JP5860583B2 - Metal surface treatment agent and metal surface treatment method - Google Patents

Description

  The present invention relates to a surface treatment film capable of improving the adhesion between the surface of a metal material and a laminate film or a resin coating film, a metal surface treatment agent for forming the surface treatment film, and the metal surface treatment agent. The present invention relates to a method of treating a metal surface using More specifically, even when a resin film is laminated or a resin coating film is formed on the surface of a metal material, and then severe molding processing such as deep drawing processing, ironing processing or stretch drawing processing is performed, the lamination is performed. A surface-treated film excellent in chemical resistance capable of imparting high adhesion such that the film or resin coating does not peel, and maintaining high adhesion even when exposed to an acid or the like, and the surface-treated film The present invention relates to a metal surface treatment agent or the like for forming a metal.

  Lamination is a processing means for heat-pressing a resin film (hereinafter referred to as a resin film or a laminate film) to the surface of a metal material, and is a metal for the purpose of protecting the surface or imparting design properties. This is one of the methods for coating the material surface and is used in various fields. This laminating process produces less waste gas such as solvent, carbon dioxide, etc. or warming gas generated during drying compared to the method of forming a resin coating by applying and drying a resin composition on the surface of a metal material. . Therefore, it is preferably applied in terms of environmental protection, and its uses are expanded. It is used for containers or dry battery containers.

  In particular, recently, a metal foil such as a lightweight and highly barriered aluminum foil or stainless steel foil is preferably used as an exterior material of a mobile lithium ion secondary battery used in a mobile phone, an electronic notebook, a notebook computer, a video camera, or the like. Lamination is applied to the surface of such a metal foil. In addition, lithium ion secondary batteries have been studied as driving energy for electric vehicles or hybrid vehicles, and laminated metal foils have also been examined as exterior materials.

  The laminate film used for such a lamination process is directly bonded to a metal material and then heat-pressed. Therefore, there are advantages such that the waste of the raw material can be suppressed, the number of pinholes (defects) is small, and the workability is excellent as compared with a general resin coating film formed by applying and drying a resin composition. As materials for the laminate film, polyester resins such as polyethylene terephthalate and polyethylene naphthalate, and polyolefins such as polyethylene and polypropylene are generally used.

  When laminating a laminate film to a metal material surface (hereinafter also simply referred to as “metal surface”), the metal surface is degreased and washed to improve the adhesion between the laminate film and the metal surface and the corrosion resistance of the metal surface. Thereafter, chemical conversion treatment such as phosphoric acid chromate is usually performed. However, such a chemical conversion treatment requires a washing step for removing excess treatment liquid after the treatment, and costs for waste water treatment of washing water discharged from the washing step. In particular, chemical treatments such as phosphoric acid chromate tend to be avoided from environmental considerations in recent years because a treatment solution containing hexavalent chromium is used.

  On the other hand, when the lamination process is performed without performing a chemical conversion treatment or the like on the metal surface, there is a problem that the laminate film is peeled off from the metal surface or the metal material is corroded. For example, in food containers or packaging materials, the contents are added to the container or packaging material after lamination, and then heat treatment for sterilization is performed, but the laminate film is peeled off from the metal surface during the heat treatment. There is. Moreover, in the exterior material etc. of a lithium ion secondary battery, processing with a high degree of processing is received in the manufacturing process. When such an exterior material is used for a long time, moisture in the atmosphere enters the container, which reacts with the electrolyte to produce hydrofluoric acid, which permeates the laminate film and peels the metal surface from the laminate film. And the problem of corroding the metal surface.

  In order to deal with such problems, a method, a treatment agent, and the like for forming a film on the metal surface for improving the adhesion to the laminate film have been proposed prior to lamination. For example, Patent Document 1 proposes a base treatment agent containing a specific amount of a water-soluble zirconium compound, a water-soluble or water-dispersible acrylic resin having a specific structure, and a water-soluble or water-dispersible thermosetting crosslinking agent. ing. Patent Document 2 proposes a non-chromium metal surface treatment agent comprising a specific amount of a water-soluble zirconium compound and / or water-soluble titanium compound, an organic phosphonic acid compound, and tannin. Patent Document 3 proposes a metal surface treatment agent containing an aminated phenol polymer and a specific metal compound such as Ti and Zr and having a pH in the range of 1.5 to 6.0. . Patent Document 4 proposes a resin film containing an aminated phenol polymer, an acrylic polymer, a metal compound, and, if necessary, a phosphorus compound (C).

