TW200808922A - Double-side coated steel plate for can - Google Patents

Abstract

To provide a double-side coated steel plate for a can, which has an inner coated surface showing excellence in D and I workability, retort resistance, flavor keeping, hygiene and the like, and an outer coated surface showing excellence in print color development, D and I workability and the like. There is formed, on the surface of the double-side coated steel plate becoming the outer surface when fabricated into the can, a film from a coating (I) for a can containing a hydroxy group-containing polyester resin (A), at least one cross-linking agent (B) selected from an amino resin and a resor-type phenolic resin, and an aluminum pigment (C1) or a white pigment (C2), in respective and specific amounts. There is formed on the surface of the double-side coated steel plate becoming the inner surface when fabricated into the can, a film from a coating (II) for a can containing a crystalline polyester resin fine particle (D) composed mainly of an ethylene terephthalate unit, a crystalline polyester resin fine particle (E) composed mainly of a butylene terephthalate unit, and an organic solvent (F) showing a solubility for the fine particles (D) and (E) of less than 5 mass% at a temperature of not higher than 40 DEG C and not less than 99 mass% at a temperature of not lower than 170 DEG C, in respective and specific amounts.

Description

200808922 IX. INSTRUCTIONS: TECHNICAL FIELD OF THE INVENTION C FIELD OF THE INVENTION The present invention relates to a double-sided coated steel sheet for a can. [Prior Art] BACKGROUND OF THE INVENTION Generally, a coating film is formed on the inner surface and the outer surface of a can or the like for food and beverage cans. In the past, a coating film for a can was formed by coating a metal plate such as a steel plate into a can shape using a press oil, and then coating the inner and outer surfaces of the can. In recent years, from the viewpoint of shortening the steps to reduce the manufacturing cost and eliminating the environmental problems caused by the processing of the pressed-type oil after processing, the above-mentioned post-coating method has been formed by previously performing a metal plate coated on both sides. Replaced by the previous coating method. In the pre-coating method, the coating film formed by the can, especially on the 15 side of the can, is required to have better workability than the drawing press [hereinafter, also referred to as D &amp; I (Draw and Ironing) processability] , Ret〇rt (Ret〇rt), fragrance retention, hygiene and other film properties, but these advantages are not easy to fully comply. Further, in the case of the front coating method, the coating film formed on the outer surface of the can is required to have a printing color developability superior to that of a printed product name, a product pattern, or the like, and 20 drawing workability. The two-side coated metal plate used in the pre-coating method has been disclosed as a coating film on the inner side of the can, which is formed of a coating containing a hydroxyl group-containing polyester resin and a resol resin, and is formed on the outer side of the can. The coating film is a double-sided coated metal sheet formed of a coating material 5 200808922 containing a mercapto-based polyester resin and an amino resin and/or a resol resin (refer to Japanese Laid-Open Patent Publication No. 2003-34322). However, the characteristics of the press-formability, the richness, the fragrance retention, the hygienicity, and the like, and the color development property of the outer surface of the can, are not necessarily applied to the coated metal plate on both sides. Fully equipped. Therefore, it is desirable to be able to raise these characteristics. For the above-mentioned desired coatings for the inner surface of the can, although there is a coating composition for cans of polyethylene terephthalate (PET), the crystallinity of polyethylene terephthalate is not easily dissolved. Since it is a general organic solvent, it is difficult to fully exhibit the characteristics as a coating for a front coating. 10 For example, the can coating composition which can be used in the pre-coating method is obtained by dissolving a non-crystalline polyester resin and a crystalline polyester resin in a solvent, and slowly cooling the crystalline polyester resin. The resin composition for can coating which is contained in the state is known (refer to Japanese Laid-Open Patent Publication No. 2001-234115). However, the resin-coated metal sheet coated with the resin composition for the can coating on the metal sheet is not sufficiently stretch-drawing. In addition, the resin and the non-crystalline polyester resin are heated and dissolved in an organic solvent, and then the resin solution is rapidly cooled to a crystallinity from a temperature higher than the temperature at which the crystallized polyester resin is heated and crystallized. Obtained at a temperature below the glass transition temperature of the poly 20 resin. The polyester resin dispersion is known as a coating composition for cans (refer to Japanese Laid-Open Patent Publication No. 2004-2671). However, when such a can coating composition is used for the front residing method, either one of the drawing press workability and the smoothness of the coating film may be insufficient. 6 200808922 SUMMARY OF THE INVENTION PROBLEM TO BE SOLVED BY THE INVENTION An object of the present invention is to provide a coating film which is a surface side of a can, which has excellent press workingability, smash resistance, flavor retention, hygiene, and 5 adhesiveness. A double-sided coated steel sheet for cans having excellent coating properties such as printing color developability and stretch press workability, and a coating film having a coating property on the outer surface of the can. Solution to Problem The inventors of the present invention have carefully reviewed the problems to be achieved. As a result, there is a double-coated steel sheet which is formed by coating a can coating material (1) on the outer side after the can processing, and a can coating is formed on the side which becomes the inner surface after the can processing ( II) The film coating. The can coating (1) comprises, in a specific ratio, a hydroxyl group-containing polyester resin (A), and at least one crosslinking agent (B) selected from the group consisting of an amino resin and a resol resin, and an aluminum pigment material. (C1) or white pigment (C2). Further, the can coating material (II) contains crystalline polyester resin fine particles (D) mainly composed of ethylene terephthalate units and crystals mainly composed of butylene terephthalate units in a specific ratio. The above-mentioned problems can be attained by the polyester resin fine particles (E) and the specific organic solvent (F), and the present invention is completed based on the aforementioned knowledge. Z0 The present invention provides the following double-coated steel sheets for cans. 1 . A double-sided coated steel sheet for a can, which is coated on both sides with a steel sheet, and a coating film for the can coating (1) is formed on the outer side after the can processing, and the can coating (I) contains a hydroxypolyacetate ( A), and at least one crosslinking agent (B) selected from the group consisting of amino tree wax and resole phenolic resin, and having a solid content of 100 parts by mass relative to the resin of the polyester resin (A) of 7 200808922, a coating film containing a can coating (π) formed on the side of the inner surface after the processing, which has an aluminum pigment (ci) of 5 to 60 parts by mass or a white pigment (C2) of 60 to 140 parts by mass, and the can coating (II) a crystalline 5-mer polyester resin microparticle (D) mainly composed of ethylene terephthalate unit and a crystalline polyester resin microparticle (Ε) mainly composed of a butylene terephthalate unit, and The solubility of the fine particles (D) and the solubility of the fine particles (E) each include an organic solvent (F) of less than 5% by mass at 40 ° C or less and 99% by mass or more at 170 ° C or more, and the fine particles ( D) and the proportion of the fine particles (E), relative to the total, the former is 0 95~30% by mass 'the latter is 5~7〇 The mass %, and the content of the organic solvent (F) is 40 to 80 parts by mass based on the total mass of the fine particles (9) and the fine particles (E). 2. The can of claim 1, wherein the coating film thickness of the can coating (1) is a dry film thickness of 丨~如(5), and the coating film 15 of the can coating (1) is dried. The film thickness is 1 to 30 μm. 3. The can of the first item is coated with a double-sided steel plate, wherein the Cui Lu pigment (C1) of the can coating (1) is a non-floating type (N〇n_ieafing). 4. The can of the first item is coated on both sides with a steel plate, wherein the can coating (ιι) is buckled, and the crystalline polyester resin microparticles (D) are intrinsic viscosity of the resin. 4~1. 4 〇 / g, broken glass transition temperature (Tg) 55 ~ 13 (rc money point (Tm) i6 〇 ~ · · c. 5. The first item of the can is coated with two sides of the steel plate, the aforementioned can coating (1) = Crystallinity "Tree-based particles (D) material The aforementioned ethylene terephthalate is only contained in the resin composition of 8G. 6. The can of the first item is coated with two sides|steel plate, wherein the above-mentioned can coating (9) 8 200808922 crystalline polyester resin fine particles (E), the resin inherent viscosity is 0. 4~1. 4 dl / g, glass transition temperature (Tg) 0 ~ 40 ° C and melting point (Tm) 130 ~ 250 ° C. 7. The can of claim 1, wherein the crystalline polyester resin fine particles (E) of the can coating (II) are from the above-mentioned unit content of the butylene dibutyl phthalate of 90 mol%. The above polyester resin is composed of. 8. The can of the first aspect, wherein the can coating material (11) is a total of 1% of the crystalline polyester resin fine particles (D) and the crystalline polyester resin fine particles (E). Quality points, more 〇·〗 ~! The mass of the crucible is divided into the above-mentioned coatings each containing the polyester resin (A). 9. The can of item 8, wherein the can coating (H) contains the hydroxy polyester resin microparticles (A) and the glass transition temperature is (Tg) 55 to 150 °C. 10. The tank of the first item is coated with a double-sided steel sheet, wherein the can coating (η) further contains a coating material of the dispersing agent (G). 