JP2002307604A - Lubricating steel panel excellent in draw squeezing processability - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a lubricating steel panel excellent in toughness and processability and capable of withstanding draw squeezing processing. SOLUTION: In the lubricating steel panel for a draw squeezed can, a film, which comprises a paint containing a hydroxyl group-containing polyester resin (A) with a number average mol.wt. of 8,000-50,000, an amino resin and/or a resole type phenol resin (B) and wax (C) with a softening point of 30 deg.C or higher, is formed on both surfaces of a metal panel in a dry coating amount of 10-85 mg/100 cm<2> , and the coefficient of dynamic friction at 60 deg.C of the film is 0.03-0.20 and the pencil hardness at 60 deg.C thereof is not less than H.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a lubricated steel sheet, and in particular, to drawing and ironing (DI processing, Draw an
d Ironing).

[0002]

2. Description of the Related Art 2 used for food cans and the like
Depending on the manufacturing method, a piece can is drawn and ironed (DI can: Draw and Irone)
d Can) and squeezed can (DR can: Drawn)
Can, DRD can: Drawn and Redrawn
Can) and DTR cans (Drawn Thin Redraw Can). Of these, DI cans are often used for positive pressure beverage cans such as beer and carbonated beverages because of their aesthetics and thin and light weight. However, the conventional method of ironing unpainted materials requires a large amount of lubricant and coolant during ironing, and after degreasing, washing and surface treatment,
It is necessary to spray paint the inside and bake and dry it,
There is a problem that the load on the environment such as wastewater treatment is large.

[0003] In order to solve such a problem, there have been various proposals that can be made without using a lubricant by using a thermoplastic solid film laminated on a steel sheet in advance, and that a later inner surface spray coating is not performed.

[0004] For example, a method of thermally laminating a biaxially stretched thermoplastic film directly or via an adhesive to a metal plate (for example, JP-A-56-10451, JP-A-57-65463, etc.) ), Instead of processing a thermoplastic resin into a film and then laminating it on a metal plate, a method in which the resin is hot melted and directly extruded and laminated on the metal plate (for example, JP-A-51-17988). Although it has been disclosed and some have been put to practical use,
The performance required for resin coatings for cans is, for example, a wide variety of moldability, impact resistance, corrosion resistance, retort resistance, etc.
It is not easy to meet all of them.

On the other hand, studies have been made to eliminate lubricants and coolants by using a lubricating steel sheet having a lubricating film formed on a steel sheet in place of an unpainted material. The use of lubricated steel sheets has been delayed because processing is more difficult than in the field. Particularly, the epoxy resin-based coating film conventionally used for the inner surface of the can has good adhesion to the material and high hardness, but is inferior in workability and cannot follow severe processing. On the other hand, a polyester resin-based coating film generally has good workability, but hardly exhibits hardness, and has a problem that it is scraped off during processing.

An object of the present invention is to solve the above-mentioned problems and to obtain a lubricated steel sheet which is tough, has good workability, and can withstand drawing and ironing.

[0007]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies to solve the above-mentioned problems, and as a result, have found that a system in which a hydroxyl group-containing polyester resin is combined with an amino resin and / or a resole type phenol resin as a curing agent is used. Adhesion to metal by adjusting the kinetic friction coefficient at 60 ° C of the coating obtained by adding a wax of 30 ° C or higher to the range of 0.03 to 0.20 and the pencil hardness to H or higher. The present inventors have found that a lubricated steel sheet having excellent properties, toughness, good workability, and which can withstand drawing and ironing can be obtained, thereby completing the present invention.

