JPH07290644A - Resin coated metal panel and drawn/squeezed can or drawn can composed thereof - Google Patents

Abstract

PURPOSE:To provide a resin coated metal panel coated with a resin excellent in drawing/squeezing or drawing moldability, the close adhesiveness with a metal panel and impact resistance, free from a pinhole and excellent in flavor properties and a drawn/squeezed can or drawn can formed from the resin coated metal panel. CONSTITUTION:A resin coated metal panel consists of a metal panel and the resin compsn. film provided on the single surface or both surfaces of the metal panel and the resin compsn. film consists of a crystalline saturated polyester resin layer [A] and a resin compsn. layer [B] consisting of 50-95 pts.wt. of a saturated polyester resin (a), 1-30 pts.wt. of a polyester elastomer (b) and 1-25 pts.wt. of an ionomer resin (c). A drawn/squeezed can or drawn can is composed of the above mentioned resin coated metal panel.

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 squeezing and ironing can or a squeezing can made of this resin-coated metal plate. The present invention relates to a squeezing ironing can or a squeezing can made of a metal plate.

[0002]

BACKGROUND OF THE INVENTION Conventionally, drawn and ironed cans (hereinafter referred to as DI cans) or drawn cans (DRD cans) obtained by drawing and ironing a steel plate such as a tin plate or an aluminum plate are seamless. It has excellent physical properties and is widely used.

In such DI cans and DRD cans, in order to prevent deterioration of taste, deterioration of flavor, alteration of contents and generation of pinholes due to metal elution from a metal plate, the inner surface of the can is prevented. A resin layer may be provided.
As such a can having a resin layer on the inner surface side and a resin-coated metal plate capable of forming such a can, for example, Japanese Patent Laid-Open No. 51-130647 discloses a steel plate coated with a saturated polyester layer. And containers derived therefrom have been proposed. Further, JP-A-1-180336 proposes a steel sheet coated with a polybutylene terephthalate layer, and is disclosed in JP-A-1-192545, JP-A-2-57339, and JP-A-3-10835. Proposes a steel sheet coated with a specific saturated copolyester layer and a container obtained therefrom.

By the way, the coating resin used for the steel sheet for drawn and ironed cans is required to have excellent formability capable of following the drawn and ironing work and the drawing work, and at the same time, has excellent adhesiveness so as not to be peeled from the steel sheet. Required. Further, this resin is required to have excellent impact resistance capable of withstanding impacts during canning, canning process and transportation. In addition, there are required pinholes that do not cause corrosion during storage, and characteristics that do not affect the taste of the beverage, that is, have excellent flavor properties.

However, the resin coated on the conventional steel sheet for cans does not always satisfy such requirements. For example, pinholes may occur in the resin coating during drawing and ironing or drawing. Moreover, the impact resistance of the cans that have been heated in the processes such as drying, printing, and baking after the cans may decrease.

[0006]

DISCLOSURE OF THE INVENTION The present invention has been made in view of the above-mentioned prior art, and is excellent in drawing ironing property or drawing formability, excellent adhesion to a metal plate and excellent impact resistance. Further, it is an object of the present invention to provide a resin-coated metal plate having a pinhole-free resin layer having characteristics such as excellent flavor properties, and a drawn and ironed can or a drawn can made of such a resin-coated metal plate. .

[0007]

SUMMARY OF THE INVENTION A resin-coated metal sheet according to the present invention comprises a metal sheet and a resin coating provided on one side or both sides of the metal sheet. The resin coating is [A] crystalline saturated polyester resin. A layer, and [B] (a) saturated polyester resin; 50 to 95 parts by weight,
(b) Polyester elastomer; 1 to 30 parts by weight, and (c) Ionomer resin; 1 to 25 parts by weight and a resin composition layer consisting of two layers, and the resin composition layer [B] is the metal plate. It is characterized in that it is laminated so as to be in contact with.

The above-mentioned [B] resin composition layer comprises each component (a)
, (B), (c) are [(b) + (c)] / [(a) + (b) + (c)
] (Weight ratio) is preferably contained in an amount of 0.05 to 0.30.

