JP2006272765A - Resin coated metal sheet - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a resin coated metal sheet equipped with a resin film having excellent corrosion resistance and further having other excellent characteristics, concretely excellent ablation resistance, the adhesion with a coating film, conductivity and alkali degreasing resistance. <P>SOLUTION: The resin coated metal sheet comprising the resin film is obtained from a resin composition comprising an aqueous liquid of a carboxyl group-containing polyurethane resin and an aqueous dispersion of an ethylene/unsaturated carboxylic acid copolymer, wherein the resin composition comprises at least one kind of a chelating agent selected from the group consisting of EDTA, DTPA, HEDP, EDTMP, NTA, HEDTA and salts of them in an amount of 0.1-5 pts.mass per 100 pts.mass of the solid component of the resin composition. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a resin-coated metal plate, and more particularly, to a chromium-free resin-coated metal plate excellent in corrosion resistance, abrasion resistance, adhesion to other coating films, conductivity and alkali degreasing resistance. .

  As materials used for automobiles, home appliances, and building materials, zinc-plated steel sheets such as electrogalvanized steel sheets and hot-dip galvanized steel sheets, or inorganic materials that have been chromated on the galvanized steel sheets for the purpose of further improving corrosion resistance Many surface-treated steel sheets are used. However, due to the recent increase in environmental awareness, there is an increasing demand for steel sheets not subjected to chromate treatment.

  As means for improving corrosion resistance in place of such chromate treatment, for example, methods using tannic acid have been proposed (for example, Patent Documents 1 and 2). However, these methods have failed to obtain sufficient corrosion resistance.

  Therefore, surface-treated steel sheets provided with a film mainly composed of a high molecular weight chelating agent have been proposed (Patent Documents 3 and 4). In these documents, it is proposed to use a high molecular weight chelating agent as the main component of the film. For comparison with these, low molecular weight chelating agents such as tannic acid and ethylenediaminetetraacetic acid (EDTA) are insufficient. It is listed as a comparative example that shows only corrosion resistance.

However, since the characteristics of the films described in Patent Documents 3 and 4 depend on the type of the high molecular weight chelating agent that is the main component, it is difficult to impart further characteristics other than corrosion resistance to the film. Further, in Patent Document 4, it is proposed that a chelate-forming group is imparted to an organic polymer matrix in order to produce a high-molecular-weight chelating agent, but a polymer reaction for imparting such a chelate-forming group is generally performed. As a result, the manufacturing cost of the surface-treated steel sheet increases.
JP-A-51-71233 JP 2001-89868 A Japanese Patent Laid-Open No. 11-158649 JP-A-11-166151

  Accordingly, an object of the present invention is to provide a resin film having excellent corrosion resistance and further excellent characteristics, specifically excellent abrasion resistance, adhesion to a coating film, conductivity and alkali degreasing resistance. It is providing the resin coating metal plate provided.

  The resin-coated metal plate of the present invention that has solved the above problems is a resin obtained from a resin composition containing a carboxyl group-containing polyurethane resin aqueous solution and an ethylene-unsaturated carboxylic acid copolymer aqueous dispersion. A resin-coated metal plate provided with a coating, wherein the resin composition comprises ethylenediaminetetraacetic acid (EDTA), diethylenetriaminepentaacetic acid (DTPA), hydroxyethylidene diphosphonic acid (HEDP), N, N, N ′, N ′ -One or more chelating agents selected from the group consisting of tetrakis (phosphonomethyl) ethylenediamine (EDTMP), nitrilotriacetic acid (NTA) and hydroxyethylethylenediaminetetraacetic acid (HEDTA), and salts thereof; 0.1 to 5 parts by mass in the proportion of 100 parts by mass of solid content The features.

  Preferred among the chelating agents are (1) a salt form containing Na ions, (2) at least one metal ion containing Na ions and selected from Mg, Ca, Co, Zn, Mn and Fe ions. (3) a salt form containing an amine ion or ammonium ion, or (4) a salt containing an amine ion or ammonium ion and selected from Na, Mg, Ca, Co, Zn, Mn and Fe ions A salt form of EDTA, DTPA, HEDP, EDTMP, NTA or HEDTA containing at least one metal ion.

  In a preferred embodiment of the present invention, the resin composition comprises 5-45 parts by mass of a carboxyl group-containing polyurethane resin aqueous solution and an ethylene-unsaturated carboxylic acid copolymer aqueous dispersion as a nonvolatile resin component, and an average. It contains 55 to 95 parts by mass of silica particles having a particle diameter of 4 to 20 nm so that the total amount becomes 100 parts by mass, and the silane coupling agent is further added at a ratio of 5 to 25 parts by mass with respect to 100 parts by mass in total. The blending ratio of the nonvolatile resin component (PU) of the polyurethane resin aqueous liquid and the nonvolatile resin component (EC) of the ethylene-unsaturated carboxylic acid copolymer aqueous dispersion is PU: EC in a mass ratio. = 9: 1 to 2: 1.

  The carboxyl group-containing polyurethane resin is obtained by subjecting a urethane prepolymer to a chain extension reaction with a chain extender. The polyisocyanate component constituting the urethane prepolymer includes tolylene diisocyanate, diphenylmethane diisocyanate and dicyclohexylmethane. Using at least one selected from the group consisting of diisocyanates, and using all of 1,4-cyclohexanedimethanol, polyether polyol and polyol having a carboxyl group as the polyol component constituting the urethane prepolymer Is preferred. The chain extender is preferably, for example, ethylenediamine or hydrazine. The mass ratio of the 1,4-cyclohexanedimethanol and the polyether polyol is preferably 1,4-cyclohexanedimethanol: polyether polyol = 1: 1 to 1:19. As the polyether polyol, for example, polyoxypropylene glycol or polytetramethylene ether glycol is suitable. The acid value of the carboxyl group-containing polyurethane resin is preferably 10 to 60 mgKOH / g.

  As the aqueous dispersion of ethylene-unsaturated carboxylic acid copolymer used in the present invention, in addition to the ethylene-unsaturated carboxylic acid copolymer, 1 mol of the carboxyl group of the ethylene-unsaturated carboxylic acid copolymer is used. And an amine having a boiling point of 100 ° C. or less corresponding to 0.2 to 0.8 mol and 1 mol of carboxyl group of the ethylene-unsaturated carboxylic acid copolymer is equivalent to 0.02 to 0.4 mol. What contains the basic compound of a group 1 element is suitable. The ethylene-unsaturated carboxylic acid copolymer is preferably one in which 10 to 40% by mass of an unsaturated carboxylic acid component is copolymerized when the total amount of monomers of the copolymer is 100% by mass. As the amine having a boiling point of 100 ° C. or lower, for example, triethylamine is preferable.

The ethylene-unsaturated carboxylic acid copolymer aqueous dispersion further reacts with a carboxyl group when the nonvolatile resin component (EC) of the ethylene-unsaturated carboxylic acid copolymer aqueous dispersion is 100 parts by mass. It is also a preferred embodiment of the present invention to contain a crosslinking agent having 2 or more functional groups that can be used at a ratio of 1 to 20 parts by mass. Furthermore, the aqueous ethylene-unsaturated carboxylic acid copolymer dispersion is preferably substantially free of amine and ammonia having a boiling point of more than 100 ° C.

  As the silane coupling agent used in the present invention, for example, a silane coupling agent represented by the following chemical formula (1) is suitable.

（化学式（１）中、Ｒ¹：グリシドキシ基、Ｒ²、Ｒ³：低級アルコキシ基、Ｒ⁴：低級アルコキシ基または低級アルキル基、Ｘ：低級アルキレン基）

(In the chemical formula (1), R ¹ : glycidoxy group, R ² , R ³ : lower alkoxy group, R ⁴ : lower alkoxy group or lower alkyl group, X: lower alkylene group)

The adhesion amount of the resin film on the resin-coated metal plate of the present invention is preferably 0.05 to 1 g / m ² .

  According to the present invention, a resin-coated metal plate having excellent corrosion resistance can be obtained. In particular, it is provided with a film formed from a resin composition containing a small amount of a low molecular weight chelating agent such as EDTA or a salt thereof (0.1 to 5 parts by mass in 100 parts by mass of the solid content of the composition). It is surprising that the resin-coated metal sheet exhibits excellent corrosion resistance. This is because, conventionally, such a low molecular weight chelating agent has been considered to be insufficient in the effect of improving the corrosion resistance.