[0008] Thus, the present invention provides (A)
A coating film containing a hydroxyl group-containing polyester resin having a number average molecular weight of 8,000 to 50,000, (B) an amino resin and / or a resol type phenol resin, and (C) a wax having a softening point of 30 ° C. or higher is dried and coated. 10-85
mg / 100 cm ² , at 60 ° C.
The present invention relates to a lubricated steel plate for drawn and ironed cans having a dynamic friction coefficient of 0.03 to 0.20 and a pencil hardness at 60 ° C. of not less than H, and to a drawn and ironed can using the lubricated steel plate for cans.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION The lubricated steel sheet of the present invention has a hydroxyl group-containing polyester resin (A), an amino resin and / or a resol type phenol resin (B), and a wax (C) having a softening point of 30 ° C. or more on both sides of a metal material. ) As an essential component, and has a film formed by applying and thermally curing the coating composition. The coating composition applied to each surface may be the same or different. The coating composition to be on the inner surface side of the can is preferably composed of a hydroxyl group-containing polyester resin and a resol type phenol resin in terms of retort resistance, adhesion, flavor, etc. A coating composition comprising a hydroxyl group-containing polyester resin, a melamine resin and, if necessary, a novolak type epoxy resin (D) is preferred in terms of appearance, hardness, workability, and the like. Arbitrariness.

[0010] The coating obtained by applying the above coating composition, baking and drying, must withstand severe drawing and ironing. In particular, since the production is performed at high speed and continuously in a line, the apparatus generates heat up to about 60 ° C., softens the film, reduces slipperiness, and deteriorates moldability. The present inventors have paid attention to physical properties at a high temperature of 60 ° C., and have a dynamic friction coefficient of 0.03 to 0.20, preferably 0.05 to 0.1.
5. It has been found that a pencil hardness of not less than H, preferably not less than 2H is suitable for drawing and ironing.

In a film formed from a general thermosetting polyester-based paint, when heated to 60 ° C., the pencil hardness (destruction) decreases to about HB, and the dynamic friction coefficient is 0.3 to less. It shows a large value of about 0.5.

Hydroxyl-containing polyester resin (A) The above-mentioned hydroxyl-containing polyester resin (A) is synthesized by directly esterifying or transesterifying an acid component and an alcohol component, and has sufficient hardness and processability. Therefore, it is preferable that the molecular weight is large and the functional group weight is small, and the number average molecular weight is from 8,000 to
50,000, especially 10,000 to 30,000, and a hydroxyl value of 1 to 22, especially 3 to 20 mgKOH /
It is preferably within the range of g.

The acid component constituting the hydroxyl group-containing polyester resin (A) includes, for example, phthalic anhydride, isophthalic acid, terephthalic acid, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, hexahydroisophthalic acid,
One or more dibasic acids selected from hexahydroterephthalic acid, succinic acid, fumaric acid, adipic acid, sebacic acid, maleic anhydride and the like, and lower alkyl esterified products of these acids are mainly used, and if necessary, benzoic acid acid,
Monobasic acids such as crotonic acid, pt-butylbenzoic acid,
A tribasic or higher polybasic acid such as trimellitic anhydride, methylcyclohexenetricarboxylic acid, or pyromellitic anhydride is used in combination.

The alcohol component constituting the polyester resin (A) includes, for example, ethylene glycol, diethylene glycol, propylene glycol,
1,3-butanediol, 1,4-butanediol, neopentyl glycol, 2-methyl-1,3-propanediol, 3-methylpentanediol, 1,4-hexanediol, 1,6-hexanediol, A dihydric alcohol such as 1,4-dimethylolcyclohexane is mainly used, and a trihydric or higher polyhydric alcohol such as glycerin, trimethylolethane, trimethylolpropane, and pentaerythritol can be used in combination, if necessary. These alcohol components can be used alone or in combination of two or more.

When the acid component and the alcohol component are synthesized by a conventional method by direct esterification or transesterification, if the reaction is carried out under conditions in which the carboxyl groups are excessive with respect to the hydroxyl groups, the carboxyl groups are mainly formed. Is obtained, and the reaction is carried out under the condition that the hydroxyl group is excessive relative to the carboxyl group, to obtain a polyester resin mainly containing a hydroxyl group. Furthermore, the amount of the hydroxyl group and the carboxyl group in the single resin can be adjusted by adding an acid anhydride to the polyester resin mainly containing the hydroxyl group. Examples of the acid anhydride to be reacted with the polyester resin mainly containing a hydroxyl group include phthalic anhydride, succinic anhydride, maleic anhydride, hexahydrophthalic anhydride, and trimellitic anhydride.

