more excellent.)
The upper limit of 30 mg / m ² was defined as 30 mg / m ^2.
If the amount exceeds mg / m ² , the color tone will deteriorate.

In the eighth invention, the lower limit of the heating temperature of the metal plate is set to the melting point Tm-70 ° C. of the polyester resin of the layer A which is in close contact with the metal plate.
This is because the adhesion to the metal plate is not sufficient, and the upper limit is set to the melting point Tm of the polyester resin + 30 ° C., because if it exceeds the upper limit, the film layer is fused to the laminating roll.

The method for producing a laminated metal sheet of the present invention is not limited to the film laminating method as in the eighth invention, but may be a general resin extrusion method.

Further, in the present invention, a primer layer may be provided as an adhesion layer to a metal plate as long as the effects of the present invention are not hindered. The laminated metal plate of the present invention is excellent in both the primary adhesion of the resin layer and the metal plate and the adhesion after processing, but in a more severe corrosive environment, or in an environment where higher adhesion is required, a primer layer is used. Is provided to provide characteristics according to the request. For example, when used as a metal can, when a more corrosive content is filled, the content penetrates into the interface with the metal plate through the resin layer, corrodes the metal plate, and deteriorates the adhesion to the film. There is a possibility. In such a case, peeling of the resin can be prevented by providing an appropriate primer layer.

The type of the primer is not particularly limited, but a known effect is exhibited by using a known primer layer. The method for forming the primer layer is not particularly limited, but a primer coating may be applied to a metal plate and dried, or a primer coating may be applied and dried on the film of the present invention, or a primer may be applied to the metal plate. A film may be laminated, and further, a film obtained by laminating the film of the present invention and a primer layer may be laminated.

The laminated metal sheet of the present invention can be suitably used for coating the inner surface of a two-piece metal can manufactured by drawing or ironing. Further, it can be preferably used for covering a lid portion of a two-piece can or a body, a lid, and a bottom of a three-piece can because it has good metal adhesion and moldability.

The laminated metal plate coated with the film is excellent in workability, impact resistance and flavor resistance.
It is suitable as a material to be used for thin-walled deep-drawing cans, in which gauge down of the material progresses and particularly severe molding is required.

[0038]

DESCRIPTION OF THE PREFERRED EMBODIMENTS TFS (thickness: 0.1 mm) heated by an electric heating method.
18mm, temper degree DR9, metal chrome layer 80mg /
m ² , chromium oxide layer 15 mg / m ² (converted to chromium metal)
A layer having a thickness of 8 to 45 μm and B having a thickness of 20 μm
A two-layer resin film of layer A / layer B or a resin film of only layer A having a thickness of 25 μm, which is thermocompressed so that layer A is on the metal plate side, and then quenched in water A laminated metal plate was obtained by the method. Table 1 shows the test films.
Table 2 shows the lamination conditions.

The plane orientation coefficient of the laminated metal plate obtained above was examined. Further, the laminated metal plate obtained above was subjected to a can-making process, subjected to a strain removing heat treatment to prepare a test can, and the workability and impact resistance of the can-made can body were examined.
The details of the survey method are described below.

(1) Can Making Process The laminated metal plate was first drawn and redrawn under the following conditions to obtain a thinned deep drawn can.・ First-stage drawing Blank diameter: 150 to 160 mm 1-stage drawing: Drawing ratio: 1.65 ・ Re-drawing First re-drawing: Drawing ratio: 1.25 Secondary re-drawing: Drawing ratio: 1.25 Re-drawing Curvature radius of die corner in process: 0.4mm Wrinkle pressing weight at redrawing… 4000kg ・ Average thinning rate of can body 40 to 55% of the thickness of the laminated metal plate before molding

(2) Strain relief heat treatment The processing strain of the film introduced during the can-making process was heated and held for 30 seconds in a thermal environment having a film melting point of -15 ° C. and then rapidly cooled.