  Further, when a high molecular weight chelating agent that has been considered preferable for imparting corrosion resistance is mixed with a resin composition containing an organic resin or the like, problems such as gelation may occur, but EDTA or a salt thereof used in the present invention, etc. This low molecular weight chelating agent has good compatibility with other resin composition components, does not cause gelation, and can impart good corrosion resistance to the resin-coated metal plate.

  Furthermore, according to the present invention, in the resin composition, by adjusting the components other than the chelating agent such as EDTA and a salt thereof and the composition thereof to those of the above preferred embodiments, the resin coated metal sheet can be coated. Further preferred properties, i.e. adhesion to other coatings, abrasion resistance, electrical conductivity and alkali degreasing resistance can be imparted. Moreover, the corrosion resistance implement | achieved by the chelating agent can be further improved by using the resin composition of a preferable aspect.

BEST MODE FOR CARRYING OUT THE INVENTION

  The resin-coated metal plate of the present invention has, on at least one surface of a metal plate, one or more chelating agents selected from the group consisting of EDTA, DTPA, HEDP, EDTMP, NTA and HEDTA, and salts thereof, having a resin composition It is provided with a film formed from a resin composition containing 0.1 to 5 parts by mass in a proportion of 100 parts by mass of the solid content of the product. In the present invention, the solid content refers to a solid residue that remains on the metal plate as a film after evaporation of a volatile component (for example, water or an organic solvent) by heating and drying the resin composition. Therefore, the solid content includes a resin (including solid or liquid at room temperature), an inorganic solid (for example, silica), and the like.

  The low molecular weight chelating agents used in the present invention are EDTA, DTPA, HEDP, EDTMP, NTA and HEDTA, and salts thereof, and among these, using a chelating agent in a salt form is a resin composition containing an aqueous liquid From the viewpoint of solubility in products. The salt-form chelating agent in the present invention refers to a product obtained by neutralizing some or all of the plurality of acid functional groups contained in the chelating agent. Thus, for example, an EDTA salt is one in which only one of the four carboxyl groups is neutralized with a base such as NaOH (for example, a monosodium salt: EDTA · Na), and all carboxyl groups are neutralized with a base such as NaOH. The sum (for example, tetrasodium salt: EDTA · 4Na) is included. Further, in the salt form chelating agent, a part of the plurality of acid functional groups is neutralized with NaOH or the like, and another acid functional group is neutralized with an amine. Kirest M-50: EDTA · 2Na · amine salt) and the like.

  Preferred among the chelating agents in the salt form are (1) those containing Na ions (Na salts), (2) containing Na ions, and selected from Mg, Ca, Co, Zn, Mn and Fe ions. One containing at least one metal ion (a complex salt of Na and other metals), (3) One containing an amine ion or ammonium ion (amine or ammonium salt), or (4) An amine ion or ammonium ion And those containing at least one metal ion selected from Na, Mg, Ca, Co, Zn, Mn and Fe ions (a complex salt of amine or ammonium / metal).

  The chelating agent is commercially available from, for example, Kirest Co., Ltd., and as an EDTA chelating agent manufactured by Kirest Co., Ltd., Kirest Mg-40, Kirest M-50, Kirest OD, etc .; Examples include Cylest PC-45 and the like; Cylest PH-212 and Cylest PH-214 and the like as the HEDP system; Cylest HP and 540 as the EDTMP system; Cylest 70 and Cylest NTA as NTA; Cylest H and the like as HEDTA.

  Here, the mechanism by which a low molecular weight chelating agent such as EDTA or a salt thereof contributes to an improvement in corrosion resistance is not necessarily clear. However, for example, in the case of a zinc-based plated steel sheet, it elutes in the corrosive environment with these low molecular weight chelating agents. It is considered that metal ions such as Zn ions form a stable chelate compound, and this stable chelate compound covers a corroded portion, thereby preventing further corrosion.

  Content of low molecular weight chelating agents, such as EDTA and its salt, in the resin composition of this invention is 0.1-5 mass parts in the ratio occupied in 100 mass parts of solid content of a resin composition. When the content of the low molecular weight chelating agent is less than 0.1 parts by mass, the production of a stable chelate compound is insufficient, and the corrosion resistance is also insufficient. On the other hand, even if the low molecular weight chelating agent exceeds 5 parts by mass, the corrosion resistance tends to decrease. The reason why the corrosion resistance can be lowered by blending a large amount of low molecular weight chelating agent is not clear, but the chelating agent reacts with organic resin, crosslinking agent or silane coupling agent that can be included in the resin composition. This may affect the film forming property of the film. From the viewpoint of the film-forming property of the film and the adhesion to other coating films, the more preferable upper limit of the chelating agent content is 3 parts by mass in terms of the proportion in 100 parts by mass of the solid content of the resin composition. A preferable upper limit is 1 part by mass, and a more preferable lower limit of the chelating agent content is 0.3 part by mass.

  Examples of the aqueous carboxyl group-containing polyurethane resin liquid that can be used in the present invention include an aqueous dispersion in which a carboxyl group-containing polyurethane resin is dispersed in an aqueous medium, and an aqueous solution in which the carboxyl group-containing polyurethane resin is dissolved in an aqueous medium. Can be used. The aqueous medium may contain a trace amount of a hydrophilic solvent such as alcohol, N-methylpyrrolidone and acetone in addition to water.

  The carboxyl group-containing polyurethane resin is preferably obtained by chain extension reaction of a urethane prepolymer with a chain extender, and the urethane prepolymer is obtained by reacting, for example, a polyisocyanate component and a polyol component described later. can get. As the polyisocyanate component constituting the urethane prepolymer, at least one polyisocyanate selected from the group consisting of tolylene diisocyanate (TDI), diphenylmethane diisocyanate (MDI) and dicyclohexylmethane diisocyanate (hydrogenated MDI) is used. Is preferred. This is because by using such a polyisocyanate, a resin film having excellent corrosion resistance and reaction control stability can be obtained. In addition to the polyisocyanate, other polyisocyanates can be used as long as the corrosion resistance and the stability of reaction control are not lowered. However, the content of the polyisocyanate component is 70% by mass or more of the total polyisocyanate component. It is desirable to keep This is because when the content of the polyisocyanate component is less than 70% by mass, the corrosion resistance and the stability of reaction control tend to decrease. Examples of the polyisocyanate other than the polyisocyanate component include tetramethylene diisocyanate, hexamethylene diisocyanate, dodecane methylene diisocyanate, isophorone diisocyanate, xylene diisocyanate, and phenylene diisocyanate. The said polyisocyanate can be used individually or in mixture of 2 or more types.

  As the polyol component constituting the urethane prepolymer, all three kinds of polyols, preferably 1,4-cyclohexanedimethanol, polyether polyol, and polyol having a carboxyl group, are used. In a more preferred embodiment, all three types of polyol are diols. This is because by using such a polyol component, a resin film having excellent corrosion resistance and slidability can be obtained. Moreover, the rust prevention effect of the polyurethane resin obtained can be heightened by using 1, 4- cyclohexane dimethanol as a polyol component.

  The polyether polyol is not particularly limited as long as it has at least two hydroxyl groups in the molecular chain and the main skeleton is composed of alkylene oxide units. For example, polyoxyethylene glycol (simply “polyethylene”). Glycol ”), polyoxypropylene glycol (sometimes called simply“ polypropylene glycol ”), polyoxytetramethylene glycol (sometimes called simply“ polytetramethylene glycol ”or“ polytetramethylene ether glycol ”) And the like, and commercially available products can be used. Among the polyether polyols, it is preferable to use polyoxypropylene glycol or polytetramethylene ether glycol. The number of functional groups of the polyether polyol is not particularly limited as long as it is at least 2 or more, and may be, for example, trifunctional, tetrafunctional, or more polyfunctional.

