JP3300527B2 - Resin-coated metal plate and drawn ironing can or drawn can - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a resin-coated metal plate and a drawn or ironed can or drawn can made of the same, and more particularly to a resin-coated metal plate coated with a specific resin composition and a drawn or drawn iron or drawn can made of the same. About cans.

[0002]

2. Description of the Related Art Conventionally, a drawn ironing can (hereinafter referred to as a DI can) or a drawn can (hereinafter referred to as a DRD can) obtained by drawing and ironing a steel plate or an aluminum plate such as a tin plate or the like is used as a seam. It is excellent in various physical properties without being used, and is widely used.

[0003] Such DI cans and DRD cans are provided with an inner surface on the inner side of the can in order to prevent a decrease in taste, a decrease in flavor due to metal elution from the metal plate, deterioration of contents and generation of pinholes. A resin layer may be provided.
Such a can having a resin layer provided on the inner surface side of the can and a resin-coated metal plate capable of forming the can are disclosed in, for example, JP-A-51-130647, a steel sheet coated with a saturated polyester layer and a steel sheet coated therewith. Containers have been proposed. JP-A-1-180336 proposes a steel sheet coated with a polybutylene terephthalate layer, which is disclosed in JP-A-1-192545 and JP-A-2-5.
No. 7339 and JP-A-3-10835 propose a steel sheet coated with a specific saturated copolymerized polyester layer and a container obtained therefrom.

By the way, a coating resin used for a steel plate for drawing and ironing can is required to have excellent formability capable of following the drawing and ironing process and the drawing process, and also to have excellent adhesion so as not to peel off from the steel plate. Required. Further, this resin is required to have excellent impact resistance so that it can withstand impacts during canning, canning and transportation. In addition, it is required that there be no pinholes that cause corrosion during storage, and that properties such as not affecting the taste of the beverage, that is, being excellent in flavor, are provided.

[0005] However, the resin coated on the conventional steel plate for cans does not always satisfy such a requirement. For example, pinholes may be formed in the resin film during drawing and ironing or drawing. Further, after the can was made, the can heated in the steps of drying, printing, baking and the like sometimes had a reduced impact resistance.

Conventionally, in order to improve the impact strength of such a saturated polyester resin, generally known is a method of blending a polycarbonate, a maleic acid-modified ethylene propylene random copolymer, or the like with the saturated polyester resin. . However, all of these resin blends become hard and brittle when subjected to annealing treatment, and their impact strength is not sufficient.

[0007]

DISCLOSURE OF THE INVENTION The present invention has been made in view of the above prior art, and has excellent draw ironing or draw formability, excellent adhesion to a metal plate, and excellent impact resistance. A resin-coated metal plate coated with a resin that has no pinholes and has properties such as excellent flavor properties,
Further, it is an object of the present invention to provide a drawn ironing can or drawn can formed from such a resin-coated metal plate.

[0008]

SUMMARY OF THE INVENTION A resin-coated metal plate according to the present invention comprises a metal plate and a resin composition film provided on one or both surfaces of the metal plate, and the resin composition film has a saturation of [A]. 50 to 95 parts by weight of a polyester resin, [B] a polyester elastomer; 1 to 30 parts by weight, and [C] an ionomer resin; 1 to 25 parts by weight.

These [A], [B] and [C] are:

[0010]

(Equation 2)

It is preferred that The drawn ironing can or drawn can according to the present invention is made of the above resin-coated metal plate.

[0012]

DETAILED DESCRIPTION OF THE INVENTION Hereinafter, a resin-coated metal plate according to the present invention and a drawn ironing can or drawn can formed from such a resin-coated metal plate will be described.

The resin-coated metal plate according to the present invention comprises a metal plate and a resin composition film provided on one or both surfaces of the metal plate. In the present invention, conventionally known metals generally used for cans are widely used as the metal plate. Specifically, a steel plate (tin) whose surface is plated with Sn (tin) by a known method, tin An uncoated steel sheet (tin-free steel, electrolytic chromic acid-treated steel sheet) or an aluminum sheet is used.