In the above method, the reaction by the direct esterification method or the transesterification method can be promoted by pressurizing or depressurizing operation, or by flowing an inert gas. Further, at the time of the reaction, an organic metal catalyst such as di-n-butyltin oxide or the like can be used as an esterification catalyst.

The hydroxyl group-containing polyester resin may be an oil-free polyester resin, an oil-modified alkyd resin, or a modified product of these resins, such as a urethane-modified polyester resin or a urethane-modified alkyd resin. However, an oil-free polyester resin is preferred.

Curing agent (B) As the curing agent to be combined with the hydroxyl group-containing polyester resin, an amino resin and / or a resol-type phenol resin are preferable from the viewpoint of curability, hygiene and the like. A resol-type phenol resin can be suitably used from the viewpoints of adhesion and flavor, and an amino resin having no problem such as coloring on the outer surface of the can can be suitably used.

As the amino resin, melamine, urea,
Examples include methylolated amino resins obtained by reacting an aldehyde with an amino component such as benzoguanamine, acetoguanamine, steroganamin, spiroguanamine, dicyandiamide and the like. Examples of the aldehyde include formaldehyde, paraformaldehyde, acetaldehyde, and benzaldehyde. In addition, those obtained by etherifying the methylolated melamine resin with one or more alcohols are also included in the amino resin. Examples of the alcohol used for the etherification include monohydric alcohols such as methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, isobutyl alcohol, 2-ethylbutanol, and 2-ethylhexanol. . Among them, at least a part of the methylol group of the methylolated amino resin is substituted with 1 to 4 carbon atoms.
Amino resins obtained by etherification with a dihydric alcohol are preferred.

Specific examples of the melamine resin include Cymel 300, 303, 325, 327, 350, 730, 736, and 738 (all manufactured by Mitsui Cytec), Melan 522, and the like. 523 (all of which are manufactured by Hitachi Chemical Co., Ltd.), Nicaraq MS001,
MX430 and MX650 (both manufactured by Sanwa Chemical Co., Ltd.), Sumimar M-55, M-100, and M
-40S (all of which are manufactured by Sumitomo Chemical Co., Ltd.), Regin 7
Methyl etherified melamine resins such as No. 40 and No. 747 (all of which are manufactured by Monsanto Co.);
225 (all of which are manufactured by Mitsui Chemicals, Inc.), Super Beckamine J820-60, L-117-60, L-
109-65, 47-508-60, L-118-
Butyl etherified melamine resins such as No. 60 and G821-60 (all of which are manufactured by Dainippon Ink and Chemicals, Inc.);
Cymel 202, 232, 266, XV-51
4, 1130 (all of which are manufactured by Mitsui Cytec), Nicarax MX45, MX500, MX60
Methyl ethers and butyl ethers such as 0, MS35, MS95 (all manufactured by Sanwa Chemical Co., Ltd.), REMININ 753, 755 (all manufactured by Monsanto), Sumimar M-66B (Sumitomo Chemical Co., Ltd.) And mixed etherified melamine resins. These melamine resins can be used alone or in combination of two or more.

The resole type phenol resin includes:
A phenol component and formaldehyde are heated in the presence of a reaction catalyst to cause a condensation reaction to introduce a methylol group, and a part of the methylol group of the methylolated phenolic resin is alkyl etherified with alcohol.

In the production of the resol-type phenolic resin crosslinking agent, the phenol component as a starting material is
A bifunctional phenol compound, a trifunctional phenol compound, a phenol compound having four or more functional groups, or the like can be used.

Examples of the bifunctional phenol compound used for producing the resol type phenol resin crosslinking agent include o-cresol, p-cresol, p-tert-butylphenol, p-ethylphenol, 2,3-xylenol,
Examples include bifunctional phenols such as 2,5-xylenol, and examples of the trifunctional phenol compounds include phenol, m-cresol, m-ethylphenol, 3,5-xylenol, and m-methoxyphenol. In addition, examples of the tetrafunctional phenol compound include bisphenol A and bisphenol F. These phenol compounds can be used alone or in combination of two or more.