JP 2002-265821 A JP 2003-313680 A JP 2003-138382 A JP 2004-262143 A

  The purpose of the present invention is to laminate a resin film on the surface of a metal material or to form a resin coating film, and then apply severe molding processing such as deep drawing processing, ironing processing or stretch drawing processing, An object of the present invention is to provide a surface-treated film capable of imparting high adhesion such that the laminate film or resin film does not peel off, and to provide a metal material having the surface-treated film.

  Another object of the present invention is to provide a metal surface treatment agent for forming the surface treatment film and to provide a metal surface treatment method using the metal surface treatment agent.

  The surface treatment film according to the present invention for solving the above problems is a surface treatment film formed by coating on the surface of a metal material, and a mass ratio (N / C) of nitrogen and carbon contained in the surface treatment film. 0.005 to 0.5, and the total mass of metal elements selected from Cr (III), Zr, Ti, V, Nb, Mo, W and Ce and the mass ratio of carbon (TM / C) is 0. .01 to 1.3.

  According to this invention, the mass ratio (N / C) of nitrogen and carbon contained in the surface treatment film, and the total of the metal elements contained in the surface treatment film and the mass ratio of carbon (TM / C) are within the above range. Therefore, it is possible to improve both the adhesion between the surface of the metal material and the surface treatment film and the adhesion between the laminate film and the surface treatment film, good corrosion resistance, and preferable in terms of acid resistance. It becomes.

  In particular, by making the mass ratio of nitrogen and carbon (N / C) within the above range, sufficient adhesion can be obtained between the surface treatment film and the laminate film, and the water resistance of the surface treatment film can be improved. It is possible to prevent the deterioration of the corrosion resistance (particularly acid resistance, the same applies hereinafter) on the surface of the metal material by preventing the decrease, and thus the decrease in the adhesion between the surface of the metal material and the surface treatment film. In addition, by setting the total mass of metal elements and the mass ratio of carbon (TM / C) within the above range, the deterioration of adhesion between the surface of the metal material and the surface treatment film is prevented, and the corrosion medium is formed on the surface of the metal material. In addition to preventing the corrosion resistance from entering and reducing the adhesion between the metal surface and the surface treatment film, especially in a high humidity environment, and further preventing the surface treatment film from becoming brittle, There is an advantage that the adhesion between the surface-treated film and the laminate film is not lowered even if processing is added thereafter.

  The metal surface treatment agent according to the present invention for solving the above problems provides the following two metal surface treatment agents capable of obtaining the surface treatment film according to the present invention.

  The first metal surface treatment agent includes one or more water-based resins (P) selected from urethane resin, epoxy resin, acrylic resin, polyolefin resin, formalin condensation resin, natural polysaccharide, polyamide and polyacrylamide. And a water-soluble metal compound containing one or more metal elements selected from Cr (III), Zr, Ti, V, Nb, Mo, W and Ce, and among the aqueous resins (P) At least 1 type has 1 type, or 2 or more types of nitrogen-containing functional groups chosen from following structural formula (1)-(8), It is characterized by the above-mentioned.

  The second metal surface treatment agent includes one or more first water-based resins (P1) selected from urethane resins, epoxy resins, and acrylic resins, polyolefin resins, formalin condensation resins, natural polysaccharides, polyamides, and the like. One or more second water-based resins (P2) selected from polyacrylamide and one or more metals selected from Cr (III), Zr, Ti, V, Nb, Mo, W and Ce A water-soluble metal compound containing an element, and at least one of the first aqueous resin (P1) and the second aqueous resin (P2) is selected from the following structural formulas (1) to (8) Or it has 2 or more types of nitrogen-containing functional groups, It is characterized by the above-mentioned.