This metal plate has a thickness of usually 0.01 to 5
mm, preferably 0.1 to 2 mm. One or both sides of the metal plate are coated with a resin composition comprising [A] a saturated polyester resin, [B] a polyester elastomer, and [C] an ionomer resin.

[A] Saturated Polyester Resin The [A] saturated polyester used in the present invention comprises a dicarboxylic acid such as terephthalic acid or an ester derivative thereof (eg, lower alkyl ester, phenyl ester, etc.) and ethylene glycol or an ester derivative thereof ( For example, monocarboxylic acid ethylene oxide)
And a structural unit derived from a dihydroxy compound.

The saturated polyester may contain structural units derived from other dicarboxylic acids and / or other dihydroxy compounds in an amount of 40 mol% or less. Specific examples of dicarboxylic acids other than terephthalic acid include aromatic dicarboxylic acids such as phthalic acid, isophthalic acid, naphthalenedicarboxylic acid, diphenyldicarboxylic acid, diphenoxyethanedicarboxylic acid; adipic acid, sebacic acid, azelaic acid, decanedicarboxylic acid Aliphatic dicarboxylic acids such as acids; alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid;

These dicarboxylic acids other than terephthalic acid may be used as their ester derivatives. Examples of the dihydroxy compound other than ethylene glycol include trimethylene glycol (propylene glycol), tetramethylene glycol, neopentyl glycol, hexamethylene glycol, dodecamethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, and polyethylene. Aliphatic glycols such as glycol; alicyclic glycols such as cyclohexanedimethanol; aromatic diols such as bisphenols, hydroquinone, and 2,2-bis (4-β-hydroxyethoxyphenyl) propane.

These dihydroxy compounds may be used as their ester derivatives. The [A] saturated polyester resin used in the present invention has a small amount of structural units derived from a polyfunctional compound such as trimesic acid, pyromellitic acid, trimethylolethane, trimethylolpropane, trimethylolmethane, and pentaerythritol, for example, It may be contained in an amount of 2 mol% or less.

Such a [A] saturated polyester resin is substantially linear, which is confirmed by the fact that the saturated polyester is dissolved in o-chlorophenol. The saturated polyester resin used in the present invention is o-
Intrinsic viscosity [η] measured at 25 ° C in chlorophenol
Is usually 0.5 to 1.4 dl / g, preferably 0.5 to
1.3 dl / g, more preferably 0.6 to 1.2 dl / g
It is desirable that

The saturated polyester (a) having such an intrinsic viscosity [η] is preferable because it has excellent melt moldability and drawability, and has excellent mechanical strength such as impact resistance.

The [A] saturated polyester resin used in the present invention has a glass transition temperature (Tg) of usually 50 to 12.
It is desirably 0 ° C, preferably 60 to 100 ° C. This (a) saturated polyester resin may be amorphous or crystalline, and when crystalline, the crystal melting temperature (Tm) is usually 210 to 265 ° C, preferably 220 to 265 ° C. 260 ° C, low temperature crystallization temperature (Tcc)
However, usually 110 to 210 ° C, preferably 120 to 200 ° C
C. is desirable.

[B] Polyester Elastomer As the [B] polyester elastomer used in the present invention, a conventionally known polyester elastomer can be used without limitation, and this polyester elastomer is crystalline and has a high melting point. A thermoplastic elastomer having a hard segment and a soft segment, wherein the hard segment comprises (i) an aromatic polyester, and the soft segment comprises (ii) a polyether or (iii) an aliphatic polyester [B-1 ] Polyester / polyether block copolymer or [B-
2] It is desirable to be a polyester / polyester block copolymer.

The [B-1] polyester / polyether block copolymer or [B-2] polyester / polyester
The polyester block copolymer is obtained by co-condensing (i) an aromatic polyester with (ii) a polyether or (iii) an aliphatic polyester by a known method.