Formaldehyde used in the production of resole type phenol resin includes formaldehyde,
Examples include paraformaldehyde and trioxane, which can be used alone or as a mixture of two or more.

The alcohol used to alkyl etherify a part of the methylol groups of the methylolated phenolic resin has 1 to 8 carbon atoms, preferably 1 to 8 carbon atoms.
Four monohydric alcohols can be suitably used.
Suitable monohydric alcohols include methanol, ethanol, n-propanol, n-butanol, isobutanol and the like.

The resol type phenol resin has an average of 0.5 or more, preferably 0.6 to 3 alkoxymethyl groups per benzene nucleus in terms of reactivity with the hydroxyl group-containing polyester resin (A). Those having zero are suitable.

The mixing ratio of the hydroxyl group-containing polyester resin (A) and the curing agent (B) is such that the hydroxyl group-containing polyester resin (A) / the curing agent (B) = 80/20 to 98/2, preferably 90/10. The range of 97/3 is preferable from the viewpoint of the balance between curability and workability.

Wax (C) The wax is added to adjust the kinetic friction coefficient of the obtained film, and the wax has a softening point of 30 ° C. or higher, preferably 33 ° C. or more, for adjusting the kinetic friction coefficient at a high temperature. Suitable are those in the range of 150 ° C., for example, waxes such as fatty acid ester wax, which is an esterified product of a polyol compound and a fatty acid, silicon-based wax, fluorine-based wax, polyolefin wax, animal-based wax, and plant-based wax. And the like.

The polyol compound used as a raw material of the fatty acid ester wax includes ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, 1,3- or 1,4-butanediol, neopentyl glycol, 1,6-hexane. Diol, glycerin, di- or higher polyglycerin, trimethylolpropane, pentaerythritol, dipentaerythritol and the like can be mentioned. Of these, polyol compounds having three or more hydroxyl groups in one molecule are preferable, and polyglycerin, trimethylolpropane, and pentaerythritol are particularly preferable.

The fatty acid used as the other raw material of the fatty acid ester wax may be a saturated or unsaturated fatty acid, and is preferably a fatty acid having 6 to 32 carbon atoms. Specific examples of suitable fatty acids include caprylic acid, pelargonic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, arachiic acid,
Saturated fatty acids such as behenic acid, cerotic acid, montanic acid, and melicic acid; caproleic acid, undecylenic acid, palmitoleic acid, oleic acid, linoleic acid, linolenic acid, eleostearic acid, cetreic acid, erucic acid, licanoic acid, ricinoleic acid And unsaturated fatty acids such as arachidonic acid. As the fatty acid ester wax, at least one of the number of hydroxyl groups of the above polyol compound is used.
It is preferable that / 3 is esterified with a fatty acid.

As the silicon-based wax, for example, B
YK-300, BYK-320, BYK-330 [manufactured by BYK Chemie (Big Chemie)], Silwet L-77, L-720, L-7602 [manufactured by Nippon Konica Co., Ltd.], Paintad 29 , 3
2, M (above, manufactured by Dow Corning), Shin-Etsu Silicone KF-96 (manufactured by Shin-Etsu Chemical Co., Ltd.) and the like, and as the fluorine-based wax, for example, shamrock wax SST-1MG, SST-3 Fluoroslip 231 [or more, manufactured by Shamrock Chemicals], POL
YFLUO (polyfluo) 120, 150, 400
[Micro Powders Co., Ltd.] and the like.

Examples of the polyolefin wax include shamrock waxes S-394 and S-395.
[The above, manufactured by Shamrock Chemicals Co., Ltd.], Hoechst Wax PE-520, the same PE-521 [The above, manufactured by Hoechst Co., Ltd.], Mitsui High Wax [Mitsui Petrochemical Co., Ltd.], and the like. Is, for example,
Lanolin, beeswax and the like can be mentioned, and examples of the vegetable wax include carnauba wax and water wax.