In the above structural formulas (1) to (8), R ₁ , R ₂ and R ₃ are each independently hydrogen, a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms, or an alkenyl group. , A hydroxyalkyl group, a hydroxyalkenyl group, an aryl group, an arylalkyl group, a hydroxyaryl group or a hydroxyarylalkyl group. X is one or more selected from hydroxide ions, halogen ions, sulfate ions, sulfonate ions, phosphate ions and phosphonate ions.

  According to these inventions, since the specific type of water-based resin having a specific type of nitrogen-containing functional group is contained, the water-based resin can be stably present in the treatment agent and has high adhesion to the metal surface. It is possible to form a surface-treated film that brings about properties. As a result, a surface treatment film formed by treatment with these metal surface treatment agents is formed on a metal surface, and a resin film is laminated thereon or a resin coating film is formed by deep drawing, ironing or stretch drawing. Even when severe molding processing such as processing is performed, the laminate film or resin coating film is difficult to peel off. In particular, according to the second metal surface treatment agent, from the first aqueous resin (P1) and the first aqueous resin (P1) which are easily oriented on the surface of the obtained treatment film (the surface opposite to the surface side of the metal material). Since the second aqueous resin (P2) having high polarity and easy to be oriented on the surface of the metal material is used in combination, a surface-treated film that provides better moldability and adhesion can be formed.

  In the first and second metal surface treatment agents according to the present invention, the aqueous resin containing the nitrogen-containing functional group has a number average molecular weight per nitrogen-containing functional group of 50 to 3000, and the metal surface The said water-soluble metal compound with respect to the total solid in a processing agent is contained 1-50 mass% in conversion of a metal.

  According to this invention, the water-based resin containing a nitrogen-containing functional group has a number average molecular weight per nitrogen-containing functional group within the above range, and the water-soluble metal compound is contained in the total solid content in the metal surface treatment agent. Since the amount is within the above range, the mass ratio (N / C) of nitrogen and carbon contained in the surface treatment film obtained using this metal surface treatment agent is within the range of 0.005 to 0.5. The mass ratio (TM / C) of the total of metal elements and carbon contained in the surface treatment film can be within a range of 0.01 to 1.3. As a result, if this metal surface treatment agent is used, both 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 are improved. In addition, it has good corrosion resistance and can form a surface treatment film that is preferable in terms of acid resistance.

  In order to solve the above problems, the metal surface treatment method according to the present invention is such that the first or second metal surface treatment agent according to the present invention is applied to the surface of a metal material and then heated at a temperature of 60 to 250 ° C. It is characterized by drying.

  A metal material according to the present invention for solving the above-described problems is characterized by having the surface treatment film according to the present invention.

  According to the surface treatment film according to the present invention, the “nitrogen / carbon” ratio and the “total of metal elements / carbon” ratio included in the film are within a specific range. Both the adhesion between the laminate film and the adhesion between the laminate film and the surface treatment film can be enhanced, the corrosion resistance is good, and the acid resistance is preferable.

  According to the first and second metal surface treatment agents according to the present invention, the water-based resin can be stably present in the treatment agent, and a surface treatment film that provides high adhesion to the metal surface is formed. be able to. As a result, a surface treatment film is formed on the metal surface with the metal surface treatment agent according to the present invention, and a resin film is laminated thereon or a resin coating film is formed by deep drawing, ironing or stretch drawing. Even when a severe molding process such as the above is performed, there is an effect that the laminate film or the resin coating film is hardly peeled off.

  According to the metal surface treatment method of the present invention, the metal surface treatment agent according to the present invention is applied to the surface of the metal material (the surface of the metal to be treated) and then dried by heating. A surface-treated film with good adhesion can be formed.

  According to the metal material of the present invention, since the surface treatment film is provided on the surface, the adhesion of the laminate film to the surface treatment film can be enhanced. As a result, a laminate of a resin film or a resin coating film on the surface treatment film is laminated even when severe molding processing such as deep drawing processing, ironing processing or stretch drawing processing is performed. There is an effect that the film or the resin coating film is hardly peeled off.

