TWI255225B - Resin-coated metal sheet and manufacturing method thereof - Google Patents

Abstract

Disclosed is a resin-coated metal sheet which includes a resin film resulting from an emulsion composition containing an ethylene/unsaturated carboxylic acid copolymer as a main component. The emulsion composition contains, other than the ethylene/unsaturated carboxylic acid copolymer, an amine having a boiling point of 100 DEG C or less in an amount equal to 0.2 to 0.8 mol per mole of the carboxyl groups contained in the ethylene/unsaturated carboxylic acid copolymer, and a monovalent metal compound in an amount equal to 0.02 to 0.4 mol per mole of the carboxyl groups contained in the ethylene/unsaturated carboxylic acid copolymer, and in addition, a crosslinking agent having two or more functional groups capable of reacting with the carboxylic groups in an amount of 1 to 20 mass% per 100 mass% of the solid content of the emulsion composition, and does not substantially contain an amine having a boiling point of more than 100 DEG C, and ammonia. The resin-coated metal sheet is not only excellent in various characteristics such as coatability, lubricity, formability, grounding property, but also excellent in corrosion resistance after an alkali degreasing step, and also excellent in tape peeling resistance.

Description

1255225 (1) EMBODIMENT OF THE INVENTION [Technical Field] The present invention relates to a resin-coated metal sheet excellent in corrosion resistance, which is preferably used in household appliances, building materials, etc. The method. [Prior Art] _ In addition to aluminum and stainless steel sheets, surface-treated steel sheets such as galvanized steel sheets and hot-dip galvanized steel sheets are widely used as metal sheets for household appliances and building materials. Among them, conventionally, galvanized surface-treated steel sheets have been subjected to chromizing or phosphating, and are widely used for various structural parts of acoustic instruments, computer parts, and bottom plates of microwave ovens, including most household electronic equipment. However, in recent years, users have become increasingly demanding these surface treated steel sheets, resulting in a demand for various film properties. For example, when surface treated steel sheets are used in bare form, they are required to have anti-corrosion properties, grounding properties, and anti-fingerprint properties, so that even in contact with them, fingerprints are not so obvious, chemical resistance, pollution resistance, etc. , tolerance to alkali, solvent, etc. However, when the steel sheets are press-formed or punched, they are required to have lubricity, crack resistance, drawability, mold wear resistance, stampability, resistance to forming sliding surface blackening, and to stamping oil/quick drying. Oil resistance of oil, etc. In order to satisfy these requirements for performance, for example, Japanese Laid-Open Patent Publication No. 6 - 2 4 6 2 2 9 discloses an organic composite-coated steel sheet including a resin film on a chromium layer in which an olefin is ionized 60-80% of the thiol (2) 1255225 was neutralized by sodium ions. However, Japanese Patent No. 2 7 5 9 6 20 discloses a resin-coated metal sheet comprising a film formed on the surface of a metal sheet by a composition containing molecules in association via ion clusters. A polyolefin copolymer resin emulsion and an organic compound having an aziridine group. Japanese Patent No. 2 7 5 9620 describes the effect after the metal plate is preferably chromized. However, in recent years, resin membranes have been required to have higher corrosion resistance than ever before due to the development of products containing no chromium (non-chromium) in order to protect the global environment. As described above, each of the resin films to be stacked on the chrome-free metal plate is also required to have the same level of corrosion resistance as that of each of the resin films coated on the chrome metal plate. Under such circumstances, the inventors conducted continuous research even after applying for the transcript of the patent N 〇 · 2 7 5 9 6 2 0.树脂 The resin film described in this patent 27 27 5 9620 also exhibits some excellent corrosion resistance to chrome-free sheets. However, for example, after the lubricating oil applied during the press forming process is removed in the degreasing step, the resin film is disadvantageously degraded by the treatment with alkali, resulting in a decrease in corrosion resistance. However, a resin film is coated on a chromium-free metal plate, and then a tape is attached to the surface of the resin film and kept for a long time. Then, the tape was peeled off, which even peeled off the resin film. Therefore, there is a problem that the tape peeling resistance (adhesion force between the metal plate and the resin film) is insufficient. SUMMARY OF THE INVENTION Therefore, in such a case, an object of the present invention is to provide a metal plate coated with -6 - (3) 1255225 resin, which has a resin film having excellent properties in various aspects, such as: coatable The properties of the coating (adhesion of the film on the resin-coated metal sheet), lubricity, formability, and grounding properties, and excellent corrosion resistance and tape peeling resistance after the degreasing step. One embodiment of the present invention resides in a resin-coated metal sheet comprising: a metal sheet; and a resin film coated on the surface of the metal sheet, the resin film being obtained from an emulsion composition, wherein the emulsion combination The article comprises: an ethylene/unsaturated carboxylic acid copolymer having p as a main component; and an amine having an amount of from 0.2 to 0.8 mol per mol of the carboxyl group contained in the ethylene/unsaturated carboxylic acid copolymer per mole. 