The wax (C) can be used alone or in combination of two or more. The amount of the wax (C) added depends on the total solid content of the hydroxyl group-containing polyester resin (A) and amino resin and / or phenol resin (B). Suitably the range is from 0.1 to 5 parts by weight, preferably from 0.5 to 2 parts by weight, based on 100 parts by weight.

Novolak-type epoxy resin (D) Novolak-type epoxy resin is a resin used as necessary for improving the adhesion to the material and the film hardness, and includes phenol novolak-type epoxy resin and cresol novolak-type epoxy resin. And various novolak type epoxy resins such as a phenol glyoxal type epoxy resin having a large number of epoxy groups in the molecule. Among them, a phenol novolak type epoxy resin and a cresol novolak type epoxy resin which are easy to balance the coating film performance are preferable.

A bisphenol-type epoxy resin can also be used. However, it has been pointed out that bisphenol A is suspected of being an endocrine disrupting substance.

Commercial products of the novolak type epoxy resin (D) include phenol novolak type as Epicoat 152 and 154 (all of which are manufactured by Japan Epoxy Resin), EPPN-201 (manufactured by Nippon Kayaku), Epototo YDPN-638 (manufactured by Toto Kasei Co., Ltd.), and as a cresol novolak type, Epicoat 180
S65, 180H65 (both manufactured by Japan Epoxy Resin), EOCN-102S, -103
S, the same -104S (all, manufactured by Nippon Kayaku Co., Ltd.), Epototh YDCN-701, the same -702, the same -703,
No. 704 (all manufactured by Toto Kasei Co., Ltd.), and other novolak type epoxy resins such as Epototh ZX-1071T, ZX-1015, and ZX-
1247 and YDG-414S (both manufactured by Toto Kasei).

When the novolak type epoxy resin (D) is used for the paint for the outer surface of a can, the amount of the hydroxyl group-containing polyester resin (A) is 80 to 98 parts by weight, preferably 90 to 97 parts by weight, and the curing agent ( B) is in the range of 1 to 15 parts by weight, preferably 2 to 8 parts by weight, and the novolak type epoxy resin (D) is in the range of 1 to 15 parts by weight, preferably 1 to 8 parts by weight. Is preferred.

An acid catalyst can be added to the above-mentioned coating composition, if necessary, to accelerate the curing reaction. For example, specific examples include acid catalysts such as paratoluenesulfonic acid, dodecylbenzenesulfonic acid, dinonylnaphthalenesulfonic acid, dinonylnaphthalenedisulfonic acid, and phosphoric acid, and amine neutralized products of these acids.
Among them, the above-mentioned sulfonic acid compounds or amine neutralized sulfonic acid compounds are preferred.

The amount of the acid catalyst is determined by the amount of acid (for example, in the case of an amine neutralized product of a sulfonic acid compound, the remaining sulfone obtained by removing the amine from the neutralized product) (Acid compound amount), based on 100 parts by weight of the total of the hydroxyl group-containing polyester resin (A) and the curing agent (B), in the range of 0.1 to 5 parts by weight, preferably 0.2 to 2 parts by weight. Is preferred.

The coating composition contains a hydroxyl group-containing polyester resin (A), a curing agent (B) and a wax (C) as essential components, and optionally contains a novolak type epoxy resin (D). From the viewpoint of paintability and the like, a solvent is usually blended. In addition, if necessary,
Other resins can be blended for the purpose of modifying the coating film, and further pigments such as coloring pigments and extender pigments; and paint additives such as anti-agglomeration agents, leveling agents, and defoamers can do.

As the solvent, the above-mentioned component (A),
Those which can dissolve or disperse each component such as (B) and (C) and other resins used as necessary can be used, and specifically, for example, toluene, xylene, high-boiling petroleum hydrocarbon, etc. Hydrocarbon solvents, ketone solvents such as methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, isophorone, ester solvents such as ethyl acetate, butyl acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether acetate, methanol, ethanol, butanol Such as alcohol solvents, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ether alcohol solvents such as diethylene glycol monobutyl ether, and the like,
These can be used alone or in combination of two or more.