It is typical sectional drawing which shows embodiment of the surface treatment film | membrane which concerns on this invention.

  Hereinafter, the surface treatment film, metal surface treatment agent, and metal surface treatment method according to the present invention will be described.

[Surface treatment film]
As shown in FIG. 1, the surface treatment film 2 according to the present invention is a surface treatment film applied and formed on the surface of the metal material 1 (hereinafter referred to as “metal surface”), and is included in the surface treatment film 2. Of nitrogen and carbon mass ratio (N / C) of 0.005 to 0.5, and a total of metal elements selected from Cr (III), Zr, Ti, V, Nb, Mo, W and Ce And the carbon mass ratio (TM / C) is 0.01 to 1.3. As shown in FIG. 1, the surface treatment film 2 is a film obtained by applying a metal surface treatment agent according to the present invention, which will be described later, to a metal surface and then drying by heating at a predetermined temperature. And a laminate film (or resin coating film) 3.

  By making the mass ratio (N / C) of nitrogen (N) and carbon (C) within the above range, sufficient adhesion between the surface treatment film 2 and the laminate film 3 can be obtained, It is possible to prevent a decrease in water resistance of the surface treatment film 2 to prevent a decrease in corrosion resistance of the metal surface (particularly acid resistance, the same applies hereinafter), and thus a decrease in adhesion between the metal surface and the surface treatment film 2 can be prevented. .

  When the mass ratio (N / C) of nitrogen and carbon is less than 0.005, sufficient adhesion may not be obtained between the surface treatment film 2 and the laminate film 3. On the other hand, when the mass ratio (N / C) of nitrogen and carbon exceeds 0.5, the water resistance of the surface treatment film 2 is lowered, the corrosion resistance of the metal surface is lowered, and consequently between the metal surface and the surface treatment film 2. May cause reduced adhesion. The mass ratio (N / C) of nitrogen and carbon improves the adhesion between the metal surface and the surface treatment film 2 and the corrosion resistance of the surface treatment film 2, and further aggregates by introducing nitrogen-containing functional groups that are polar groups. From the viewpoint of increasing the force and improving the film formability, it is preferably within the range of 0.008 to 0.4, and the adhesion between the surface treatment film 2 and the laminate film 3 and the surface treatment film 2 are further improved. From the viewpoint of particularly improving the corrosion resistance, it is particularly preferably in the range of 0.05 to 0.3. The reason why the upper limit value of the preferable range is 0.4 and the upper limit value of the particularly preferable range is 0.3 is based on the viewpoints of water resistance and adhesion.

  By setting the total mass of metal elements and the mass ratio of carbon (TM / C) within the above range, the adhesion between the metal surface and the surface treatment film 2 is prevented from decreasing, and a corrosion medium enters the metal surface and is corrosion resistant. Can be prevented, and in particular, in a high-humidity environment, the adhesion between the metal surface and the surface treatment film 2 can be prevented from being lowered, and further, the surface treatment film 2 can be prevented from becoming brittle. There is an advantage that the adhesion between the surface-treated film 2 and the laminate film 3 is not lowered even if processing is added to the above.

  When the total mass of metal elements and the mass ratio of carbon (TM / C) is less than 0.01, the adhesion between the metal surface and the surface treatment film 2 is lowered, and as a result, a corrosive medium enters the metal surface. Corrosion resistance may be insufficient. In particular, the adhesion between the metal surface and the surface treatment film 2 may deteriorate in a high humidity environment. On the other hand, if the mass ratio (TM / C) of the total of metal elements and carbon exceeds 1.3, the surface treatment film 2 becomes too brittle, and when processing is added thereafter, the surface treatment film 2 and the laminate film 3 The adhesiveness of is reduced. Further, the mass ratio (TM / C) of the total of metal elements and carbon is 0.01% from the viewpoint of improving the adhesion and corrosion resistance and further improving the film forming property so as not to cause cracks. It is preferably in the range of -0.7, and from the viewpoint of enhancing the adhesion between the metal surface and the surface treatment film 2 in a high humidity environment, it is preferably in the range of 0.05-0.3. Particularly preferred.