'The amine has a boiling point of 10 (TC or lower; a monovalent metal compound in an amount of from 0.02 to 0.4 mol per mol of the carboxyl group contained in the copolymer of the molar/unsaturated carboxylic acid; and the amount thereof) 1-20% by mass/100% by mass of the emulsion composition solid content crosslinking agent having two or more functional groups capable of reacting with a carboxyl group contained in the ethylene/unsaturated carboxylic acid copolymer And wherein the emulsion composition is substantially free of an amine having a boiling point higher than 100 ° C, and does not contain ammonia on the solid. According to this embodiment, in the ethylene/unsaturated carboxylic acid copolymer, preferably 10-40% by mass of unsaturated carboxylic acid is copolymerized, preferably 15-25% by mass of unsaturated The acid is copolymerized. The amine having 1 〇 (TC or lower boiling point is triethylamine is also one of the preferred embodiments of the invention. According to this embodiment, it is preferably at every 1% by mass. The solid content of the emulsion composition contains 5 to 40% by mass of cerium oxide particles having an average particle diameter of b20 〇 nin. Further preferably, it contains 0.5 to 20% by mass of spherical polyethylene ruthenium. Resin film of various properties such as: -7 - (4) 1255225, lubricity, formability and grounding properties, and the resin film has excellent anti-corrosion properties and tape peeling after the degreasing step Resistance. Incidentally, the resin-coated metal sheet of the present invention exhibits excellent corrosion resistance even in the case where a chrome film is not formed. According to this embodiment of the present invention, in the resin In a coated metal sheet, an ethylene/unsaturated carboxylic acid copolymer is neutralized by using a specific amount of an amine and a metal compound having a boiling point of 100 ° C or lower to form an emulsion P ° An emulsion composition having a very small particle size is obtained. Thus, a resin-coated metal sheet coated with a film having various excellent properties such as coatability, lubricity, formability, and grounding properties, and excellent corrosion resistance and tape peeling after the degreasing step can be obtained. Another embodiment of the present invention resides in a method of producing a resin-coated metal sheet, which comprises the steps of: preparing an emulsion composition; coating the emulsion composition on a metal sheet; and coating the emulsion composition The metal plate is heated and dried. [Embodiment] The resin-coated metal plate of the present invention comprises a resin film formed on at least one side of a metal plate by a specific emulsion composition. Limitations. For example, a zinc-plated or zinc-based steel sheet, an aluminum plate, an aluminum-based alloy plate or a titanium plate may be mentioned. Moreover, it is also acceptable to subject the metal sheet to a known rust-proof surface treatment such as phosphating or other surface treatment, and to form a resin film thereon. From the standpoint of environmental issues, it is preferred that the sheet is not subjected to chromizing. (5) Γ 255225 The emulsion composition for forming a resin film in the present invention contains, as a main component, an ethylene/unsaturated carboxylic acid copolymer (including a neutralized state), which is copolymerized with respect to each mole of ethylene/unsaturated carboxylic acid. a carboxyl group contained in an amount of 0.2 - 0 · 8 mol (20 - 80 mol%) and an amine having a boiling point of 10 ° C or lower, relative to each mole of ethylene / unsaturated a carboxyl group contained in a carboxylic acid copolymer in an amount of from 0.02 to 0.4 mol (2 to 40 mol%) of a monovalent metal compound, and an amount of from 0.5 to 20% by mass per 100% by mass of the emulsion composition. A crosslinker having a content of φ having two or more functional groups capable of reacting with a carboxyl group, and the composition is substantially free of amines and ammonia having a boiling point higher than 1 〇〇t. The ethylene/unsaturated carboxylic acid copolymer described in I is a copolymer of ethylene and an ethylenically unsaturated carboxylic acid. As the unsaturated carboxylic acid, (meth)acrylic acid, crotonic acid, isocrotonic acid, maleic acid, fumaric acid, itaconic acid and the like can be mentioned. The copolymer can be obtained by polymerizing one or more of them with ethylene by a known high-temperature high-pressure polymerization method or the like. The copolymer is preferably a random copolymer. However, it may also be a block copolymer or a copolymer grafted at the unsaturated Φ carboxylic acid moiety. Incidentally, the unsaturated carboxylic acid is preferably (meth)acrylic acid. Further, an olefinic monomer such as propylene or 1-butene may be used instead of a part of ethylene. Further, other known vinyl type monomers (amount of about 10% by mass or less) may be partially copolymerized as long as the object of the present invention is not impaired. With respect to the copolymerization ratio of the unsaturated carboxylic acid to ethylene, when the total amount of the monomers is regarded as 100% by mass, the amount of the unsaturated carboxylic acid is preferably from 10 to 40% by mass. When the amount of the unsaturated carboxylic acid is less than 10% by mass, the amount of the residue serving as a crosslinking point for the intermolecular association of the ion cluster or the crosslinking point of the crosslinking agent is too small. Therefore, it is disadvantageous (6) 1255225 that the film strength effect cannot be exerted, so that the peeling resistance and the corrosion resistance after the degreasing step are insufficient. Further, the emulsion composition is also inferior in emulsification stability. A more preferable lower limit of the amount of the unsaturated carboxylic acid is 15% by mass. On the other hand, when the amount of the unsaturated carboxylic acid exceeds 40% by mass, the corrosion resistance and water resistance of the resin film are poor. Therefore, it is disadvantageous that the corrosion resistance after the degreasing step is also lowered. A better upper limit is 25% by mass. The ethylene/unsaturated carboxylic acid copolymer has a carboxyl group. Therefore, it can be neutralized with an organic base or a metal ion, thereby preparing an emulsion (made into an aqueous dispersion). In the present invention, an amine having a boiling point of 1 〇〇 ° C or lower is used as the organic base. The amine having a boiling point higher than 1 〇〇 °c tends to remain on the steel