The squeezed ironing can or the squeezed can according to the present invention is formed from the resin-coated metal plate as described above.

[0010]

DETAILED DESCRIPTION OF THE INVENTION A resin-coated metal plate according to the present invention and a drawn and ironed can or a drawn can made of the resin-coated metal plate will be described below.

The resin-coated metal plate according to the present invention comprises a metal plate and a resin composition coating film provided on one side or both sides of the metal plate. In the present invention, conventionally known metals that are generally used for cans are widely used as the metal plate, and specifically, a steel plate (tin plate) or tin whose surface is Sn (tin) plated by a known method. None steel plate (tin-free steel, electrolytic chromic acid treated steel plate) or aluminum plate is used.

This metal plate usually has a thickness of 0.01-5.
mm, preferably 0.1 to 2 mm. On one or both sides of this metal plate, [A] a crystalline saturated polyester resin layer and [B] (a) a saturated polyester resin; 50 to 95 parts by weight,
A resin coating composed of two layers, a resin composition layer comprising (b) a polyester elastomer; 1 to 30 parts by weight, and (c) an ionomer resin; 1 to 25 parts by weight, is formed.

The crystalline saturated polyester resin (A) and the saturated polyester resin (a) used in the present invention are formed from structural units derived from a dicarboxylic acid and a dihydroxy compound.

The dicarboxylic acid component forming the crystalline saturated polyester resin [A] used in the present invention is 99 to 80 mol% terephthalic acid, preferably 95 to 100 mol% when the dicarboxylic acid component is 100 mol%. 85 mol%,
It is desirable that the isophthalic acid is composed of 1 to 20 mol%, preferably 5 to 15 mol%.

Further, as the dihydroxy component forming [A] the crystalline saturated polyester resin, specifically,
Aliphatic dihydroxy compounds such as ethylene glycol, trimethylene glycol, propylene glycol, tetramethylene glycol, pentamethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol and polytetramethylene glycol can be mentioned.

The crystalline saturated polyester [A] as described above is trimesic acid, within a range not impairing the object of the invention.
The constitutional unit derived from a polyfunctional compound such as pyromellitic acid, trimethylolethane, trimethylolpropane, trimethylolmethane, and pentaerythritol may be contained in a small amount, for example, 2 mol% or less.

The crystalline saturated polyester [A] used in the present invention is substantially linear, which is confirmed by the fact that the saturated polyester is dissolved in o-chlorophenol.

The crystalline saturated polyester [A] used in the present invention has an intrinsic viscosity [η] measured in o-chlorophenol at 25 ° C. of usually 0.5 to 1.4 dl /
g, preferably 0.5 to 1.0 dl / g, and more preferably 0.6 to 1.0 dl / g.

Saturated polyesters having such an intrinsic viscosity [η] are preferable because they are excellent in melt moldability and draw-squeeze ironing moldability as well as mechanical strength such as impact resistance.

The crystalline saturated polyester resin [A] used in the present invention usually has a glass transition temperature (Tg) of 50.
To 120 ° C, preferably 60 to 100 ° C, the low temperature crystallization temperature (Tc) is usually 130 to 210 ° C, preferably 140 to 200 ° C, and the crystal melting temperature (Tm) is
It is usually 210 to 265 ° C., preferably 220 to 260 ° C.

The crystalline saturated polyester resin [A] used in the present invention has a crystallinity of 5 to 75%, preferably 10 to 60% as measured by an X-ray diffraction method.

The crystalline saturated polyester resin [A] used in the present invention having the above composition is excellent in processability, and the film formed from the crystalline saturated polyester resin [A] is terephthalic. Compared to a coating film formed of a conventionally known polyester resin derived from an acid and ethylene glycol, it is less likely to adsorb terpene-based odor and is excellent in aroma retention.

In the present invention, the saturated polyester resin (a) used in forming the resin composition layer [B] is a dicarboxylic acid such as terephthalic acid or its ester derivative (eg lower alkyl ester, phenyl ester). , A structural unit derived from a dihydroxy compound such as ethylene glycol or an ester derivative thereof (for example, monocarboxylic acid ester ethylene oxide).