11. The can of item 10 is coated on both sides with a steel plate, wherein the dispersant (G) is of the formula (1) [Chemical 1] R1〇- (1) -p-0R3 OR2 is less (RR and ruler in the middle) They are the same or different, and represent a carbon number of 6 to 18, which is not a group (4) or an aromatic hydrocarbon. Here, ❿ and n are integers of 1 or more, and m + n is an integer of 6 or more. Phosphoric acid compound. The tank of the first aspect is coated with a double-sided steel sheet, wherein the can coating (II) 9 20 200808922 is a total of 1% with respect to the crystalline polyester resin fine particles (D) and the crystalline polyester resin fine particles (E). 〇 mass fraction, more than ι·ι~1〇 mass of the above-mentioned phenolic resin coating. </ RTI> </ RTI> </ RTI> </ RTI> </ RTI> </ RTI> </ RTI> </ RTI> </ RTI> </ RTI> </ RTI> </ RTI> </ RTI> </ RTI> </ RTI> </ RTI> </ RTI> </ RTI> </ RTI> 〇〇Quality points, more containing 〇·5~2〇 quality epoxy resin coating. • 14. A steel can system is obtained by coating a steel sheet on both sides of the above-mentioned item with a steel sheet by a drawing process or a drawing press. 10 Canned rain-coated steel sheet The double-coated steel sheet for a can according to the present invention is formed by forming a coating film for a can coating (1) on the outer side of the steel sheet, and forming a side surface of the inner surface after processing the steel can. A coated steel plate composed of a coating film of a can coating (II). 15 Steel sheets which are formed into coating films for the can coating (1) and the can coating (9) are not particularly limited as long as they are used for various cans such as food cans. For example, a cold-rolled steel sheet, a tin-plated steel sheet, a galvanized steel sheet, a chrome-plated steel sheet, a tin-free steel sheet, or the like. These steel sheets may also be used without surface treatment, and may be used after surface treatment such as sulphate treatment, salt fault treatment or chromate treatment. . 2〇 Riding, the shape of the steel plate, as long as the plate shape can be rolled into a coil-shaped metal belt. 3. The thickness of the steel plate is usually about 015~〇·4_, and the lengths of the length and the width are arbitrary. In addition, when the metal strip is used, the width is usually about 丨. Coating for coatings (I) The coating for cans (1) is a hydroxy polyester resin (Α), and at least one crosslinking agent (B) selected from the group consisting of amino 200808922 eucalyptus and glutinous resin. And a coating material containing 5 to 60 parts by mass of the aluminum pigment (Cl) or 6 to 140 parts by mass of the white pigment (C2) with respect to the solid content of the hydroxyl group-containing polyester resin (A). 5 The can coating (1) is the outer side of the steel plate after processing, and the black color of the bottom steel plate after the can coating is covered by the coating, so that the excellent color of the outer surface of the can is obtained, and the stretching is performed. The film properties such as press workability are also excellent. Gold _ hydroxy polyester resin Α, containing each base of polyester resin (Α) is measured by differential scanning calorimeter, and 10 can not show a clear melting point, resin soluble in organic solvent at room temperature, and The crosslinking agent (B) undergoes a crosslinking hardening reaction to form a coating film. As the base-containing polyester resin (A)', the number average molecular weight is preferably from 8,000 to 100,000, and preferably from about 1 Torr to about 8 Torr. Further, the base price is preferably about 1 to 20 mgKOH/g, and more preferably about 1 to i5 mg K?H/g. ～ The resin (A) ′ containing a poly-based polymer is obtained by reacting a polybasic acid component with a polyvalent alcohol component. The polybasic acid component may, for example, be selected from the group consisting of anhydrous oleic acid, isodecanoic acid, p-citric acid, tetrahydroanhydroiodic acid, hexahydroanhydrous citric acid, succinic acid, fumaric acid, hexamic acid, sebacic acid, anhydrous More than one type of dibasic acid such as maleic acid, 2,6-naphthalenedicarboxylic acid, 1,6-octanedicarboxylic acid, cyclohexane-burned diveric acid, and the like, and lower-grade alkyl acetate; anhydrous benzene A polybasic acid having a trivalent or higher valence such as an acid, a mercaptocyclohexane, a tribasic acid or an anhydrous tetrabasic acid is used; a monobasic acid such as benzoic acid, crotonic acid or pt-butylbenzoic acid may be used in combination. 11 200808922 The polyvalent alcohol component may, for example, be ethylene glycol, diethylene glycol, propylene glycol, butanediol, neopentyl glycol, 3-methylpentanediol, di 4-hexanediol 'i, hexanediol, A divalent alcohol such as butyl ethyl propylene glycol or cyclohexane methyl glycol; or a trivalent or higher valent alcohol having glycerin, dimethylol ethoxy, dimethylolpropane or pentaerythritol may be used. Commercially available products can be used as the hydroxyl group-containing polyester resin (A). Commercially available products include, for example, "UE-3201", "UE-3203", "XA-0653" (product name, above Unitica), "GK-640", "GK-880" (product name, above Toyo) Textile stock system). 1〇 Crosslinking agent Β 父 The parenting agent (Β) may be at least one selected from the group consisting of amino resins and resole resins. The crosslinking agent (Β) is a thiolated amino resin obtained by a reaction of an amino component with an aldehyde group component; the 15-hydroxymethyl group of the methylolated amino resin may be etherified by an alcohol And so on. The amino component may, for example, be melamine, urea, benzoguanamine, acetaminophen, guanamine, guanosine, or dicyandiamine. The base component can be exemplified by formaldehyde, formaldehyde, acetaldehyde, benzaldehyde and the like. Further, examples of the alcohol used for the etherification include methanol, ethanol, η-propanol, i-propanol, η-butanol, butanol, 20 2 -ethylbutanol, 2-ethylhexanol and the like. The amino resin is preferably an alkoxy guanamine resin obtained by using a methylol group of a methylolated amino resin and a mixture of etherification of methyl etherification or methyl etherification with butyl etherification. The methyl etherified oxy melamine resin or the methyl etherified butyl etherified alkoxy melamine resin preferably has a molecular weight of about 300 to 2,000. 12 200808922 The above resol phenolic resin is obtained by introducing a methylol group in a formaldehyde-based heat condensation reaction in the presence of a reaction catalyst to obtain a methylolated phenol resin; and secondly, a part of the methylol group is an alcohol It is preferred to obtain an alkyl etherification. 5 A phenol compound used for producing a resol phenol resin, for example, phenol, 〇_甲, p-methyl, p-tert-butyl phenol, p-ethyl phenol, 2,3-diphenyl phenol, 2 ' 5-xylenol, m-cresol, m•ethylphenol, 3, xylenol, m_decyloxyphenol, bisphenol A, bisphenol F, and the like. These phenol compounds may be used singly or in combination of two or more kinds. 10 The formaldehyde used in the production of the resol phenol resin may, for example, be furfural, formaldehyde or trioxane. These may be used alone or in combination of two or more. The alcohol used for the alkylation of a part of the methylol group of the methylolated phenol resin is preferably a monovalent alcohol having 1 to 8 carbon atoms, preferably a carbon number of 4 t-valent alcohols. Specifically, a monovalent alcohol such as decyl alcohol, ethanol, n-propanol, n-butanol or 15 isobutanol is preferably used. The blending amount of at least one crosslinking agent (B) selected from the group consisting of amino resin and resole phenolic resin is about 0% with respect to the solid content of the hydroxy polyester resin (A). The mass of 1 to 20 is preferably divided into good, and the mass fraction of about 〇·5 to 5 is preferred. 20 Aluminium pigment (C1) and chalk The can coating (1) used in the present invention, when it is required to have a metallic brilliance, is to cover the black color peculiar to the steel can to obtain the excellent color development of the outer portion of the can. See, it is necessary to blend aluminum pigment (C1). In addition, aluminum pigment (ci) is a metal with excellent process ductility, so it is easy to change during drawing processing. 2008 20082222 Γ ' 故 故 故 由于 由于 由于 由于 由于 由于 由于 由于 外面 外面 外面 外面 外面 外面 外面 外面 外面 外面 外面 外面 外面 外面 外面 外面 外面 外面 外面 外面 外面 外面 外面. .  The average particle diameter of the paving material (4) is expected to be about 5 to 5 from the point of the brilliance of the can or the point of the miscellaneous point measured by the laser scattering type particle size distribution measuring device. () μη^Laser scattering type particle size distribution measuring apparatus 'a commercially available product can be used. Commercially available products are exemplified by "SALD-1100 type" (trade name, manufactured by Shimadzu Corporation). • The material (C1) can also be surface treated by evaporation, coating, surface grinding, etc. For example, such a pigment (C1) may be, for example, a floating type pigment, a non-floating type 10 type pigment, or the like, and a non-floating type pigment is preferably used for obtaining a can body by a drawing press process. Non-floating type pigments are surface-treated with fatty acids such as oleic acid. The surface has a small surface tension, a strong affinity with a solvent and a coating, and is uniformly dispersed in a coating film, thereby exhibiting excellent gloss. Furthermore, the purity of the pigment (C1), from the viewpoint of ductility or surface coating by the stretching process, is expected to be φ in addition to the surface treatment portion. More than 5% is an aluminum pigment. Commercially available products can be used for the Ming pigment (C1). For example, "Alumium paste MC-666", "Ming powder MH_8 Xie", "Ming powder MH-8805" (trade name, The above is made by Asahi Kasei Metals Co., Ltd., "Almnipaste 564NS", "Aluminum Mortar 195〇M", "Aluminum Sulphur • 1700NAL", "Sauer Slurry 7160N", "Aluminum Sulphur 768_" ( Commodity ^ - The above is manufactured by Toyo Aluminum Co., Ltd.). The blending amount of the pigment (C1) is about 5 to 60 parts by mass relative to 100 parts by mass of the solid content of the base-containing resin (a). The content of the pigment (C1) 14 200808922 For the household, the coating film on the outer surface of the can is formed into a film after the canning, and the black color of the bottom steel plate can be masked, and the printing color development of the outer portion of the can is obtained. In addition, when it is 60 parts by mass or less, it is possible to prevent a decrease in the drawing workability due to the protrusion of the surface of the coating film, or a decrease in the precipitation stability of the coating. The blending amount of the aluminum pigment (C1) is relatively The solid content of the hydroxyl group-containing resin (4) is preferably 100 parts by mass, preferably about 10 to 5 parts by mass, and preferably about 15 to 40 parts by mass. Further, the can coating (1) is not required to have a metallic brilliance. In the sense of time, in order to cover the black color unique to the steel can, (4) the white color pigment (C2) must be blended for the printing color development of the outer part of the excellent can. The white pigment (C2) may, for example, be titanium oxide or zinc oxide. Zinc sulphide, sulphur sulphate, etc., in order to obtain excellent printing color developability, titanium oxide is preferred. Usually, titanium oxide is used for coatings and inks, and the average particle diameter is about 15 0. 