  The polyether polyol can be obtained, for example, by adding an alkylene oxide such as ethylene oxide or propylene oxide using a compound having active hydrogen as an initiator. Examples of the compound having active hydrogen include diols such as propylene glycol and ethylene glycol, triols such as glycerin, trimethylolpropane, hexanetriol, and triethanolamine, tetraols such as diglycerin and pentaerythritol, and others, sorbitol, and sucrose. And phosphoric acid. At this time, if a diol is used as an initiator to be used, a bifunctional polyether polyol can be obtained, and if a triol is used, a trifunctional polyether polyol can be obtained. Polyoxytetramethylene glycol is obtained, for example, by ring-opening polymerization of tetrahydrofuran.

  As the polyether polyol, it is preferable to use a commercially available product having an average molecular weight of about 400 to 4000, for example. This is because the resin film is hard when the average molecular weight is less than about 400, and too soft when it exceeds 4000. The average molecular weight can be determined by measuring the OH value (hydroxyl value).

  In the present invention, it is also a preferable aspect that the mass ratio of 1,4-cyclohexanedimethanol and polyether polyol is 1,4-cyclohexanedimethanol: polyether polyol = 1: 1 to 1:19. It is because the rust prevention effect of the obtained polyurethane resin film can be further enhanced by using a certain ratio of 1,4-cyclohexanedimethanol having a rust prevention effect.

  The polyol having a carboxyl group that can be used in the present invention is not particularly limited as long as it has at least one carboxyl group and at least two hydroxyl groups. For example, dimethylolpropionic acid, dimethylolbutanoic acid are used. , Dihydroxypropionic acid, dihydroxysuccinic acid and the like.

  In addition to the three types of polyol components, other polyols can be used within a range that does not lower the corrosion resistance. In this respect, the content of the three types of polyol components is desirably 70% by mass or more of the total polyol components. This is because the corrosion resistance tends to decrease when the content of the three types of polyol components is less than 70% by mass. The polyol other than the above-described three types of polyol components is not particularly limited as long as it has a plurality of hydroxyl groups, and examples thereof include a low molecular weight polyol and a high molecular weight polyol. Here, the low molecular weight polyol is a polyol having an average molecular weight of about 500 or less. For example, ethylene glycol, diethylene glycol, triethylene glycol, 1,3-butanediol, 1,4-butanediol, neopentyl glycol, 1, Diols such as 6-hexanediol; and triols such as glycerin, trimethylolpropane, and hexanetriol.

  The high molecular weight polyol is a polyol having an average molecular weight exceeding about 500. For example, a condensed polyester polyol such as polyethylene adipate (PEA), polybutylene adipate (PBA), polyhexamethylene adipate (PHMA); poly-ε-caprolactone Lactone polyester polyols such as (PCL); polycarbonate polyols such as polyhexamethylene carbonate; and acrylic polyols.

  Moreover, the chain extender which carries out the chain extension reaction of the urethane prepolymer described above is not particularly limited, and examples thereof include polyamines, low molecular weight polyols and alkanolamines. As the low molecular weight polyol, the same ones as described above can be used. Examples of the polyamine include aliphatic polyamines such as ethylenediamine, propylenediamine, and hexamethylenediamine; tolylenediamine, xylylenediamine, diaminodiphenylmethane, and the like. Aromatic polyamines; alicyclic polyamines such as diaminocyclohexylmethane, piperazine and isophoronediamine; hydrazines such as hydrazine, succinic dihydrazide, adipic dihydrazide and phthalic dihydrazide. Among these, it is preferable to use ethylenediamine and / or hydrazine as a chain extender component. Examples of the alkanolamine include diethanolamine and monoethanolamine.

  A known method can be employed for the preparation of an aqueous liquid containing a carboxyl group-containing polyurethane resin that can be used in the present invention. For example, the carboxyl group of a carboxyl group-containing urethane prepolymer can be neutralized with a base in an aqueous medium. There are a method of emulsifying and dispersing to chain extension reaction, and a method of emulsifying and dispersing a carboxyl group-containing polyurethane resin in the presence of an emulsifier with a high shear force to cause chain extension reaction. Hereinafter, based on the method of neutralizing the carboxyl group of a carboxyl group-containing urethane prepolymer with a base and emulsifying and dispersing it in water, a method for preparing an aqueous polyurethane resin solution will be described, but the present invention is limited to such a method. It is not a thing.

  First, a relatively low molecular weight carboxyl group-containing isocyanate group-terminated urethane prepolymer is prepared by using the above-described polyisocyanate and the above-described polyol so that the isocyanate group becomes excessive in the NCO / OH ratio. Although the temperature which synthesize | combines a urethane prepolymer is not specifically limited, It can synthesize | combine at the temperature of 50-200 degreeC. A known catalyst can be used for the synthesis of the urethane prepolymer. Examples of the catalyst include monoamines such as triethylamine and N, N-dimethylcyclohexylamine; N, N, N ′, N′-tetramethylethylenediamine, N, N, N ′, N ″, N ″ -pentamethyldiethylenetriamine Polyamines such as 1,8-diazabicyclo [5.4.0] -7-undecene (DBU), cyclic diamines such as triethylenediamine, and tin-based catalysts such as dibutyltin dilaurate and dibutyltin diacetate .

  In synthesizing the urethane prepolymer, a one-shot method may be employed, or a prepolymer method may be employed. The one-shot method is a method in which polyisocyanate and polyol are reacted together, and the prepolymer method is a method in which polyisocyanate and polyol are reacted in multiple stages. For example, first, a low molecular weight to medium molecular weight urethane is used. After synthesizing the prepolymer, it is a method of further increasing the molecular weight.

  In the present invention, for example, an embodiment in which polyisocyanate and all of the three types of polyol are reacted together; polyisocyanate and polyether polyol in the three types of polyol component are first reacted; A mode in which 4-cyclohexanedimethanol and a polyol having a carboxyl group are further reacted; or, in the essential polyol component, a polyether polyol and 1,4-cyclohexanedimethanol are first reacted, and then a carboxyl group is The urethane prepolymer can be synthesized by appropriately selecting the mode of reacting with the polyol having it.

  In preparing the carboxyl group-containing isocyanate group-terminated urethane prepolymer, it is also a preferred embodiment to use a solvent from the viewpoint of adjusting the viscosity and improving the emulsifying dispersibility of the prepolymer. As the solvent, it is preferable to use a solvent that is inert to the isocyanate group and has a relatively high hydrophilicity. For example, N-methylpyrrolidone, acetone, ethyl acetate, methyl ethyl ketone, N, N-dimethylformamide, and the like. N-methylpyrrolidone is preferably used. This is because N-methylpyrrolidone is highly soluble in a polyol having a carboxyl group and can uniformly carry out a reaction for preparing an isocyanate group-terminated urethane prepolymer. In addition, the reaction of a urethane prepolymer can obtain | require a reaction rate by calculating | requiring an isocyanate group density | concentration, for example by the dibutylamine titration method.

  After completion of the urethane prepolymer reaction, the resulting carboxyl group-containing isocyanate group-terminated urethane prepolymer can be emulsified and dispersed in water by neutralization with a base. The neutralizing agent is not particularly limited, but ammonia; tertiary amines such as triethylamine and triethanolamine; alkali metal hydroxides such as sodium hydroxide and potassium hydroxide can be used; Preferably triethylamine is used.

  After emulsifying and dispersing the carboxyl group-containing isocyanate group-terminated urethane prepolymer, a chain extension reaction can be carried out in water using a chain extender such as polymian. The chain extension reaction can be appropriately performed before emulsification dispersion, simultaneously with emulsification dispersion, or after emulsification dispersion, depending on the reactivity of the chain extender used.

  The acid value of the carboxyl group-containing polyurethane resin that can be used in the present invention is desirably 10 mgKOH / g or more and 60 mgKOH / g or less. This is because when the acid value is less than 10 mgKOH / g, the stability of the aqueous polyurethane resin dispersion is lowered. Moreover, when an acid value exceeds 60 mgKOH / g, there exists a tendency for the corrosion resistance of the resin film obtained to fall. The acid value is measured according to JIS-K0070.