sheet when the resin coating film is dried, resulting in an increase in water absorption property of the resin coating film, which causes a decrease in corrosion resistance. For this reason, the emulsion composition for forming the film of the present invention is not required to contain an amine having a boiling point higher than 100 °C. Also, do not contain ammonia because the effect of adding ammonia is not observed. As the boiling point, the boiling point at atmospheric pressure is used. Specific examples of the amine having a boiling point of 10 (TC or lower) include: tertiary amines such as triethylamine, N,N-dimethylbutylamine, N,N-dimethylallylamine, N-methyl Pyrrolidone, tetramethyldiaminomethane and trimethylamine; secondary amines such as N-methylethylamine, diisopropylamine and diethylamine; and primary amines such as propylamine, tertiary butylamine, secondary butylamine, Isobutylamine, 1,2-dibutylpropylamine and 3-pentylamine. They may be used singly or in the form of a mixture of two or more. Among them, a tertiary amine is preferred. It is preferably triethylamine. The amount of the amine having a boiling point of 1 〇〇 ° C or lower is set to 〇.2-〇·8 mol with respect to the carboxyl group in each mole of the ethylene/unsaturated carboxylic acid copolymer. (20- -10- (7) 1255225 8 0 mole %). This is because the amount in this range will result in good corrosion resistance and tape peel resistance. When the boiling point is 1 〇〇 ° C or lower When the amount of the amine is less than 0.2 mol, the particle diameter of the resin particles in the emulsion is large. For this reason, it is conceivable that the above effect cannot be exerted. However, the amount of the amine having a boiling point of 100 ° C or lower is used. Big At 0.8 mol, the emulsion composition may disadvantageously increase in viscosity and gel. The upper limit of the amount of amine is preferably 〇·6 m ο 1, more preferably 0.5 m ο 1. The lower limit of the amount of amine is preferably 0.3 m. ο 1. p In the present invention, monovalent metal ions are also used for neutralization, which is effective for improving solvent resistance and film hardness. Therefore, a monovalent metal compound is added to the emulsion composition. The compound preferably contains one or two or more metals selected from the group consisting of sodium, potassium and lithium. Preferred are hydroxides, carbon oxides or oxides of these metals. Among them, preferred are NaOH, KOH, Li OH. Etc., the best one is NaOH because it has the best performance. Further, regarding the metal compounds of two or higher valences, the effects of adding them are not observed. Therefore, it is used in the present invention for formation. The emulsion group φ compound of the film does not contain a metal compound of two or more valence as a reaction object of the ethylene/unsaturated carboxylic acid copolymer. The amount of the monovalent metal compound is relative to that per mole of the ethylene/unsaturated carboxylic acid copolymer. The carboxyl group is set at 〇·02-〇.4 (2_40 mol %) When the amount of the metal compound is less than 〇.〇2 mol, the emulsion stability becomes insufficient. However, when the amount exceeds 〇.4 m〇l, the moisture absorption property of the obtained resin film ( In particular, the increase in the alkaline solution adversely causes the corrosion resistance after the degreasing step to deteriorate. The lower limit of the amount of the metal compound is preferably 0.03 m ο 1. A further lower limit is 〇·1 m ο 1 . The upper limit of the amount of the metal compound -11 - (8) 1255225 is 〇. 5 ill ο 1, and the further upper limit is 0 · 21110 1 °, respectively, preferably using a boiling point of 1 〇〇 °c in the above range. Or lower amines and monovalent metal compounds. Both of these are used to neutralize the carboxyl groups in the susceptor/unsaturated carboxylic acid copolymer and to emulsify the copolymer. Therefore, when the total amount (neutralization amount) is too large, it is disadvantageous that the viscosity of the emulsion composition is rapidly increased and solidified, and in addition, the excess alkali component causes deterioration of the anti-corrosion uranium property. Moreover, a large amount of energy is required to volatilize the excess alkali component. However, the neutralization amount P is too small, and it is disadvantageous that the emulsifiability is also disadvantageously deteriorated. Therefore, the total amount of the amine and the monovalent metal compound having a boiling point of 100 ° C or lower is preferably set at 0 · 3 -1 · 0 mol per mol of the carboxyl group per mole of the ethylene/unsaturated carboxylic acid copolymer. ear. The emulsion composition used in the present invention is formed by emulsification by using an amine having a boiling point of 100 ° C or lower and a monovalent metal compound in combination. As a result, the resin particles in the composition are stably present in the aqueous medium in the form of extremely fine particles (oil droplets) having a size of 5 to 5 Onm. This is the improvement of the film-forming properties of the resin film obtained by φ, the adhesion to the metal plate, and the densification of the film, and the improvement of the resistance against uranium and the peeling resistance of the tape are obtained. The aqueous medium may contain a hydrophilic solvent such as an alcohol or an ether other than water. Incidentally, the particle diameter of the resin particles in the emulsion can be measured by, for example, a laser diffraction method using a light scattering photometer (manufactured by OTSUKA ELECTRONICS Co., Ltd.). In the neutralization step (emulsification step) of the ethylene/unsaturated carboxylic acid copolymer using an amine having a boiling point of 1 〇〇t or less and a monovalent single compound, it is advantageous to have a boiling point of 1 〇〇° The c or lower amine and the monovalent metallization-12-(9) 1255225 compound are added to the copolymer almost simultaneously, or an amine having a boiling point of 100 ° C or lower is first added. This is because the addition of a monthly hardness of 1 〇 〇 °c or lower may result in insufficient corrosion resistance/tape peeling resistance improvement, although the cause