05~Mm. It is better, but about 0. 1~Ιμηι is preferred. Oxidation can be used as a commercial product. Commercially available products include, for example, "1", "JR-600", "JR-701", "JR_301", rJR-9〇1" (product name, the above is manufactured by Imperial Chemical Co., Ltd.), and "CR-50" ( The product name, the above is manufactured by Ishihara Industrial Co., Ltd.). The amount of the white pigment (C2) is about 60 to 140 parts by mass relative to 100 parts by mass of the solid content of the hydroxypolyresin (A). When the content of the white pigment (C2) is 60 parts by mass or more, the coating film on the outer surface of the can is thinned after the canning, and the black color of the underlying steel sheet can be masked, and the excellent color development of the outer portion of the can is obtained. On the other hand, if it is 140 parts by mass or more, it is possible to prevent the reduction in the press workability due to the hardness rise of the coating film 15 200808922 or the occurrence of a problem in the processing of the mold. The blending amount of the white pigment (C2) is preferably about 60 to 120 parts by mass, and about 8 to 80 parts by mass, based on 100 parts by mass of the solid content of the hydroxyl group-containing polyester resin (A). The score is better. Aluminum pigment (C1) and white pigment (C2) can be used in combination in the can coating (1). In addition to the hydroxy polyester resin (A), the crosslinking agent (B), and the pigment (ci) or the white pigment (C2), the component coating material (1) may be added to promote the hardening reaction. Acid catalyst. Examples of the catalyst include p-sulfonic acid, sulfonic acid compound such as dodecylbenzenesulfonic acid, dinonylnaphthalenesulfonic acid, and dinonylnaphthalene disulfonic acid, and acid such as phosphoric acid; and the like; The amine neutralizer or the like can also be exemplified. Among them, the above-mentioned sulfonic acid compound and an amine neutralizer of a sulfonic acid compound are suitable. 15 The amount of the acid catalyst to be blended is from the point of the physical properties of the obtained coating film, etc., to the mass fraction of the solid content of the hydroxyl group-containing polyester resin (4), and the amount of the acid is about 0.1 to 5 mass%. Preferably, it is preferably about 5 to 2 parts by mass. The acid amount, for example, the amine neutralizer of the sulfonic acid compound means the amount of the rhein compound remaining in the neutralized amine. - 罐 Can coatings (1) Add organic resins, butterflies, defoamers, leveling agents, precipitation inhibitors, coloring pigments, extender pigments, organic solvents, etc., as needed. The uranium-based organic resin is particularly excellent in hardness, adhesiveness, stagnation resistance, etc. due to the addition of an epoxy resin, and an epoxy-type phenolic resin 16 200808922 (Epoxy-novolac resin) is preferred. The epoxy-type novolac resin may, for example, be a Phenol-novolac epoxy resin, a cresol-novolac epoxy resin, or a majority of epoxy in the molecule. The base 5 is an acid-type phenolic resin such as an epoxy resin (Phenol_glyoxalic epoxy resin). Among them, it is also suitable for the balance of the coating film performance, the linear type epoxy resin and the cresol-line novolac epoxy resin. The butterfly system is added to adjust the dynamic friction coefficient of the coating film of the can coating material (1), and is useful for suppressing scratches such as scratches caused during handling or forming. The wax has a softening point of 3 (it is preferably TC or more, and a spoon is 33 to 150 C. For example, a fatty acid ester wax, an anthraquinone wax, a fluorine-based wax, which are a compound of a polyhydric alcohol compound and a fatty acid, Polyene wax, animal woven fabric, vegetable wax, etc. The polyalcohol compound which cites the raw material of the fatty acid ester wax, for example, ethylene hexahydrin, decyl monoethanol, diethylene glycol, tetraethylene glycol , 丨, 3_butanediol, 1, ertanol, neopentyl glycol, hydrazine, 6-hexanediol, glycerol, two or more of gan's, dihydroxyalkylpropane, amyl red In the case of sterol, dipentyl erythritol, etc., a polyalcohol compound having three or more hydroxyl groups in one molecule is preferable, and among these, polyglycerin, trimethylolpropane, and pentyl are also used. Preferably, it is a fatty acid which is a raw material of the other side of the fatty acid ester wax, and, as an example, a fatty acid having a carbon number of 6 to 32 is suitable as a fatty acid. For example, octanoic acid, citric acid, citric acid, lunar rainbow trout, meat ugly acid, palmitic acid, stearic acid, arachidic acid, behenic acid, 17 20080892 2 5 saturated fatty acids such as waxy acid, montanic acid and melamine; hexenoic acid, undecylenic acid, palmitic acid, oleic acid, linoleic acid, linolenic acid, tungstic acid, cetyl acid, erucic acid, Unsaturated fatty acids such as Licanic acid, ricinoleic acid, and peanut pickled acid. Commercially available products can be used as the oxime wax. Commercially available products such as "BYK-300", "BYK-320", and "BYK-" 330" (trade name, the above is made by BYK Chemical Co., Ltd.); "Sherwin (L-77), "Shervert L-720", "Shervert L-7602" (trade name) , the above is made by Japan Nikki Co., Ltd.); "Pinte 29", "Pinette 32", "Pinte M" 10 (trade name, above is made by Dow Corning);矽KF-96" (trade name, Shin-Etsu Chemical Co., Ltd.). For example, "Shamrock wax SST-1MG", "Shamrock wax 8!5丁-3", "Shamrock wax 15 fhioloslip 231" (product name, the above is made by Shamrock Chemical Co., Ltd.); "Polyfluo 120", "Polyfluo 150", "P〇lyfluo 400" (trade name, above Micro Po For the purpose of the product, a commercially available product can be used. For example, "Shamrock wax S_394" and "Shamrock wax S-395" (trade name, the above-mentioned Shamrock Chemical Co., Ltd.); "Hoechst waxPE-520" "Hoechst 20 waxPE_521" (trade name, the above is manufactured by Hoechst Co., Ltd.); "Mitsui Hiwax" (trade name, Mitsui Chemicals Co., Ltd.). Further, the animal wax may, for example, be a water-containing lanolin wax or a beeswax; and the plant wax may, for example, be carnauba wax or water butterfly. These waxes may be used alone or in combination of two or more. The amount of these waxes added is better than the stability of the coating and the resistance of the film. 18 200808922 The processing surface of the extrusion processing is relative to the solid content (10) of the carboxyl group-containing resin (a), and the mass is 20 mass. Preferably, the following is preferably from about 0. 01 to 10 parts by mass. As the aforementioned coloring pigment, those conventionally used as coating materials can be used. Examples of the colored pigments include, for example, Az〇lake pigments, ugly pigments, woven pigments, Perynone pigments, Peryiene pigments, Quinophtharone pigments, and An inorganic pigment such as an organic pigment such as an enamel, a reciprocating, an Isoindolmene pigment or a metal disinfectant pigment, or a chrome yellow, yellow iron oxide or red magnesia. 1 〇 I color · Add 4, arbitrarily set with the color of the color. The monthly physique pigments can be used as a painter. Specific examples thereof include sulfuric acid lock, carbonic acid conversion, sulphur dioxide, white clay, oxidized lock, and the like, and these may be used alone or in combination of two or more. The organic solvent can be used to dissolve or disperse the components. Specifically, for example, a tobacco system such as toluene, xylene, or a high-boiling petroleum-based tobacco, a methyl ester, a methyl ethyl ketone, or the like can be used. a ketone solvent such as methyl isobutyl ketone, cyclohexanone or isophorone; an ester solvent such as ethyl acetate, butyl ethoxide, ethylene glycol monoethyl ether acetate or diethylene glycol monoethyl ether acetate; An ether solvent such as methanol, ethanol or butanol-specific alcohol solvent, ethylene glycol monoethyl sulphate, ethylene glycol monobutyl ether or diethylene succinyl alcohol monobutyl ether may be used alone or in combination of two or more. Coating (I) The coating for cans (I) used in the present invention is composed of a hydroxyl group-containing polyester resin (a crosslinking agent) and an aluminum pigment ((:1) or a white pigment ((:: 1) the necessary ingredients, and if necessary, 'adjust any other ingredients according to the accepted method. 19 200808922. Usually 'the obtained coating (i) is the organic solvent type coating composition, the solid content of the coating composition, usually The coating material for cans (II) used in the present invention contains crystalline polyester resin fine particles mainly composed of ethylene terephthalate unit ( D) and the crystalline polyester resin microparticles mainly composed of butylene terephthalate units, and the solubility with respect to the fine particles (D) and the solubility with respect to the fine particles (Ε) a coating of 10 organic/grain (F) which is less than 5% by mass in C and 99% by mass in the case of i7〇°c or more, and a ratio of the coating material for the can (in the crucible, the fine particles p) and the fine particles (8). Relative to the total, the former (10) ~ shoulder%, the latter 5~70% by mass, and relative The total amount of the fine particles (D) and the fine particles (E) is 100 parts by mass, and the content of the organic solvent (F) is 40 to 800 parts by mass. The can coating (II) is formed on the side of the inner surface after processing the can of the steel sheet. Paint coated with 15 coats to form excellent coating film properties such as stretch pressability, smear resistance, flavor retention, hygiene, adhesion, corrosion resistance, and smoothness of coating film. Among the resins, the intrinsic viscosity of the resin, the glass-coupled moxibustion/magnification, the melting point, and the average particle diameter were measured by the following methods: (1) Resin inherent viscosity: according to the method specified in JIS z 8803 It is determined by a mixed solution of phenol/tetrachloroethane = 1/1 (mass ratio) at 25 ° C. (2) Glass transition temperature: according to HS K 7121 9. The value obtained by the method specified in 3 (1987). 