The above-mentioned coating composition is coated on both sides of a flat metal plate by a known coating method such as a roll coater or a curtain flow coater, and baked to form a coating film suitable as a lubricating steel plate for drawing and ironing cans. be able to. The coating amount is 10 to 85 mg / dry coating amount.
100 cm ² , preferably 15-60 mg / 100 cm
It is preferably in the range of ² . The baking conditions of the coating film
Usually, it is about 5 seconds to about 30 minutes under the condition that the maximum temperature of the metal plate is about 90 to 300 ° C.

The coating composition of the present invention may further contain, if necessary, an organic solvent, a coating surface improving agent, a coloring pigment, a body pigment, a modified resin, and the like, which are known per se for a coating. .

The coating composition of the present invention is excellent in storage stability, water resistance, processability and the like of the coating, and has bisphenol A
Since a coating film from which environmental hormones such as environmental hormones do not elute can be formed, the effects of the present invention can be sufficiently exerted by coating on the inner and outer surfaces of the can, especially on the inner surface of the can.

Examples of the material for the can include a non-treated steel sheet, a tin-plated steel sheet, a galvanized steel sheet, a chromium-plated steel sheet, a phosphate-treated steel sheet, a chromate-treated steel sheet, an untreated aluminum sheet, and a chromate-treated aluminum sheet. And other metal materials.

After the lubricating steel sheet of the present invention is drawn and ironed in a can shape, the outer surface of the can is coated with a conventionally known paint for the outer surface of a can, and the inner surface of the can requires the conventionally known paint for the inner surface of a can. Will be painted according to. Known coating methods such as roll coater coating and spray coating can be used as the coating method. The bottom of the inner surface of the can is not subjected to severe drawing and ironing, and damage to the film can be omitted because it is minor.

[0047]

The present invention will be described below in more detail with reference to examples. In the following description, "part" and "%"
Represents "parts by weight" and "% by weight" unless otherwise specified.

Production of Paints for Inner and Outer Surfaces Paints for can inner surfaces A1 to A based on the composition shown in Table 1 below
No. 16 and paints B1 to B16 for can outer surfaces were prepared based on the composition shown in Table 2 below. In addition, A11 to A16 and B11 to B16 are prepared for comparison, each composition is indicated by solid content or active ingredient, and the contents of the raw materials used therein are shown below. UE9200: manufactured by Unitika Ltd., polyester resin, number average molecular weight 15,000, glass transition point 65 ° C, hydroxyl value 6 mgKOH / g. UE3201: manufactured by Unitika, polyester resin, number average molecular weight 20,000, glass transition point 65 ° C, hydroxyl value 3 mgKOH / g. UE3500: Unitika, polyester resin, number average molecular weight 30,000, glass transition point 35 ° C, hydroxyl value 4 mgKOH / g. UE3300: Unitika, polyester resin, number average molecular weight 8,000, glass transition point 45 ° C, hydroxyl value 1
8 mg KOH / g. UE3360: Unitika, polyester resin, number average molecular weight 5,000, glass transition point 55 ° C, hydroxyl value 2
5 mg KOH / g. UE3223: Unitika, polyester resin, number average molecular weight 21,000, glass transition point 1 ° C, hydroxyl value 8
mg KOH / g. Hitachil 3305N: Hitachi Chemical Co., Ltd., cresol / p-tert-butylphenol / formaldehyde type phenol resin solution, solid content: about 42%. Durato P-97: BORDEN CHEMICAL
(Boden Chemical) cresol / formaldehyde type phenol resin solution, solid content about 50%. VALCOM 29-101: BTL SPECIALTY
RESINS, xylenol / formaldehyde phenolic resin, 100% solids. Cymel 303: manufactured by Mitsui Cytec, methylated melamine resin, solid content 100%. Cymel 1123: Ethylated benzoguanamine resin, manufactured by Mitsui Cytec, 100% solids. Tesazine 3003-60: a product of Hitachi Chemical Polymer, butylated urea resin, solid content 60%. Epicoat 154: manufactured by Japan Epoxy Resin, phenol novolak type epoxy resin, solid content 100% CRODALAN SWL: manufactured by Crawler Japan,
Refined lanolin wax, softening point 30-38 ° C HI-DISPER F-10PC: manufactured by Gifu Shellac Manufacturing Co., Ltd., carnauba wax, NV = 10%, softening point 81
-86 ° C AC polyethylene 316A: Allied chemical, acid value polyethylene wax, softening point 136-140 ° C NACURE 5925: King Industries Co., Ltd., amine neutralized solution of dodecylbenzenesulfonic acid, active ingredient 25% Modaflow: Monsanto, USA Acrylic resin oligomer surface modifier, 100% solids.