is not known. The ethyl carboxylate/unsaturated residual acid copolymer in which the carboxyl group is neutralized by an amine having a boiling point of 100 ° C or lower and a monovalent metal compound forms an intermolecular association (conversion into an ionomer) via an ion cluster. To form a resin film excellent in corrosion resistance/tape peel resistance. However, in order to form a stronger film, it is understood that the polymer chain is cross-linked to each other via a chemical bond using a reaction between functional groups. In such a case, the emulsion composition of the present invention contains a crosslinking agent as a necessary component, and the crosslinking agent has two or more functional groups capable of reacting with a carboxyl group. The amount of the emulsion composition is set to be 1 to 20% by mass / 1% by mass based on the solid content of the emulsion composition. When the amount is less than 1 mass ° /. At the time, the effect of cross-linking by chemical bonds becomes insufficient, and therefore, it is less likely to exert an improvement effect against corrosion resistance/tape peeling resistance. On the other hand, when the crosslinking agent is mixed in an amount of more than 20% by mass, the crosslinking density of the resin film is excessively increased to cause an increase in hardness. Therefore, the resin film does not become deformed smoothly at the time of press molding. This causes crack formation. As a result, the corrosion resistance and coatability were disadvantageously lowered. A more preferable amount of the crosslinking agent is a solid content of the emulsion composition of 5·10 mass%/100 mass%. Incidentally, the ratio of the amount of the crosslinking agent to the amount of the ethylene/unsaturated carboxylic acid copolymer is advantageously changed by appropriately changing the amount of the crosslinking agent depending on the amount of the carboxyl group in the copolymer. Usually, the amount of the crosslinking agent is preferably from 0.5 to 50 parts by mass (more preferably from 5 to 20 parts by mass) per 100 parts by mass of the copolymer. -13- (10) 1255225 A crosslinking agent having two or more functional groups capable of reacting with a carboxyl group per molecule is not particularly limited. However, preferred examples thereof may include a glycidyl group-containing crosslinking agent including a polyglycidyl ether such as sorbitol polyglycidyl ether, (poly)glycerol polyglycidyl ether, and isoprene. Glycidyl ether, trimethylolpropane polyglycidyl ether, neopentyl glycol diglycidyl ether and (poly)ethylene glycol diglycidyl ether, and polyglycidylamine; difunctional aziridine Compounds such as 4,4'-bis(cycloethyliminecarbenylamino)diphenylmethyl, hydrazine, Ν'-hexamethylene-1,6-bis(1-aziridinylcarboxy amide), hydrazine , Ν'-diphenylmethane-4,4'-bis(1-propionylcarboxy decylamine) and toluene diaziridine carboxy guanamine; and aziridine-containing crosslinking agent, including three or more a polyfunctional aziridine compound such as tris-dipyridinylphosphine oxide, tris[1-(2-methyl)aziridine]phosphine oxide, trimethylolpropane tris(/3-aziridine) Propionate), tris-2,4,6-(1-aziridinyl)-1,3,5-triazine and tetramethylpropane tetraaziridine propionate, or derivatives thereof. They may be used singly or in combination of two or more. Among them, a preferred one is an aziridine-containing crosslinking agent. Incidentally, it is possible to use a combination of a polyfunctional guanidine D and a monofunctional guanidine D (e.g., a cyclic imine). The emulsion composition for use in the present invention may contain 5 - 40% by mass of cerium oxide particles based on the solid content. It can effectively improve corrosion resistance, coatability, crack resistance, etc., and is effective for improving anti-corrosion uranium performance and tape peeling resistance after degreasing. When the amount is less than 5% by mass, these effects are less likely to occur. However, when the amount exceeds 40% by mass, the proportion of the cerium oxide particles is excessively increased, resulting in a decrease in film forming properties. Therefore, -14-(11) 1255225 cracks occur in the resin film in the drying step, disadvantageously causing a decrease in corrosion resistance. Further, the cerium oxide particles become a polishing agent which improves the lubricity of the film and causes a decrease in the friction coefficient. This causes wear on the mold during the molding process and shortens the life of the mold. A more preferable lower limit of the amount of the cerium oxide particles is 20% by mass, and the upper limit is 30% by mass. In order to maximize the above effects of the cerium oxide particles, the average particle diameter of the cerium oxide particles is preferably from 1 to 2,000 nm. As the particle size of the cerium oxide particles decreases, the performance of the film's anti-corrosion uranium is improved. It is conceivable due to the following facts. The resin film is densified and the adhesion is improved, which further improves the corrosion resistance. From this point of view, the cerium oxide particles preferably have a smaller particle size. However, when they are extremely fine particles, the aforementioned effects reach a saturated state. For this reason, the lower limit of the particle diameter is preferably 1 n m. On the other hand, when the particle size of the cerium oxide particles exceeds 20 Onm, the surface of the resin film is roughened. Therefore, it is impossible to form a dense resin film. Moreover, the cerium oxide particles also become a polishing agent, which undesirably causes deterioration in formability. In particular, when the corrosion resistance after degreasing is emphasized, the average particle size of the cerium oxide particles is preferably set to 4 to 20 nm. These cerium oxide particles are generally known as colloidal cerium oxide. In the present invention, it is preferable to use, for example, ''Snow Tex system 歹 ij π (Nissan C hemica 1 I ndustries, L td · produced colloidal silica sand) " χ s ', " ss '', Μ 0 π, π N π, π ϋ P '' and the like. In the emulsion composition of the present invention, it may contain 0.5 to 20% by mass of a wax based on the solid content. This wax has