The saturated polyester resin (a) may contain a structural unit derived from another dicarboxylic acid and / or another dihydroxy compound 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. , An aliphatic dicarboxylic acid such as decanedicarboxylic acid; an alicyclic dicarboxylic acid such as cyclohexanedicarboxylic acid.

Dicarboxylic acids other than these terephthalic acids may be used as their ester derivatives. Specific 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, polyethylene. Aliphatic glycols such as glycols; alicyclic glycols such as cyclohexanedimethanol; bisphenols, hydroquinone, and aromatic diols such as 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 contains a small amount of a structural unit 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) saturated polyester resin is
It is substantially linear, which means that the saturated polyester
Confirmed by dissolving in o-chlorophenol. The saturated polyester resin used in the present invention has an intrinsic viscosity [η] measured at 25 ° C. in o-chlorophenol.
Is usually 0.5 to 1.4 dl / g, preferably 0.5 to
1.0 dl / g, more preferably 0.6-1.0 dl / g
Is desirable.

The saturated polyester (a) having such an intrinsic viscosity [η] is preferable because it is excellent in melt moldability and draw-ironing moldability, and also excellent in 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 120.
It is desirable that the temperature is 60 ° C, preferably 60 to 100 ° C.
This (a) saturated polyester resin may be amorphous or crystalline, and when it is crystalline, its crystal melting temperature (Tm) is usually 210 to 265 ° C., preferably 2
It is desired that the temperature is 20 to 260 ° C., and the low temperature crystallization temperature (Tcc) is usually 130 to 210 ° C., preferably 140 to 200 ° C.

As the polyester elastomer (b) forming the resin composition layer [B] in the present invention, conventionally known polyester elastomers can be used without limitation, and the polyester elastomer is crystalline. A thermoplastic elastomer having a hard segment having a high melting point 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. It is preferably (b-1) a polyester / polyether block copolymer or (b-2) a polyester / polyester block copolymer.

Such (b-1) polyester / polyether block copolymer or (b-2) polyester / polyester block copolymer comprises (i) an aromatic polyester and (ii) a polyether or (iii) ) It is obtained by cocondensing an aliphatic polyester with a known method.

(B-1) Polyester used in the present invention
Forming a polyether block copolymer or (b-2) polyester / polyester block copolymer (i)
The aromatic polyester segment is composed of constitutional units derived from an aromatic dicarboxylic acid and a dihydroxy compound.

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

Specific examples of the dihydroxy compound include ethylene glycol, trimethylene glycol (propylene glycol), tetramethylene glycol, pentamethylene glycol, neopentyl glycol, 2,
Examples thereof 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
It may be a combination of two or more species.

(I) The aromatic polyester segment may be a homopolyester of terephthalic acid and one alkylene glycol, and either one of the dicarboxylic acid component and the dihydroxy component is composed of two or more kinds, or A copolyester composed of two or more types of both components may be used.

(B-1) Polyester used in the present invention
Forming a polyether block copolymer and (b-2) polyester-polyester block copolymer (i)
The aromatic polyester segment contains 50 mol% of terephthalic acid when the dicarboxylic acid component is 100 mol%.
Dicarboxylic acid component contained in the above amount and having 2 to 1 carbon atoms
It is preferably formed from a dihydroxy component consisting of 0 alkylene glycol.

(B-1) The polyester segment forming the polyester / polyether block copolymer (ii) The polyether segment is
It is formed from poly (alkylene oxide) glycol having a molecular weight of 300 to 6000. Specific examples of such poly (alkylene oxide) glycols include polyethylene glycol, polypropylene glycol, and polybutylene glycol.

Further, (b-2) the polyester / polyester block copolymer is formed. (Iii) The aliphatic polyester segment comprises an aliphatic dicarboxylic acid component and 2 to 1 carbon atoms.
It consists of a structural unit derived from an alkylene glycol of 0.

As the aliphatic dicarboxylic acid, specifically,
Examples thereof include adipic acid, sebacic acid, azelaic acid and decanedicarboxylic acid. Specific examples of the alkylene glycol having 2 to 10 carbon atoms include those shown above as the (i) dihydroxy compound forming the aromatic polyester segment.

In the present invention, the (b) ionomer resin used when forming the [B] resin composition layer is
Although a conventionally known ionomer resin is widely used, this ionomer resin is an ion in which a part or all of carboxyl groups in a copolymer of ethylene and α, β-unsaturated carboxylic acid is neutralized with a metal cation. It is a natural salt.

As the α, β-unsaturated carboxylic acid,
Unsaturated carboxylic acids having 3 to 8 carbon atoms, specifically acrylic acid, methacrylic acid, maleic acid, itaconic acid, maleic anhydride, maleic acid monomethyl ester, maleic acid monomethyl ester and the like can be mentioned.

With such ethylene and unsaturated carboxylic acid
Cations Neutralizing Carboxyl Groups in Copolymers of Polystyrene
Specifically, Na⁺, K⁺, Li⁺, Zn⁺,
Zn ⁺⁺, Mg⁺⁺, Ca⁺⁺, Co⁺⁺, Ni⁺⁺, Mn⁺⁺, P
b⁺⁺, Cu⁺⁺And monovalent divalent metal cations such as
It In addition, the residual carboxylate not neutralized with metal cations
Some of the silyl groups are esterified with lower alcohols
May be.

The (b) ionomer resin used in the present invention is a metal salt of a copolymer of ethylene and an unsaturated carboxylic acid as described above, but an ethylene / unsaturated carboxylic acid for forming the metal salt is used. The copolymer with is composed of a structural unit derived from ethylene in an amount of 80 to 99 mol%, preferably 8
5 to 98 mol% of the structural unit derived from an unsaturated carboxylic acid (a structural unit having a carboxyl group)
It is contained in an amount of 20 mol%, preferably 2 to 15 mol%.

In the (b) ionomer resin used in the present invention, some or all of the carboxyl groups in the copolymer of ethylene and unsaturated carboxylic acid, specifically 15 to 1
00% of the carboxyl groups are neutralized. This degree of neutralization is preferably 20-80%, more preferably 30-
The composition formed from the (b) ionomer resin having a degree of neutralization of 70% is excellent in melt extrudability.

Specific examples of the (b) ionomer resin include a copolymer of ethylene and an unsaturated monocarboxylic acid such as acrylic acid or methacrylic acid or an unsaturated monomer such as ethylene and maleic acid or itaconic acid. Examples thereof include ionomer resins in which a part or all of the carboxyl groups in the copolymer with a dicarboxylic acid are neutralized with a monovalent or divalent metal ion such as sodium, potassium, lithium, zinc, magnesium or calcium.

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

As these ionomer resins, commercially available products such as "HIMILAN" (trade name: manufactured by Mitsui DuPont Polychemical Co., Ltd.) can be used. In the present invention,
[B] The resin composition layer has a composition of (a) when the total amount of (a) the saturated polyester resin, (b) the polyester elastomer and (c) the ionomer resin as described above is 100 parts by weight.
Saturated polyester resin in an amount of 50 to 95 parts by weight, preferably 60 to 90 parts by weight, (b) polyester elastomer in an amount of 1 to 30 parts by weight, preferably 1 to 20 parts by weight, (c) an ionomer resin. It is contained in an amount of 1 to 25 parts by weight, preferably 5 to 20 parts by weight.

Further, the resin composition layer [B] is prepared by adding the above (a), (b) and (c) to [(b) + (c)] / [(a) +
(b) + (c)] (weight ratio) is preferably 0.05 to 0.30, and more preferably 0.10 to 0.25.

When the resin composition layer [B] is composed of the components (a), (b) and (c) in the above quantitative ratios, it is possible to form a pinhole-free coating and to form a metal plate. Excellent adhesion and also excellent impact strength. If the above-mentioned amount ratio is less than 0.05, the adhesion to the metal plate and impact strength may be insufficient, while if it exceeds 0.30, gel is likely to be generated during molding, and pinholes A coating may form.

The resin composition as described above can be prepared by a conventionally known method for preparing a resin composition. Specifically, (a) a saturated polyester resin, (b) a polyester elastomer and (c) an ionomer. It can be prepared by mixing the resin with a tumbler blender, a Henschel mixer, a V-type blender, etc., and then melt-mixing it with an extruder, a kneader Banbury mixer, or the like.

In the present invention, the resin film laminated on the metal plate is composed of two layers of the above [A] crystalline saturated polyester resin layer and [B] resin composition layer, and this resin The composition layer [B] is laminated so as to be in contact with the metal plate.

The thickness of the resin layer thus laminated is 2
The total number of layers is usually 5 to 500 μm, preferably 10 to 1
00 μm, particularly preferably 20 to 60 μm. Further, these [A] crystalline saturated polyester resin layers and [B]
The film thickness ratio of the two layers to the resin composition layer is preferably [A] layer: [B] layer = 2: 1 to 1: 9.

The resin-coated metal plate according to the present invention as described above is manufactured, for example, as follows. (1) A crystalline saturated polyester resin [A] and a resin composition [B] prepared as described above are placed on a metal plate by a two-layer extrusion T-die so that the [B] resin layer contacts the metal plate. Push out at the same time.

(2) A film consisting of the [A] crystalline saturated polyester resin layer and the [B] resin composition layer is formed once, and the [B] resin composition layer is used as the metal plate. Laminate them so that they touch each other.

(3) It is also possible to form the [B] resin composition layer on the metal plate and then form the [A] crystalline saturated polyester resin layer on the [B] resin composition layer. When the resin layer is coated on the metal plate as described above, it is preferable that the resin coating extruded in a molten state from the extruder and coated on the metal plate is rapidly cooled.

The resin-coated metal sheet according to the present invention comprises the metal sheet as described above, and the [A] crystalline saturated polyester resin layer and the [B] resin composition layer as described above on one side or both sides thereof. And a coating film in which the resin composition layer [B] is laminated so as to be in contact with a metal plate, and has excellent impact resistance, and particularly excellent drawability such as drawability and drawability, It is processed uniformly without forming pinholes in the film during molding. In addition, the resin coating film has excellent adhesion to the metal plate and excellent processing followability during molding, so that a can having an excellent appearance can be obtained.

The drawn and ironed can or the drawn can according to the present invention is obtained by drawing and ironing or drawing such a resin-coated metal plate. A method for producing a drawn and ironed can (DI can) or a drawn can (DRD can) is a method in which a resin-coated metal plate as described above is drawn and ironed or drawn so that the resin-coated surface comes into contact with the contents of the can. In this case, the can manufacturing method is not particularly limited, and various known methods can be adopted. As the most general method, it can be manufactured by a one-step or several-step ironing method using an ironing punch.

For example, the drawing and ironing process can be performed under the following conditions. Plank diameter: 120-150 mm Drawing conditions: 1-step drawing ratio H / D = 20-40 / 70
〜95mmφ 2 step drawing ratio H / D = 30〜60 / 50〜80mmφ drawing ironing diameter ・ ・ ・ 3 step ironing 50-80mmφ total ironing rate ・ ・ ・ 60-80% The drawing ironing can or drawing can according to the present invention is on a metal plate. And a [A] crystalline saturated polyester resin layer and a [B] resin composition layer are formed so that the [A] crystalline saturated polyester resin layer is in contact with the contents of the can. It has little adsorption of system odors and is excellent in flavor property (fragrance retention), and there is no pinhole in the coating film, and the long-term storage property of the contents is excellent.

[0060]

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

Further, the squeezed ironing can or the squeezed can according to the present invention has excellent impact resistance capable of withstanding impacts in the canning, canning process and transportation, and after drying, printing, baking, etc. Even if it is heated in the process of 1, it retains excellent impact resistance.

The squeezed ironing can or the ironing can according to the present invention does not have pinholes and is excellent in long-term storability of the contents, and is also excellent in storability such as scent and flavor (aroma retention) of the contents. .

[0063]

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

[0064]

Examples 1 to 13 [A] Crystalline saturated polyester resin shown in Table 1 and [B] having the composition shown in Table 1
(a) saturated polyester resin, (b) polyester elastomer (Hytrel 4057, manufactured by Toray DuPont, trade name), and (c) ionomer resin (Himilan 170
7: Mitsui DuPont Co., Ltd., trade name), and a steel plate having a Sn composition of 2.8 g / m ^{2 on} each side (plate thickness 0.30 mm, hardness T-1 equivalent). On the Sn plated layer on one side, a two-kind two-layer extruded T die was used to cover the [B] layer with the steel sheet at a film thickness ratio shown in Table 1 to a total film thickness of 30 μm.

The thickness of the [A] layer is 6 μm,
The thickness of the [B] layer was 24 μm. At this time, the resin melting temperature in the T die was 265 to 300 ° C, and the steel plate 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 lower within 10 seconds.

Table 2 shows the intrinsic viscosities [dl / g] of [A] crystalline saturated polyester resin and (a) saturated polyester resin.
And Tg (glass transition temperature), Tm (melting point), Tcc (low temperature crystallization temperature), and QTcc of the [A] crystalline saturated polyester resin and the [B] resin composition, respectively.
(Cooling crystallization heat) and QTm (heat of fusion) are shown.

Tg, Tm, Tcc, QTcc, QTm
Is 10 ° C using a differential thermal analyzer (Perkin Elmer-7 type)
It was measured at a temperature rising rate of / min. Cold crystallization heat [J / g]
Is 10 ° C using a differential thermal analyzer (Perkin Elmer-7 type)
The heating value due to crystallization observed when measured at a heating rate of 1 / min, and the heat of fusion [J / g] was increased by 10 ° C / min using a differential thermal analyzer (Perkin Elmer-7 type). It is the amount of heat absorbed by the melting of the resin observed when measured at the temperature rate.

The resin-coated steel sheet at room temperature thus obtained was subjected to drawing and ironing under the following molding conditions so that the inner surface of the can became the resin-coated surface to obtain a drawn and ironed can (DI can). Manufactured.

<Molding conditions> 1. Resin temperature just before drawing and ironing: normal temperature 2. Plank diameter: 137 mm 3. Aperture conditions: One-stage aperture ratio H / D = 33/86 mmφ Two-stage aperture ratio H / D = 50/65 mmφ 4. Ironing punch diameter: 3-stage ironing 65.5 mmφ 5. Total ironing rate: 70.5% <Copper sulfate test on can inner surface (resin-coated surface)> The obtained DI can was subjected to the following copper sulfate test.

A chemical plating solution of Cu containing 20 g / l of sulfuric acid and 50 g / l of copper sulfate (CuSO ₄ .7H ₂ O) was placed in a can and left for 10 minutes to remove the solution, washed with water, and then deposited. Cu was observed.

If the resin layer on the inner surface of the can has a lack (pinhole), iron is eluted from the lack and Cu is displacement-plated. <Evaluation of impact resistance of resin composition coating> (i) Current test after impact Assuming a state in which the can is heated by a drying, printing, baking process or the like after the can is manufactured, a resin-coated steel sheet is prepared as follows. After heating, 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 such that the convexly swollen side is the upper surface and forming a wall of soft steel-like resin at the end of the steel plate, add 1.0% saline to the convexly swollen side,
Current value (mA) that flows when a voltage of + 6V is applied with a steel plate as the anode and platinum installed near the bulge as the cathode
Was measured.

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

0.0 mm was marked with ⊚, 0.0 to 0.5 was marked with ◯, 0.5 to 2.0 was marked with Δ, and 2.0 to was marked with x. Table 3 shows the results of the copper sulfate test, the post-impact current test and the adhesion test.

[0075]

Comparative Examples 1 to 3 Resin-coated steel sheets were obtained in the same manner as in Examples except that the resin composition shown in Table 1 was used instead of the resin composition [B].

Intrinsic viscosity [dl / g] of the saturated polyester resin as a raw material and Tg, Tm, Tc of the resin composition,
Table 1 shows QTc and QTm. The resin-coated steel sheet at room temperature thus obtained was squeezed and ironed in the same manner as in Example 1 so that the inner surface of the can became the resin-coated surface,
A squeezed ironing can (DI can) was produced.

With respect to the obtained DI can, a copper sulfate test, a post-impact current test and an adhesion test were conducted in the same manner as in Example 1. The results are shown in Table 2.

[0078]

[Table 1]

* 1) The dicarboxylic acid component of [A] crystalline polyester resin is 100 mol%. The dicarboxylic acid component other than isophthalic acid is terephthalic acid. * 2) Saturated polyester resin; when the dicarboxylic acid component is composed of two or more kinds, the molar ratio of TA ... terephthalic acid and IA ... isophthalic acid (however, the total of these is 100 mol%) * 3) Saturated polyester resin When the dihydroxy component is composed of two or more kinds, EG ... ethylene glycol and CH
DM: molar ratio with cyclohexanedimethanol (however, the total of these is 100 mol%) * 4) Homo PET; homopolyester of terephthalic acid and ethylene glycol * 5) Polyester elastomer; Hytrel 4057
(Toray DuPont) polyester / polyether block copolymer polyester composition; acid component terephthalic acid / isophthalic acid, glycol component 1,4-butanediol, polyether; polybutylene oxide * 6) decane diacid copolymerized polyester; polyester·
Polyester block copolymer Acid component Terephthalic acid / decane diacid, glycol component
1,4-Butanediol * 7) Ionomer resin; Himilan 1707 (Mitsui DuPont Chemical Co., Na type)

[0080]

[Table 2]

[0081]

[Table 3]

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Claims (7)

[Claims] 1. A metal plate and a resin film provided on one or both sides of the metal plate, wherein the resin film comprises [A] a crystalline saturated polyester resin layer and [B] (a) saturated. Polyester resin; 50 to 95 parts by weight,
(b) a polyester elastomer; 1 to 30 parts by weight, and (c) an ionomer resin; 1 to 25 parts by weight and a resin composition layer consisting of two layers, and the resin composition layer [B] is the metal plate. A resin-coated metal plate, wherein the resin-coated metal plate is laminated so as to be in contact with. 2. A crystalline saturated polyester resin layer [A],
The resin-coated metal plate according to claim 1, wherein a film thickness ratio of the [B] resin composition layer is [A] layer: [B] layer = 2: 1 to 1: 9. 3. The (b) polyester elastomer is an aromatic compound derived from (b-1) (i) a dicarboxylic acid component containing 50 mol% or more of terephthalic acid and an alkylene glycol having 2 to 10 carbon atoms. Polyester segment and (i
i) a polyester / polyether block copolymer composed of a polyether segment composed of poly (alkylene oxide) glycol having a molecular weight of 300 to 6000, or (b-2) (i) terephthalic acid of 50 mol% or more An aromatic polyester segment derived from a dicarboxylic acid component contained and an alkylene glycol having 2 to 10 carbon atoms;
ii) A resin according to claim 1, which is a polyester / polyester block copolymer comprising an aliphatic dicarboxylic acid component and an aliphatic polyester segment derived from an alkylene glycol having 2 to 10 carbon atoms. Coated metal plate. 4. The (c) ionomer resin is a copolymer of ethylene and an α, β-unsaturated carboxylic acid in which some or all of the carboxyl groups are neutralized with a monovalent or divalent metal cation. The resin-coated metal plate according to claim 1, wherein the resin-coated metal plate is a prepared ionic salt. 5. The [B] resin composition layer comprises the components (a), (b) and (c) described above in [(b) + (c)] / [(a) + (b )
+ (C)] (weight ratio) is contained in an amount of 0.05 to 0.30, The resin-coated metal plate according to claim 1, wherein 6. The resin-coated metal plate according to claim 1, wherein the metal plate is a steel plate or an aluminum plate. 7. A drawn and ironed can or drawn can obtained by drawing and ironing the resin-coated metal plate according to claim 1 so that the resin coating surface faces the inner surface of the can.