20 200808922 (3) Melting point: The value measured by a differential scanning calorimeter. For the commercially available product of the differential scanning type hot mash, for example, rDSC_6〇A" [product name, ～津株式会社(share) system] can be used. (4) Volume average particle size: measured by a laser scattering particle size distribution analyzer. For the commercially available product of such a particle size distribution measuring device, for example, "MICROTRACHRAmodd 9320-X100" (trade name, 曰 machine-made company) can be used. Crystalline polyester crepe granules 1) Crystalline polyester resin granules (Dy in the can coating (II), which are microparticles of a polystyrene resin mainly composed of 10 units of methic acid. Means that a clear melting point is indicated in the measurement by a differential scanning calorimeter. The polyester resin of the ethylene terephthalate unit is mainly composed of terephthalic acid or its lower alkyl ester. Ethylene glycol heavy condensation reaction, and part of terephthalic acid or its lower alkyl ester is replaced by other polybasic acids such as isophthalic acid and adipic acid 15 or lower alkyl esters thereof; In part, it may be substituted by other polyvalent alcohols such as 1,4-cyclohexanedhenol. The polyester resin having a main unit of ethylene terephthalate is mainly from the viewpoint of excellent flavor retention. The content of terephthalic acid or its lower alkyl group is preferably 80% by mole of ethylene glycol or ethylene terephthalate. The polyester resin is preferably 20%. The content of the ester unit is in the range of 80 mol% or more, for example, although the ethylene terephthalate unit Polyethylene terephthalate (PET) having a content of 100 mol%, and may also be a copolymer with other units such as ethylene terephthalate units and ethylene terephthalate units. Further, a structure having a spherical polyester resin (for example, a chain-like segment having a low glass transition temperature of 21 200808922) is also used to obtain the fine particles (j), although it may be pulverized, for example. The method, the dissolution cooling method, the spray drying method, and the like are used in the surface of the coating film, and are used in the case where the resin is heated and dissolved by the organic agent and then cooled (4). The fine particles of the crystalline polyester resin can be used in the crystalline polyester resin fine particles 1), and the intrinsic viscosity of the resin is about 〇·4~1. Preferably, 4 dl/g is preferred, and about 〇7~j · 2 dl/g is preferred. In addition, the glass transition temperature is preferably about ^^, and the melting point is about 160 to 26 (rC is preferred. Further, the volume average particle diameter of the crystalline polyester resin microparticles (D) is usually about 〇·1~25μιη, especially in the range of 〇. For the crystalline polyester resin fine particles (D), commercially available products can be used. Commercially available products include, for example, "PA-200" (trade name, Mitsubishi snail shares) "J125" 15 (trade name, Mitsui Chemicals Co., Ltd.), "J135" (trade name, Mitsui Chemicals Co., Ltd.), and "TN8756" (trade name, Teijin Chemical Co., Ltd.). Crystalline poly-SI resin Microparticle (E) The crystalline polyester resin microparticle (E) in the coating (II) is a microparticle of a polyester resin mainly composed of a butylene dicarboxylate unit. Crystallinity refers to a root 20 differential scanning type. In the calorimeter measurement, a clear melting point is indicated. The polyester resin of the main unit of butylene phthalate is mainly composed of decanoic acid or hydrazine lower alkyl ester and 1,4-butane. Alcohol heavy condensation reaction, and a part of decanoic acid or its lower alkyl ester, from isophthalic acid, adipic acid Substituting other polybasic acids such as sebacic acid or lower alkyl esters thereof; one part of 1 '4-succinic acid, 22 200808922 6_hexyl alcohol, b 4_cyclohexanediol, etc. The unit of benzoic acid is the main component of the polyester resin, relative to the phthalic acid or its lower alkyl group S with 'butane diol, terephthalic acid butyl octopus 5 = content rate of 90 mol% or more Preferably, the poly-ester is in the range of 9 〇 mol% or more for the unit of the bismuth dicarboxylate, for example, the content of the unit of the two pairs of stupid-formic acid is only the % of the aggregate. For KPBT in the case of dimethyl benzoate, it may be a copolymer of other units with the butyl benzene terephthalate and the benzoic acid. Further, a spheroidal polyester resin structure (for example, a chain segment of a scaly structure having a low glass transition temperature) is also included. For obtaining the fine particles (E), the fine particles of the resin may be, for example, a pulverization method, a dissolution cooling method, or (4) dry age, but the use of the surface of the coating film is based on The crystalline polyester resin fine particles obtained by the dissolution cooling method after the organic solvent is heated to dissolve 15 and then cooled are preferably used. The characteristics of the crystalline polyester resin fine particles (E) which can be used in the present invention, the intrinsic viscosity of the resin is about 〇. 4~14 (11/§ is preferred, and is preferably about 〇7~Udl/g. In addition, the glass transition temperature is about 〇~4〇t: preferably, and the ratio is 130%. Further, the volume average particle diameter of the crystalline polyester resin fine particles (E) is usually about 〜1 to 25 μm, particularly in the range of about 0.1 to 7 μm. Crystalline polyester resin fine particles (Ε), commercially available products can be used. Commercially available products can be exemplified by “Ν_1〇〇〇” (trade name, Mitsubishi Screw Co., Ltd.). 23 200808922 H. Crystalline polyester resin micro scorpion (D) and crystalline granules 83⁄4 _ 脂微叙早 (yellow polyester resin fine particles (D) and crystalline polyester resin granules in the coating (II) (E) is used in a ratio of 95 to 30% by mass based on the total of the fine particles, and the latter is 5 to 70% by mass. When the fine particles are dispersed in an organic solvent, the fine particles (D&quot; When the ratio of the crystalline polyester resin fine particles (D) exceeds 95% by mass, the solid content of the fine particles (E) is mixed. When the ratio of the crystalline polyester resin fine particles (D) exceeds 95% by mass, the draw pressability of the coating film is lowered. When the ratio of the polyester resin fine particles (D) 10 is less than 5% by mass, the flavor retention of the coating film is lowered. The ratio of use of the crystalline polyester resin fine particles (D) and the crystalline polyester resin fine particles (E) is relatively In the total of the fine particles, the former is 90 to 40% by mass, and the latter is preferably 1 to 60% by mass; the former is 8 to 55% by mass, and the latter is preferably 20 to 50% by mass. Solvent (F) Organic solvent (F) is relative to crystalline polyester resin microparticles (D) The degree of solubility of the crystalline polyester resin fine particles (E) is preferably less than 5% by mass and not more than 5% by mass and not more than 99% by mass in the case of 40 ° C or less. The organic solvent (F) has With such solubility, the coating group 2 of the present invention exhibits excellent fluidity and dispersion state at normal temperature, and when heated by forming a coating film, the microparticles (D) and the microparticles are simultaneously melted to form a uniform coating film. The granule (F) may, for example, be a mixed solvent of dimethyl adipate, dimethyl glutarate and dimethyl succinate (boiling point is about 170 to 205 ° C), N-methyl sirka An alkane ketone, isophorone, etc. The mixed solvent of the 2008 dimethyl dimethyl ester, dimethyl glutarate and dimethyl succinate can be used as a mixed solvent of the adipic acid 24, and the commercially available product can be "DBE" ( The product name, manufactured by DuP〇nt Co., Ltd., is an example. The content of the organic solvent (F) is 1 〇〇 mass of the total of the crystalline polyester resin fine particles 5 (D) and the crystalline polyester resin fine particles (E). , although it is about 40 to 800 parts by mass, the dispersibility and coating workability of the fine particles It is good in terms of surface. The content of the organic solvent (F) is preferably 1 part by mass relative to the total of the fine particles (D) and the fine particles (E), and is preferably about 5 〇 to 5 〇〇. 10 Containing _ a certain ester resin (A) In the can coating (Π), if necessary, the hydroxy-containing polyester resin (A) used in the above-mentioned can coating (1) may be blended. Containing a hydroxy polyester resin (a) It is a resin which is not soluble in a clear melting point when measured by a differential scanning calorimeter, and is easily dissolved in an organic solvent at a normal temperature, and when a coating film is formed, a crystalline polyester having a molten state of 15 may be mentioned. a resin having high affinity or compatibility with the resin fine particles (D) and the crystalline polyester resin fine particles (E), or reacting with the crystalline polyester resin fine particles (D) and the crystalline polyester resin fine particles (E) in a molten state And forming a continuous layer of a resin. Due to such properties, the polyester resin (A) is useful for improving the appearance of the coating film such as the smoothness of the coating film (II). The hydroxy-containing polyester resin (A) blended in the coating (II) is preferably a glass transition temperature (Tg) of about 55 to 150 ° C, more preferably about 60 to 120 ° C, and about 65 °. Ll 〇 ° C is better. A raw material containing a hydroxy polyester resin (A), a production method, a commercially available product, and the like, as described in 25 200808922, the same as the above-mentioned coating (i). In the can coating (II), the solid content of the crystalline polyester resin fine particles (D) and the crystalline polyester resin fine particles (E) is 100 parts by mass, by blending the hydroxyl group-containing polyester resin (A). 0. 1 to 1 〇〇 mass point, you can improve the outside of the film. The blending amount of the resin (A) is preferably 100 parts by mass based on the total of the fine particles (D) and the fine particles (E), and is preferably about 5 to 100 parts by mass. Dispersing agent (G)