an effect of improving the lubricity and crack resistance of the resulting resin film. Moreover, it is preferred to use it for the -15-(12) 1255225 press-forming and punching required for pull-out and stampability, resistance to mold wear and resistance to sliding surface blackening in forming and providing Excellent Formability When the amount of the wax is less than 0.5% by mass based on the solid content, the lubricity of the formed resin film becomes insufficient. Therefore, it is impossible to improve the crack resistance and obtain satisfactory formability. On the other hand, when the amount exceeds 2 〇 mass%, the formed resin film has sufficient lubricity, but when it is subjected to post-electrodeposition, powder coating or screen printing, film adhesion Sex (coatability) is poor. Moreover, the anti-corrosion performance and the tape peeling resistance after degreasing are also deteriorated. It is understandably due to the following facts. The wax may be softened/liquefied or bloomed by heating in the post-coating step, or may change over time, and concentrated at the interface between the resin film and the post-coating film or between the metal plate and the resin film. Interface. Therefore, the adhesion to the post-coated film or the adhesion to the metal plate deteriorates. A better upper limit is 1% by mass, and even a better upper limit is 5.0% by mass. There is no particular limitation on the hydrazine, and the usable waxes are natural waxes and synthetic waxes, mixtures thereof and the like. Examples of the natural cockroaches which can be used include carnauba wax, rice bran, candula tree and lignite type quinone, and derivatives thereof, mineral oil type, microcrystalline wax, paraffin wax and the like, and derivatives obtained by adding a carboxyl group. As the synthetic initiator, mention may be made of ruthenium oxide of polyethylene, polyethylene oxide, polypropylene, ethylene/propylene copolymer type ruthenium and a copolymer wax of ethylene and other monomers. As the system, various types including ternary copolymer types can be widely used depending on the change of the copolymerization reaction object. Further, mention may be made of maleic acid adduct wax, fatty acid ester type and the like. Further, -16-(13) 1255225, a fluorine-containing resin type wax such as polytetrafluoroethylene, polyvinyl fluoride, polyvinylidene fluoride or tetrafluoroethylene can also be used. As the wax, it is preferred to select a softening point of from 80 to 140 °C from the above examples. When the softening point is lower than 80 ° C, the wax particles soften/liquefy as the mold temperature increases during press forming or punching. Therefore, at the sliding surface between the resin-coated steel sheet and the mold, liquid depletion of the liquefied niobium occurs, resulting in a decrease in moldability, which disadvantageously causes scratches and biting p. Moreover, blackening substances adhere to the sliding portion, which seriously damages the appearance of the product. Further, from the viewpoints of corrosion resistance and tape peeling resistance after the degreasing step, it also shows that a too low softening point is not preferable. On the other hand, when the softening point exceeds 1 40 ° C, the lubricity of the wax becomes insufficient, so that punchability, mold abrasion resistance, drawability, or the like cannot be improved. The performance of anti-corrosion uranium after degreasing also showed a slight decline. The wax is preferably a spherical polyethylene crucible. In this case, in order to maximize the effect of the φ spherical polyethylene crucible, the particle diameter of the wax particles is preferably 〇. 1 -3 // m. When the particle size of the niobium particles is less than 0 · 1 μ m, it is difficult to significantly improve the lubricity, the stampability, the mold wear resistance and the pull-out property. On the other hand, when the particle size of the wax particles exceeds 3 // m, it is difficult to uniformly disperse the wax particles into the emulsion composition in the form of fine particles. This may reduce the adhesion of the resin film to the metal sheet. More preferably, the spherical polyethylene wax has a particle diameter of 0 · 3 · 1 . 0 // ηι 〇 as the aforementioned spherical polyethylene bismuth, for example, a commercially available product such as ''DAIJET E-17'' (GOO Chemical Co) can be used. ·, Ltd. produced), -17- (14) 1255225,, KUE-1', , " KUE-5n and ''KUE-8,, (Sanyo I ndustries, L td · produced)," C hemipear " W -1 0 0'', "W-200", '' MW - 4 0 0 ”, ', W _ 5 0 0,,, '' W - 6 4 0 from 1 ''Series Chemicals) "," W - 7000 '' and similar ''Elepon E-20n (manufactured by NICCA Chemical Co., Ltd.). The emulsion composition according to the present invention preferably contains an ethylene/non-copolymer as a main component, and has a boiling point. An amine I compound of 1 oot or less, a crosslinking agent such as an aziridine compound, and an optional cerium oxide particle, a wax, and the like. The content of the ethylene/unsaturated substance is advantageously adjusted to the amount of the bismuth compound, the oxidized stone, and the like, so that the content of these resin components is 50% by mass or more based on the solid content of the solid. Preferably, the emulsion composition is prepared in the following manner. The ethylene/unsaturated carboxylic acid copolymer, which is the main component, is fed together with an aqueous feed to, for example, a homogenizer unit or the like, if necessary, under heating of φ 2 5 〇 °C. Under high-shear agitation, an amine and a monovalent boiling point of 100 ° C or lower are appropriately added in a water-soluble form (the first is to add an amine having a boiling point of 10 ° C or lower, or a few boiling points are added. The amine and the monovalent metal compound at 10 ° C or lower are added with cerium oxide particles, cerium, a crosslinking agent, etc. at any stage. After the crosslinking agent is added, it is advantageously not heated to prevent cross-linking gelation. The dilution solvent, the leveling agent, the defoaming agent, the penetrating agent, the emulsifier, and the film forming auxiliary agent may be appropriately added to the emulsion composition.