  The ethylene-unsaturated carboxylic acid copolymer aqueous dispersion used in the present invention is not particularly limited as long as it is a liquid in which the ethylene-unsaturated carboxylic acid copolymer is dispersed in an aqueous medium. The ethylene-unsaturated carboxylic acid copolymer is a copolymer of ethylene and an ethylenically unsaturated carboxylic acid. Examples of the unsaturated carboxylic acid include (meth) acrylic acid, crotonic acid, isocrotonic acid, maleic acid, fumaric acid, itaconic acid, etc., and one or more of these and ethylene are known at a high temperature and high pressure polymerization method. A copolymer can be obtained by polymerizing with. As the copolymer, a random copolymer is most preferable, but a block copolymer or a copolymer in which an unsaturated carboxylic acid moiety is grafted may be used. As the unsaturated carboxylic acid, (meth) acrylic acid is suitable. In addition, an olefin monomer such as propylene or 1-butene may be used instead of a part of ethylene, and another known vinyl monomer may be partially copolymerized as long as the object of the present invention is not impaired. About 10% by mass or less).

  The ethylene-unsaturated carboxylic acid copolymer is preferably one in which an unsaturated carboxylic acid component is copolymerized in an amount of 10 to 40% by mass when the total amount of monomers of the copolymer is 100% by mass. . When the amount of unsaturated carboxylic acid is less than 10% by mass, there are few carboxyl groups that serve as a base point for intermolecular association by ion clusters or a cross-linking point with a cross-linking agent, so that the film strengthening effect is not exhibited, and the corrosion resistance after the degreasing process. May not improve, and the emulsification stability of the aqueous dispersion is lowered. A more preferable lower limit of the unsaturated carboxylic acid is 15% by mass. On the other hand, when the unsaturated carboxylic acid exceeds 40% by mass, the corrosion resistance and water resistance of the resin film are lowered, and the corrosion resistance after the alkaline degreasing step is lowered, which is not preferable. A more preferred upper limit is 25% by mass.

  The ethylene-unsaturated carboxylic acid copolymer that can be used in the present invention has a carboxyl group, and an aqueous dispersion can be obtained by neutralizing the carboxyl group with an organic base or a metal ion. .

  It is preferable to use an amine having a boiling point of 100 ° C. or lower as the organic base. Amines having a boiling point exceeding 100 ° C. tend to remain in the resin film on the metal plate when the resin composition is dried, and the water absorption of the resin film increases, resulting in a decrease in corrosion resistance. Therefore, it is preferable that the amine-unsaturated carboxylic acid copolymer aqueous dispersion that can be used in the present invention does not contain amines having a boiling point exceeding 100 ° C. Moreover, since the addition effect of ammonia was not recognized, it is preferable that ammonia is not contained. As the boiling point, a boiling point under atmospheric pressure is adopted.

  The ethylene-unsaturated carboxylic acid copolymer aqueous dispersion corresponds to 0.2 to 0.8 mol (20 to 80 mol%) with respect to 1 mol of the carboxyl group of the ethylene-unsaturated carboxylic acid copolymer. Of a group 1 element corresponding to 0.02 to 0.4 mol (2 to 40 mol%) with respect to 1 mol of an amine having a boiling point of 100 ° C or less and a carboxyl group of the ethylene-unsaturated carboxylic acid copolymer. It is preferable to contain a basic compound.

  Specific examples of the amine having a boiling point of 100 ° C. or less include tertiary amines such as triethylamine, N, N-dimethylbutylamine, N, N-dimethylallylamine, N-methylpyrrolidine, tetramethyldiaminomethane, and trimethylamine; N-methylethylamine Secondary amines such as propylamine, t-butylamine, sec-butylamine, isobutylamine, 1,2-dibutylpropylamine, and 3-pentylamine. Two or more kinds can be mixed and used. Of these, tertiary amines are preferred, and triethylamine is the most preferred.

  The amount of the amine having a boiling point of 100 ° C. or less may be in the range of 0.2 to 0.8 mol (20 to 80 mol%) with respect to 1 mol of the carboxyl group in the ethylene-unsaturated carboxylic acid copolymer. preferable. This is because the corrosion resistance is better in this range. When the amine having a boiling point of 100 ° C. or less is less than 0.2 mol, it is considered that the particle size of the resin particles of the aqueous dispersion is increased, and the effect of improving the corrosion resistance and the like is lowered. In addition, use of an amine having a boiling point of more than 0.8 mol and a boiling point of 100 ° C. or less is not preferable because the aqueous dispersion may thicken and gel. The upper limit of the amount of the amine is more preferably 0.6 mol, still more preferably 0.5 mol, and the lower limit of the amount of the amine is more preferably 0.3 mol.

  In the present invention, it is preferable to use a basic compound of a Group 1 element for neutralization in addition to the amine having a boiling point of 100 ° C. or less. Effective for improving solvent resistance and film hardness. The basic compound of the Group 1 element preferably contains one or more metals selected from sodium, potassium, and lithium, and a hydroxide, carbonate, or oxide of these metals is preferable. Among these, NaOH, KOH, LiOH and the like are preferable, and NaOH has the best performance and is preferable.

  The amount of the basic compound of the Group 1 element is in the range of 0.02 to 0.4 mol (2 to 40 mol%) with respect to 1 mol of the carboxyl group in the ethylene-unsaturated carboxylic acid copolymer. It is preferable. If the amount of the basic compound of the Group 1 element is less than 0.02 mol, the emulsion stability becomes insufficient, but if it exceeds 0.4 mol, the hygroscopicity of the resulting resin film (especially hygroscopicity with respect to an alkaline solution). ) Increases and the corrosion resistance after the degreasing process tends to decrease, which is not preferable. More preferably, the lower limit of the basic compound amount of the Group 1 element is 0.03 mol, and a more preferable lower limit is 0.1 mol, and the more preferable upper limit of the amount of the basic compound of the Group 1 element is 0.3 mol, A preferable upper limit is 0.2 mol.

  The preferred ranges of the amounts of the amines having a boiling point of 100 ° C. or less and the basic compounds of the Group 1 elements are as described above, and these are all carboxyl groups in the ethylene-unsaturated carboxylic acid copolymer. It is used to neutralize and make it aqueous. If the total amount (neutralization amount) is too large, the viscosity of the aqueous dispersion may rapidly increase and solidify, and a large amount of energy is required to volatilize excess alkali which may cause a decrease in corrosion resistance. Is not preferable. However, if the neutralization amount is too small, the emulsifiability is inferior, which is not preferable. Therefore, the total amount of the amine having a boiling point of 100 ° C. or less and the basic compound of the Group 1 element is 0.3 to 1.0 mol with respect to 1 mol of the carboxyl group in the ethylene-unsaturated carboxylic acid copolymer. It is preferable to set it as the range.

  An aqueous dispersion of an ethylene-unsaturated carboxylic acid copolymer that can be used in the present invention is obtained by combining and emulsifying an amine having a boiling point of 100 ° C. or less and a basic compound of a Group 1 element. Is dispersed in an aqueous medium in the form of extremely small fine particles (oil droplets) of 5 to 50 nm. For this reason, it is presumed that the film forming property of the obtained resin film, the adhesion to the metal plate, the densification of the film are achieved, and the corrosion resistance is further improved. The aqueous medium may contain a hydrophilic solvent such as alcohol or ether in addition to water. The particle size of the resin particles in the aqueous dispersion can be measured by a laser diffraction method using, for example, a light scattering photometer (manufactured by Otsuka Electronics Co., Ltd.).

  In the neutralization step (aqueous step) of an ethylene-unsaturated carboxylic acid copolymer with an amine having a boiling point of 100 ° C. or less and a basic compound of a Group 1 element, the basicity of the amine having a boiling point of 100 ° C. or less and the Group 1 element It is desirable to add the compound to the copolymer almost simultaneously or to add an amine having a boiling point of 100 ° C. or lower first. The reason is not clear, but if an amine having a boiling point of 100 ° C. or lower is added later, the effect of improving the corrosion resistance may be insufficient.

  As a method for preparing an aqueous dispersion of an ethylene-unsaturated carboxylic acid copolymer that can be used in the present invention, an ethylene-unsaturated carboxylic acid copolymer is put together with an aqueous medium into, for example, a homogenizer device or the like. The mixture is heated to 70 to 250 ° C., and an amine having a boiling point of 100 ° C. or less and a basic compound of a Group 1 element are appropriately added in the form of an aqueous solution or the like (an amine having a boiling point of 100 ° C. or less is added first, or a boiling point of 100 For example, an amine having a temperature of 0 ° C. or less and a basic compound of a Group 1 element are added almost simultaneously), stirring with high shearing force, and the like.

  The resin composition that can be used in the present invention is 5 to 45 parts by mass of the above carboxyl group-containing polyurethane resin aqueous solution and ethylene-unsaturated carboxylic acid copolymer aqueous dispersion as a nonvolatile resin component, and A total of 100 mass parts of 55-95 mass parts of silica particles are contained, and a silane coupling agent is further contained in a ratio of 5-25 mass parts with respect to the total of 100 mass parts. In the present invention, by using a carboxyl group-containing polyurethane resin and an ethylene-unsaturated carboxylic acid copolymer in combination, in addition to corrosion resistance, a resin-coated metal plate excellent in coating film adhesion, abrasion resistance and alkali degreasing resistance Is obtained. Moreover, when the amount of the non-volatile resin component is too small, the corrosion resistance, alkali degreasing resistance, and coating film adhesion tend to decrease. On the other hand, if the amount of the non-volatile resin component is too large, abrasion resistance and conductivity tend to decrease. From such a viewpoint, the resin composition contains 20 parts by mass or more, more preferably 25 parts by mass of a carboxyl group-containing polyurethane resin aqueous solution and an ethylene-unsaturated carboxylic acid copolymer aqueous dispersion as a nonvolatile resin component. The content is 40 parts by mass or less, more preferably 35 parts by mass or less. Here, the nonvolatile resin component of the polyurethane aqueous liquid is the carboxyl group-containing polyurethane resin described above, and the nonvolatile resin component of the ethylene-unsaturated carboxylic acid copolymer aqueous dispersion is the ethylene-unsaturated carboxylic acid described above. It is an acid copolymer. The non-volatile resin component can be measured by a method known in the technical field of aqueous solutions or aqueous dispersions. For example, an evaporation residue when the aqueous solution or aqueous dispersion is heated and dried at 100 ° C. to 130 ° C. for 1 to 3 hours. Minutes.

  The blending ratio of the carboxyl group-containing polyurethane resin (PU) and the ethylene-unsaturated carboxylic acid copolymer (EC) is PU: EC = 9: 1 to 2: 1 by mass ratio, preferably 6. 5: 1 to 3.3: 1, more preferably 5: 1. As a blending ratio of the non-volatile component (PU) of the polyurethane resin aqueous liquid and the non-volatile component (EC) of the ethylene-unsaturated carboxylic acid copolymer aqueous dispersion, when the PU ratio is larger than 9: 1, the corrosion resistance, Alkali resistance tends to decrease. On the other hand, if the PU ratio is less than 2: 1, the abrasion resistance decreases.

  The resin composition that can be used in the present invention is a non-volatile resin component of 5 to 45 parts by mass of the above-described aqueous carboxyl group-containing polyurethane liquid and ethylenic-unsaturated carboxylic acid copolymer aqueous dispersion. 55 parts by mass or more, preferably 60 parts by mass or more, and 95 parts by mass or less, preferably 80 parts by mass or less, more preferably 75 parts by mass or less of silica particles (however, with the nonvolatile resin component) The total amount is 100 parts by mass).

  The silica particles impart conductivity and coating film adhesion to the resulting resin film, increase the hardness of the film to improve abrasion resistance, and improve corrosion resistance. When the content of silica particles is less than 55 parts by mass, conductivity and abrasion resistance tend to be lowered. Moreover, when content of a silica exceeds 95 mass parts, there exists a tendency for the film forming property of a resin film to fall and for corrosion resistance to fall. In order to maximize the effect of the silica particles, the average particle size of the silica particles is preferably in the range of 4 to 20 nm. The smaller the average particle size of the silica particles, the better the corrosion resistance of the resin film. However, when the average particle size is less than about 4 nm, the effect of improving the corrosion resistance tends to be saturated, and the stability of the resin composition decreases. May become easy to gel. On the other hand, if the average particle diameter of the silica particles exceeds 20 nm, the film-forming property of the resin film is lowered, and the corrosion resistance, coating film adhesion, and alkali degreasing resistance may be lowered.

  As a method for measuring the average particle diameter of the silica particles, it is preferable to employ a Sears method (4 to 6 nm) or a BET method (4 to 20 nm). In the case of chain silica, it is preferable to employ a dynamic light scattering method. Such silica particles are generally known as colloidal silica. In the present invention, for example, “XS”, “SS”, “40” of “Snowtex” series (colloidal silica manufactured by Nissan Chemical Industries, Ltd.), “N”, “UP” and the like can be preferably used.

  The resin composition that can be used in a preferred embodiment of the present invention contains a silane coupling agent. The silane coupling agent is used for improving abrasion resistance, coating film adhesion, corrosion resistance, and the like, and improving adhesion between the metal plate and the resin film formed on the metal plate.

  The content of the silane coupling agent in the resin composition is the total mass part of the nonvolatile resin component and the silica particles of the carboxyl group-containing polyurethane aqueous liquid and the ethylenic-unsaturated carboxylic acid copolymer aqueous dispersion described above. Is 100 parts by mass, 5 parts by mass or more, preferably 7 parts by mass or more, and 25 parts by mass or less, preferably 15 parts by mass or less. If the content of the silane coupling agent is too small, the reactivity between the silica particles, the above-mentioned carboxyl group-containing polyurethane resin and the ethylenic-unsaturated carboxylic acid copolymer is lowered, and abrasion resistance and coating film adhesion are reduced. Corrosion resistance will decrease. On the other hand, if the content of the silane coupling agent is too large, the stability of the resin composition may be reduced and gelation may occur, and the amount of the silane coupling agent that does not contribute to the reaction increases. Adhesion between the plate and the resin film formed on the metal plate may be reduced.

  As the silane coupling agent, a silane coupling agent represented by the following chemical formula (1) is preferably used.

（化学式（１）中、Ｒ¹：グリシドキシ基、Ｒ²、Ｒ³：低級アルコキシ基、Ｒ⁴：低級アルコキシ基または低級アルキル基、Ｘ：低級アルキレン基）
ここで低級とは、炭素数が１〜５、より好ましくは炭素数が１〜３であることを意味する。

(In the chemical formula (1), R ¹ : glycidoxy group, R ² , R ³ : lower alkoxy group, R ⁴ : lower alkoxy group or lower alkyl group, X: lower alkylene group)
Here, “lower” means that the number of carbon atoms is 1 to 5, more preferably 1 to 3 carbon atoms.

  By containing the silane coupling agent, the coating film adhesion and corrosion resistance of the formed resin film can be improved. Examples of the silane coupling agent having a glycidoxy group at the terminal represented by the chemical formula (1) include γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, and vinyltris (β-methoxyethoxy). Examples include silane. Since the silane coupling agent having a glycidoxy group is rich in cross-linking reactivity with respect to a carboxyl group-containing polyurethane resin and an ethylene-unsaturated carboxylic acid copolymer, the hardness of the resulting resin film is increased when the silane coupling agent is used. Increases to improve lubricity.

  The ethylene-unsaturated carboxylic acid copolymer having a carboxyl group neutralized by the above-described amine having a boiling point of 100 ° C. or less and a basic compound of a Group 1 element forms an intermolecular association by an ion cluster (ionomerization). Forms a resin film with excellent corrosion resistance. However, in order to form a tougher film, it is desirable to crosslink the polymer chains by chemical bonding utilizing a reaction between functional groups.

  Therefore, the ethylene-unsaturated carboxylic acid copolymer aqueous dispersion that can be used in the present invention preferably contains a crosslinking agent having two or more functional groups capable of reacting with a carboxyl group. The content ratio of the crosslinking agent is 1 part by mass or more, more preferably 5 parts by mass or more when the nonvolatile resin component (EC) in the ethylene-unsaturated carboxylic acid copolymer aqueous dispersion is 100 parts by mass. And it is desirable to contain it in a ratio of 20 parts by mass or less, more preferably 10 parts by mass or less.

  When the amount is less than 1 part by mass, the effect of crosslinking by chemical bonding becomes insufficient, and the effect of improving corrosion resistance is difficult to be exhibited. On the other hand, if it exceeds 20 parts by mass, the crosslink density of the resin film becomes excessively high, the hardness increases, and cracks are generated because it becomes impossible to follow the deformation during pressing, resulting in corrosion resistance and adhesion of the coating film. This is not preferable because it decreases the properties.

  The crosslinking agent having two or more functional groups capable of reacting with a carboxyl group per molecule is not particularly limited, but sorbitol polyglycidyl ether, (poly) glycerol polyglycidyl ether, pentaerythritol polyglycidyl ether, trimethylolpropane polyglycidyl ether Glycidyl group-containing crosslinking agents such as polyglycidyl ethers such as neopentyl glycol diglycidyl ether and (poly) ethylene glycol diglycidyl ether, and polyglycidyl amines; 4,4′-bis (ethyleneiminecarbonylamino) diphenylmethane, N, N′-hexamethylene-1,6-bis (1-aziridinecarboxamide), N, N′-diphenylmethane-4,4′-bis (1-aziridinecarboxyamide), toluenebisazi Bifunctional aziridine compounds such as gincarboxamide; tri-1-aziridinylphosphine oxide, tris [1- (2-methyl) aziridinyl] phosphine oxide, trimethylolpropane tris (β-aziridinylpropionate), tris Aziridinyl group-containing crosslinks such as tri- or more functional aziridines such as 2,4,6- (1-aziridinyl) -1,3,5-triazine, tetramethylpropanetetraaziridinylpropionate, or derivatives thereof An example is a suitable agent, and one or more of these can be used. Of these, aziridinyl group-containing crosslinking agents are preferred. Polyfunctional aziridines and monofunctional aziridines (such as ethyleneimine) may be used in combination.

  The resin composition that can be used in the present invention is a cross-linking agent, diluent, anti-skinning agent, leveling agent, antifoaming agent, penetrating agent, emulsifier, dispersant, preparation, etc., as long as the object of the present invention is not impaired. Film auxiliary agents, dyes, pigments, thickeners, lubricants and the like can be contained. In order to further impart processability and lubricity to the resin film, spherical polyethylene wax having an average particle size of 0.1 to 3 μm is added to the resin composition in an amount of 0.5 to 100 parts by mass in the solid content of the resin composition. It is also effective to contain 20 parts by mass.

  The method for preparing the resin composition is not particularly limited. For example, the chelating agent may be added to a carboxyl group-containing polyurethane aqueous liquid, an ethylene-unsaturated carboxylic acid copolymer aqueous dispersion, or silica particles, if necessary. , A silane coupling agent and, if necessary, a wax, a crosslinking agent and the like are blended in a predetermined amount. Silica particles, silane coupling agent, wax, cross-linking agent, etc. may be added at any stage, but after addition of cross-linking agent and silane coupling agent, gelation does not occur due to the progress of the cross-linking reaction. It is desirable to minimize heat.

  In order to form a resin film on a metal plate, the resin composition is applied to one or both surfaces of the metal plate surface using a known coating method, that is, a roll coater method, a spray method, a curtain flow coater method, or the like. And heat drying. When using a crosslinking agent, the heat drying temperature is preferably a temperature at which the crosslinking reaction between the crosslinking agent and the carboxyl group-containing resin proceeds. In the case of using a spherical polyethylene wax, in order to maintain the spherical shape of the wax and improve the processability in the subsequent processing step, the resin is dried by heating at a temperature below the softening point of the wax, for example, in the range of 70 to 130 ° C. It is desirable to do.

  The metal plate that can be used in the present invention is not particularly limited, but is preferably a zinc-based plated steel plate, such as a hot-dip galvanized steel plate (GI), an alloyed hot-dip Zn-Fe-plated steel plate (GA), or an alloy. A heat treated Zn-5% Al-plated steel sheet (GF), an electric pure galvanized steel sheet (EG), an electric Zn-Ni plated steel sheet, an aluminum plate, a Ti plate, or the like can be suitably used. Before forming the resin film, the surface of the metal plate may be treated with Co or Ni, treated with an inhibitor, or treated with various nonchromates.

Amount of adhesion to the metal plate of resin film (thickness), after drying, 0.05 g / m ² or more, more preferably be at 0.2 g / m ² or more, 1 g / m ² or less, more preferably 0 It is desirable that it is not more than 5 g / m ² . When the adhesion amount is too small, abrasion resistance, corrosion resistance, and alkali degreasing resistance decrease. On the other hand, if the amount of adhesion is too large, the conductivity and weldability tend to decrease. This resin-coated metal plate is used as it is after undergoing a processing step depending on the application, or used after being subjected to electrodeposition coating, powder coating, silk printing (about 130 to 160 ° C., about 20 to 30 minutes) under conventional conditions. May be.

[Evaluation methods]
(1) Corrosion resistance About the obtained resin coating metal plate (steel plate), the salt spray test of the edge-sealed flat plate material was implemented according to JIS-Z2371, and it evaluated in time until 1% of white rust generate | occur | produces.
(Evaluation criteria in Table 1)
◎: White rust generated 264 hours or more ○: White rust generated 240 hours or more to less than 264 hours Δ: White rust generated 120 hours or more to less than 240 hours ×: White rust generated less than 120 hours

(2) Abrasion resistance The obtained resin-coated metal plate (steel plate) was subjected to a vibration test in accordance with the packaging cargo-vibration test (JIS-Z0232). It was evaluated with. The product name “BF-500UC” manufactured by IDEC Co., Ltd. was used as the vibration test apparatus.
(Evaluation criteria)
◎: No damage to the film ○: Damage to the film, but no damage to the galvanized surface △: Damage to the galvanized surface that can be visually confirmed ×: Significant damage to the galvanized surface

(3) Paintability (coating adhesion)
The resulting resin-coated metal plate (steel plate) was spray-coated with a melamine alkyd paint (manufactured by Kansai Paint Co., Ltd .: Amirac # 1000) so that the coating thickness after drying was about 20 μm, and baked at 130 ° C. for 20 minutes. After painting. Subsequently, after immersing the test steel plate in boiling water for 1 hour, taking it out and letting it stand for 1 hour, 100 mm of 1 mm square grids were cut with a cutter knife, and a tape peeling test was carried out on this. The coating film adhesion was evaluated in four stages according to the number of residual cells.
(Evaluation criteria)
A: Residual rate: 100%
○: Residual rate: 90% to less than 100% Δ: Residual rate: 80% to less than 90% ×: Residual rate: 70% to less than 80%

(4) Conductivity The surface resistance of the obtained resin-coated metal plate (steel plate) was measured at 10 points with a surface resistance meter (Diais Instruments Co., Ltd .: Loresta-EP) / 4 probe type.
(Evaluation criteria)
◎: 1 mΩ or less overload 0 times / 10 locations ○: 1 mΩ or less overload 1 times / 10 locations Δ: 1 mΩ or less overload 2 times / 10 locations x: 1 mΩ or more overload 5 times / 10 locations

(5) Alkali degreasing resistance The test steel plate was immersed for 2 minutes in 20 g / l of an alkaline degreasing agent (manufactured by Japan Parker Rising Co., Ltd .: CL-N364S) adjusted to a liquid temperature of 60 ° C., washed with water and dried. The test steel sheet was subjected to a salt spray test according to JISZ2371, and evaluated by the time until 1% of white rust was generated.
(Evaluation criteria)
◎: 192 hours or more ○: 168 hours or more to less than 192 hours Δ: 96 hours or more to less than 168 hours ×: less than 96 hours

[Preparation of carboxyl group-containing polyurethane resin aqueous solution]
Polytetramethylene ether glycol (average molecular weight 1000) 60 g manufactured by Hodogaya Chemical Co., Ltd., 14 g of 1,4-cyclohexanedimethanol as a polyol component in a 0.8 L internal synthesizer equipped with a stirrer, thermometer and temperature controller Then, 20 g of dimethylolpropionic acid was charged, and 30.0 g of N-methylpyrrolidone was further added as a reaction solvent. 104 g of tolylene diisocyanate (hereinafter sometimes simply referred to as “TDI”) was charged as an isocyanate component, and the temperature was raised from 80 ° C. to 85 ° C. and reacted for 5 hours. The obtained prepolymer had an NCO content of 8.9%. Further, 16 g of triethylamine was added for neutralization, a mixed aqueous solution of 16 g of ethylenediamine and 480 g of water was added, emulsified at 50 ° C. for 4 hours, and subjected to chain extension reaction to obtain an aqueous polyurethane resin dispersion (nonvolatile resin component 29 0.1% by mass, acid value 41.4).

[Preparation of aqueous dispersion of ethylene-unsaturated carboxylic acid copolymer]
In an autoclave of an emulsification facility having an internal capacity of 0.8 L equipped with a stirrer, a thermometer, and a temperature controller, 626 parts by mass of water, ethylene-acrylic acid copolymer (acrylic acid 20% by mass, melt index (MI) 300) Add 160 parts by mass, add 40 mol% of triethylamine and 15 mol% of sodium hydroxide to 1 mol of carboxyl group of ethylene-acrylic acid copolymer, and stir at high speed under an atmosphere of 150 ° C and 5 Pa. And cooled to 40 ° C. to obtain an aqueous dispersion of an ethylene-acrylic acid copolymer. Subsequently, 4,4′-bis (ethyleneiminocarbonylamino) diphenylmethane (manufactured by Nippon Shokubai: Chemite (registered trademark) DZ-22E) as a crosslinking agent was added to the aqueous dispersion, and the non-volatile property of the ethylene-acrylic acid copolymer. It added so that it might become a ratio of 5 mass parts with respect to 100 mass parts of resin components.

(Example 1)
A carboxyl group-containing polyurethane resin aqueous solution obtained as described above, an ethylene-acrylic acid copolymer aqueous dispersion, and silica particles (manufactured by Nissan Chemical Co., Ltd .: Snowtex XS, average particle size of 4 to 6 nm) 1 to 100 parts by mass in terms of nonvolatile components so that the mixing ratio shown in FIG. 1 is obtained, and γ-glycidoxypropyltrimethoxysilane as a silane coupling agent with respect to 100 parts by mass in total. 15 parts by mass (manufactured by Shin-Etsu Chemical: KBM403) was added. Furthermore, a chelating agent (Cyrest PH-214 (HEDP · 4Na)) is added to this mixture so that the chelating agent content is 0.5 parts by mass in 100 parts by mass of the solid content of the resin composition, and the resin composition A product was prepared.

This resin composition was applied to the surface of an electropure galvanized steel sheet (Zn deposition amount 20 g / m ² , plate thickness 0.8 mm) with a squeeze roll and dried by heating at a plate temperature of 90 ° C. A resin-coated metal plate (steel plate) on which a m ² resin film was formed was obtained. Table 1 shows the evaluation results on the corrosion resistance, conductivity, abrasion resistance, alkali degreasing resistance and paintability of the obtained resin-coated steel sheet.

(Example 2)
A carboxyl group-containing polyurethane resin aqueous solution obtained as described above, an ethylene-acrylic acid copolymer aqueous dispersion, and silica particles (manufactured by Nissan Chemical Co., Ltd .: Snowtex XS, average particle size of 4 to 6 nm) are non-volatile. 30 parts by mass of the functional resin component and 70 parts by mass of the silica particles are blended so that the total amount is 100 parts by mass, and γ-glycidoxypropyltrimethoxysilane is further added as a silane coupling agent to the total of 100 parts by mass. 15 parts by mass (manufactured by Shin-Etsu Chemical: KBM403) was added. In addition, the compounding ratio of the carboxyl group-containing polyurethane resin (PC) and the ethylene-unsaturated carboxylic acid copolymer (EC) in the nonvolatile resin component was set to PC: EC = 5: 1 by mass ratio. Furthermore, various chelating agents shown in Table 2 were added to this mixture to prepare a resin composition.

This resin composition was applied to the surface of an electropure galvanized steel sheet (Zn deposition amount 20 g / m ² , plate thickness 0.8 mm) with a squeeze roll and dried by heating at a plate temperature of 90 ° C. A resin-coated metal plate (steel plate) on which a m ² resin film was formed was obtained. Table 2 shows the evaluation results on the corrosion resistance, conductivity, abrasion resistance, alkali degreasing resistance and paintability of the obtained resin-coated steel sheet.

(Example 3)
A carboxyl group-containing polyurethane resin aqueous solution obtained as described above, an ethylene-acrylic acid copolymer aqueous dispersion, and silica particles (manufactured by Nissan Chemical Co., Ltd .: Snowtex XS, average particle size of 4 to 6 nm) are non-volatile. 30 parts by mass of the functional resin component and 70 parts by mass of the silica particles are blended so that the total amount is 100 parts by mass, and γ-glycidoxypropyltrimethoxysilane is further added as a silane coupling agent to the total of 100 parts by mass. (Shin-Etsu Chemical KBM403) was added in an amount of 0 to 30 parts by mass. In addition, the compounding ratio of the carboxyl group-containing polyurethane resin (PC) and the ethylene-unsaturated carboxylic acid copolymer (EC) in the nonvolatile resin component was PC: EC = 5: 1 in terms of mass ratio. Furthermore, a chelating agent (Cyrest PH-214 (HEDP · 4Na)) is added to this mixture so that the chelating agent content is 0.5 parts by mass in 100 parts by mass of the solid content of the resin composition, and the resin composition A product was prepared.

This resin composition was applied to the surface of an electropure galvanized steel sheet (Zn deposition amount 20 g / m ² , plate thickness 0.8 mm) with a squeeze roll and dried by heating at a plate temperature of 90 ° C. A resin-coated metal plate (steel plate) on which a m ² resin film was formed was obtained. Table 3 shows the evaluation results of the stability of the resin composition and the corrosion resistance, conductivity, abrasion resistance, alkali degreasing resistance and paintability of the resin-coated steel sheet.

(Example 4)
A polyurethane resin aqueous solution obtained as described above, an ethylene-acrylic acid copolymer aqueous dispersion, and silica particles having an average particle size of 4 to 100 nm (manufactured by Nissan Chemical Co., Ltd .: Snowtex series) It mix | blends so that a component may be 30 mass parts and a silica particle may be 70 mass parts in total, and with respect to this total 100 mass parts, it is (gamma-glycidoxypropyl trimethoxysilane (Shin-Etsu) as a silane coupling agent further. 15 parts by mass of Chemical: KBM403) was added. In addition, the compounding ratio of the carboxyl group-containing polyurethane resin (PC) and the ethylene-unsaturated carboxylic acid copolymer (EC) in the nonvolatile resin component was set to PC: EC = 5: 1 by mass ratio. Furthermore, a chelating agent (Cyrest PH-214 (HEDP · 4Na)) is added to this mixture so that the chelating agent content is 0.5 parts by mass in 100 parts by mass of the solid content of the resin composition, and the resin composition A product was prepared.

This resin composition was applied to the surface of an electropure galvanized steel sheet (Zn deposition amount 20 g / m ² , plate thickness 0.8 mm) with a squeeze roll and dried by heating at a plate temperature of 90 ° C. A resin-coated metal plate (steel plate) on which a m ² resin film was formed was obtained. Table 4 shows the evaluation results on the corrosion resistance, conductivity, abrasion resistance, alkali degreasing resistance and paintability of the obtained resin-coated steel sheet.

(Example 5)
A polyurethane resin aqueous solution obtained as described above, an ethylene-acrylic acid copolymer aqueous dispersion, and silica particles (manufactured by Nissan Chemical Co., Ltd .: Snowtex XS, average particle diameter of 4 to 6 nm) are combined into a nonvolatile resin component. 30 parts by mass and 70 parts by mass of silica particles were added in a total of 100 parts by mass, and 15 parts by mass of the silane coupling agent shown in Table 4 was further added to the total of 100 parts by mass. In addition, the compounding ratio of the carboxyl group-containing polyurethane resin (PC) and the ethylene-unsaturated carboxylic acid copolymer (EC) in the nonvolatile resin component was set to PC: EC = 5: 1 by mass ratio. Furthermore, a chelating agent (Cyrest PH-214 (HEDP · 4Na)) is added to this mixture so that the chelating agent content is 0.5 parts by mass in 100 parts by mass of the solid content of the resin composition, and the resin composition A product was prepared.