The knife release agent (G) can be used to improve the dispersibility of the crystalline polyester resin fine particles (d) and the crystalline polyester resin fine particles (6) in the organic solvent (F). For example, in the end of the main chain or at both ends, a linear polymer dispersing agent having a surface and a spheroid (D) and fine particles (6) may be used. The affinity group may, for example, be mentioned. Examples thereof include a tertiary gas group, a fourth-order woven fabric, and a gas heterocyclic group; and the linear polymer may, for example, be a polypropylene, a urine, or a polystyrene. Further, such a heterocyclic group may, for example, be a sulfhydryl group or a stilbene. And a commercially available product can be used as a molecularly-based dispersing agent. For example, "ΒΫκ 1 60", ΒΥΚ_161", "ΒΥΚ_162", and "ΒΥΚ-180" are commercially available. "Q t ΒΥΚ-181", "ΒΥΚ_182" (product name, the above system is made by B YK Chemical Co., Ltd., "Q") 'Solspass2〇_" (product name, redundant (3) coffee company 20 system). Further, the 'dispersant (G) is represented by the following formula (1): 化 R10 - axe - 〇 R3 OR2 26 (1) 200808922 (wherein R1, R2 and R3 are the same or different, respectively, and represent carbon An aliphatic or aromatic hydrocarbon of 6 to 18 or _CmH2m〇CnH2n+i. Here, the melon and the compound are an integer of 1 or more, and m+n is an integer of 6 or more. (5) The phosphoric acid-based compound of the formula (1), specifically, for example, 2-ethylhexyl group- &quot;this base acid vinegar, bis(2·ethylhexyl) linic acid g, three (butoxy) Base ethyl) phosphate, triphenyl phosphate, tricresyl phosphate, and the like. • These dispersants (G) may be used alone or in combination of two or more. (10) The amount of the dispersing agent (G) is increased from the viewpoint of improving the dispersibility of the crystalline polyester resin fine particles (D) and the crystalline polyester resin fine particles (E) with respect to the resin fine particles (D) and the resin. The total mass fraction of the fine particles (E) is preferably about 0.1 to 10 parts by mass, and more preferably about 〇 5 to 5 parts by mass. In the can coating (1), a resin other than a polyester resin such as a resol resin, a cyclooxy resin or an amino resin may be blended as needed. From the viewpoint of improving the adhesion to the coating film of the steel sheet, a resol or epoxy resin is preferred among these. a second-order phenolic resin, in particular, a part of a methylated methyl group obtained by introducing a phenol component and a furfural under a reaction catalyst to be subjected to a fine reaction, and introduced into a methyl group; It is preferred that the alkyl group is formed by alkylation. The phenol compound used in the production of the resole phenol resin may, for example, be phenol, 0, cresol, P-cresol, tert butyl phenol, ρ·ethyl phenol, 2,3_2 27 200808922 phenol, 2, 5-diphenylphthalide, m-nonylphenol, m-ethylphenol, 3,5-xylenol, m-methoxyphenol, bisphenol A, bisphenol F, and the like. These phenol compounds may be used singly or in combination of two or more kinds. The formaldehyde used in the production of the resol phenol resin may, for example, be a methyl acid, p-formaldehyde or trioxane. These may be used alone or in combination of two or more. The alcohol used for alkyl etherification of a part of the methylol group of the methylated phenol resin has 1 to 8 carbon atoms, and preferably 1 to 4 of the monovalent alcohol is suitable for use. Suitable examples of the mussel alcohol include methanol, ethanol, η-propanol, η-butanol, and isobutylene alcohol. The blending amount of the A-step expectant resin is 1 〇〇 in mass from the viewpoint of the balance coating film appearance and the stretch press processability with respect to the crystalline polyester resin fine particles (D) and the crystalline polyester resin fine particles. The fraction is preferably about 〇1 to 1 〇, and preferably about 0.5 to 5% by mass. 15 Having a description of the bad oxygen resin, when the crystalline polyester resin fine particles (D) and/or the crystalline polyester resin fine particles (the magic polyester resin has a carboxyl group, although it acts effectively as a crosslinking agent, When the polyester resin does not have a Weiji, it can also be used as a reinforcing material for the water eucalyptus, or it can effectively act by crosslinking with the aforementioned A-grade resin as a film-forming component. Addition, although it can improve the hardness, adhesion, resistance to Zengwa = and other coating film m. The epoxy-line type secret resin is better because it does not contain the suspected a-series. For example, various types of rings such as a phenolic epoxy resin, a yoke, a cresol-novolak epoxy resin, and a styrene-based epoxy resin having a plurality of saccharides in the molecule may be mentioned. Oxygen-residue 28 200808922 ° It is also suitable for the balance of film properties. The type of oxygen resin is suitable for blending the appearance of the coating film and the stretch stamping process. From the viewpoint of 'relative to crystalline polyester resin fine particles (D) and crystalline 5 water-known resin micro The total mass of (10) of the sub-(6) is preferably about 〇·$~2〇, and preferably about 2~1〇. For the can coating (II), more can be added as needed. Organic tree 曰 曰 ^ / Shabu foam, leveling agent, agglutination inhibitor, coloring pigment, brilliant pigment, body pigment, bright pigment, organic solvent (F) and other organic solvents, etc. In the case of adjusting the dynamic friction coefficient of the coating film of the can coating material (11), the steel sheet to which the coating composition is applied is added to the steel sheet during transportation or molding, and the film is softened by a softening point. Preferably, the above is preferably from about 33 to 15 〇 °c, and for example, a polyalcohol compound and a fatty acid of the compound 15 of the fatty acid (four), a stone stalk, a fluorine genus, a smear, Animal wax, plant wax, etc. Specific examples of the wax are the same as those used in the above coating (1), and the raw materials, preparation methods, and commercial products are as described in the above coating (1). The amount of wax added is from the processing surface which is superior to the coating stability and is resistant to the stretching process of the 2〇 film. In other words, the total mass of the crystalline polyester resin fine particles (D) and the crystalline fine resin fine particles (6) is preferably 5 Å or less, and more preferably about 5 to 25 Å. The organic solvent other than the organic solvent (F) described above may, for example, be acetone, methyl ethyl fluorenone, decyl butyl carbaryl, decyl isobutyl ketone, cyclohexanone, 29 200808922 decylpentanone Ketones: methanol, ethanol, 2-propanol, &amp; alcohol, isopropanol, 2-methyl-1-propanol, 1-propanol, 2-methoxyethanol, etc. Alcohols: tetrachloro Ethers such as furan, 1,4-dioxane and 1,2-dimethoxyethane: esters such as methyl acetate, ethyl acetate and butyl acetate: dimethylformamide, dimethyl 5 Amines such as acetamide; hydrocarbons such as toluene, xylene, cyclohexylbenzene and η-hexane; methyl decanoate, diethyl phthalate, dibutyl phthalate, ethylene glycol monobutyl ether, digan Alcohol monobutyl ether and the like. One type or two or more types may be used. The hardening catalyst described above may be catalyzed by an acid such as p-toluenesulfonic acid, dodecylbenzenesulfonic acid, dinonylnaphthalenesulfonic acid, dinonylnaphthalene disulfonic acid or phosphoric acid, or an amine of the acid. Specific examples such as the object. The coating material for the preparation of the coating material (II) is composed of the essential components of the crystalline polyester resin fine particles (D), the crystalline polyester resin fine particles (Ε) and the organic solvent (F), and will be contained as needed. Each of the optional components of the base polyester resin and the dispersant (G) and 15 of the other components described above are prepared by mixing according to a recognized method. Generally, the obtained coating (II) is an organic solvent type coating composition, and the solid content of the coating composition is usually about 5 to 5 % by mass. In the coating material for cans, the crystalline polyester resin particles 20 (D) and the crystalline polyester are used in terms of the solidity of the coating film to be sufficient for the drawing workability of the coating film. The total solid content of the resin fine particles (Ε) is preferably adjusted to about 50% by mass or more. The cans of the cans are coated on the sides of the plate. The cans of the present invention are coated on both sides of the steel plate, and are formed on the outer side of the cans of the steel plate. The coating film is formed by coating the can coating (I), and The cans of the steel plate 30 200808922 are processed to the inner side, and the paint for coating (II) of the coating can form a coating film thereof, which can be easily prepared. The order of coating of the can coating (1) and the can coating (π) is not particularly limited, and any of the coatings may be applied first. In addition, it is preferred that the two films are baked at the same time. Specifically, for example, a steel sheet for use in food and beverage cans can be adjusted to a coated steel sheet coated on both sides by the following coating step. In the coating method of the can coating material (1), the coating step of the can coating material (II) is performed on the side of the inner surface of the can of the steel sheet, and the coating step of the can coating material (II) is performed on the side of the inner surface of the steel sheet. The two coating films are coated with 10 heat, and a method of coating the steel sheets on both sides is obtained by a baking step. The method of coating the can coating (I) and the can coating (11) on the steel sheet is not particularly limited. Any of the coating materials can be carried out, for example, by spray coating, roll coating, curtain coating, rod coating, etc., and the method for efficiently coating the steel sheet is preferably a light coating. 15 The coating amount of each coating is as follows. The dry coating film 1' of the can coating (I) before processing is preferably about 1 Torr to 2 〇〇 mg/l 〇〇 cm 2 , and more preferably about 1 〇 to 8 〇 mg / 100 cm 2 . In addition, the amount of the dried coating film of the can coating (11) before processing is preferably about 10 to 30 〇 mg / l 〇〇 cm 2 , and about 5 〇 〜 2 〇〇 mg / 1 〇〇 cm 2 good. 10 The baking temperature of the two coated films is preferably higher than the melting point of the crystalline polyester resin microparticles (D) and (E) contained in the coating (II), and is preferably about The temperature of the melting point of 30 to l ° C is preferred. Specifically, in general, the baking temperature is preferably about 180 to 300 ° C, and preferably about 200 to 280 ° C. Further, the baking time is usually about 1 to 180 seconds, particularly about 5 to 6 seconds, to preferably maintain the temperature of the steel sheet to be coated with 31 200808922. Thus, the two coating films of the can and the _&quot;_ are dried or hardened. Next, the film after baking is desirably cooled by cold air or a large number of cooling nozzles, and immersed in cooling water. From the viewpoint of improving the five properties of the stretching process, the baking is rapidly cooled to make the polyester resin contained in the can coating (1) and the can coating (9) amorphous. . From the viewpoint of obtaining the stretch stamping and reading the excellent reading film, the cold ip speed is preferably cooled to 4 (r/s or less) in 5 seconds. 7 Such as this, it becomes external after processing the steel can. On the side, the coating film of the 10 can coating (I) is formed to have a dry film thickness of about 22 to 2, especially about 1 to ΙΟμηη; and after the steel can is added to the inner side, the can coating ( The coating film of ID forms a dry film thickness of about i~3 〇μιη, particularly in the case of about Μ Μ. Effect of the invention 15 _ The double-coated steel sheet for a can of the present invention can obtain the following remarkable effects. The can coating (π) is formed as a coating film on the inner surface of the can, which is usually a transparent coating film, and is superior to the stretch stamping processability, and has the properties of freshness, fragrance retention, hygiene, adhesion, resistance, and coating film. The film coating performance such as smoothness, and the coating film formed on the outer surface side of the can by the 20-can coating (1) is a metal coating film or a white coating film, and is superior to coating film properties such as printing color developability and stretch press workability. (2) The double-coated steel sheet for the can of the present invention is applied to the outside of the can by performing drawing processing or drawing punching and adding i It will damage the color development of the printing, and the potassium can be obtained on the inner surface of the can, which is superior to the stretching and stamping processability, the financial property, the fragrance retention property, and the like. Therefore, the two-side coating of the present invention is used. The can body obtained by mounting a steel plate is suitable for use as a beverage can and a food can. L·^ BEST MODE FOR CARRYING OUT THE INVENTION The present invention provides a manufacturing example, an example and a comparative example, and the present invention will be described in more detail. The month is as follows. However, the present invention is not limited by the above. In each of the examples, "minute" and "%" are based on the mass basis. Can_5 Paint Production Example 1 10 In a container equipped with a stirrer, the resin (A) "Beilong 200" (Note 1) 1 〇〇 (solid part), cross-linking agent (B) "Semel 3" (Note 2) 6.3 points, "Alpaste 5640NS" of pigment (C1) (Note 3) 43.8 (solid fraction), "S-394N1" of wax (Note 4) 6.3 (solid fraction), mixed solvent (ring) The ketone/xylene = 5 〇 / 5 )) adjusted to a viscosity of 5 〇 15 (Ford Cup #4, 25. 〇 〇 〇 ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( (Note 1) "Beilong 200": trade name, manufactured by Toyobo Co., Ltd., containing hydroxy polyester resin, number average molecular weight 17000, hydroxyl value 6 mgKOH/g, glass transition temperature 67 ° C. 2〇 (Note 2 "Semmel 303": trade name, manufactured by Scientic Industries, thiol etherified melamine resin, molecular weight 600. (Note 3) "Aluminum powder 5640NS": trade name, manufactured by Toyo Aluminum Co., Ltd., non-floating The average particle diameter of the type of pigment paste and the Ming particles is 14μπι, and the purity of 99.80/〇〇33 200808922 (Note 4) "S_394N1": polyethylene wax made by Shamrock Co., Ltd. Production Examples 2 to 3 In the same manner as in Production Example 1, except for the blending contents of the first table, paints 1-2 to 1-3 for the outer surface of the can were obtained. 5 Production Example 4 In the container equipped with the mixer, "Beilong 200" (Note 1) 100 points (solid content), "Semmel 303" (Note 2) 5.7 points, and pigment (C2) "JR- 301" (Note 5) 64.9 points (solid fraction), "S-394N1" (Note 4) 5.4 minutes (solid fraction), and mixed with a mixed solvent (cyclohexanone / xylene = 50 minutes / 50 minutes), In the sand mixer 10, 1 mm (D glass beads were used to disperse to obtain a paint 1-4 having a pigment dispersion particle size of 5 μm or less and a viscosity of 50 seconds (Ford Cup #4, 25 ° C). (Note 5) (Note 5) "JR-301": Imperial Chemicals Co., Ltd., anatase titanium dioxid, average particle diameter 0·3μηι. 15 Production Example 5 Blending with Table 1 In the same manner as in Production Example 4, the coating material 1-5 for the outer surface of the can was obtained. Comparative Production Examples 1 to 4 In the same manner as in Production Example 1, 20 was carried out in the same manner as in Production Example 1. In the same manner as in the production example 4, the coating material for outer surface of the can was obtained in the same manner as in the production example 4, except that the coating material for the outer surface of the can was 1-6 to 1-9. 1 and 2 in the table The content of the coating outside the can is Μ~[-10. 34 200808922 The blending amount is expressed by solid content (minutes). Table 1 Production Example 1 2 3 4 5 Can coating material No. 1-1 1- 2 1-3 1-4 1-5 Resin (A) "Beilong 200" (Note 1) 100 100 100 100 "Elite Teller UE-3600" (Note 6) 100 Crosslinking agent (B) "Saimei 303" (Note 2) 6.3 5.6 6.1 5.7 4.6 Pigment (C1) "Aluminum slurry 5640NS" (Note 3) 43.8 27.8 9.8 Pigment (C2) "JR-301" (Note 5) 64.9 99.6 Wax "S-394N1" (Note 4) 6.3 5.6 6.1 5.4 6.8