Chemical (Mitsui W - 3 0 0 π, 、, and ο saturated carboxylic acid, monovalent gold, using carboxylic acid copolymer particles, hydrazine emulsion combination, first as a medium and in a 70-liquid or similar metallization simultaneously ). However, it is possible to use the reaction and anti-corrosion agent, coloring matter -18-(15) 1255225 material, thickener, decane coupling agent and other resins and the like as long as it is not harmful to the object of the present invention. A resin film can be formed on the metal plate in the following manner. The emulsion composition is applied to one side surface or the opposite side surface of the metal plate by a known coating method such as a roll coater method, a spray coating method, a curtain flow coater method, or the like, and is heated and dried. The heating and drying are preferably carried out at a temperature at which the crosslinking reaction between the crosslinking agent and the carboxyl group used is carried out. Moreover, when a spherical φ-shaped polyethylene wax is used as the lubricant, the spherical shape is maintained to obtain more excellent formability in the subsequent molding step. Therefore, it is advantageous to carry out the drying at a temperature ranging from 7 〇 to 130 °C. The amount (thickness) of the coated resin film is preferably 〇 2 _ 2· 5 g/m 2 after drying. When the resin film is too thin, it is difficult to uniformly coat the metal plate, and it is difficult to obtain a balanced target film property such as moldability, corrosion resistance, and coatability. However, when the coating amount exceeds 2.5 g/m2, when the resin-coated metal plate is used for a computer core or the like, the grounding property, φ, that is, the conductivity is disadvantageously lowered. Further, the amount of the resin film peeled off during the press molding is increased so that the release film is deposited on the mold. This hinders press molding and is priceless in terms of manufacturing cost. The lower limit of the deposition amount of the more preferable resin film is 〇.5 g/m2, and the upper limit is 2.0 g/m2. By forming a resin film, it is possible to obtain the resin-coated metal sheet of the present invention. It allows the resin-coated metal sheet to undergo a molding step and is used for the purpose for which it is intended. Alternatively, it may be subjected to electrodeposition/powder coating/silk printing (about 20 to 30 minutes at 130 to 160 °C) under a known condition. -19- (16) I255225 Embodiments Hereinafter, the present invention will be described in more detail by way of examples. However, the following examples are not to be construed as limiting the scope of the invention; it is understood by those skilled in the art that the invention can be practiced with the appropriate modifications within the scope of the invention. Lu [Test Method] The test methods in the following examples are as follows. ' (1) Corrosion resistance after degreasing step. The resin coated metal plate is adjusted to 6 (TC 20g / l alkaline decoction! l (Nihon Parkerizing C ο, L td. produced , CL-N 3 6 4 S',) soak for 2 minutes, then pull it out, then wash it with water and dry it. Then perform a neutral salt spray test according to JIS Z2 3 7 1 and measure until it forms 1%. The length of time required for white rust. The evaluation criteria are as follows: double circle: 240 hours φ or longer, circle: less than 120 to 24 hours, triangle: less than 72-120 hours, cross: less than 72 hours. (2) Tape peeling resistance, a tape (No. 9510 silk tape manufactured by Silentec Corp.; rubber type adhesive) was adhered to a resin-coated metal plate. In a constant temperature and humidity device, at 40 ° C, The metal plate was stored in a 98% RH atmosphere for 24 hours. Then, the tape was peeled off from the tape according to ΠSK 5400 to determine the residual area ratio of the film. The evaluation criteria were as follows: double circle: film retention ratio 100%, circle: film retention Ratio 9 0 - 9 9 %, triangle: film retention ratio 8 9 - 70%, cross: thin - 20- (17) 12552 25 Membrane retention ratio is 70% or lower. (3) Dynamic friction coefficient In order to evaluate the lubricity of the resin-coated metal sheet, the sliding test apparatus is used to measure the sliding force at a pulling speed of 5.4 MPa and a drawing speed of 300 mm/min. The load, from which the coefficient of dynamic friction was calculated. Experimental Example 1 (Effect of the type and amount of organic base and metal salt) | Using an electrogalvanized steel sheet (a coating amount of Zn of 20 g/m2, a thickness of 0.8 mm) as a metal Plate material. To prepare the emulsion composition, 626 parts by mass (hereinafter referred to as "parts") of water, 160 parts of ethylene/acrylic acid copolymer (20% by mass of acrylic acid, 300% melt index (MI)) were placed in an autoclave. Further, an organic base and a metal compound were added in various amounts as shown in Table 1 at 150 ° C, 5 Pa atmosphere under high-speed stirring to form an ethylene/acrylic acid copolymer emulsion. Subsequently, in the obtained emulsion. And the amount of 4,4'-bis(cycloethylimine) based on the solid content (φ when the solid content of the emulsion composition is taken as 1% by mass as the following:) Alkylcarbonylamino)diphenyl (''CHEMITITE DZ-22E"; ''CHEMITITE' is a trade name; produced by NIPPON SHOKUBAI Co., Ltd.) as a crosslinking agent. In the obtained mixture, the amount is added under stirring based on the solid content of 5 % by mass of a glycidyl group-containing compound (''EPICLON CR5L' is hereinafter referred to as CR5L: "EPICLON" is a trade name; manufactured by DAINIPPON INK AND CHEMICALS Inc.) as another - 21 - (18) 1255225 The crosslinking agent (external crosslinking agent) was added in an amount of 30% by mass based on the solid content. The cerium oxide particles having a particle diameter of 10 to 20 nm (nsN0WTECHS 40', manufactured by NISSAN CHEMICAL INDUSTRIES Ltd.), and the softening point of the amount of 5% by mass based on the solid content of 1,200 ° C and the average particle diameter A spherical polyethylene crucible of 1 // m was prepared to prepare each emulsion composition. Each composition was applied to one side of a galvanized steel sheet by a wire bar coater, heated at a plate temperature of 90 ° C and dried for 1 minute. Thus, a steel sheet coated with a tree φ grease was produced, in which a resin film having a coating amount of 1.0 g/mm 2 was formed. Their respective evaluation results are shown in Table 1.