  Here, the carbon content is a total organic carbon analyzer (TOC: 5000-A) manufactured by Shimadzu Corporation, oxygen flow rate: 0.5 L / min, temperature: 580 ° C. (aluminum ), 700 ° C. (iron-based material), measurement time: 120 seconds, sample size: 10 mm × 20 mm. The nitrogen content is based on the organic nitrogen analysis method (JIS-K0102), and the metal material on which the surface treatment film is formed is immersed in concentrated sulfuric acid for 30 seconds to peel and dissolve the film, and the stripping solution (sulfuric acid solution) The total nitrogen concentration was measured according to JIS-K0102. The pretreatment was Kjeldahl method, and the measurement was performed by indophenol blue absorptiometry. The total mass of the metal elements was measured using a fluorescent X-ray analyzer “3270E” manufactured by Rigaku Denki Kogyo Co., Ltd. under the conditions of tube: Rh, voltage-current: 50 KV-50 mA.

  As described above, according to the surface treatment film according to the present invention, the “nitrogen / carbon” ratio and the “total of metal elements / carbon” ratio of the film are within a specific range. It is possible to improve both the adhesion between the two and the adhesion between the laminate film 3 and the surface treatment film 2, and the corrosion resistance is good, which is preferable in terms of acid resistance.

  A metal material having such a surface treatment film on the surface can enhance the adhesion of the laminate film to the surface treatment film. As a result, a laminate of a resin film or a resin coating film on the laminate film or resin, even when subjected to severe molding such as deep drawing, ironing or stretch drawing There is an effect that the coating film is difficult to peel off.

[Metal surface treatment agent]
The metal surface treatment agent according to the present invention is a treatment agent for obtaining the surface treatment film according to the present invention, and provides the metal surface treatment agent of the following two aspects.

  The first metal surface treatment agent includes one or more water-based resins (P) selected from urethane resin, epoxy resin, acrylic resin, polyolefin resin, formalin condensation resin, natural polysaccharide, polyamide and polyacrylamide. , Cr (III), Zr, Ti, V, Nb, Mo, W, and Ce, and a water-soluble metal compound containing one or more metal elements. And at least 1 sort (s) among the water-system resin (P) has 1 type, or 2 or more types of nitrogen-containing functional group chosen from above-described structural formula (1)-(8). Here, a code | symbol (P) points out the water-system resin which comprises a 1st metal surface treating agent.

  On the other hand, the second metal surface treatment agent includes one or more first water-based resins (P1) selected from urethane resins, epoxy resins, and acrylic resins, polyolefin resins, formalin condensation resins, natural polysaccharides, One or more second water-based resins (P2) selected from polyamide and polyacrylamide, and one or more selected from Cr (III), Zr, Ti, V, Nb, Mo, W and Ce. And a water-soluble metal compound containing a metal element. And at least 1 sort (s) among the 1st water system resin (P1) and the 2nd water system resin (P2) is 1 type, or 2 or more types of nitrogen-containing functional groups chosen from above-mentioned structural formula (1)-(8). have. The first aqueous resin (P1) has a property of being easily oriented on the surface of the obtained surface treatment film (opposite surface on the metal surface side), and the second aqueous resin (P2) is more than the first aqueous resin. It has a high polarity and is easily oriented on the metal surface.

  Hereinafter, the configuration of the present invention will be described in detail in the order of an aqueous resin and a water-soluble metal compound.

(Water-based resin)
The first metal surface treatment agent is one or more water-based resins (P) selected from urethane resin, epoxy resin, acrylic resin, polyolefin resin, formalin condensation resin, natural polysaccharide, polyester, polyamide and polyacrylamide. ) Is used. In this embodiment, 1 to 3 types of aqueous resins are usually blended and used, but more than that may be used.