Table 2 Comparative Production Example 1 2 3 4 5 Can coating material No. 1-6 1-7 1-8 1-9 1-10 Resin (A) "Beilong 200" (Note 1) 100 100 100 100 100 "Elite Teller UE-3600" (Note 6) Crosslinking agent (B) "Semmel 303" (Note 2) 6.3 6.3 6.3 6.3 6.3 Pigment (C1) "Aluminum slurry 5640NS" (Note 3) 1.0 3.0 80 100 Pigment (C2) "JR-301" (Note 5) 160 Fill in "S-394N1" (Note 4) 6.3 6.3 6.3 6.3 6.3 5 In the tables 1 and 2, "Elite Teller UE-3600" (Note) 6) indicates the following substances. (Note 6) "Elite (UE) UE-3600": trade name, manufactured by Unitica, containing hydroxy polyester resin, number average molecular weight 20,000, hydroxyl value 4 mgKOH/g 〇35 200808922 Can coating (ID manufacturing) Production Example 6 Production of crystalline poly(p-ethylene dicarboxylate) resin microparticles The polybasic acid component was composed of citric acid/isodecanoic acid = 85 mol 5 mol%, and the polyvalent alcohol component was ethylene glycol 1 〇. Polyethylene terephthalate resin (PET) obtained by using 〇Mool% as a raw material component is cooled and pulverized by a jet mill according to a conventional method, and the crystalline polyethylene terephthalate resin microparticles are obtained by complicated classification ( It is called ΡΕΤ·Νο·1). Production Example 7 Production of crystalline poly(p-ethylene dicarboxylate) resin fine particles The polyethylene terephthalate resin 10 which is shown in the raw material composition of Table 3 is used. It is stirred and heated together with "DBE" (product name, Dup0nt company, adipic acid monomethyl phthalate, dimethyl sebacate dimethyl succinate mixed solvent, boiling point 205 C), and then, Cooling 5 〇〇 cyclohexanone (boiling point 155 ° C) to crystallization After the particles were precipitated, they were filtered and dried under reduced pressure to obtain a crystalline polyethylene terephthalate resin fine particle (referred to as 15 ΡΕΤ-Νο·2). Production Example 8 Crystalline Polyethylene terephthalate resin fine particles Manufactured using the polyethylene terephthalate tree of the raw material composition shown in Table 3, the solvent was changed to Ν-methyl-2-pyrrolidone (Buddha 202. In the same manner as in Example 2, crystalline polybutylene terephthalate 20 resin fine particles (referred to as ΡΕΤ-Νο. 3) were obtained. The use of the crystalline polybutylene terephthalate resin fine particles of Example 9 was shown. The polybutylene terephthalate tree of the second table is composed of a resin and "DBE" (trade name, manufactured by DuPont, dimethyl hydrazine adipate, dimethyl sebacate, succinic acid). Mixed solvent of dimethyl ester, boiling point 2〇5 36 200808922 °C) 400 parts together with stirring and heating, 5 〇〇 cyclohexane (boiling point 155 ° C) to cool and precipitate crystal granules, filtered and dried under reduced pressure , obtaining crystalline polybutylene terephthalate resin microparticles (referred to as PBT-No.1 Production Example 10 Production of Crystalline Polybutylene Terephthalate Resin Fine Particles 5 The same procedure as in Production Example 4 was carried out except that the polybutylene terephthalate resin shown in the material composition of the third table was used. Crystalline polybutylene terephthalate resin microparticles (referred to as PBT-No. 2).