- 22- (19)1255225

Table 1

Type of amine and its amount 1 > (Mole%) Type of metal salt and its amount 1 > (Mole%) Corrosion-resistant tape peeling resistance after degreasing 1 Triethylamine 20 NaOH 15 ◎ ◎ 2 Triethylamine 40 NaOH 15 ◎ ◎ 3 Triethylamine 60 NaOH 1 5 ◎ ◎ 4 Triethylamine 70 NaOH 15 ◎ ◎ 5 Triethylamine 80 NaOH 15 〇 ◎ 6 Triethylamine 40 NaOH 2 〇〇 7 Triethylamine 40 NaOH 5 ◎ 〇 8 Diethyl cumin 40 NaOH 10 ◎ ◎ 9 Triethylamine 40 NaOH 20 ◎ ◎ 10 Triethylamine 40 NaOH 30 ◎ ◎ 11 Triethylamine 40 NaOH 40 〇 ◎ 1 2 Triethylamine 20 NaOH 2 〇 〇13 Triethylamine 80 NaOH 40 〇◎ 14 Triethylamine 20 NaOH 40 〇◎ 15 Triethylamine 80 NaOH 2 〇〇16 Triethylamine 40 KOH 15 〇〇17 Triethylamine 40 LiOH 15 〇〇18 Triethylamine 40 NaOH 1 Δ X 19 Triethylamine 40 NaOH 45 Δ 〇 20 Triethylamine 18 NaOH 15 Δ Δ 2 1 Triethylamine 85 NaOH 15 Δ Δ 22 Tetramethyl _^ Amino guanidine 20 NaOH 15 ◎ 〇23 Sijia Methylaminomethane 40 NaOH 15 ◎ ◎ 24 tetramethyldiaminomethane 60 NaOH 15 ◎ ◎ 25 tetramethyldiaminomethane 8 0 NaOH 15 ◎ 〇26 ammonia 40 NaOH 15 Δ X 27 ethylenediamine 40 NaOH 15 Δ X 28 monoethanolamine 40 NaOH 1 5 XX 29 diethanolamine 40 NaOH 15 XX 30 ammonia 60 NaOH 15 XX 1), 2): Mohr %/ per mole of ethylene-acrylic acid copolymer carboxy-23-(20) 1255225 Experimental Example 2 (Effect of crosslinking agent amount) Each of the resin-coated steel sheets was obtained in the same manner as Experimental Example 1. However, the amount of triethylamine used was kept fixed at 40%, while the amount of NaOH was kept fixed at 15%, and the amount of "CHEMITITE DZ_22E" was changed as shown in Table 2. Then, the characteristics of each of the resin-coated steel sheets were evaluated, and the results are shown in Table 2.

Table 2 No. DZ-22E Mixed Concentration 1 > (% by mass) Corrosion-resistant tape peeling resistance after degreasing 3 1 1 〇〇 32 3 ◎ 〇 33 5 ◎ ◎ 34 10 ◎ ◎ 3 5 15 〇〇 3 6 20 〇〇3 7 0.3 X Δ 3 8 25 XX 1 ): concentration in the solid content of the emulsion composition. Experimental Example 3 (Effect of cerium oxide particles) Each of the resin coatings was prepared in the same manner as in Experimental Example 2. The steel sheet was coated with -24-(21) 1255225, except that the amount of the crosslinking agent was the same as in Experimental Example 1, and the particle size and mixed concentration of the cerium oxide particles were changed as shown in Table 3. Then, the characteristics of each of the resin-coated steel sheets were evaluated, and the results are shown in Table 3.