The [B-1] polyester-polyether block copolymer or [B-2] polyester-polyester block copolymer used in the present invention is formed.
(i) The aromatic polyester segment is composed of structural units derived from an aromatic dicarboxylic acid and a dihydroxy compound.

Specific examples of the aromatic dicarboxylic acid include:
Examples include terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid, diphenyldicarboxylic acid, and the like. These may be a combination of two or more.

Specific examples of the dihydroxy compound include ethylene glycol, trimethylene glycol (propylene glycol), tetramethylene glycol, pentamethylene glycol, neopentyl glycol,
Examples include aliphatic dihydroxy compounds such as 2-dimethyltrimethylene glycol, hexamethylene glycol, dodecamethylene glycol, aromatic dihydroxy compounds such as p-xylene glycol, and alicyclic dihydroxy compounds such as cyclohexanedimethanol. These are 2
A combination of more than one kind may be used.

(I) The aromatic polyester segment may be a homopolyester of terephthalic acid and one type of alkylene glycol, and either one of the dicarboxylic acid component and the dihydroxy component may be composed of two or more types, or Both components may be copolymerized polyesters composed of two or more types.

The [B-1] polyester / polyether block copolymer and [B-2] polyester / polyester block copolymer used in the present invention are formed.
(i) The aromatic polyester segment comprises a dicarboxylic acid component containing terephthalic acid in an amount of 50 mol% or more, when the dicarboxylic acid component is 100 mol%, and a carbon number of 2
And a dihydroxy component comprising an alkylene glycol of from 10 to 10.

[B-1] Forming Polyester / Polyether Block Copolymer (ii) The polyether segment is formed from poly (alkylene oxide) glycol having a molecular weight of 300 to 6000. Specific examples of such a poly (alkylene oxide) glycol include polyethylene glycol, polypropylene glycol, polybutylene glycol, and the like.

[B-2] (iii) The aliphatic polyester segment forming the polyester / polyester block copolymer is composed of an aliphatic dicarboxylic acid component and an aliphatic dicarboxylic acid component.
And a structural unit derived from 10 alkylene glycols.

Specific examples of the aliphatic dicarboxylic acid include:
Adipic acid, sebacic acid, azelaic acid, decanedicarboxylic acid and the like can be mentioned. Specific examples of the alkylene glycol having 2 to 10 carbon atoms include those described above as (i) the dihydroxy compound forming the aromatic polyester segment.

[C] Ionomer resin [C] ionomer resin used in the present invention includes:
Conventionally known ionomer resins are widely used, and this ionomer resin is an ion in which some or all of the carboxyl groups in a copolymer of ethylene and an α, β-unsaturated carboxylic acid are neutralized with a metal cation. It is a salt.

The α, β-unsaturated carboxylic acid includes
Examples of the unsaturated carboxylic acid having 3 to 8 carbon atoms include acrylic acid, methacrylic acid, maleic acid, itaconic acid, maleic anhydride, maleic acid monomethyl ester, and maleic acid monomethyl ester.

Such ethylene and unsaturated carboxylic acid
Cation Neutralizes Carboxyl Groups in Copolymers
Specifically, Na⁺, K⁺, Li⁺, Zn⁺,
Zn ⁺⁺, Mg⁺⁺, Ca⁺⁺, Co⁺⁺, Ni⁺⁺, Mn⁺⁺, P
b⁺⁺, Cu⁺⁺And monovalent metal cations such as
You. Residual carboxyls not neutralized by metal cations
Some of the sil groups are esterified with lower alcohols.
You may.

The [C] ionomer resin used in the present invention is a metal salt of a copolymer of ethylene and an unsaturated carboxylic acid, as described above. The ethylene / unsaturated carboxylic acid for forming the metal salt is used. Is a copolymer derived from ethylene in an amount of 80 to 99 mol%, preferably 85 to 98 mol%, and a structural unit derived from an unsaturated carboxylic acid (a structural unit having a carboxyl group). 1
-20 mol%, preferably 2-15 mol%.