  On the other hand, the second metal surface treatment agent includes one or more first water-based resins (P1) selected from urethane resins, epoxy resins, and acrylic resins, polyolefin resins, formalin condensation resins, natural polysaccharides, It is characterized in that it is used in combination with one or more second aqueous resins (P2) selected from polyester, polyamide and polyacrylamide. In this embodiment, one or two kinds of first aqueous resins and one or two kinds of second aqueous resins are usually used in combination, but more than that may be used.

  These 1st and 2nd metal surface treating agents contain 1 type, or 2 or more types of aqueous resin, The 1 type or 2 types from which at least 1 type is chosen from above-described structural formula (1)-(8). It has the above nitrogen-containing functional groups. Structural formula (1)-(8) has shown the 1-3 primary amino group, the quaternary ammonium group, and the 1-2 secondary amide group. The nitrogen-containing functional groups of the structural formulas (1) and (2) are present in the side chain of the aqueous resin, and the nitrogen-containing functional groups of the structural formulas (3) to (6) are all present in the main chain of the aqueous resin. The aqueous resin having a nitrogen-containing functional group of any one of these structural formulas (1) to (6) exhibits a cationic property in water. The nitrogen-containing functional groups in the structural formulas (7) and (8) indicate a structure having an amide bond in the side chain or main chain of the aqueous resin.

  The water-based resin contained in the metal surface treatment agent only needs to have at least one nitrogen-containing functional group as described above, and all of the water-based resins contained include one or two of the nitrogen-containing functional groups described above. You may have more than one seed. Since the water-based resin has a nitrogen-containing functional group, the adhesion between the obtained surface treatment film and the metal surface is excellent, and the water dispersibility (stability in the liquid) of the metal surface treatment agent is good. Become.

  In the above structural formulas (1) to (8), the amino group has an effect of exhibiting cationic property in water and improving the water solubility or water dispersibility of the resin. In addition, although the amide group is nonionic, it exhibits high polarity due to the lone pair of nitrogen (lone pair) and the polarization of the carbonyl group. Therefore, as with the amino group, it has high water solubility or water dispersibility in the resin. Has the ability to grant.

  By including a certain amount of nitrogen-containing functional groups in the water-based resin constituting the metal surface treatment agent, adhesion between the metal surface and the obtained surface treatment film and the laminate film and the obtained surface treatment film It is possible to improve both the adhesion between them and to improve the corrosion resistance. Furthermore, the stability of the metal surface treatment agent is improved, and a metal treatment film with good adhesion can be formed stably.

  The number average molecular weight per nitrogen-containing functional group of the water-based resin having a nitrogen-containing functional group is preferably in the range of 50 to 3000. The mass of nitrogen and carbon contained in the surface treatment film formed with the metal surface treatment agent by adjusting the metal surface treatment agent with the number average molecular weight of the water-based resin per nitrogen-containing functional group within this range. The ratio (N / C) can be 0.005 to 0.5.

  When the mass ratio (N / C) of nitrogen (N) and carbon (C) contained in the surface treatment film formed with the metal surface treatment agent is within the above range, the surface treatment film and the laminate film Sufficient adhesion between the metal surface and the surface treated film to prevent deterioration of the water resistance to prevent deterioration of the corrosion resistance of the metal surface, and thus the adhesion between the metal surface and the obtained surface treated film. Decline can be prevented.

  In addition, as long as the number average molecular weight of the aqueous resin per nitrogen-containing functional group of the aqueous resin 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 Although it does not specifically limit and it is arbitrary according to content of a nitrogen-containing functional group, if it dares to prescribe, it is preferable that it is the range of 1000-100000. If it is less than 1000, the film forming property tends to be poor, and if it exceeds 100,000, the viscosity is too high and it becomes difficult to produce a stable treatment liquid.

  In any of the first and second metal surface treatment agents, the aqueous resin contained does not contain a nitrogen-containing functional group regardless of whether the nitrogen-containing functional group is contained in all of the aqueous resin or one or a part thereof. The number average molecular weight per nitrogen-containing functional group of the aqueous resin containing a nitrogen functional group may be in the range of 50 to 3000 described above. In particular, it is preferable that all types of water-based resins contained in the metal surface treatment agent have a nitrogen-containing functional group and fall within the above range.