Table 3 Corrosion-resistant tape peeling resistance particle size after degreasing of bismuth dioxide particles (nm) Mixed concentration 1 > (% by mass) 3 9 4 to 6 30 ◎ ◎ 40 10 to 20 30 ◎ ◎ 4 1 30 to 50 30 〇 ◎ 42 40 to 200 30 〇 ◎ 43 10 to 20 5 〇〇 44 10 to 20 10 〇〇 45 10 to 20 15 〇〇 46 10 to 20 20 ◎ ◎ 47 10 to 20 26 ◎ ◎ 48 1 0 to 20 30 ◎ ◎ 49 1 0 to 20 35 ◎ ◎ 50 10 to 20 40 〇〇 5 1 10 to 20 3 Δ Δ 52 10 to 20 45 Δ Δ 53 1 or less 30 〇〇 54 200 or more 30 Δ Δ 1): Concentration in the solid content of the emulsion composition - 25 - (22) (22) 1255225 Experimental Example 4 (effect of ruthenium) Each resin-coated one was prepared in the same manner as in Example 2 The steel sheet 'only the particle size and the mixed concentration of the silica sand particles were the same as in Experimental Example 1, and the particle diameter, mixing concentration and softening temperature of the spherical polyethylene crucible were changed as shown in Table 4. Then, the characteristics of each of the resin-coated steel sheets were evaluated, and the results are shown in Table 4.

-26- (23)1255225 Table 4

No. Spherical polyethylene wax dynamic friction coefficient Corrosion-resistant tape after degreasing 离ί] Detached particle size (// 111 ) Mixed concentration 1 ] (% by mass) Softening temperature (°C) 55 1 .0 0.5 120 0.085 ◎ ◎ 56 1 .0 1 120 0.070 ◎ ◎ 57 1.0 5 120 0.065 ◎ ◎ 58 1.0 10 120 0.065 ◎ ◎ 59 1 .0 15 120 0.065 ◎ ◎ 60 1 .0 20 120 0.065 〇〇6 1 1 .0 0.3 120 0.125 ◎ ◎ 62 1.0 25 120 0.065 Δ Δ 63 0.1 5 120 0.085 ◎ ◎ 64 0.3 5 120 0.065 ◎ ◎ 65 0.5 5 120 0.065 ◎ ◎ 66 1 .0 5 120 0.065 ◎ ◎ 67 1.5 5 120 0.077 ◎ ◎ 68 3.0 5 120 0.085 〇〇69 <0.1 5 120 0.248 ◎ ◎ 70 3.5 5 120 0.125 Δ Δ 7 1 1.0 5 80 0.068 〇 ◎ 72 1 .0 5 100 0.064 ◎ ◎ 73 1.0 5 120 0.065 ◎ ◎ 74 1.0 5 140 0.072 ◎ ◎ 75 1.0 5 70 0.070 Δ Δ 76 1.0 5 1 50 0.262 Δ ◎ 1 ): Concentration in solid content of the emulsion composition -27-(24) (24) 1255225 The present invention is described in terms of preferred examples. However, it will be apparent to those skilled in the art that many variations of these specific embodiments are possible. These different variations are also within the scope of the invention and the claimed patent application.

-28-

Claims (1)

1255225 (1) 10. Patent application scope 1. A resin-coated metal plate comprising: a metal plate; and a resin film coated on a surface of the metal plate, the resin film being obtained from an emulsion composition The emulsion composition comprises: an ethylene/unsaturated carboxylic acid copolymer as a main component; an amine in an amount of 0.2-0.8 mol per mol of the carboxyl group contained in p per mole of the ethylene/unsaturated residual acid copolymer. , the amine has a boiling point of 10 ° C or lower monovalent metal compound, the amount of which is 0.02-0.4 mol per carboxy group contained in the ethylene / unsaturated carboxylic acid copolymer per mole; and cross-linking An agent in an amount of from 1 to 20% by mass per 100% by mass of the solids content of the emulsion composition, the crosslinking agent having two or more functional groups capable of reacting with a carboxyl group contained in the ethylene/unsaturated carboxylic acid copolymer And wherein the emulsion composition does not substantially contain a φ amine having a boiling point above 100 ° C and does not substantially contain ammonia. 2. The resin-coated metal sheet of claim 1, wherein in the ethylene/unsaturated carboxylic acid copolymer, 10 to 40% by mass of the unsaturated carboxylic acid is copolymerized. 3. A resin-coated metal plate according to claim 1, wherein the amine having a boiling point of 1 oo ° C or lower is triethylamine. 4. The resin-coated metal sheet according to claim 1, wherein an average particle diameter of -20 Onm is contained in an amount of from 5 to 40% by mass per 100% by mass of the emulsion composition solid content. The cerium oxide particles. -29- (2) 1255225 5 A resin-coated metal sheet according to the first aspect of the patent application, wherein a spherical content of 0.5 to 20% by mass per 100% by mass of the emulsion composition solid content is contained. Polyethylene wax. 6. A resin-coated metal sheet according to claim 1, wherein a chromium film is not formed on the metal sheet. 7. A method of manufacturing a resin-coated metal sheet according to the first aspect of the invention, comprising the steps of: preparing the emulsion composition; coating the emulsion composition on a metal plate; and heating and drying the A metal plate to which the emulsion composition is applied. 8. The method of claim 7, wherein in the heating and drying step, at a temperature at which a reaction between the crosslinking agent and the carboxyl group contained in the ethylene/unsaturated carboxylic acid copolymer is allowed to proceed This heating and drying are carried out. 9. The method of claim 7, wherein in the coating step φ, the emulsion composition is applied such that the amount of the resin film applied after the heating and drying steps becomes 0.2 to 2.5 g/m2. -30-