In the [C] ionomer resin used in the present invention, part or all of the carboxyl groups in the copolymer of ethylene and the unsaturated carboxylic acid are specifically 15 to
100% of the carboxyl groups are neutralized. This neutralization degree is preferably 20 to 80%, more preferably 30 to 80%.
The composition formed from the [C] ionomer resin having such a degree of neutralization is excellent in melt extrudability.

Specific examples of the [C] ionomer resin include copolymers of ethylene and unsaturated monocarboxylic acids such as acrylic acid and methacrylic acid, and unsaturated copolymers such as ethylene and maleic acid and itaconic acid. An ionomer resin in which part or all of the carboxyl groups in the copolymer with a dicarboxylic acid is neutralized with a monovalent or divalent metal ion such as sodium, potassium, lithium, zinc, magnesium, and calcium.

Of these, 30 to 30 of carboxyl groups in a copolymer of ethylene and acrylic acid or methacrylic acid (2 to 15 mol% of structural units having a carboxyl group)
Preferably, 70% is neutralized with a monovalent metal ion such as Na.

As these ionomer resins, commercially available products such as "Himilan" (trade name: manufactured by Du Pont-Mitsui Polychemicals) can be used. Resin composition In the present invention, the resin composition coated on the metal plate,
When the total of the above [A] saturated polyester resin, [B] polyester elastomer and [C] ionomer resin is 100 parts by weight, the [A] saturated polyester resin is 50 to 95 parts by weight, preferably 60 parts by weight. The amount of the polyester elastomer (B) is 1 to 30 parts by weight,
The [C] ionomer resin is contained in an amount of 1 to 25 parts by weight, preferably 5 to 20 parts by weight in an amount of 1 to 20 parts by weight.

The coating comprising the resin composition containing [A] the saturated polyester resin, [B] the polyester elastomer, and [C] the ionomer resin in the above amounts has excellent impact resistance and adheres to a metal plate. It has excellent formability, and exhibits excellent formability that can follow extrusion molding, drawing and ironing or drawing, and forms a uniform film without pinholes after drawing and ironing or drawing.

In the resin composition comprising the above components, the amount of the [B] polyester elastomer is 1
If the amount is less than 10 parts by weight, the [A] saturated polyester resin and the [C] ionomer resin are not sufficiently compatible with each other, so that a film in which pinholes, gels, etc. are generated may be formed, and the impact strength of the film may be increased. May be insufficient. On the other hand, if the amount of the (B) polyester elastomer exceeds 30 parts by weight, a resin film can be formed without generating pinholes, but the flavor property is significantly reduced.

When the amount of the ionomer resin (C) is less than 1 part by weight, a coating film having poor adhesion to a metal plate and poor impact strength may be formed. On the other hand, if the amount of the [C] ionomer resin exceeds 25 parts by weight, compatibility with other components is reduced, and surging occurs during extrusion molding, so that it is difficult to form a film having a uniform thickness. .

In the present invention, the resin composition coated on the metal plate is formed from the components [A], [B] and [C] in the amounts described above.

[0044]

(Equation 3)

0.05-0.3, preferably 0.10-0.2
5 is desirable. When the weight ratio shown above is less than 0.05, the coating has an adhesion to a metal plate,
In some cases, the impact strength is inferior. On the other hand, when it exceeds 0.3, the flavor properties may be remarkably reduced, and a gel may be generated during extrusion molding.

Resin-Coated Metal Sheet The resin-coated metal sheet according to the present invention can be produced by coating the above resin composition on one or both sides of the metal sheet by a known composite material laminating method. The method is not particularly limited. Specifically, for example, it is performed as follows.

(1) [A] Saturated polyester resin and [B]
The polyester elastomer and the [C] ionomer resin are mixed by a tumbler blender, Henschel mixer, V-type blender, and the like, and then melt-mixed by an extruder, a kneader-banbury mixer, and the like, and then an extruder or a gear pump having a T-die at the tip. And can be coated on a metal plate by extruding quantitatively.