(3) Evaluation of film processability The following ratings were given according to the limit of can-making without damaging the film. Limit processing degree (thinning rate) Rating Unable to form 40% thinning rate: 1 (Poor) Can be molded up to 40% thinning rate: 2 成形 Can be molded up to 45% thinning rate: 3 Can be molded up to 50% thinning rate Acceptable: 4 ↓ Moldable up to 55% thinning rate: 5 (excellent)

(4) Evaluation of Impact Resistance The can body (thinning rate: 40%) subjected to the strain relief heat treatment was subjected to neck processing, the can body was filled with water, a lid was attached, and the can was tightened. The bottom was impacted with a punch. Next, open the lid, fill the can with 3% saline so that the impacted part is immersed, immerse for 2 minutes, apply a 6V load to the platinum electrode and the metal part of the can immersed in the liquid, Read the current value after 5 minutes,
The evaluation was as follows. Test results
Evaluation Current value is 10 mA or more: × Current value is 1 mA or more and less than 10 mA: Current value is less than 1 mA: ◎

(5) Evaluation of Flavor Resistance After the can was made, the inside of the can was filled with a 50 ppm aqueous solution of d-limonene and left at 25 ° C. for 7 days. After standing, take out the aqueous solution, wipe off the water droplets well, then 80 ° C, 20ml / mi
The flavor was driven out under an atmosphere of nitrogen flow of n and the adsorption amount was measured by gas chromatography.
(Small amount of adsorption), Δ (small amount of adsorption), and × (large amount of adsorption) were evaluated.

(6) Measurement of Plane Orientation Coefficient Using an Abbe refractometer, the light source was sodium / D line, the intermediate liquid was methylene iodide, the temperature was 25 ° C., and the refractive index was measured. The refractive index Nx in the direction, the refractive index Ny in the width direction of the metal plate on the film surface, and the refractive index Nz in the thickness direction of the film were determined, and the plane orientation coefficient Ns was calculated from the following equation. Plane orientation coefficient (Ns) = (Nx + Ny) / 2-Nz

(7) Measuring method of melting point (Tm) The mixed resin (polyester resin) of the layer A is crystallized, and is subjected to a differential scanning calorimeter (DSC-2, manufactured by Perkin-Elmer).
The melting point of the polyester resin was measured at a heating rate of 10 ° C./min. Table 3 shows the survey results.

[0047]

[Table 1]

[0048]

[Table 2]

[0049]

[Table 3]

The following can be seen from Tables 1 to 3. Invention Example 1
Nos. 4 to 4 are films in which the copolymerization ratio of ethylene terephthalate and ethylene isophthalate in the layer A was changed, and Examples 20 to 20 in which these were laminated under the lamination conditions of the present invention.
No. 23 has extremely good moldability and impact resistance.

Inventive Examples 23 to 27 were obtained by varying the laminating conditions of the film of Inventive Example 4 within the range of the present invention, and were excellent in both moldability and impact resistance. On the other hand, Comparative Example 31 was obtained by laminating the film of Inventive Example 4 under the lower limit of the laminating temperature range of the present invention, and could not be evaluated because the film did not adhere to the steel sheet. In Comparative Example 32, since the film of Inventive Example 4 was laminated under the condition exceeding the upper limit of the laminating temperature range of the present invention, the film was fused to a laminating roll and could not be evaluated.

Inventive Examples 5 to 7 are examples in which the particle size of the resin having a glass transition temperature of 3 ° C. or less to be mixed is varied within the scope of the present invention. Inventive Examples 28 to 30 obtained by laminating this under the laminating conditions of the present invention exhibited good workability and impact resistance. Inventive Example 5 has a low contribution to the improvement of impact resistance because the particle size of the resin to be mixed is close to the lower limit. Inventive Example 28 obtained by laminating the resin is evaluated as 評 価. Inventive Examples 6 and 7 have a particle size within the range of the present invention, but are out of a particularly desirable range. Therefore, Inventive Examples 29 and 30 obtained by laminating them have a workability rating of 4.

On the other hand, in the film of Comparative Example 5, since the particle size of the resin to be mixed is below the lower limit of the present invention, Comparative Example 20 in which this is laminated is inferior in impact resistance. Comparative Example 6
Exceeds the upper limit of the range of the particle size of the present invention, so that Comparative Example 21 in which this is laminated is inferior in workability.

In Inventive Examples 8 and 9, the thickness of the layer A of the film was varied within the range of the present invention. Inventive Examples 31 and 32 obtained by laminating this with the laminating method of the present invention show good performance. Inventive Example 9 was obtained by laminating the layer A because the thickness of the layer A was close to the lower limit of the present invention.
Is slightly inferior in both workability and impact resistance as compared with Invention Example 31.

On the other hand, in Comparative Example 7, the film thickness of the layer A was less than the lower limit of the film thickness of the present invention.
No. 2 is inferior in workability and impact resistance.

Inventive Examples 10 and 11 are examples in which the volume ratio of the resin having a glass transition point of 3 ° C. or less mixed in the A layer was varied within the range of the present invention. Invention Examples 33 and 34 obtained by laminating this under the lamination conditions of the present invention have good processability,
It showed impact resistance. Inventive Example 10 has a low contribution to the improvement in impact resistance because the volume ratio of the resin mixed in the layer A is close to the lower limit of the present invention.
Indicates that the evaluation of impact resistance is ○. Invention Example 1
1 is a volume ratio in the range of the present invention, but it is out of a particularly desirable range.
Has a workability rating of 4.

On the other hand, in the film of Comparative Example 8, since the volume ratio of the resin mixed in the layer A is lower than the lower limit of the present invention, Comparative Example 23 in which this is laminated is inferior in impact resistance. Also,
In Comparative Example 9, since the volume ratio of the resin mixed in the layer A exceeded the upper limit of the present invention, Comparative Example 2 in which this was laminated was used.
No. 4 is inferior in workability.

Inventive Example 12 is a film of the present invention formed by a biaxial stretching method, and Inventive Example 3 in which this is laminated.
Nos. 5 and 36 show good performance. Invention Example 35
Has a surface orientation coefficient of 0.015 in a direction parallel to the film surface of the film, and is slightly inferior in workability. However,
As a result of conducting a stricter impact resistance test than the evaluation method of this example, it was also confirmed that the impact resistance was slightly higher than that of a low plane orientation coefficient. Invention Example 36 has a plane orientation coefficient in the range of the sixth invention, and has extremely good workability and impact resistance.

Inventive Examples 13, 14, and 19 are polyolefins other than polypropylene as the mixed resin, and Inventive Examples 37, 38, and 43 in which the mixed resin is laminated are compared with Inventive Example 23 in which the mixed resin is laminated with a polypropylene film. Although the processability is slightly inferior, sufficiently good processability,
Has impact resistance. In addition, Invention Examples 15 to 18 and 20 are:
Mixed resin other than polyolefin, glass transition point is 3 ℃
The following is an example using a resin within the scope of the present invention. Inventive Examples 39 to 42 and 44 obtained by laminating these films
Has good workability and impact resistance, although the workability is slightly inferior.

On the other hand, in Comparative Examples 10 to 13, since the glass transition point of the mixed resin is out of the range of the present invention, Comparative Examples 25 to 28 in which the resin is laminated are inferior in impact resistance.

Comparative Examples 1 to 4 are single films in which the copolymerization ratio of ethylene terephthalate and ethylene isophthalate is changed, and are examples in which the resin of the present invention is not mixed. In Comparative Examples 16 to 19 in which this was laminated, the workability was excellent, but the impact resistance was poor.

Comparative Example 14 is an example in which the outermost layer B is polypropylene, and Comparative Example 29 obtained by laminating this is
Poor flavor resistance. Further, Comparative Example 30 in which a film having only the A layer (Comparative Example 15) was laminated had a result that the flavor resistance was slightly inferior.