10 The raw material composition of the crystalline polyethylene terephthalate resin micro-melting point and the volume average particle obtained in the production example 6~1〇, and the crystallized poly-p-dibenzoic acid butyl diacetate resin fine particle, and the resin inherent viscosity, The glass transition temperature and the particle diameter are shown in Table 3.

Production Example Resin Microparticle Name: Ethylene Glycol 1,4-Butanediol Raw Material for Tannic Acid Group-- (Mor%) Isophthalic Acid Adipic Acid Sebacate Product Characteristics Table 3 Intrinsic Viscosity of Resin (IV) Glass Transition Temperature (°c) Melting point (°c) Volume average particle diameter (μιη)

37 200808922 Production Example 11 The manufacture of the can coating composition π-l is shown in Table 3, where PET-No.l is 50, PBT-No.l is 50, and "DBE" (Note 7) is 500. "BYK-161" (Note 8) is 5 points (solid points) and "矽诺尔 (CK) 394" (Note 9) is 2 points (solid points), mixed with paint shaker for 60 minutes to mix and disperse The solid content was adjusted in cyclohexane/methyl ethyl ketone (50/50 by mass ratio) to obtain a solid content of 12% of the inner surface coating material II·b (Note 7)~(Note 9) Substance. (Note 7) "DBE": a product name, a product of DuPont, a mixture of dimethyl adipate, dimethyl sebacate, and dimethyl succinate. 10 (Note 8) "BYK-161": a product name, a dispersing agent of a polyurethane resin having an amine price of llmgKOH/g, manufactured by BYK Chemical Co., Ltd. (Note 9) "矽诺尔CKS394": trade name, Showa Polymer Co., Ltd., resol phenolic resin. Production Example 12 to 18 Production of the inner surface coating material II-2 to Π-8 In the same manner as in Production Example 11, except that the blending contents of the fourth table were used, the inner surface of the can obtained 12% of the solid content was obtained. Use coatings II-2 to II-8. In the fourth table, the blending contents of the coating materials Π-1 to II-8 on the inner surface of the can are shown. The blending amounts are shown in solid fractions (minutes). 38 200808922 Table 4 Manufacturing Example 11 12 13 14 15 16 17 18 Paint for can inner surface No. II-1 II-2 II-3 II-4 ΙΙ·5 ΙΙ-6 ΙΙ-7 ΙΙ-8 PET-No· 1 50 30 10 95 Resin microparticles (D) PET-No.2 80 30 30 50 PET-No.3 40 10 20 Resin micro PBT-No.l 50 60 30 70 40 50 Particles (E) PBT-No.2 20 10 20 5 Special machine solvent N-mercapto-2-pyrrolidone 200 100 100 50 100 40 (F) "DBE" (Note 7) 500 300 200 100 200 100 300 10 Resin (A) -—I__ "GK- 640" (Note l〇) 60 10 100 Dispersant (G) "BYK-161" (Note 8) 5 5 3 5 2 2-Ethylhexyl acid diphenyl ester 3 3 _^ 石夕诺尔CKS394" (Note 9) 2 5 3 5 Diluted solvent cyclohexanone / methyl ethyl ketone Appropriate amount In Table 4, the blending ratio of the resin (D) and the dispersing agent (G) is expressed in terms of solid content (minutes). In addition, "GK-640" (Note 1) indicates the following substances. (Note 10) "GK-640": trade name, manufactured by Toyobo Co., Ltd., containing a hydroxy 5 -based polyester resin, a number average molecular weight of 18,000, a hydroxyl value of 5 mgKOH/g, and a glass transition temperature of 79 °C. Comparative Production Examples 5 to 6 The production of the inner coating materials for the cans II-9 to II-10 was carried out in the same manner as in the production example 11 except that the blending contents of the fifth table were used. Coating II-9~11-10. ° Table 5 shows the blending contents of the coating materials for the inner surface of the cans II-9 to 11_10. The blending amounts are shown in solid fractions (minutes). 39 200808922 Brother 5 Table Comparison Manufacturing Example 5 6 Can J 3 Surface Coating No. II-9 11-10 Resin Microparticles 〇)) PET-No. 1 PET-No. 2 100 PET-No.3 20 Resin Microparticles (Ε ) PBT-No.l PBT-No.2 80 Organic solvent (F) N-methyl-2-u than alkaloid 200 50 "DBE" (Note 7) 200 Resin (Α) "GK-640" (Note) L〇) Dispersant (G) "BYK-161" (Note 8) 5 2-ethylhexyl acid diphenyl hydrazine 5 "矽诺尔CKS394" ([9] 2 Diluting solvent cyclohexanone / thiol Base armor

Preparation of Fish Noodle Coating Steel Plate 实施 Example 1 5 A tin-free steel plate (thickness 0.22 mm, total chromium adhesion amount 120 mg/m 2 ) was used for the coated object, and a double-sided coated steel plate was prepared according to the following steps 丨 to 3

No.l. - Step 1: The surface of the object to be coated obtained in Production Example 19 was coated with a coating material on the outside of the can coating container to have a dry film thickness of 5 μm, and dried at 80 ° C for 10 60 seconds to evaporate the solvent. Step 2: The surface of the object to be coated was coated with a paint Π-1 on the inner surface of the can coated with a bar coater to make the dry film thickness ι〇μηι. 40 200808922 Step 3: Next, after the coated object reaches the maximum reaching temperature of 270 ° C, it is baked for 20 seconds and immediately put into 2 (TC cooling water. Examples 2 to 8 use the coating of Table 6 and In the same manner as in the first embodiment, the steel sheets Νο·2 to Νο·8 were coated on both sides in the same manner as in the first step. In the sixth table, the coated steel sheets No. 1 to Νο·8 were displayed, and steps 1 to 3 were displayed. Table 6 Example 1 2 3 4 5 6 7 8 Both sides "Coated steel plate No. 1 2 3 4 5 6 7 8 Step 1 Can outer coating 1-1 1-2 1-3 1-4 1-5 1 -1 Μ 1-1 Film thickness (μπι) 5 5 5 5 5 5 5 5 Step 2 Coating for inner surface II-1 II-2 II-3 II-4 II-5 II-6 11-7 ΙΙ-8 Membrane Thickness (μτη) 10 10 10 10 10 10 10 10 Step 3 Baking temperature (°C) 270 270 270 270 280 280 280 280 Baking time (seconds) 20 20 20 20 20” 20 20 20 Comparative example 1 Painted A tin-free steel sheet (thickness 0e22 mm, total chromium adhesion amount 12 〇mg/m2) was used, and two-side coated steel 2 Νο·9 was prepared according to the following steps 丨 to 3: Step 1: Painted in Production Example 19 On the surface of the object, paint the outside of the can with a rod-type cloth machine; The dry film thickness is 50111. Second step 2: On the inner surface of the object to be coated, the can coating paint ΙΙ-9 is applied by a bar coater to make the dry film thickness (10)^^, and the inner surface step 3: to reach the material. Bake at a maximum temperature of 270 ° C. 41 200808922 After baking for 20 seconds, it was immediately placed in cooling water at 20 ° C. Comparative Examples 2 to 9 In the same manner as in Comparative Example 1, except for the paint and the steps of the seventh table. 'Making double-coated steel sheets No. 1 to No. 17 ° In the seventh table, the coated steel sheets Νο.9 to Νο·17 are shown in steps 1 to 3. Table 7 Comparative Example 1 2 3 4 5 6 7 8 9 Two-sided coated steel plate No. 9 10 11 12 13 14 15 16 17 Step can coating paint 1-1 1-2 1-3 1-4 1-6 1-7 1-8 1-9 1-10 1 film Thick (μιη) 5 5 5 5 5 5 5 5 5 Step m Cannery coating II-9 II-9 11-10 11-10 II-1 II-1 II-1 II-1 II-1 Chat 2 Film thickness (μπι) 10 10 10 10 10 10 10 10 10 Step 3 Baking temperature (°C) 270 270 270 270 270 270 270 270 270 Baking time (seconds) 20 20 20 20 20 20 20 20 20