[0049]

[Table 1]

[0050]

[Table 2]

Preparation of Test Coated Plates Examples 1 to 20 and Comparative Examples 1 to 12 One of aluminum plates (aluminum alloy 3004 having a plate thickness of 0.30 mm) was coated with a paint for outer surface shown in Table 4 to a film thickness of 30%.
mg / 100 cm ^2, and after coating the inner surface paint shown in Table 4 on the back surface so as to have a film thickness of 60 mg / 100 cm ² , under the condition that the aluminum plate temperature reaches 270 ° C. in 25 seconds, Each baked coated plate was obtained.

A test was conducted on each of the obtained coated plates according to the following test method. Table 4 shows the results.

Test method Dynamic friction coefficient: The temperature of the test coated plate was kept at 60 ° C., and MOBILITY / LUBRICIT was measured on both sides of the test coated plate.
Y TESTER MODEL 9505AER (ALT
(Manufactured by EK Co., Ltd.), and the dynamic friction coefficient was measured at a pulling speed of 100 mm / min. The smaller the coefficient of kinetic friction, the better the lubricity.

Pencil hardness: The test coated plate was placed on a heat panel whose temperature was controlled at 60 ° C.
A pencil scratch test specified in IS K5400 8.4.2 was performed, and the evaluation based on the destruction of the coating film was performed.

Workability 1: A test coated plate was subjected to a blank diameter 82 using a metal thin plate deep drawing tester type 142 manufactured by Eriksen.
As shown in Table 3 below, processing was performed in order from 1 mm to 5 stages, and finally drawing and ironing was performed with a drawing ratio of about 37% and an ironing rate of about 60%.

[0056]

[Table 3]

At this time, the drawing and ironing workability was evaluated according to the following criteria. ：: Formable. ×: Destruction of the material occurs, and molding cannot be performed until the end.

Workability 2: Processing similar to workability 1 is performed.
The state of the coating film on the outer side of the formed cylinder was visually observed and evaluated according to the following criteria. A: There is no change in the coating film. ：: Slight cracks are observed in the coating film. Δ: Cracks are formed in the coating film, and there is a rough part. X: A deep crack is formed in the coating film, and the coating film is entirely rough.

Two-piece can for evaluation of flavor and corrosion resistance
Creating each test coated plate, blank stamping, cupping, D & I
Drawing and ironing (ironing) processing and trimming were performed by a machine to form a can having a can height of 125 mm and an outer diameter of 65 mm. Using an airless spray device for this can, SJ
-6839-009 (Kansai Paint, paint for can inner surface)
Was applied to only the inner wall excluding the bottom of the can so as to have a dry film thickness of about 6 μm, and was baked at 200 ° C. for 60 seconds. Further, the aluminum cover is flanged by a flanging machine so that the aluminum lid can be tightened.
A piece can was made.

Flavor: The above two-piece can was filled with 350 cc of tap water treated with activated carbon, and the aluminum lid was tightly wound. After sterilization at 100 ° C. for 30 minutes, 37 ° C.
After storing for 6 months, a flavor test was performed and evaluated according to the following criteria. ：: No change was observed at all. ：: slight change is observed. Δ: A considerable change is observed. X: A remarkable change is recognized.