[0063]

According to the present invention, a resin film for laminating a metal plate, a laminated metal plate, and a method for producing the same, which are excellent in workability, impact resistance, and flavor resistance, can be obtained.

The laminated metal sheet of the present invention can be suitably used for two-piece metal cans manufactured by drawing or ironing. Further, it can be preferably used with a lid part of a two-piece can or a body, a lid, and a steel plate for a bottom of a three-piece can.

The laminated metal sheet of the present invention is also suitable as a material for use in thin-walled deep-drawing cans, in which gauge down of the material proceeds and particularly severe molding is required.

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Yoichiro Yamanaka 1-2-1, Marunouchi, Chiyoda-ku, Tokyo Nihon Kokan Co., Ltd. (72) Inventor Takeshi Takeshi 1-2-1, Marunouchi, Chiyoda-ku, Tokyo Sun (72) Inventor Yoshinori Yomura 1-1-2 Marunouchi, Chiyoda-ku, Tokyo Japan In-tube (72) Inventor Shinichiro Mori 1-2-1, Marunouchi, Chiyoda-ku, Tokyo Japan Inside the Kokan Co., Ltd. (72) Inventor Shinsuke Watanabe 1-2-2 Marunouchi, Chiyoda-ku, Tokyo F-term in Nihon Kokan Co., Ltd. 3E033 AA06 BA07 BA14 BA18 BB08 CA20 FA01 4F071 AA20 AA45 AA46 AA86 AB06 AE09 AE17 AF23 AF53 AF58 AH04 BA01 BB06 BC01 4F100 AA22C AB01C AK01A AK03A AK05 AK06 AK07A AK41A AK41B AK42A AK42B AL05A AL05B BA02 BA03 BA10B BA10C BA25A BA25B CA13A C A13B CA23A DE01A EJ69C GB16 GB18 JA05A JK10 YY00A YY00B 4J002 BB122 CF041 CF061 DA066 DE096 FA082 FD096

Claims (8)

[Claims] 1. A polyester resin having a basic skeleton of ethylene terephthalate and / or ethylene isophthalate, having a glass transition point of 3 ° C. or less and an average particle diameter of 0.01.
A mixed resin in which a granular resin of about 5 μm is dispersed, wherein the granular resin has a volume ratio of 3 to 50 vol% in the mixed resin.
When the organic resin layer mixed in the range of A is layer A and the polyester resin layer having ethylene terephthalate and / or ethylene isophthalate as a basic skeleton is layer B,
A film having a two-layer structure of layer / layer B, wherein layer A has a thickness of 10 to 50 μm, layer B has a thickness of 5 to 30 μm, and layer B is the outermost layer when laminated on a metal plate. A resin film for laminating metal plates designed to be. 2. The resin film for laminating a metal plate according to claim 1, wherein the resin having a glass transition point of the layer A of 3 ° C. or lower is a polyolefin. 3. The resin film for metal plate lamination according to claim 2, wherein the polyolefin is polypropylene. 4. A laminated metal plate, wherein at least one surface of the metal plate is coated with the resin film according to claim 1. 5. The resin film is provided with a coloring pigment of 5 to 40 watts.
The laminated metal sheet according to claim 4, wherein the metal sheet contains t%. 6. The laminated metal sheet according to claim 4, wherein a plane orientation coefficient of the resin film in a direction parallel to the film surface is less than 0.01. 7. The metal plate has an adhesion amount of 50 to 200 m on the surface.
7. An electrolytic chromate-treated steel sheet having a g / m ² metal chromium layer and a chromium oxide layer having a chromium metal equivalent of 3 to 30 mg / m ^2. The laminated metal plate as described. 8. In producing the laminated metal plate according to any one of claims 4 to 7, a resin film is applied to a metal plate heated to a range of −70 ° C. to + 30 ° C. of the melting point of the polyester resin of the layer A. A method for producing a laminated metal sheet, comprising laminating.