About the coated sheets of Examples 1 to 8 and Comparative Examples 1 to 9 • Νο.10 to Νο.17, 50°C pencil hardness of the outer coating film, 60°C dynamic friction system number 10, and drawing press workability And the coating film performance of the printing color development; the film coating property of the inner surface coating film, the squeezing processability, the scent resistance, the hygienic property, and the hygienic property of the coating film were measured according to the following test methods. 50 °C pencil hardness: Each coated steel plate was placed on a hot plate set to 50 ° C, and after confirming the surface of the test sample to 50 ° C with a surface thermometer, root 15 according to JIS K-5400 8.4.2 (1990) A scratch test was performed with a pencil. Evaluate by the rupture method. 6〇°C dynamic friction coefficient: Set the heating plate of “Friction Tester TR-2” (trade name, 42 200808922 manufactured by Toyo Seiki Co., Ltd., dynamic friction measuring device) to 6 (rc, and place each coated steel plate on it to surface After confirming that the surface of the sample to be tested reaches 60 C, the dynamic friction coefficient is measured under the conditions of a load of 2 kg and a tensile speed of 1〇〇〇1111]1/111丨11. 5 Stretching workability: Each coated steel plate is under In the formula, the tube is subjected to a drawing press process to reduce the thickness of the thinnest portion of the can body by 60%. The thickness reduction ratio N = 1 - (m/n.) (wherein, (1) is a coating The thickness after the processing of the steel sheet is as follows: the thickness of the coated steel sheet is increased by 10 parts.) Next, the obtained drawn press tank is cut, and the "coating film for the inner surface" and the "coating film for the outer surface" are evaluated on the basis of the following criteria. ◎ • There is no crack on the coating film and whitening due to processing, and the smoothness is excellent. 〇··There is no crack on the coating film, and it can be confirmed that it is slightly whitened. 15 △: Cracks are confirmed on the coating film, and the coating film cannot be confirmed. Peeling or peeling off X: Confirm that the film peeled off or peeled off. Color developability: The can body portion of the drawn press can obtained by the above-mentioned "stretching pressability" test was cut, and the outer surface of the film was coated with a polyester resin/melamine resin by a bar coater. The coloring paint (trade name, 20 "κρ-1593 white", Kansai Paint Co., Ltd. 'painting white) makes the amount of coating after drying 3.6g/m2 'the maximum temperature of the adjustment material is 22 〇. Bake and dry for 60 seconds to form a white printed film. The white printed film is based on the brightness (L* value) of the 1/ a* b* color system specified in JIS Z 8729, and the color computer SM_4 (trade name) , Suga test machine 43 200808922 Co., Ltd., color measurement) measurement, evaluation of printing color developability according to the following criteria. 〇: L* value is 70 or more, printing color development is good. X: L* value is less than 7 0, The printing coloring property was poor. The smear resistance: Each of the coated steel sheets was immersed in water at a temperature of 125 ° C for 30 minutes in the retort, and the inner surface of the coating film was whitened and evaluated according to the following criteria. 〇: It is impossible to confirm whitening at all. △: It is confirmed that there is some whitening. X: It is confirmed that there is significant whitening. 10 Aroma retention: Add d-limonene (fragrance) to the deionized water to a concentration of 30 mg/l, and add "S-1170" (trade name, 'sugar fatty acid vinegar made by Mitsubishi Chemical Corporation) to disperse into lg/ In the liquid of the concentration of ruthenium, the coated steel sheets sealed on the outer side of the coating film were immersed and stored at 35 ° C for one month. After storage, the eucalyptus (perfume) adsorbed on the coating film was measured, and rubbed. 15 After wiping the surface of the inner side coating film, it was immersed in diethyl ether for 1 week at 2 ° C, and the extracted d-limonene (perfume) was measured by a gas chromatograph, and the price was evaluated on the basis of the following. 〇: The extracted d-moneylene (perfume) corresponds to an inner side coating film weight of less than 0.6 mg per 120 g, and is excellent in flavor retention. 2〇 △: Extracted heart limonene (fragrance), which corresponds to the weight of the inner side coating film - 〇.6 mg or more and less than 1.6 mg per 12 〇g, and the flavor retention is excellent. &quot; X · Extracted d-moneylene (fragrance), equivalent to the weight of the inner side coating film 1.6mg or more per 120g, the fragrance retention is inferior. Hygiene: Each of the coated steel sheets sealed on the outer side with the coating film is made to have a ratio of 1 cm 2 of the coating area of 44 200808922 to the amount of tap water treated with activated carbon, and is impregnated with the heat of the tap water filled with activated carbon. The glass-made container was treated at 120 ° C in a covered retort for 3 minutes. The treated liquid was evaluated for hygiene based on the consumption of potassium permanganate (ppm) according to the test method described in the Food Sanitation Law. ◎: The consumption is less than 2 ppm, and the hygiene is excellent. 〇· Consumption is 2ppm or more and less than 5ppm, and the hygiene is good. △: The consumption was 5 ppm or more and less than 1 〇 ppm, and the hygiene was poor. X: The consumption is more than 10 ppm, and the hygiene is inferior. 0 The results of the film performance test are shown in Tables 8 and 9.

Table 8

45 200808922 Table 9 Comparative Example 1 2 3 4 5 6 7 8 9 Double-coated copper plate No. 9 10 11 12 13 14 15 16 17 Can coating film outside the can 50 ° C Pencil hardness 2 Η 2 Η 2 Η 2 Η 2 Η 2 Η 2 Η 2 Η 2 Η 60°C dynamic friction coefficient 0.20 0.14 0.12 0.11 0.16 0.14 0.11 0.12 0.12 Tensile press workability 〇 ◎ ◎ ◎ ◎ XXX Printing color development 〇〇〇〇 XX — - - Coating film on the inner surface of the can is stretched and processed Δ Δ 〇〇 ◎ ◎ ◎ ◎ ◎ 甑 甑 XX Δ Δ 〇〇〇〇〇 〇〇〇〇〇 保持 保持 〇〇 〇〇 〇〇〇〇〇 〇〇〇〇〇 〇〇〇〇〇 Δ ◎ ◎ ◎ ◎ ◎ ◎

In the ninth table, the "-" of the coloring property was printed because the coating film was peeled off or peeled off, so that it could not be evaluated. 5 [Simple description of the diagram] (None) [Explanation of main component symbols] (None) 46

Claims (1)

200808922 X. Applying for a patent: 1· - Coating the steel plate on both sides of the can, coating the steel plate on both sides, and forming the coating film for the can coating (I) on the outer side after the can processing, and the can is used for the can The coating material (1) comprises a crosslinking agent (B) containing at least one of a light-based polyester resin (A) and a group selected from the group consisting of an amino resin and a resol resin, and is relative to the polyester resin (A). The solid content of 100 parts by mass, containing aluminum pigment (C1) 5 to 60 parts by mass or white pigment (C2) 60 to 140 parts by mass, and forming a coating film for can coating (H) on the side which becomes the inner surface after processing. 'The can coating (II) contains crystalline polyester resin microparticles (D) mainly composed of ethylene terephthalate units, and crystalline polyester mainly composed of butylene dibutyl phthalate units. The resin fine particles (E) have a solubility with respect to the fine particles (D) and a solubility with respect to the fine particles (E), and are contained at least 40% by mass or less and less than 5% by mass or more. Solvent (F), and the ratio of the microparticles (D) to the microparticles (E), relative to the total, the former 95 to 3 % by mass, the latter is 5 to 70% by mass, and the content of the organic solvent (F) is -$(10) parts by mass relative to the fine particles (D) and 0 of the fine particles. A double-sided coated steel sheet for cans according to the first aspect of the invention, wherein the coating film thickness of the can coating (I) is a dry film thickness, and the coating film of the can coating (II) is dried. The film thickness is 3. The double-coated steel plate for cans according to the first aspect of the patent application, wherein the aluminum pigment (C1) of the can coating (I) is a non-floating aluminum pigment. The tank of the item is coated on both sides with the steel sheet, wherein the above-mentioned 47 200808922 can coating (π) crystalline polyester resin microparticle (D) resin has an intrinsic viscosity of 0.4 to 1.4 dl/g, and the glass transition temperature (1^) is 55 to 13 〇. (: and the melting point (Tm) is 160 to 260 ° C. 5. The double-coated steel plate for cans of the first application of the patent scope, wherein the crystallinity of the above five can coatings (Π) The polyester resin fine particles (D) are composed of the above-mentioned polyester resin having a unit content of 8 mil% or more of ethylene glycolate. The double-coated steel sheet for cans of the first aspect of the patent application, wherein the crystalline polyester resin fine particles (Ε) resin of the can coating (II) inherently has a viscosity of 10 degrees 0·4 to L4 dl/g, and a glass transition temperature ( Tg) 〇 ~ 40 ° C and melting point (Tm) 130 ~ 250 ° C. 7_ as claimed in the scope of the scope of the two-sided coated steel plate, wherein the can coating (II) crystalline polyester The resin fine particles (6) are composed of the above-mentioned polyester resin 15 having a unit content of butylene dibutyl phthalate of 9 〇 mol% or more. 8. The double-sided coated steel sheet for cans according to the first aspect of the invention, wherein the can coating (II) is based on the crystalline polyester resin fine particles (D) and the crystalline polyester resin fine particles (E) A total of 100 parts by mass, more preferably 0.1 to 100 parts by mass of the aforementioned coating material containing the hydroxy polyester resin (A). 20 9. A double-sided coated steel sheet for cans according to item 8 of the patent application, wherein the can coating (II) contains a hydroxy polyester resin fine particle (A) having a glass transition temperature (Tg) of 55 to 150 t. 10. The double-coated steel sheet for cans according to the first aspect of the patent application, wherein the can coating (II) is a coating material further containing a dispersing agent (G). 48 200808922 11. A double-sided coated steel sheet for cans according to claim 10, wherein the dispersing agent (G) is of the formula (1) [Chemical Formula 1] 0 R10-P-OR3 (1) OR2 (Formula In the above, R1, R2 and R3 are the same or different, and represent an aliphatic or aromatic hydrocarbon having 6 to 18 carbon atoms or CmH2mOCnH2n+1. In this case, m and η are integers of 1 or more, and m +η is an integer of 6 or more.) The phosphate compound represented by the formula. 12. The double-coated steel sheet for cans according to the first aspect of the patent application, wherein the ten-coat paint (II) is based on the crystalline polyester resin fine particles (D) and the crystalline polyester resin fine particles (Ε) A total of 100 parts by mass, more preferably 0.1 to 10 parts by mass of the coating of the above resol phenolic resin. 13. The double-sided coated steel sheet for cans according to the first aspect of the patent application, wherein the can coating (II), the crystalline polyester resin microparticles (D) and the 15 crystalline polyester resin microparticles (Ε) A total of 100 parts by mass, more containing 0.5 to 20 parts by mass of epoxy resin coating. 14. A steel can body which is a double-sided coated steel plate for cans of the first application of the patent scope, which is obtained by stamping or stamping and drawing. % 49 200808922 VII. Designated representative map: (1) The representative representative of the case is: (). (None) (2) A brief description of the symbol of the representative figure: 8. If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention: