TW201139735A - Surface treatment membrane, metal surface treatment agent and metal surface treatment method - Google Patents

Abstract

Provided are a surface treatment membrane and a metal surface treatment agent which are not susceptible to peeling of the laminate film or resin coating film, even if molding is carried out subsequent to a resin film being laminated or resin-coated onto the surface of a metal material. Specifically provided is a surface treatment membrane which is formed by application to the surface of a metal material. The mass ratio of nitrogen to carbon (N/C) contained in said surface treatment membrane falls within the range 0.005 to 0.5, and the mass ratio of the total metal elements selected from Cr (III), Zr, Ti, V, Nb, Mo, W and Ce to carbon (TM/C) falls within the range of 0.01 to 1.3. This surface treatment membrane contains a first water-based resin such as urethane resin, a second water-based resin such as a polyolefin resin, and a water-soluble metal compound containing a metal element such as Cr (III), and the membrane is preferably formed by applying the coating with a metal surface treatment agent wherein the first water-based resin and/or the second water-based resin contains a nitrogen-containing functional group.

Description

[Technical Field] The present invention relates to a surface treatment film which can improve the adhesion of a surface of a metal material to a laminate film or a resin coating film, and a metal surface for forming the surface treatment film a treatment agent, and a metal surface treatment method using the metal surface treatment agent. More specifically, after laminating a resin film or forming a resin coating film on the surface of a metal material, the layer can be imparted even when subjected to severe forming processing such as deep-drawing, extrusion, or drawing. A surface treatment film which is excellent in chemical resistance which can maintain high adhesion even when exposed to an acid or the like, and a metal surface treatment agent for the surface treatment film, etc. . [Prior Art] Lamination processing is a method of heat-pressing a film made of a resin (hereinafter referred to as a resin film or a laminate film) onto a surface of a metal material, which is a metal material for protecting a surface or imparting an artistic property. The surface coating method - 'is used in various fields. This lamination process is a method of forming a resin coating film by coating and drying a resin composition on the surface of a metal material, thereby reducing the amount of waste gas or warm gas generated by drying of a solvent or carbon dioxide generated during drying. Therefore, the environmental protection is generally better, so the use thereof is expanded, for example, a can body or a cover material for a food can, which is used for an aluminum sheet material, a steel sheet material, a packaging name box, or a stainless steel foil, and a food container. Or dry battery containers, etc. In particular, recent mobile phones, electronic notebooks, notebook computers, or recording and playback devices such as the 201139735 video camera are suitable for use in lithium-ion batteries, and the use of materials such as aluminum foil or stainless steel foil that are lightweight and highly barrier-resistant. The box, and the surface of the metal box is suitable for lamination processing. It has also reviewed the use of lithium-ion batteries for driving energy in electric vehicles or hybrid electric vehicles. It has also reviewed the use of laminated metal foil as its outer packaging material. The laminate film for lamination processing is directly bonded to a metal material and then heated and pressed. Therefore, the resin film obtained by generally coating the dried resin composition can suppress the ineffectiveness of the raw material, reduce pinholes (defective portions), and have excellent workability and the like. The material of the laminate film is usually a polyester resin such as polyethylene terephthalate or polyethylene naphthalate, or a polyolefin such as polyethylene or polypropylene. When laminating a laminate film on the surface of a metal material (hereinafter also referred to simply as "metal surface"), in order to improve the adhesion between the laminate film and the metal surface and the corrosion resistance of the metal surface, the metal surface is degreased and washed. In general, a chemical conversion treatment such as phosphoric acid phosphate or the like is carried out. However, the chemical conversion treatment requires a washing step for removing the excess treatment liquid, so that the waste water treatment cost of the washing water discharged from the washing step is required. In particular, since a treatment liquid containing hexavalent chromium is used for the chemical conversion treatment such as chromate phosphate, it has been apt to avoid environmental considerations in recent years. Further, when laminating a metal surface without performing a chemical conversion treatment or the like, the laminate film is peeled off from the metal surface and the metal material is corroded. For example, when the contents are added to the container or packaging material after the lamination processing, the heat treatment causes the laminate film to be peeled off from the metal surface in order to sterilize the food container or the packaging material. Lithium ion battery

S 201139735 The outer packaging material is equal to the processing required for the manufacturing process. Therefore, when the outer packaging material is used for a long period of time, moisture in the atmosphere may invade the container and react with the electrolyte to form hydrofluoric acid, and the acid is transmitted through the laminate film to peel the metal surface from the laminate film and corrode the metal surface. problem. In response to this problem, a method of forming a film for improving the adhesion between a metal surface and a laminate film, a treating agent, and the like have been proposed. For example, as disclosed in Patent Document 1, a water-soluble or water-dispersible acrylic resin having a specific amount, a water-soluble or water-dispersible acrylic resin having a specific structure, and a primer treatment agent for a water-soluble or water-dispersible thermosetting crosslinking agent are contained. Further, as proposed in Patent Document 2, a non-chromium metal surface treatment agent formed of a specific amount of a water-soluble chromium compound and/or a water-soluble titanium compound, an organic phosphonic acid compound, and tannin is used. Further, as proposed in Patent Document 3, a metal surface treatment agent containing an aminated phenol polymer and a specific metal compound such as titanium or a pin and having a pH of 1.5 to 6 is used. Further, as proposed in Patent Document 4, a resin film containing an aminated phenol polymer, an acrylic polymer, a metal compound, and, if necessary, a phosphorus compound (C). PRIOR ART DOCUMENT PATENT DOCUMENT Patent Document 1: JP-A-2002-26582 No. Patent Document 2: JP-A-2003-3 1 [Problem to be Solved by the Invention] The object of the present invention is to provide a deep-screw after laminating a resin film or forming a resin coating film on the surface of a metal material. In the case of severe molding processing such as processing, extrusion processing, or drawing processing, the surface treatment film which imparts high adhesion to the laminate film or the resin film without peeling off, and the metal material having the surface treatment film can be provided. . Further, another object of the present invention is to provide a metal surface treatment agent for forming the surface treatment film, and a metal surface treatment method using the metal surface treatment agent. Solution to Problem The surface treatment film of the present invention for solving the above problems is characterized in that the surface is coated with a surface treatment film formed on the surface of a metal material, and the mass ratio of nitrogen to carbon contained in the surface treatment film (N/C) The mass ratio (TM/C) of the metal element selected from 0.005 to 0.5, and the metal element selected from chromium (III), zirconium, titanium, vanadium, niobium, molybdenum, tungsten and niobium is 0.01 to 1.3. In the invention, the mass ratio of nitrogen to carbon (N/C) contained in the surface treatment film, and the total mass of metal elements contained in the surface treatment film and the mass ratio of carbon (TM/C) are in the above range, so that the metal can be improved. Any of the adhesion between the surface of the material and the surface treatment film, and the adhesion between the laminate film and the surface treatment film, and the corrosion resistance is good, and the acid resistance is preferable. In particular, when the mass ratio (N/C) of nitrogen to carbon is within the above range, sufficient adhesion between the surface treated film and the laminate film can be obtained, and the watch can be prevented.

S -8 - 201139735 The water resistance of the surface treatment film is lowered, so that the corrosion resistance of the surface of the metal material (especially the acid resistance, the same applies hereinafter) can be prevented from being lowered, and the adhesion between the surface of the metal material and the surface treatment film can be prevented from being lowered. When the mass ratio of the total of the metal elements to the carbon (ΤΜ/C) is within the above range, the adhesion between the surface of the metal material and the surface treatment film can be prevented from being lowered, thereby preventing the corrosion medium from invading the surface of the metal material and reducing the corrosion resistance. In particular, it can prevent the adhesion between the metal surface and the surface treatment film in a high-humidity environment from being lowered, and prevent the surface treatment film from being embrittled, so that it can be processed later without reducing the density of the surface treatment film and the laminate film. The advantages of the nature. The metal surface treatment agent of the present invention for solving the above problems can be the metal surface treatment agent of the above-mentioned surface treatment film of the present invention which is provided below. The first metal surface treatment agent is characterized by containing a urethane, an epoxy resin, an acrylic resin, a polyolefin resin, a formal water condensation resin, a natural polysaccharide, a polyamine, and a polyacrylamide. One or more water-based resins (P)' and water-soluble metal compounds containing one or more metal elements selected from the group consisting of chromium (111), zirconium, titanium, vanadium, niobium, molybdenum, tungsten and niobium In addition, at least one of the water-based resins (P) has one or two or more nitrogen-containing functional groups selected from the following structural formulas (1) to (8). The second metal surface treatment agent is characterized in that it contains one or two or more kinds of first water-based resins (P 1 )′ selected from urethane resins, epoxy resins, and acrylic resins, and polyolefin resins. One or more selected from the group consisting of formaldehyde water condensation resin, natural polysaccharides, polyamines and polyacrylamides. 9-201139735 second water resin (P2), and containing chromium (ΠΙ), cone, titanium, At least one of the first water-based resin (P 1 ) and the second water-based resin (P2) is one or more of the water-soluble metal compounds of the metal elements selected from the group consisting of vanadium, niobium, anchors, cranes, and samarium. It has one or two or more nitrogen-containing functional groups selected from the following structural formulae (1) to (8). [1] n( (1) nr2

Ri + N — R2 X· (2) R3 R1 N——(3) N--X- (4) R2

N (5)

N X- (6) — C — N — R1 (7) — C — N — (8) II i 11 1 0 R2 0 R1 Each of 'R丨, R2, R3 in the above structural formulae (1) to (8) Independently hydrogen, or a linear, branched or cyclic alkyl, alkenyl, hydroxyalkyl, hydroxyalkenyl, aryl, aralkyl, hydroxyaryl or hydroxyarylalkyl group having a carbon number of 1 to . -10- 201139735 The hydrazine is one or more selected from the group consisting of a hydroxyl ion, a halogen ion, a sulfate ion, a sulfonate ion, a phosphate ion, and a phosphonic acid ion. Since these inventions contain a specific type of water-based resin having a specific nitrogen-containing functional group, the aqueous resin can be stably present in the treating agent to form a surface-treated film having high adhesion to the metal surface. As a result, after the surface-treated film obtained by treating with the metal surface treatment agent is formed on the metal surface, the resin film is laminated thereon or a resin coating film is formed thereon, even if deep-drawing, extrusion, or In the severe forming process such as drawing processing, the laminate film or the resin coating film is also not easily peeled off. In particular, the second metal surface treatment agent is a first water-based resin (P 1 ) which is easily oriented on the surface of the obtained treatment film (opposite side of the surface side of the metal material), and has a higher polarity than the first water-based resin ( P1), and the second aqueous resin (P2) which is easily oriented on the surface of the metal material, can form a surface treatment film having better moldability and adhesion. In the first and second metal surface treatment agents of the present invention, the nitrogen-containing functional group containing the nitrogen-containing functional group has an average number average molecular weight of 50 to 3,000, which is relative to the metal surface treatment. The content of the water-soluble metal compound in the total solid content in the agent is 1 to 5 % by mass in terms of metal. In the present invention, the average number average molecular weight of the nitrogen-containing functional group containing the nitrogen-containing functional group is within the above range, and the content of the water-soluble metal compound relative to the total solid content in the metal surface treatment agent is in the above range. Therefore, the mass ratio (N/C) of nitrogen to carbon contained in the surface treatment film obtained by using the metal surface treatment agent may be 0.005 to 0.5, and the total amount of metal elements contained in the film is 0.001 - 201139735 The mass ratio (ΤΜ/C) can be from 0·0 1 to 1.3. As a result, the metal surface treatment agent can be used to form any one of improving the adhesion between the surface of the metal material and the obtained surface treatment film, and the adhesion between the laminate film and the obtained surface treatment film, and obtaining good corrosion resistance. Sex, the surface treatment film is good for acid resistance. The metal surface treatment method of the present invention for solving the above problems is characterized in that the first or second metal surface treatment agent of the present invention is applied to the surface of a metal material at a temperature of 60 to 250 ° C. Heat and dry. The metal material of the present invention for solving the above problems is characterized by having the surface treatment film of the present invention described above. Advantageous Effects of Invention The surface treatment film of the present invention has a ratio of "nitrogen/carbon" ratio to "metal element total/carbon" contained in the film to a specific range, so that the adhesion between the surface of the metal material and the surface treatment film can be improved. Any one of the properties and the adhesion between the laminate film and the surface treatment film, and good corrosion resistance, is preferable as the acid resistance. In the first and second metal surface treatment agents of the present invention, since the aqueous resin can be stably present in the treatment agent, a surface treatment film having high adhesion to the metal surface can be formed. As a result, after the surface treatment film is formed on the metal surface by the metal surface treatment agent of the present invention, a resin film or a resin coating film is laminated thereon, and the obtained product can be obtained, even if it is subjected to deep-drawing, extrusion processing or drawing. In the severe forming process such as stretching, the laminate film or the resin coating film is not easily peeled off.

S -12-201139735 The metal surface treatment method of the present invention is characterized in that the treatment agent of the present invention is applied to the surface of a metal material (the surface of the metal to be treated is dried, so that a good adhesion treatment film can be formed on the surface of the metal material. The metal material of the invention has an adhesion to the laminate film of the surface treatment film due to the surface treatment on the surface thereof. The surface treatment film is laminated with a resin film or a resin coating film, and even deep twisting and extrusion are performed. The surface processing film, the metal surface, and the metal surface treatment method of the present invention will be described below. As shown in FIG. 1, the surface treatment film 2 of the present invention is coated with a surface film (hereinafter referred to as "metal surface") of the genus material 1 and the mass ratio of nitrogen to carbon contained in the surface treatment film 2 is 0.005. To the total mass ratio of metal elements selected from 0.5' chromium (III), chromium, titanium, vanadium, niobium, and molybdenum to carbon (TM/(to 1.3. The surface treated film 2 is as shown 1 shows that after the hard metal surface treatment agent is applied to the metal surface, the film obtained at a certain temperature is disposed between the metal material 1 and the laminate film (or) 3. The metal surface is heated after heating. The surface film, so that the obtained material can be formed into a surface treatment agent (N/C), tungsten and tantalum: 0. 01 The heat-drying resin coating film of the present invention • 13 - 201139735 By the mass ratio (Ν/C) of nitrogen (N) to carbon (C) being in the above range, sufficient adhesion between the surface treatment film 2 and the laminate film 3 can be obtained, and the surface treatment film can be prevented. When the water resistance of 2 is lowered, the corrosion resistance of the metal surface (especially the acid resistance, the same applies hereinafter) is lowered, and the adhesion between the metal surface and the surface treatment film 2 is prevented from being lowered. The mass ratio of nitrogen to carbon (Ν/ When C) is less than 0.005, sufficient adhesion cannot be obtained between the surface treated film 2 and the laminate film 3. Further, when the mass ratio of nitrogen to carbon (N/C) exceeds 0.5, the surface treated film 2 is lowered. Water resistance reduces corrosion resistance of metal surfaces, thereby reducing metal surface and surface The adhesion between the film 2 is treated. The mass ratio of nitrogen to carbon (Ν/C) further improves the adhesion between the metal surface and the surface treatment film 2 and the corrosion resistance of the surface treatment film 2, and is introduced by The nitrogen-containing functional group of the polar group is preferably from 0.008 to 0.4, and particularly improves the adhesion between the surface-treated film 2 and the laminate film 3 and the surface treatment film 2, from the viewpoint of improving the cohesive force and improving the film formation property. The viewpoint of corrosion resistance is particularly preferably from 0.05 to 0.3. The upper limit 値 of the above preferred range is 0.4, and the upper limit of the particularly preferred range is 0.3 based on the viewpoints of water resistance and adhesion. When the mass ratio (TM/C) is within the above range, the adhesion between the metal surface and the surface treatment film 2 can be prevented from being lowered, thereby preventing the corrosion medium from invading the metal surface and reducing the corrosion resistance, particularly in a high humidity environment. The adhesion between the metal surface and the surface treatment film 2 is lowered, and the surface treatment film 2 is prevented from being embrittled. Therefore, there is an advantage that the adhesion between the surface treatment film 2 and the laminate film 3 is not deteriorated thereafter. When the ratio of metal elements to carbon rt (TM/C) is less than 0.01, 201139735 reduces the adhesion between the metal surface and the surface treatment film 2, and as a result, the corrosive medium invades the metal surface and the corrosion resistance is insufficient. It will reduce the adhesion between the metal surface and the surface treatment film 2 in a high humidity environment. Further, when the mass ratio of metal elements to carbon (TM/C) exceeds 1.3, the surface treatment film 2 is excessively embrittled, and as a result, the subsequent treatment reduces the adhesion between the surface treatment film 2 and the laminate film 3. Further, the total mass ratio of metal elements to carbon (TM / C ) further enhances the adhesion and corrosion resistance, and the film forming property is good, and cracking is not caused, and it is preferably 〇. 〇1 to 〇. 7 In particular, from the viewpoint of improving the adhesion between the metal surface and the surface treatment film 2 in a high-humidity environment, it is particularly preferably from 0.05 to 0.3. The carbon content at this time is a total organic carbon meter (TOC: Total Organic Carbon Analyzer "T0C-5000A" manufactured by Shimadzu Corporation, with oxygen flow rate: 0.5 L/min, temperature: 580 °C (aluminum), 7 00 °C (iron-based material), measurement time: 120 seconds, sample size: 10 mm x 20 mm. The nitrogen content is based on the organic nitrogen analysis method (J IS-K0 1 02), and the metal material forming the surface treatment film is immersed in After concentrated sulfuric acid for 30 seconds, the film was peeled off and dissolved, and then the total nitrogen concentration of the stripping solution (sulfuric acid solution) was measured according to IS - K 0 1 0 2 . Further, the pretreatment was the Chieda method, and the determination was based on indophenol. The blue spectrophotometric method is used. The total mass of the metal elements is measured by the fluorescent X-ray analyzer "3 270E" of the Rigaku Electric Industrial Co., Ltd., and is measured by the tube: Rh, voltage-current: 50KV-50mA. In the surface treated film of the present invention, the ratio of "nitrogen/carbon" ratio to "metal element total/carbon" in the film is in a specific range, so that the adhesion between the metal surface and the surface treatment film 2 can be improved and the laminated film can be formed. 3 and Table-15- 201139735 It is preferable that the surface is treated with any one of the adhesion between the film 2 and good corrosion resistance is obtained, and the acid resistance is preferable. The metal material having the surface treatment film on the surface is a laminated film which can improve the film relative to the surface treatment film. The adhesiveness is obtained by laminating a resin film or forming a resin coating film thereon, and even if it is subjected to severe forming processing such as deep rubbing, extrusion processing or drawing processing, the laminated film is obtained. [Metal surface treatment agent] The metal surface treatment agent of the present invention is a treatment agent for a surface treatment film of the present invention, and a metal surface treatment agent of the following two aspects is provided. The first metal surface treatment agent is selected from the group consisting of urethane resin, epoxy resin, acrylic resin, polyolefin resin, formal water condensation resin, natural polysaccharide, polyamine and polypropylene decylamine. One or more water-based resins (P), and water-soluble metal compounds containing one or more metal elements selected from the group consisting of chromium (yttrium), lanthanum, titanium, vanadium, niobium, molybdenum, tungsten, and niobium Further, at least one of the water-based resins (P) has one or two or more nitrogen-containing functional groups selected from the above structural formulas (1) to (8), wherein the symbol (P) means the first one. The water-based resin of the metal surface treatment agent. The second metal surface treatment agent contains one or more of the first water-based resins selected from the group consisting of urethane resins, epoxy resins, and acrylic resins. 1), with polyolefin resin, formal water condensation resin, natural

S -16- 201139735 One or more selected second water-based resins (P2) selected from the group consisting of polyamines and polyacrylamides, and containing chromium (III), zirconium, titanium, vanadium, niobium and molybdenum A water-soluble metal compound of one or more metal elements selected from tungsten and rhenium. In addition, at least one of the first aqueous resin (P 1 ) and the second aqueous resin (P 2 ) has one or more nitrogen-containing functional groups selected from the above structural formulas (1) to (8). base. In this case, the first water-based resin (P 1 ) has a property of being easily oriented on the surface (opposite surface of the metal surface side) of the obtained surface-treated film, and the second water-based resin (P2) has a higher polarity than the first water-based resin. And easy to be oriented to the nature of the metal surface. Hereinafter, the aqueous resin and the water-soluble metal compound which are constituent components of the present invention will be described in detail below. (Aqueous resin) The first metal surface treatment agent is a urethane resin, an epoxy resin, an acrylic resin, a polyolefin resin, a formalin condensation resin, a natural polysaccharide, a polyester, a polyamide, and a poly One or two or more kinds of water-based resins (p) selected from acrylamide. This aspect is generally the addition of 1 to 3 aqueous resins, but may be the above. Further, the second metal surface treatment agent is characterized in that one or two or more kinds of the first water-based resins (P 1 )' and polyolefin selected from the group consisting of urethane resins, epoxy resins and acrylic resins are used. One or two or more kinds of the second aqueous resins (P2) selected from the group consisting of a resin, a formalin condensation resin, a natural polysaccharide, a polyester, a polyamide, and a polyacrylamide. This aspect is generally one or two kinds of first water-based resins' and one or two kinds of second water-based resins, but it may be -17-201139735. The first type and the second type of metal surface treatment agent are one or more types of water-based resins, and at least one of them has one or more types selected from the above structural formulas (1) to (8). Nitrogen functional group. The structural formulae (1) to (8) are a 1 to 3 amine group, a 4th ammonium group, and a 1 to 2 guanamine group. The nitrogen-containing functional groups of the structural formulae (1) and (2) are present in the branch of the aqueous resin, and the nitrogen-containing functional groups of the structural formulae (3) to (6) are present in the main chain of the aqueous resin. The aqueous resin having the nitrogen-containing functional group of any of the structural formulae (1) to (6) is cationic in water. The nitrogen-containing functional groups of the structural formulae (7) and (8) have a structure in which a branch or a main chain of the aqueous resin has a guanamine bond. The water-based resin contained in the metal surface treatment agent may have at least one of the above-mentioned nitrogen-containing functional groups, and all of the aqueous resins contained may have one or two or more kinds of the nitrogen-containing functional groups. The water-based resin can have a nitrogen-containing functional group, and the obtained surface-treated film is excellent in adhesion to a metal surface, and the water-dispersibility (stability in liquid) of the metal surface treatment agent is good. In the above structural formulae (1) to (8), the amine group has an effect of exhibiting cationicity in water to enhance water solubility or water dispersibility of the resin. Further, although the sulfhydryl group is nonionic, the unpolarized electron pair of nitrogen (individual group) and the carbonyl group can exhibit higher polarity, and thus have the same high water solubility or water dispersibility as the amine group. Ability. The aqueous resin constituting the metal surface treatment agent contains a certain amount of the nitrogen-containing functional group, so that the adhesion between the surface of the lifted metal and the obtained surface treated film and the adhesion between the laminated film and the obtained surface treated film can be formed. Any of the properties of -18-201139735 and having good corrosion resistance. Further, the stability of the metal surface treatment agent can be improved, and the metal treatment film having good adhesion can be stably formed. The average number of nitrogen-containing functional groups of the aqueous resin having a nitrogen-containing functional group is preferably from 50 to 3,000. When the number average molecular weight of the water-based resin having an average of one nitrogen-containing functional group is adjusted to be in this range, the mass ratio of nitrogen to carbon contained in the surface-treated film formed of the metal surface treatment agent (N) /C) can be from 0.005 to 0.5. When the mass ratio (N/C) of nitrogen (N) to carbon (C) contained in the surface treatment film formed of the metal surface treatment agent is within the above range, the surface treatment film and the laminate film can be sufficiently obtained. The adhesion is improved, and the water resistance of the surface treatment film is prevented from being lowered, so that the corrosion resistance of the metal surface is prevented from being lowered, and the adhesion between the metal surface and the obtained surface treatment film is prevented from being lowered. When the number average molecular weight of the water-based resin having an average of one nitrogen-containing functional group having a nitrogen-containing functional group has the above relationship, the number average molecular weight of the aqueous resin having no nitrogen-containing functional group in the structure is not particularly limited, and may be contained The content of the nitrogen functional group is any hydrazine, but it is preferably from 1 000 to 100,000. When it is less than 1,000, it tends to lack film-forming property, and when it exceeds 1,000, it will make the viscosity too high and it is difficult to make a stable treatment liquid. The water-based resin contained in any one of the first or second metal surface treatment agents may be any one of the water-based resins containing the nitrogen-containing functional group or not containing all of the water-based functional groups. The number average molecular weight of one of the nitrogen-containing functional groups is in the range of 50 to 3,000 described above. -19-201139735 It is preferable that all kinds of water-based resins contained in the metal surface treatment agent have a nitrogen-containing functional group and are within the above range. In particular, as a whole, the second metal surface treatment agent may have a number average molecular weight of from 50 to 3,000, but in more detail, a urethane, on average, of the nitrogen-containing functional group containing the nitrogen-containing functional group. One or two or more of the first water-based resin (P 1 )' selected from the group consisting of a resin, an epoxy resin, and an acrylic resin, a polyolefin resin, a formal water condensation resin, a natural polysaccharide, a polyamine, and a polyacrylamide One or two or more kinds of the second water-based resins (P2) selected in the above may be specified. In other words, the first aqueous resin (P 1 ) contained in the second metal surface treatment agent is preferably such that the average number average molecular weight of the nitrogen-containing functional group of the first aqueous resin (P1) containing the nitrogen-containing functional group is one. 50 to 3000. The first water-based resin (P1) of the crucible has a surface treatment film, and can suppress the penetration of corrosion factors such as oxygen, moisture, and corrosive ions from the outside of the system. Further, the second water-based resin (P2) contained in the second metal surface treatment agent is preferably such that the average number of nitrogen-containing functional groups of the second aqueous resin (P2) containing the nitrogen-containing functional group is 50. To 1500 things. The second water-based resin (P2) in this range is contained in the surface-treated film, and is strongly adsorbed on the metal surface to suppress the intrusion of the corrosion factor and the interface between the metals. Moreover, it is particularly preferable that the second aqueous resin (P2) has a nitrogen-containing functional group and contains the first aqueous resin (P1) and the second aqueous resin (P2) having the above-described functions. In the second metal surface treatment agent, the first water-based resin (p 1 ) is easily oriented on the surface of the obtained surface-treated film, and as a result, the water resistance of the surface-treated film of Table -20-201139735 can be improved, and the effect of good formability can be obtained. . Further, the second water-based resin (P2) having a higher polarity than the first water-based resin (P1) is easily oriented on the surface of the metal, and as a result, the effect of further improving the adhesion of the film formed on the surface of the metal surface can be obtained. In the second metal surface treatment agent, the addition ratio (P 1 / P 2 ) of the first water-based resin (P1) and the second water-based resin (P2) having the above-described effects is not particularly limited, and can be in a wide range, for example, quality. The ratio can be from 1/99 to 99/1 (ie 0_01 to 99). The addition ratio (P1/P2) is preferably from 20/80 to 95/5 (βρ 0.25 to 95), but it is preferably from 4 0 / 60 to 9 5 / 5 in consideration of the balance of the respective characteristics (i.e., 0.6). 6 to 9 5 ). Further, when a resin or a compound having a high reactivity with active hydrogen such as a glycidyl group or an isocyanate group is used, the stability of the treating agent is applied because a tertiary amine, a secondary amine or a resin having a mercapto group is used. Better. The water-based resin having a nitrogen-containing hydrazine group is as follows. The urethane resin can be used as 'the first polyol component of the raw material monomer', for example, a hospital (carbon number 1 to 6) diol (ethylene glycol, propylene glycol, butanediol, neopentyl glycol, and hexamethyl glycol). Etc.), polyether polyol (polyethylene glycol such as diethylene glycol and triethylene glycol, polyethylene/propylene glycol, etc.), polyester polyol (such as the above alkanediol and polyether polyol, bisphenol) A, hydrogenated biguanide a, trimethylpropane, and glycerol and other polyalcohol, and succinic acid, glutaric acid 'adipate, azelaic acid, citric acid, isophthalic acid, terephthalic acid, and partial A polyester polyol having a hydroxyl group at the terminal obtained by polycondensation of a polyvalent acid such as trimellitic acid, and a polyol component such as a polycarbonate polyol. Further, a cationic polyalcohol having a part or all of the polyol component and having an amine group or a thio group as a part of the branched or main chain of the aforementioned polyol structure (for example, N_院-21 - 201139735基-N,N - II a hydroxyalkylamine-like main chain having an amine group, or an N,N-alkylaminoalkanol-like branched cationic polyalcohol having an amine group, and a polyalcohol with an aromatic, alicyclic or aliphatic group Polyisocyanate (tolylene cyanate, diphenylmethane diisocyanate, xylylene diisocyanate, dicyclohexylmethane diisocyanate, cyclohexyl diisocyanate, methyl diisocyanate, lysine diisocyanate, etc.) After condensation of the reaction mixture, the emulsion is dispersed in an aqueous solution of alkyl sulfuric acid, formic acid or acetic acid-like carboxylic acid or phosphonic acid, and then subjected to chain extension reaction with water or/and ethylamine or melamine amine compound. Ester resin and the like. As the epoxy resin, a modified epoxy resin obtained by an addition reaction of a bisphenol type, a novolak type or an olefin type resin with a polyfunctional amine can be used. , bisphenol A-diglycidyl ether, bisphenol diglycidyl ether, phenolic glycidyl ether, glycidyl hexahydrophthalate, dimer acid glycidyl, tetraglycidylamino diphenylmethane, 3 , 4-epoxy-6-methylcyclomethylcarboxylate, triglycidyl trimer isocyanate, 3,4-epoxymethylcarboxylate 'polyallyl diglycidyl ether, polybutane Both ends of the olefin or a diglycidyl ether modified product, and a polysulfide modified resin. The above polyfunctional amine is specifically one having two or more active hydrogens in one molecule, for example, isopropanolamine, monopropanolamine, monobutanolamine, monoethylidene diethylamine, ethylidene diamine, and butyl Amine, propylamine, isophora diamine, tetrahydrofurfurylamine 'xylylenediamine, diamine diphenylmethane, hydrazine, octylamine, m-phenylenediamine, amylamine, hexylamine, hydrazine Alkylamine, tri-extension ethyltetramine, tetramethylammoniumamine, dimethylaminopropane, etc., such as a pre-organic epoxy such as varnish oleyl hexyl ring Polysulfide epoxy amine. Amine, ketone diamine, mercaptoamine

S-22-201139735, N-aminoethylpiperazine, metal diamine', and diaminodiphenylphosphonium. The solubility in water is particularly preferably an alkanolamine. As the acrylic resin, at least one of the monomers constituting the resin may be used, and the monomer having a nitrogen-containing functional group selected from the group consisting of a 1 to 3-group amine group, a 4-stage ammonium group, and a 1 to 2-order guanamine group. Further, it is also possible to use a part of the monomer component which is acrylamide, and which is aminated by a Mannich reaction or a Huffman reaction or the like. An acrylic-based monomer having the above nitrogen-containing functional group such as amino methacrylate, aminomethyl methacrylate, aminoethyl acrylate, aminoethyl methacrylate, aminopropyl acrylate A (meth)acrylic acid aminoalkyl group (carbon number 1 to 8) ester such as an ester or an aminobutyl acrylate, (meth) acrylamide, and hydroxymethyl (meth) acrylamide. The polyolefin-based resin is, for example, a Mannichamine modified polyvinylphenol, a polyvinylimidazole, a polyvinylpyridine, and a cationic olefin such as a polyethylenimine. Formaldehyde water condensation resin such as melamine, Mannich modified aminated phenol resin, and cationic formaldehyde water condensation resin such as Mannich modified aminated resin of aniline and formal water condensation resin. Natural polysaccharides such as cationic natural polysaccharides such as chitin and chitosan. A cationically modified polyamine which is a cationic nylon such as a polyamine obtained by condensation polymerization of an aminopiperazine and adipic acid. A polyacrylamide such as a acrylamide homopolymer, and a copolymer of acrylamide and another monomer (acrylic acid, acrylate, etc.) which can be copolymerized. Each of the water-based resins has a nitrogen-containing functional group of any one of the above-mentioned structural formulas (1) to (8), and is preferably a combination of one or two or more kinds of such water-based resins. Agent. The water-based resin constituting the metal surface treatment agent may be a water-based cross-linkable resin such as a water-based resin or a water-based emulsion or an aqueous dispersion obtained by a self-emulsification or an emulsifier by emulsification with or without a nitrogen-containing functional group. Or water based polymer resin. These polymer resins may be those having a crosslinking reactive functional group without impairing the effects of the present invention. As described above, the aqueous resin constituting the first and second metal surface treatment agents can contain the above-mentioned surface treatment film because all or at least one or a part thereof has a specific amount of the nitrogen-containing functional group. The mass ratio of nitrogen to carbon (N/C) is adjusted to be 0.005 to 0.5. As a result, the surface treatment film formed by the metal surface treatment agent of the present invention can be obtained by (a) improving the adhesion of the formed surface treatment film to the laminate film to improve the formability, and (b) improving the surface treatment formed. The water resistance of the film prevents the corrosion resistance of the metal surface from being lowered, improves the adhesion between the metal surface treatment film and the metal surface, and enhances the special effect of the formability. (Water-soluble metal compound) The water-soluble metal compound contained in the first and second metal surface treatment agents, for example, contains chromium (III), pin, titanium, vanadium, niobium, molybdenum, tungsten, and niobium. One or two or more kinds of water-soluble metal compounds of a ruthenium element. Further, chromium (III) means that hexavalent chromium is not contained. The water-soluble metal compound is a salt, a compound of a mismatch or a complex compound of the above metal element. Specifically, for example, chromium fluoride, chromium nitrate, chromium sulfate,

S -24- 201139735 Trivalent chromium compounds such as chromium oxalate, chromium acetate and chromium dihydrogen phosphate; sales of zirconium hydrofluoric acid, potassium zirconium hydrofluoride, sodium chrome hydrofluoride, cerium nitrate, zirconium sulfate and acetic acid cone a compound; titanium hydrofluoric acid, titanium hydrofluoric acid potassium, titanium hydrogen fluoride sodium, titanium sulfate, diisopropoxy titanium bisacetone acetone, a reaction of lactic acid and titanium alkoxide, and titanium such as titanium laurate a compound; vanadium pentoxide, vanadic vanadate, ammonium metavanadate, sodium metavanadate, and vanadium trichloride, etc., five-valent vanadium compounds; vanadium trioxide, vanadium dioxide, vanadium oxysulfate, vanadium The oxidation number of vanadium of oxyacetamidine acetate, vanadium acetonitrile acetate, vanadium trichloride and phosphorus vanadium molybdate is a pentavalent, tetravalent or trivalent vanadium compound; molybdic acid, ammonium molybdate, Molybdenum compounds such as sodium molybdate and molybdenum phosphate compounds (such as ammonium molybdate phosphate, sodium molybdate phosphate, etc.); tungsten compounds such as tungsten, ammonium metatungstate, sodium metatungstate, paratungstic acid, ammonium paratungstate, and sodium paratungstate Anthracene compounds such as cerium acetate, cerium (III) nitrate or (IV) and cerium chloride; cerium compounds such as cerium fluoride and cerium phosphate; The corrosion resistance of the surface treatment film formed by the metal surface treatment agent is preferably selected from the group consisting of chromium (III), chromium, titanium and vanadium from the viewpoint of adhesion to the metal surface and the laminate film. A water-soluble metal compound of two or more kinds of metal elements. A metal compound having such a specific metal element is a compound which can react with a metal surface, and therefore has an effect of improving the adhesion between the metal surface and the surface treatment film. When the metal surface treatment agent contains a certain amount of the water-soluble metal compound, the adhesion between the metal surface and the obtained surface treatment film and the adhesion between the laminate film and the obtained surface treatment film can be improved. When it contains a certain amount, it can form a film which retains sufficient flexibility. As a result, the adhesion of the surface treated film to the laminate film can be maintained even after -25-201139735. The water-soluble metal compound contained in the metal surface treatment agent preferably contains 1 to 50% by mass of the total solid content of the metal surface treatment agent in terms of metal. The metal surface element (chromium (III), pin, titanium, The mass ratio of metal elements selected from vanadium, niobium, molybdenum, tungsten and niobium to carbon (TM/C) is from 0.01 to 1.3. The mass ratio (TM/C) of the total metal element (TM) to carbon (C) contained in the surface treatment film formed by the metal surface treatment agent is within the above range, and between the metal surface and the obtained surface treatment film can be prevented. When the adhesion is lowered, the corrosion medium can be prevented from invading the metal surface to reduce the corrosion resistance, and in particular, the adhesion between the metal surface and the obtained surface treatment film can be prevented from being lowered in a high-humidity environment, and the resulting surface treatment film can be prevented from being embrittled. The softness of the surface-treated film itself can be improved, so that the adhesion between the obtained surface-treated film and the laminate film is not lowered even if it is processed afterwards. When the content of the water-soluble metal compound contained in the metal surface treatment agent is less than 1% by mass in terms of metal, the mass ratio of the metal element (TM) to carbon (C) contained in the surface treatment film formed (TM/C) If it exceeds the above range, the result is that the adhesion between the metal surface and the obtained surface treatment film is lowered, so that the etching medium invades the metal surface to lower the corrosion resistance. In particular, it is easy to reduce the adhesion between the metal surface and the resulting surface treatment film in a high humidity environment. Moreover, the content of the water-soluble metal compound contained in the metal surface treatment agent is

S -26- 201139735 When the metal conversion exceeds 50% by mass, the mass ratio (TM/C) of the total metal element (TM) to carbon (C) contained in the surface treatment film formed will exceed the above range, resulting in The film is embrittled to lower the function of the underlayer film as a laminate film. In the composition of the metal surface treatment agent, the solid component such as a volatile component such as a solvent to be described later is specifically referred to as a total amount of the water-based resin and the water-soluble metal compound. Therefore, the content of the water-soluble metal compound contained in the metal surface treatment agent is from 1 to 50% by mass in terms of metal, based on the total amount of the water-based resin and the water-soluble metal compound (all solid content) constituting the metal surface treatment agent. More preferably, it is 1 to 20% by mass in terms of metal conversion. (Solvent) The solvent constituting the metal surface treatment agent is mainly water. However, in order to improve the drying property of the film, etc., an alcohol-based, ketone-based or cellosolve-based water-soluble organic solvent may be used. (Other components) Other additives, antifoaming agents, and coating agents, antibacterial and antifungal agents, coloring agents, and hardening agents may be added to the extent of the present invention and the properties of the film. Further, an organic crosslinking agent such as methylolated melamine, carbodiimide or isocyanate for improving the corrosion resistance of the film, and r for improving adhesion can be added to the extent of the present invention and the film properties. -glycidoxypropyltriethoxydecane, r-glycidoxypropyltriethoxyphosphonium-27-201139735 alkane, r-aminopropyltriethoxydecane, N-lu-amino A decane coupling agent such as ethyl-r-aminopropyltrimethoxydecane. (Metal material) The metal surface treatment agent of the present invention is applied to the surface of the metal material 1 to be treated as shown in Fig. 1 to form the surface treatment film 2 of the present invention. The metal material 1 of the object to be treated is not particularly limited, and various materials are applicable. The present invention is particularly preferably used for laminating a resin film (3) or forming a resin coating film (3) after forming a surface treatment film 2 on the surface of a metal material crucible, and then performing deep-drawing, extrusion or stretching. Metal materials such as processing and processing that are severely shaped. 1 is an example in which the surface treatment film 2 and the resin film or the resin coating film (3) are formed on one surface of the metal material 1, but may be on both sides of the metal material 1 'that is, on the other surface Forming a surface treatment film' is further provided with a resin film or a resin coating film. The metal material is preferably a sheet material formed of aluminum or an aluminum alloy, a steel sheet material, a stainless steel sheet material, an aluminum foil or aluminum foil for packaging, or a steel box. In the present application, the metal material 1 in which the surface treatment film 2 is not provided is referred to as "metal substrate 1", and the metal material 10 obtained by providing the surface treatment film 2 on the metal substrate 1 is referred to as "metal material 10". "." The use of the metal material is, for example, a metal material such as a can body or a lid material for a food can, a food container, a dry battery container, a battery packaging material, and the like, but is not limited thereto, and may be a metal that can be used for a wide range of applications. material. In particular, it has recently been applied to mobile lithium ion batteries for mobile phones, electronic notes, notebook computers or video recorders.

S -28 - 201139735 Metal materials for materials other than lithium batteries for electric vehicles or hybrid electric vehicles. As described above, the first and second metal surface treatment agents of the present invention contain a specific type of water-based resin having a specific nitrogen-containing functional group, and a water-soluble metal compound containing a specific species, so that the aqueous resin can be used. A surface-treated film which is present in a metal surface treatment agent and which has the above-described composition (N/C ratio and TM/C ratio) having high adhesion to a metal surface. As a result, after the surface-treated film obtained by treating the metal surface treatment agent is formed on the metal surface, the resin film may be laminated thereon or the resin coating film may be formed thereon, even if deep-drawing, extrusion, or The metal forming method of the present invention is a metal surface treatment method in which the metal surface treatment agent is applied to a metal surface after a severe molding process such as a drawing process, and the laminate film or the resin coating film is not easily peeled off. The method of heating and drying at a temperature of 60 to 25 ° C. The term "metal surface" means the surface of a metal material which forms the object of the surface treatment film. The surface of the metal material can be degreased and washed if necessary. The degreaser can be selected from the materials suitable for the metal substrate. Further, the washing liquid is generally water, but may be a water-soluble solvent or an aqueous surfactant solution. Further, the degreasing method and the washing method are not particularly limited, and a spray method or a dipping method can be applied. The metal surface treatment agent is the metal surface treatment agent of the present invention described above, and may be any one of the first type and the second type of metal surface treatment agent. Metal surface -29- 201139735 The liquid temperature of the agent is generally 1 〇 to 50 °c. The coating method of the metal surface treatment agent is not particularly limited, and a spray method, a dipping method, or the like is applied. The contact time of the metal surface treatment agent with respect to the metal surface is generally from 0.5 to 180 seconds. The metal surface treatment agent of the present invention is a coating type treatment agent, so that it is not required to be washed after contacting the metal surface treatment agent, and the surface treatment film formed by drying to form a metal surface treatment film to be described later may be 60 to 250 °. The temperature of C is heated and dried. The temperature range can be arbitrarily changed depending on the kind of the resin component, and more preferably 80 to 200 °C. The method of heating and drying is not specific, and it is applicable to a batch or continuous hot air circulation type drying furnace, a conveying type hot air drying furnace, or an electromagnetic derivative heating furnace using an IH heater, and the air volume and the wind speed can be arbitrarily set. [Embodiment] Hereinafter, the present invention will be described in more detail by way of examples and comparative examples. However, the present invention is not limited to the following embodiments. In addition, the "parts" described below are "parts by mass". [Aqueous resin] (urethane resin: symbol a) The monomer composition is 200 parts of a polyester polyol (number average molecular weight: 2000) of a polyalcohol component of isophthalic acid and 1,6-hexanediol. Trimethylolpropane (molecular weight: 134) 5 parts, N-methyl-diethanolamine (molecular weight: 119) 32 parts J, isocyanate component "isophorone diisocyanate (molecular weight: 222) 1 18 parts", chain The elongation agent "extension ethyl diamine (molecular weight: 60) 5 parts".

S -30-201139735 The urethane resin a is synthesized by reacting the above polyol component with the above isocyanate component in a methyl ethyl ketone solvent at 8 Torr to obtain a urethane prepolymer. After emulsification of the urethane prepolymer in an aqueous solution of dimethylsulfuric acid (30 parts), the reaction is carried out in an aqueous solution of a chain extender in an amount of 1% by weight, and then the solvent is removed to obtain a urethane resin a. . (Epoxy Resin: Symbol b 1 ) Preparation of Component 1 "Bisphenol A-based Epoxy Resin (Yupperk 828, manufactured by Oiled Shell Epoxy Co., Ltd.) (epoxy equivalent: I87g) 235.7 parts", component 2 "bisphenol A 59.4 parts", component 3 "0.1 parts of reaction catalyst (lithium chloride)", and component 4 "14 parts of diethanolamine". In the synthesis method of the epoxy resin bl, the above components 1 to 3 and 125 parts of propylene glycol monomethyl ether acetate are placed in a 4-neck flask, and nitrogen gas is introduced, and the reaction is carried out at a temperature of 1 40 ° C under stirring to obtain a reaction product. Solution. Next, 343.3 parts of propylene glycol monomethyl ether acetate and 8.2 parts of hexamethylene diisocyanate were added, and the mixture was reacted at 65 ° C with stirring to obtain a modified polymer epoxy resin solution. Next, 92.7 parts of propylene glycol monomethyl ether acetate and the above component 4 were added, and the reaction was carried out at 65 ° C with stirring. After the reaction was completed, 15 4.7 parts of propylene glycol monomethyl ether acetate was added to obtain an amine-modified epoxy resin bl. An aqueous solution. (Epoxy resin: symbol b 2 ) Preparation of component 1 "bisphenol bismuth diglycidyl ether epoxy resin (Ya Bo Mi R3 02 by Mitsui Chemicals Co., Ltd.) (epoxy equivalent: 475 g) 1 000 parts", ingredients 2 "11-aminopropanol 118.4 parts". -31 - 201139735 The synthesis method of the epoxy resin b2 was 'The above-mentioned component 1 and ethylene glycol dimethyl ether (479.3 g) were put in a 3-neck flask, and it heated up to 60 degreeC, and was melt|dissolved. Next, component 2 was added, and the temperature was raised to 85 ° C. After 4 hours and 5 hours, the viscosity was measured. After confirming the viscosity, it was cooled to 7 〇 ° C, and then added with 8 8 parts of lactic acid for 30 minutes, and then charged with 2 5 9 1 · 9 parts of ion-exchanged water to obtain an amine having a solid content of 25% and a viscosity of 5 2 0 cps. A latex dispersion solution of epoxy resin b2. (Acrylic resin: symbol c) The monomer composition used was "methyl methacrylate (molecular weight: 100) 20 parts, butyl acrylate (molecular weight: 128) 40 parts, 2-hydroxypropyl methacrylate (Molecular weight: 144) 10 parts, styrene (molecular weight: 104) 10 parts, hydrazine, hydrazine dimethylaminopropyl methacrylate (molecular weight: 175) 20 parts". The synthetic method of the acrylic resin c is a mixed reactive emulsifier "Aidanka NE-20" (made by ADEKA AG) and a nonionic emulsifier "Yemanken 840S" (made by Kao Co., Ltd.) in a 6:4 manner. 100 parts of the emulsifier aqueous solution (S-1) obtained by mixing was mixed with the above monomer, and then emulsified at 5000 rpm for 1 minute using a homogenizer to obtain a monomer emulsion (ER). Next, 150 parts of the aqueous emulsifier solution (S-1) was placed in a 4-neck flask equipped with a stirrer, a reflux condenser, a thermometer, and a monomer supply cylinder, and kept at 50 ° C, collected in respective dropping funnels. A 5 mass% aqueous solution of ammonium sulfate (50 parts) and the above monomer emulsion (ER) were placed on the other port of the flask, and the mixture was dripped in about 2 hours. After heating to 60 art, the mixture was stirred for about 1 hour. 32-

S 201139735. The mixture was cooled to room temperature while stirring to obtain an emulsified solution of the acrylic resin C. (Phenol Resin: Symbol d) A bisphenol type cationically modified phenol resin having the following structure was used. In the following constitution, the degree of polymerization (m + n) is from 10 to 15, and n/m is 40/60. [Chemical 2]

(Polyacrylamide: symbol e) A copolymer of acrylamide (80% by mass) and methacrylic acid (20% by mass) (average molecular weight: 20,000) was used. (Natural Polysaccharide: Symbol f) Glycosylated chitosan having the following structural formula (number average molecular weight: 1 to 100,000, glycerylation 1.1) was used. [化3] o- ch2oh ‘–0, , 0H Uy -o-

H

NH-R NH-R ΌΗ

O-

CH2OH

R: —CH 2 —CH—CH 2 OH OH —33 — 201139735 (polyacrylic acid: symbol g) Polyacrylic acid (number average molecular weight: 30,000) was used. (Polyethylamine: mark h) Polyethylenimine (number average molecular weight: 1600) was used. (Acrylic resin: symbol i) The monomer composition used was "methyl methacrylate (molecular weight: 100) 20 parts, butyl acrylate (molecular weight: 128) 55 parts, 2 hydroxypropyl methacrylate (Molecular weight: 144) 10 parts, styrene (Molecular Weight: 104) 10 parts, N,N-dimethylaminopropyl methacrylate (molecular weight: 1 75 ) 5 parts". When the acrylic resin i is synthesized, it is carried out with the acrylic resin c (polyethylenimine: symbol j). Polyethylenimine (number average molecular weight: 〇〇〇〇) is used. (Epoxy Resin: Symbol k) Preparation of Component 1 "Bisphenol A-based Epoxy Resin (Yupi Ke 8 8 8 by Oiled Shell Epoxy Co., Ltd.) (Epoxy Equivalent: 1 8 7 g ) 2 3 5.7 parts" Ingredients 2 "bisphenol A 59.4 parts", component 3 "reaction catalyst (lithium chloride) 0.1 parts", and component 4 "diethanolamine 7 parts". The synthetic epoxy resin 1<: is the same as the epoxy resin b. The prepared water-based resin is shown in Table 1. As shown in Table 1, 'aqueous resin -34 - 201139735 a, b 1 , b2, c are classified into water-based resin (P1), and water-based resins d, e, and f are classified into water-based resin (P2). Further, 'water-based resins g, i, and k are classified into water-based resin (P 1 ), and water-based resins h and j are classified as water-based resins (P2 ) ° [Table 1] Table 1 Classification mark Water-based resin contains an average of one nitrogen-containing functional group. Molecular weight P P1 a Amine _ s-carboxylic acid dragon resin (3). (5) 240 bl Epoxy resin (1) 2318 b2 Epoxy resin (1) 708 c Acrylic resin (1) 875 P2 d Phenol resin (1) 484 e Polypropylene 醯Amine (7) 89 f Glycosylated chitosan (1) 278 P1 R Polyacrylic acid-P2 h Polyethylenimine (1). (3). (5) 44 P1 i Acrylic resin (1) 3496 P2 i Polyethylenimine (1). (3). (5) 44 P1 k Epoxy Resin (1) 4538 [Water-Soluble Metal Compound] The water-soluble metal compound (Μ) used is as follows.

Ml: Chromium dihydrogen phosphate Cr (H2P04)3 Μ 2 : Chromium fluoride C r F 3 · 3 Η 2 Ο M3 : Zirconium hydrofluoric acid H2ZrF6 M4 : Titanium hydroxide acid H2TiF6 M5: Vanadium acetonate pyruvate V0 ( C5H702)2 [Metal surface treatment agent] The above-mentioned aqueous resin and water-soluble metal compound were combined, and the metal surface treatment agents of Examples 1 to 39 shown in Tables 2 to 4 were prepared, and the metal surface treatments of Comparative Examples 1 to 1 were prepared. Agent. -35- 201139735 [Table 2] Table 2 Ρ PI〆P2 M Other | Ρ1 P2 Marker Marker Marker Part Marker Compound Part of Compound Example 1 a 78 - - - Ml 15 - - Fluoric Acid 7 - - 1 Example 2 a 85 — - - M2 10 M3 5 - - - - tr Example 3 a 45 d 50 0.90 Ml 20 - - - - - One W Example 4 a 65 d 28 2.3 M2 5 - - Phosphoric acid 5 - Example 5 a b2 34 20 d 33 1.6 M2 10 M3 3 One — — — ΐί Example 6 a 10 e 1 80 0.13 M2 10 - - - - - 1 Example 7 a 60 f 20 3.0 M4 15 M5 5 - - - - ^113 a 30 f 40 0.75 M2 10 - - IPA 10 - - Example 9 b1 60 - - - M2 20 - - Acetic acid 10 IPA 10 #Example 10 b1 20 d 60 0.33 M1 10 m 10 - - - - Example 11 bl 40 d 40 1.0 M3 5 M5 15 - - 1 • Sound Example 12 bl 15 e 70 0.21 M2 10 M4 5 - - - - Example 13 b1 b2 45 20 f 15 4.3 M5 20 Guide - acetic acid 10 phosphoric acid 5 啻 Example bl 45 f 25 1.8 M3 i 10 M5 5 IPA 15 - 1 case 1 ΐ 5 b2 75 - - - M1 20 M4 5 Formic acid 10 IPA 5 ΉΓ Application #! 116 b2 85 f 5 17 M2 10 I *** - - - - Zhe Shi 17 b2 40 d 40 1.0 M2 i 20 - | - - - - ;- Note) The "parts" in the table are all "quality" "." [Table 3] IP 1 PI/ P2 M Other 丨P1 1 1 P2 1 Marker part mark mark T mark compound part of compound part PM t class m 2 m 2 2 - - fluoric acid 7 - b2 30 e 40 0.75 M2 30 - - - - - - hm wm ΜΛ b2 10 f 70 0.14 M2 20 - - Phosphoric acid 5 - c 80 - - - M3 20 - - - - - One wa toilet mi 2F?1 Li Lai toilet country c 70 - - - M3 to M5 10 - - - - c 50 d 30 1.7 M2 10 M4 10 - - - - Discussion c I 30 e 50 0.60 M3 10 M4 10 - - - - c 10 f 70 0.14 M4 20 - - - - - - tiiM - - d 90 - Ml 10 - - - - - - 丨- • d 70 - M2 30 - - - - - - K-G - - d 75 - M2 10 M5 15 - - - - 垂_ de 45 25 - M3 10 M5 10 Phosphoric acid 10 _ — i lion EQ - - e 60 - Ml 30 M3 10 - - - - -* — ef 30 28 M2 30 M4 2 _ — — ¥m. nm wm 删 1 1 wa - e 55 - M3 20 M5 15 - - - - 1 - f 90 - M2 10 - - - - - - 1 - f 80 - 1 M3 10 M3 i 10 - - - - -! - f 50 1 ~ 1 M4 30 M5 i 20 — , _ I - i R i 60 d 20 3.0 i Ml 10 M5 10 Fluoric acid 3 | - — i ! 10 f 50 0.20 1 M3 10 M4 30 _ 1 - IPA 10 Marriage bl J 05 h 5 17 M2 10 one -' Fluoric acid 3 - - 13⁄4 Example 391 k 85 6 10 8.5 l M3 5 I —I One — One by one Note) The “parts” in the table are “quality fi”. -36- 201139735 [Table 4] Table 4 Comparative Example 1 Bub Comparative Example P Symbol a A 1~~~ Parts 9Γ1 3 H^P sri No.1 2 Parts Mark 1 Λ Marker part m Fluoric acid 1 part 7 Comparative Example 3 Comparative Example 4 Comparative Example 5 ε 100 80 -h 98 M3 M2 20 2 Pj Comparative Example 6 Comparative Example 7 i _ 90 h 50 M2 50 One-to-one M1 to one-one _ Comparative Example 8 〇0 mm One M1 70 _ . i 卜 90 M2 in cc loser 》 Comparative example το Comparative example 11 Note) 2 kk in the table: "parts, 17 均 r - i - » one 17 M2 83 one _ one one one M4 M4 1 83 ____ — [Preparation of test materials] A 2% aqueous solution of fencury 4377K (alkali degreaser made by Pakalai Co., Ltd.) was sprayed on an aluminum alloy plate (A3 004, plate thickness 〇.26 mm) at 5 °C. After degreasing for 10 seconds, the surface was washed with water, and then dried by heating at 80 ° C for 1 minute to evaporate the moisture on the surface of the aluminum alloy plate. Examples 1 to 3 shown in Table 2 were used using a bar coater (#3 bar). 9 and a 5% by mass aqueous solution of the metal surface treatment agent of Comparative Examples 1 to 1 1 were applied to the surface of the aluminum alloy plate after degreasing and washing, and dried in a hot air circulating drying oven at 200 t. After the clock, a surface treated film was formed on the surface of the aluminum alloy plate. The polyester film (film thickness 16) was obtained at 5 50 ° C for 5 seconds (reaching the plate temperature of 1 80 ° C) and a surface pressure of 50 kg / cm 2 . /zm) Thermal lamination to the alloy sheet forming the surface treated film to produce a "coated metal sheet". The coated metal sheets obtained by laminating the resin film were subjected to deep-drawing processing by a screwing and soiling test. A coated metal plate having a perforation diameter of 60 mm (the first time) was twisted to make a cup having a diameter of 100 mm. Next, the cup was again screwed to a diameter of 75 mm (the second time), and then the screw was processed to a diameter of 65 mm (3rd - 37 - 201139735) to prepare a can for the test material. In addition, the extrusion (thin meat fraction) rates of the second twisting process, the second screwing process, and the third screwing process were 5 %, 15 %, and 15 %, respectively. [Performance Evaluation] The initial adhesion, the durability adhesion, and the acid-resistant adhesion of the coated metal sheets after the deep-drawing processing were evaluated by the following method I. Further, the stability of the agent was evaluated by the following method, and the results are shown in Table 5. (Initial Adhesion) The initial adhesion of the test materials after the deep rub processing was evaluated. If the film can be made into a can, the film is not peeled off, and it can be made into a can, but some of the film peeling is regarded as "△", and those who cannot be made into a can are regarded as "x". In addition, those who are completely unpeeled and have a good appearance in "〇" are regarded as "◎". (Endurance adhesion) The test material after deep-drawing was subjected to a distillation test under a heated and pressurized vapor atmosphere. The distillation enthalpy test was carried out at 1 2 5 ° C for 1 hour using a commercially available sterilizing apparatus (pressure cooker). Those who did not peel the film in the test material after the test were regarded as "〇", some of the film peelers were regarded as "△", and those whose film was completely peeled off were regarded as "X". In addition, those who are not peeled off at all and have a good appearance are considered to be "◎". (acid resistance)

S -38 - 201139735 The test material after processing was immersed in 5 〇 t 〇 5 % H F aqueous solution for 16 hours to evaluate the adhesion. Those who have not peeled off the film are regarded as "〇", those who peel off the film are regarded as "△", and those who are completely peeled off by the film are regarded as "χ". Also, those who are not completely peeled off and have a good appearance are considered to be "◎". (Pharmaceutical stability) Each of the metal surface treatment agents (agents) of Examples 1 to 39 and Comparative Examples 1 to η shown in Tables 2 to 4 was sealed in respective 300 cc poly containers, and the mixture was allowed to stand in an environment of 20 ° C. The state of the drug was evaluated after 2 weeks. Those who are uncured, separated and precipitated are regarded as "〇", those who are uncured and separated but precipitated are regarded as "△", and those who are cured and separated are regarded as "X". Also, those who are completely uncured, separated and precipitated in "〇" and have excellent stability are regarded as "◎". -39-201139735 [Table 5] Table 5 Initial Adhesive Durability Adhesion Acid-Adhesiveness Drug Stability N/C TM/C Zhe Shi Example 1 ◎ ◎ ◎ ◎ 0.090 0.05 S Example 2 ◎ ◎ ◎ ◎ 0 -091 0.10 0 Example 3 ◎ ◎ ◎ ◎ 0.057 0.05 贽 Example 4 〇〇 ◎ ◎ 0.071 0.03 Η Example 5 ◎ ◎ ◎ ◎ 0-052 0.07 Zhe Shi β ◎ ◎ ◎ ◎ 0.286 0.07 Zhe Shi 7 ◎ 〇〇 ◎ 0.093 0.11 S Example ◎ ◎ ◎ ◎ ◎ 0.096 0.08 0 Example 9 〇 ◎ 〇 0.0088 0.14 0 Example 10 〇 ◎ 〇 ◎ 0.022 0.07 Η Example 11 〇 ◎ 〇 ◎ 0.018 0.08 Bao Shi Example 12 ◎ ◎ ◎ ◎ 0.257 0.10 W Example 13 〇◎ 〇◎ 0.030 0.07 哲例例 14 〇© 〇◎ 0.041 0.11 ΐί Example 15 〇◎ 〇◎ 0.027 0.09 ΗExample 16 〇◎ 〇◎ 0.032 0.05 ΒΤExample 17 〇◎ 〇 ◎ 0.028 0.11 Example t8 〇 ◎ 〇 ◎ 0.025 0.05 哲例例 t9 ◎ 〇 ◎ ◎ 0.189 0.23 S Example 20 ◎ ◎ ◎ ◎ 0.091 0.15 Example 21 〇〇〇 ◎ 0.025 0.17 Example 22 〇〇〇 ◎ 0.023 0.14 Example 23 〇◎ 〇◎ 0.026 0.11 Official Example 24 〇 ◎ 〇 ◎ 0.203 0.16 Example 25 ◎ ◎ 〇 ◎ 0.091 0.13 Example 26 〇〇〇 ◎ 0.027 0.02 Example 27 〇〇〇 ◎ 0.027 0.18 Bao Shi Example 28 〇〇〇 ◎ 0.026 0.11 13 Example 29 〇 〇〇 ◎ 0.102 0.39 贲 Example 30 〇〇〇 ◎ 0.310 0.30 Η Example 31 〇〇〇 ◎ 0.100 0.34 0 Example 32 〇〇〇 ◎ 0.310 0.39 Tube Example 33 ◎ ◎ ◎ ◎ 0.098 0.07 Example 34 ◎ 〇 〇◎ 0.101 0.21 Example 35 〇〇〇〇0.099 0.40 啻Example 36 〇〇〇◎ 0.027 0.03 ΗExample 37 〇〇〇◎ 0.120 0.20 Window Example 38 〇〇〇◎ 0.320 0.03 Example 39 〇〇〇〇 0.343 0.02 Comparative Example 1 Δ XX ◎ 0.092 0 Comparative Example 2 △ XX ◎ 0.027 0 Comparative Example 3 XXX 〇 0 0.076 Comparative Example 4 X Δ Δ Δ 0.009 0.016 Comparative Example 5 XXX Δ 0.009 0.313 Comparative Example 6 Δ XX Δ 0.03 0.0008 Comparison Example 7 XXXX 0.03 0.17 Comparative Example 8 AXX Δ 0.0014 0.034 Comparative Example 9 XXXX 0.0014 1.52 Comparative Example 10 XXX Δ 0.012 0.003 Comparative Example 11 XXXX 0.012 1.42 -40- 201139 As shown in Table 5, the metal surface treatment agents of Examples 1 to 39 can form a surface treatment film having excellent adhesion between the surface of the metal material and the laminate film. Further, the metal surface treatment agent of Comparative Example 1 containing no water-soluble metal compound and Comparative Example 2, and the metal surface treatment agent of Comparative Example 3 having an aqueous resin containing no nitrogen-containing functional group formed a surface having poor adhesion. Membrane. In particular, durability adhesion and acid resistance are significantly poor. The reason for this is that the corrosion resistance is insufficient. Further, Comparative Examples 3, 8, and 9 in which N/C exceeded 0.005 to 0.5 and initial adhesion, durability, and adhesion of Comparative Examples 1, 2, 6, and 9 to 11 in which TM/C exceeded 0.01 to 1.3, Acid resistance is poor. Further, Comparative Examples 4, 5, 6, 7, 8, 9, 10, and 11 using only one of the nitrogen-containing functional groups having an average number of molecular weights exceeding 50 to 3,000, except for the nitrogen-containing functional group, were used in addition to the initial density. The stability of the drug, the durability of the adhesive, and the acid-adhesiveness are significantly poor. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a schematic cross-sectional view showing an embodiment of a surface treatment film of the present invention. [Explanation of main component symbols] 1 : Metal material 2 : Surface treatment film 3 : Laminated film or resin coating film 1 : Metal material with surface treatment film -41 -

Claims (1)

201139735 VII. Patent application scope: 1. A surface treatment film which is coated with a surface treatment film formed on the surface of a metal material, characterized by a mass ratio of nitrogen to carbon contained in the surface treatment film (Ν/C) It is 0.005 to 0.5, and the total mass ratio of metal elements selected from chromium (III), pin, titanium, vanadium, niobium, molybdenum, tungsten and niobium to carbon (TM/C) is 0.01 to 1.3. A metal surface treatment agent for obtaining a metal surface treatment agent for a surface treatment film according to the first aspect of the invention, characterized in that it comprises a urethane resin, an epoxy resin, an acrylic resin One or more water-based resins selected from the group consisting of polyolefin resins, formal water condensation resins, natural polysaccharides, polyamines and polyacrylamides; and containing chromium (yttrium), zirconium, titanium, vanadium, niobium And a water-soluble metal compound of one or more metal elements selected from the group consisting of molybdenum, tungsten, and lanthanum, and at least one of the water-based resins is one selected from the following structural formulas (1) to (8). Or two or more nitrogen-containing functional groups, (in the structural formulas (1) to (8), R, R2, and R3 are each independently hydrogen, or a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms, Alkenyl, hydroxyalkyl, hydroxyalkenyl, aryl, aralkyl, hydroxyaryl or hydroxyaralkyl, X is hydroxide ion, halide, sulfate, sulfonate, phosphate and phosphonic acid One or more selected from the ions) -42- 201139735 [化4] (1) N —Ra X- (2) R3 N (3) (4) N (5) (6) —C —N—·Ri (7) ——C —N—(8) ][J II I 0 R2 0 Ri o 3 ·—A metal surface treatment agent, which is used to obtain a patent application A metal surface treatment agent for a surface treatment film according to the first aspect, which comprises one or more of the first water-based resins selected from the group consisting of urethane resins, epoxy resins and acrylic resins, and a poly One or two or more kinds of second water-based resins selected from the group consisting of olefin-based resins, formal water-condensed resins, and natural polysaccharides, polyamines and polyacrylamides; and containing chromium (π)), zirconium, titanium, and vanadium a water-soluble metal compound of one or more metal elements selected from the group consisting of ruthenium, molybdenum, tungsten, and lanthanum, and at least one of the first water-based resin and the second water-based resin has the following structural formula (1) Selected in (8)! Species or more than two kinds of nitrogen-containing official -43-201139735 energy bases, (in the structural formulas (1) to (8), 'R, 'R2, R3 are each independently hydrogen, or a linear or branched chain having a carbon number of 1 to 10. Or a cyclic alkyl, alkenyl, hydroxyalkyl, hydroxyalkenyl, aryl, aralkyl, hydroxyaryl or hydroxyarylalkyl group, X is a hydroxide ion, a halide ion, a sulfate ion, a sulfonate ion At least one selected from the group consisting of a phosphate ion and a phosphonic acid ion) (1) N —R2 X- (2) R3 (3) N--X- (4) R2 N (5) (6) A C-N-Ri (7)-C-N-(8) II I II I vy 0 R2 0 R! ο 4. A metal surface treatment agent according to claim 2 or 3, wherein the foregoing contains The nitrogen-containing functional group of the nitrogen-functional water-based resin has an average number of molecular weights of 50 to 3000 Å. The content of the water-soluble metal compound in the metal surface treatment agent relative to the total solid content is metal-converted S-44 - 201139735 The next 1 to 50% by mass. 5. A metal surface treatment method characterized in that a metal surface treatment agent according to any one of claims 2 to 4 is applied to a surface of a metal material to be '60 to 250 ° C. The temperature is heated and dried. A metal material having a surface treatment film as set forth in the scope of the patent application. / -45-