(2) [A] Saturated polyester resin and [B]
After mixing the polyester elastomer and the [C] ionomer resin with a tumbler blender, Henschel mixer, V-type blender or the like, the mixture can be coated on a metal plate by quantitatively extruding the mixture directly with an extruder having a T-die or a gear pump. it can.

(3) [A] Saturated polyester resin and [B]
After once forming a resin composition comprising the polyester elastomer and the [C] ionomer resin into a film, the film may be bonded to a metal plate.

When the resin composition as described above is coated on a metal plate, the resin composition extruded in a molten state from the extruder and coated on the metal plate is rapidly cooled to crystallize the resin composition. Preferably, it is prevented.

The thickness of the resin composition layer thus coated is usually 5 to 500 μm, preferably 10 to 100 μm.
m, particularly preferably 20 to 60 μm. The resin-coated metal plate according to the present invention comprises a metal plate as described above, and a resin composition film provided on one or both surfaces thereof, has excellent impact resistance, and has drawability, ironability and drawability. It is excellent in moldability and is uniformly processed without forming pinholes in the coating during molding. In addition, this resin composition is excellent in adhesion to a metal plate and excellent in processability during molding, so that a can with excellent appearance can be obtained.

The drawn ironing can or drawn can according to the present invention is formed by drawing or ironing the above-mentioned resin-coated steel sheet such that the resin composition coating is on the inner surface side.

A drawn ironing can (DI can) or a drawn can (D
Various known methods can be adopted as a method for manufacturing the RD can. The most common method can be produced by ironing a resin-coated steel sheet in one or several steps using an ironing punch.

For example, drawing and ironing can be performed under the following conditions. Plank diameter: 120 to 150 mm Aperture condition: One-stage aperture ratio H / D = 20 to 40/70
９５95mmφ 2-stage drawing ratio H / D = 30-60 / 50-80mmφ Draw ironing diameter… 3-step ironing 50-80mmφ Total ironing rate… 60-80%

[0055]

The resin-coated metal sheet according to the present invention is excellent in the adhesion between the resin and the metal sheet, is excellent in draw ironing or draw formability, and is excellent in followability of the resin during the forming process. And can form a can with excellent appearance.

The drawn ironed can or drawn can according to the present invention has excellent impact resistance to withstand the impacts during canning, canning, and transportation. After can making, drying, printing, baking, etc. Even if it is heated in the step, excellent impact resistance is maintained.

The drawn and ironed can or drawn can according to the present invention has no pinholes and is excellent in the long-term preservability of the contents and also in the preservability such as the fragrance and flavor of the contents.

[0058]

EXAMPLES Next, the present invention will be described specifically with reference to examples, but the present invention is not limited to these examples.

[0059]

Examples 1 to 13 A saturated polyester resin, a polyester elastomer and an ionomer resin as shown in Table 1 were supplied to an extruder in the amounts shown in Table 1 to obtain a resin composition.

A steel plate having both sides plated with Sn of 2.8 g / m ² per side (thickness 0.30 mm, hardness T-1)
The corresponding resin composition was coated with a thickness of 30 μm using an extrusion T die on one side of the Sn plating layer. At this time, the resin melting temperature at the T-die is 265 to 30.
0 ° C., and the steel sheet temperature during coating was 150 to 200 ° C. Further, the steel sheet coated with the resin by the T-die was rapidly cooled to 100 ° C. or less within 10 seconds.

The intrinsic viscosity [dl / g] of the saturated polyester resin as a raw material, the Tg (glass transition temperature), Tm (melting point), and Tcc of the resin composition comprising the saturated polyester resin, the polyester elastomer, and the ionomer resin
(Low temperature crystallization temperature), QTcc (cooling heat of crystallization), QT
m (heat of fusion) is shown in Table 1.

Tg, Tm, Tcc, QTcc, QTm
Is measured at 10 ° C. using a differential thermal analyzer (Perkin Elmer-7 type).
/ Min was measured at a heating rate. Heat of cold crystallization [J / g]
Is measured at 10 ° C. using a differential thermal analyzer (Perkin Elmer-7 type).
/ J is the calorific value due to crystallization observed when measured at a heating rate of / min, and the heat of fusion [J / g] is measured at a rate of 10 ° C / min using a differential thermal analyzer (Perkin Elmer-7 type). It is an endothermic amount due to melting of the resin observed when measured at a temperature rate.