Corrosion resistance: The above two-piece cans were hot-packed with 10% pine juice at 98 ° C., tightly wound with an aluminum lid, stored at 37 ° C. for 6 months, opened, and opened for corrosion. The state was observed and evaluated according to the following criteria. ：: No corrosion was observed. ：: Slight corrosion is observed. Δ: Corrosion is considerably observed. X: Corrosion is remarkable.

[0062]

[Table 4]

[0063]

[Table 5]

[0064]

The lubricated steel sheet of the present invention is tough, has good workability, can withstand severe drawing and ironing, and is extremely suitable for drawing and ironing cans.

Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat II (reference) C09D 161/06 C09D 161/06 161/20 161/20 163/04 163/04 167/00 167/00 191/06 191 / 06 C10M 107/32 C10M 107/32 129/70 129/70 143/02 143/02 145/20 145/20 147/02 147/02 149/16 149/16 149/20 149/20 159/06 159 / 06 169/04 169/04 // B21D 51/26 B21D 51/26 X C10N 20:00 C10N 20:00 A 20:04 20:04 30:12 30:12 40:00 40:00 Z 50:02 50:02 (72) Inventor Hideki Yoshiwara 4-171-1, Higashi-Hachiman, Hiratsuka-shi, Kanagawa Pref. Inside (72) Inventor Jun Shiota 4-171-1, Higashi-Hachiman, Hiratsuka-shi, Kanagawa Kansai Paint Co., Ltd. F term (reference) 3E061 AA16 AB04 AC02 BA01 BA02 DA01 3E062 AA04 AC03 JA01 JB23 JC02 4F100 AB01A AB03A AJ11B AK34B AK35B AK36C AK41B AK41C AK53C BA03 BA07 BA10B BA10C12 J48 J01 J48 J01 J48 CD01 CE12 CE14 DA05 EA03 EA 04 LA06 PA31 PA34 QA08 4J038 BA212 CB002 CL002 CR072 DA032 DA072 DA112 DA142 DA162 DA172 DB062 DB072 DB082 DD041 DD051 DD061 DD071 DD081 DD191 GA03 JA57 JA60 KA09 MA12 MA14 NA12 PA19 PB04 PC02

Claims (6)

[Claims] (1) A number average molecular weight of 8,
000 to 50,000 hydroxyl group-containing polyester resin,
A coating film containing (B) an amino resin and / or a resol-type phenol resin, and (C) a wax having a softening point of 30 ° C. or more has a dry coating amount of 10 to 85 mg / 100 c.
A lubricated steel sheet for drawn and ironed cans, which is formed in a range of m ² , wherein the coating has a dynamic friction coefficient at 60 ° C. of 0.03 to 0.20 and a pencil hardness at 60 ° C. of H or more. 2. A coating that forms a coating on the inner surface side of the can after processing and contains a hydroxyl group-containing polyester resin and a resol-type phenol resin, and a coating material that forms a coating on the outer surface side of the can after processing is a hydroxyl group-containing polyester resin. The lubricating steel sheet according to claim 1, wherein the lubricating steel sheet is made of a paint containing a melamine resin and a novolak type epoxy resin. 3. The lubricated steel sheet according to claim 1, wherein the hydroxyl value of the hydroxyl group-containing polyester resin (A) is in the range of 1 to 22. 4. The wax (C) having a softening point of 30 ° C. or more is at least one selected from fatty acid ester wax, fluorine wax, polyolefin wax, lanolin wax, montan wax, microcrystalline wax, and carnauba wax. The lubricated steel sheet according to claim 1. 5. A wax (C) having a softening point of 30 ° C. or higher is used in an amount of 0.1 to 5 parts by weight based on 100 parts by weight of the total solid content of the hydroxyl group-containing polyester resin (A) and amino resin and / or phenol resin (B). The lubricated steel sheet according to any one of claims 1 to 4, which is contained within a range of parts by weight. 6. A drawn ironing can which is obtained by drawing and ironing the lubricating steel sheet according to claim 1 and then painting the outer and inner surfaces.