This resin composition was applied to the surface of an electropure galvanized steel sheet (Zn deposition amount 20 g / m ² , plate thickness 0.8 mm) with a squeeze roll and dried by heating at a plate temperature of 90 ° C. A resin-coated metal plate (steel plate) on which a m ² resin film was formed was obtained. Table 5 shows the evaluation results of the stability of the resin composition and the corrosion resistance, conductivity, abrasion resistance, alkali degreasing resistance and paintability of the resin-coated steel sheet.

(Example 6)
A polyurethane resin aqueous solution, an ethylene-acrylic acid copolymer aqueous dispersion obtained as described above, and silica particles (Nissan Chemicals: Snowtex XS), 30 parts by mass of a non-volatile resin component, and silica particles It mix | blends so that it may become a total of 100 mass parts of 70 mass parts, 15 mass parts of (gamma) -glycidoxy propyl trimethoxysilane (Shin-Etsu Chemical: KBM403) is further used as a silane coupling agent with respect to this total 100 mass parts. Added. In addition, the compounding ratio of the carboxyl group-containing polyurethane resin (PC) and the ethylene-unsaturated carboxylic acid copolymer (EC) in the nonvolatile resin component was set to PC: EC = 5: 1 by mass ratio. Furthermore, a chelating agent (Cyrest PH-214 (HEDP · 4Na)) is added to this mixture so that the chelating agent content is 0.5 parts by mass in 100 parts by mass of the solid content of the resin composition, and the resin composition A product was prepared.

This resin composition is applied to the surface of an electropure galvanized steel sheet (Zn deposition amount 20 g / m ² , plate thickness 0.8 mm) with a drawing roll and dried by heating at a plate temperature of 90 ° C. to change the drawing pressure of the roll. Thus, a resin-coated metal plate (steel plate) on which a resin film having an adhesion amount of 0.05 to 2.0 g / m ² was formed was obtained. Table 6 shows the evaluation results on the corrosion resistance, conductivity, abrasion resistance, alkali degreasing resistance and paintability of the obtained resin-coated steel sheet.

Claims (18)

  A resin-coated metal plate provided with a resin film obtained from a resin composition containing a carboxyl group-containing polyurethane resin aqueous solution and an ethylene-unsaturated carboxylic acid copolymer aqueous dispersion, wherein the resin composition comprises ethylenediamine Tetraacetic acid (EDTA), diethylenetriaminepentaacetic acid (DTPA), hydroxyethylidene diphosphonic acid (HEDP), N, N, N ′, N′-tetrakis (phosphonomethyl) ethylenediamine (EDTMP), nitrilotriacetic acid (NTA) and hydroxyethyl 0.1 to 5 parts by mass of ethylenediaminetetraacetic acid (HEDTA) and one or more chelating agents selected from the group consisting of salts thereof in a proportion of 100 parts by mass of the solid content of the resin composition A resin-coated metal sheet characterized by that.   2. The resin composition contains one or more chelating agents selected from the group consisting of Na ion-containing EDTA salt, DTPA salt, HEDP salt, EDTMP salt, NTA salt and HETDA salt. The resin-coated metal plate described in 1.   The resin composition contains EDTA salt, DTPA salt, HEDP salt, EDTMP salt, NTA salt containing Na ions and containing at least one metal ion selected from Mg, Ca, Co, Zn, Mn and Fe ions. 2. The resin-coated metal sheet according to claim 1, which contains one or more chelating agents selected from the group consisting of HEDTA salts.   The resin composition contains one or more chelating agents selected from the group consisting of EDTA salts, DTPA salts, HEDP salts, EDTMP salts, NTA salts and HETDA salts containing amine ions or ammonium ions. The resin-coated metal plate according to claim 1.   The resin composition includes an EDTA salt, a DTPA salt, a HEDP salt containing an amine ion or an ammonium ion and containing at least one metal ion selected from Na, Mg, Ca, Co, Zn, Mn, and Fe ions. 2. The resin-coated metal sheet according to claim 1, which contains one or more chelating agents selected from the group consisting of EDTMP salts, NTA salts and HEDTA salts.   The resin composition is silica having 5 to 45 parts by mass of an aqueous carboxyl group-containing polyurethane resin and an ethylene-unsaturated carboxylic acid copolymer aqueous dispersion as a nonvolatile resin component, and an average particle size of 4 to 20 nm. It contains 55 to 95 parts by mass of particles in a total of 100 parts by mass, and further contains a silane coupling agent in a ratio of 5 to 25 parts by mass with respect to the total of 100 parts by mass. The mixing ratio of the liquid non-volatile resin component (PU) to the non-volatile resin component (EC) of the ethylene-unsaturated carboxylic acid copolymer aqueous dispersion is PU: EC = 9: 1 to 2: 1 in mass ratio. The resin-coated metal plate according to any one of claims 1 to 5. The carboxyl group-containing polyurethane resin is obtained by chain extension reaction of a urethane prepolymer with a chain extender,
As the polyisocyanate component constituting the urethane prepolymer, at least one selected from the group consisting of tolylene diisocyanate, diphenylmethane diisocyanate and dicyclohexylmethane diisocyanate is used,
The resin according to any one of claims 1 to 6, wherein all of 1,4-cyclohexanedimethanol, polyether polyol, and polyol having a carboxyl group are used as the polyol component constituting the urethane prepolymer. Painted metal plate.   The resin-coated metal sheet according to any one of claims 1 to 7, wherein the chain extender is ethylenediamine or hydrazine.   The resin according to any one of claims 1 to 8, wherein a mass ratio of the 1,4-cyclohexanedimethanol and the polyether polyol is 1,4-cyclohexanedimethanol: polyether polyol = 1: 1 to 1:19. Painted metal plate.   The resin-coated metal plate according to claim 1, wherein the polyether polyol is polyoxypropylene glycol or polytetramethylene ether glycol.   The acid value of the said carboxyl group-containing polyurethane resin is 10-60 mgKOH / g, The resin coated metal plate in any one of Claims 1-10.   In addition to the ethylene-unsaturated carboxylic acid copolymer, the ethylene-unsaturated carboxylic acid copolymer aqueous dispersion is 0.2 to 0.1 mol relative to 1 mol of the carboxyl group of the ethylene-unsaturated carboxylic acid copolymer. An amine having a boiling point of 100 ° C. or less corresponding to 0.8 mol and a base of a Group 1 element corresponding to 0.02 to 0.4 mol with respect to 1 mol of the carboxyl group of the ethylene-unsaturated carboxylic acid copolymer The resin-coated metal plate according to any one of claims 1 to 11, which contains a functional compound.   The ethylene-unsaturated carboxylic acid copolymer is a copolymer in which 10 to 40% by mass of an unsaturated carboxylic acid component is copolymerized when the total amount of monomers of the copolymer is 100% by mass. A resin-coated metal plate on any one of 12.   The resin-coated metal sheet according to any one of claims 1 to 13, wherein the amine having a boiling point of 100 ° C or lower is triethylamine.   The ethylene-unsaturated carboxylic acid copolymer aqueous dispersion further reacts with a carboxyl group when the nonvolatile resin component (EC) of the ethylene-unsaturated carboxylic acid copolymer aqueous dispersion is 100 parts by mass. The resin-coated metal sheet according to any one of claims 1 to 14, wherein the resin-coated metal sheet contains a cross-linking agent having two or more functional groups that can be used at a ratio of 1 to 20 parts by mass.   The resin-coated metal sheet according to any one of claims 1 to 15, wherein the ethylene-unsaturated carboxylic acid copolymer aqueous dispersion is substantially free of amine and ammonia having a boiling point of more than 100 ° C. The resin-coated metal sheet according to any one of claims 1 to 16, wherein the silane coupling agent is a silane coupling agent represented by the following chemical formula (1).

(In the chemical formula (1), R ¹ : glycidoxy group, R ² , R ³ : lower alkoxy group, R ⁴ : lower alkoxy group or lower alkyl group, X: lower alkylene group) The coating weight of the resin coating, the resin coated metal sheet according to any one of claims 1 to 17 is 0.05 to 1 g / m ^2.