The thus-obtained normal temperature resin-coated steel sheet is drawn and ironed under the following molding conditions so that the inner surface of the can becomes a resin-coated surface, to obtain a drawn iron can (DI can). Manufactured. The inner surface of the obtained DI can was washed and dried in an oven at 210 ° C. for about 2 minutes. Further, the outer surface of the can was painted and baked.

<Molding Conditions> 1. Resin temperature just before drawing and ironing: normal temperature Plank diameter: 137mm 3. Aperture conditions: 1-stage aperture ratio H / D = 33/86 mmφ 2-stage aperture ratio H / D = 50/65 mmφ Ironing punch diameter: 3-stage ironing 65.5mmφ5. Total ironing rate: 70.5% The obtained DI can was subjected to the following pinhole test, impact resistance test, adhesion test, flavor property evaluation, and extrusion laminate moldability evaluation. Table 2 shows the results.

<Pinhole Test on Inner Surface of Can (Resin-Coated Surface)> The obtained DI can was tested for the presence of pinholes by performing the following copper sulfate test.

[0066] and left sulfate 20 g / l in a can, putting a chemical plating solution Cu containing copper sulfate _{(CuSO 4 · 7H 2 O)} 50g / l for 10 minutes, remove the liquid, washed with water, and precipitated Cu was observed. If there is a lack (pinhole) in the resin layer on the inner surface of the can, iron elutes from the missing part,
Cu is subjected to displacement plating.

<Evaluation of Impact Resistance of Resin Composition Film> (i) Post-Impact Current Test Assuming that the can is heated by a drying, printing, baking process, etc., after the can is made, the resin is as follows. After heating the coated steel sheet, a post-impact current test was performed.

After heating the resin-coated steel sheet in an oven at 210 ° C. for 10 minutes, it was cooled to room temperature, and a 2.0 kg iron ball was dropped from a height of 30 cm from the steel sheet side not coated with the resin composition. After making the steel plate the bottom so that the convexly swelling side is the top surface, forming a wall with soft rubber-like resin on the end of the steel plate, add 1.0% saline to the convexly swelling side,
Current (mA) flowing when a voltage of +6 V is applied using a steel plate as an anode and platinum placed near the bulge as a cathode,
Was measured.

(Ii) Adhesion Test The adhesion of the resin coated on the inner surface of the can to the Sn-plated steel sheet was evaluated as follows. After immersing the resin-coated steel sheet at room temperature in an aqueous solution (UCC solution) of 1.5% by weight of citric acid and 1.5% by weight of sodium chloride for 24 hours, the peeled length of the film was measured, and the length (mm) evaluated.

0.0 mm is represented by ◎, 0.0 to 0.5 is represented by ○, 0.5 to 2.0 is represented by Δ, and 2.0 to × is represented by x. <Evaluation of flavor properties> DI obtained as described above
A can was filled with a 5% ethanol, 20 ppm limonene solution, and left at 20 ° C. for 10 minutes. The amount of limonene adsorbed on the film was compared with 100 when the upper layer was formed of homopolyethylene terephthalate. The evaluation criteria for flavor properties are as follows.

Δ: less than 70 Δ: 70 or more and less than 100 ×: 100 or more <Evaluation of extrusion lamination moldability> As described above, the resin composition was subjected to T-die extrusion lamination (resin temperature 265 to 300).
° C), the moldability was evaluated.

〇: Molding is possible without any problem. X: Gels and bumps are generated. Or the extrusion state is not stable in the width direction (surging).

[0073]

Comparative Examples 1 to 4 Resin-coated steel sheets were obtained in the same manner as in the Examples except that the resin compositions shown in Table 1 were used. The intrinsic viscosity [dl / g] of the saturated polyester resin as a raw material, and the Tg, Tm, Tc, and Q of the resin composition
Table 1 shows Tc and QTm.

The thus obtained resin coated steel sheet at room temperature was
Each of the cans was drawn and ironed in the same manner as in Example 1 so that the inner surface of the can became the resin-coated surface, and the drawn and ironed cans (DI
Cans). The obtained DI can was tested and evaluated in the same manner as in Example 1. Table 2 shows the results.

[0075]

[Table 1]

[0076]

[Table 2]

[0077][A] Saturated polyester resin * 1) Copolymers containing two or more dicarboxylic acid components
Steal TA: terephthalic acid, IA: isophthalic acid (dicarboxylic acid)
* 2) Copolymer containing two or more dihydroxy components
Stell EG: ethylene glycol, CHDM: cyclohexane
Dimethanol (100% by mole of dihydroxy compound component)
* 3) Homo PET; terephthalic acid and ethylene glycol
With homopolyester [B] Polyester elastomer * 4) Hytrel 4057 (manufactured by Toray DuPont); poly
Ester / polyether block copolymer polyester segment; acid component / terephthalic acid, iso
Phthalic acid, glycol component / 1,4-butanediol, polyether segment; polybutylene oxide, * 5) decane diacid copolymer polyester; polyester / polyester block copolymer acid component / terephthalic acid, decane diacid, glycol component /
1,4-butanediol,[C] Ionomer resin * 6) Ionomer resin; Himilan 1707 (Mitsui De)
* 7) Ionomer resin; Himilan 1706 (Mitsui De)
(Zn type, manufactured by Upon Chemical Co., Ltd.)

[0078]

[Table 3]

──────────────────────────────────────────────────の Continuation of front page (51) Int.Cl. ⁷ Identification code FI C08G63 / 91 C08G63 / 91 C08L 67/02 C08L 67/02 C09D 167/02 C09D 167/02 (56) References JP-A-7-195618 (JP, A) JP-A-7-195617 (JP, A) JP-A-6-320658 (JP, A) JP-A-54-143387 (JP, A) JP-A-1-306461 (JP, A) A) JP-A-63-39957 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) B32B 15/08 C08L 1/00-101/16

Claims (6)

(57) [Claims] 1. A metal plate, and a resin composition film provided on one or both surfaces of the metal plate, wherein the resin composition film is a saturated polyester resin (A);
0 to 95 parts by weight, and [B] a polyester elastomer;
1 to 30 parts by weight, and [C] ionomer resin;
A resin-coated metal plate comprising: parts by weight. 2. The polyester elastomer [B] comprises: [B-1] (i) an aromatic derivative derived from a dicarboxylic acid component containing at least 50 mol% of terephthalic acid and an alkylene glycol having 2 to 10 carbon atoms. A polyester / polyether block copolymer comprising a polyester segment and (ii) a polyether segment comprising a poly (alkylene oxide) glycol having a molecular weight of 300 to 6000, or [B-1] (i) terephthalic acid , An aromatic polyester segment derived from an alkylene glycol having 2 to 10 carbon atoms, (iii) an aliphatic dicarboxylic acid component, and 2 to 10 carbon atoms.
The resin-coated metal plate according to claim 1, which is a polyester / polyester block copolymer comprising an alkylene glycol and an aliphatic polyester segment derived therefrom. 3. The above [A], [B] and [C] are as follows: The resin-coated metal plate according to claim 1, wherein 4. The [C] ionomer resin is characterized in that part or all of the carboxyl groups in the copolymer of ethylene and α, β-unsaturated carboxylic acid are neutralized with a monovalent or divalent metal cation. The resin-coated metal plate according to claim 1, wherein the ionic salt is a ionic salt. 5. The resin-coated metal plate according to claim 1, wherein the metal plate is a steel plate or an aluminum plate. 6. A drawn ironing can or drawn can formed by drawing and ironing or drawing the resin-coated metal sheet according to claim 1 such that the resin coating surface is on the inner surface side.