  In particular, as for the second metal surface treatment agent, the number average molecular weight per nitrogen-containing functional group of the aqueous resin containing a nitrogen-containing functional group as a whole may be in the range of 50 to 3000 as described above. Is selected from urethane resins, epoxy resins and acrylic resins, one or more first water-based resins (P1), polyolefin resins, formalin condensation resins, natural polysaccharides, polyamides and polyacrylamides Or it can specify in more detail with 2 or more types of 2nd water based resin (P2). That is, the first aqueous resin (P1) contained in the second metal surface treatment agent has a number average molecular weight of 500 to 3000 per nitrogen-containing functional group of the first aqueous resin (P1) containing a nitrogen-containing functional group. It is more preferable to be within the range. The first aqueous resin (P1) within this range acts as a barrier that suppresses permeation of corrosion factors such as oxygen, moisture, and corrosive ions from outside the system in the surface treatment film.

  On the other hand, the second aqueous resin (P2) contained in the second metal surface treatment agent has a number average molecular weight of 50 to 1500 per nitrogen-containing functional group of the second aqueous resin (P2) containing a nitrogen-containing functional group. It is more preferable that it has a number average molecular weight. The second aqueous resin (P2) in this range strongly adsorbs to the metal surface in the surface treatment film, and acts to suppress the invasion of corrosion factors at the interface with the metal. In addition, the case where all the 2nd water based resin (P2) has a nitrogen-containing functional group is especially preferable from a viewpoint of adhesiveness with a metal surface.

  In the second metal surface treatment agent that simultaneously contains the first aqueous resin (P1) and the second aqueous resin (P2) that exert the above-described action, the first aqueous resin (P1) is oriented on the surface of the obtained surface treatment film. As a result, it has the effect of increasing the water resistance of the surface treatment film and imparting good moldability. On the other hand, the second aqueous resin (P2) having a higher polarity than the first aqueous resin (P1) is easily oriented on the metal surface, and as a result, the adhesion of the surface treatment film formed on the metal surface can be further increased. There is an effect that can be done. In the second metal surface treatment agent, the blending ratio (P1 / P2) of the first aqueous resin (P1) and the second aqueous resin (P2) that exhibits the above effects is not particularly limited and may be in a wide range. For example, the mass ratio can be 1/99 to 99/1 (that is, 0.01 to 99). The blending ratio (P1 / P2) is more preferably 20/80 to 95/5 (that is, 0.25 to 95), and a preferable range in consideration of the balance of each characteristic is 40/60 to 95/5 ( That is, 0.66 to 95).

  In addition, when a resin or a compound having high reactivity with active hydrogen such as a glycidyl group or an isocyanate group is used in combination, it is possible to apply a resin having a tertiary amine, a secondary amine or an amide to stabilize the treatment agent. This is more preferable.

  Examples of water-based resins having a nitrogen-containing functional group are shown below.

  As a urethane resin, first, as a polyol component which is a raw material monomer, for example, alkylene (1 to 6 carbon atoms) glycol (ethylene glycol, propylene glycol, butylene glycol, neopentyl glycol, hexamethylene glycol, etc.), polyether polyol ( Polyethylene glycols such as diethylene glycol and triethylene glycol, polyethylene / propylene glycol, etc.), polyester polyols (alkylene glycols and polyether polyols as described above, bisphenol A, hydrogenated bisphenol A, trimethylolpropane, and polyols such as glycerin; Polybasic acids such as succinic acid, glutaric acid, adipic acid, sebacic acid, phthalic acid, isophthalic acid, terephthalic acid, and trimellitic acid Polyester polyol having terminal hydroxyl groups obtained by the polycondensation), and using a polyol component such as a polycarbonate polyol.

  And a part or all of the polyol component is a cationic polyol (for example, N-alkyl-N, N-dihydroxyalkylamine having an amino group or an ammonium group in the side chain or part of the main chain of the polyol structure described above. Such as a polyol having an amino group in the main chain, or a cationic polyol having an amino group in the side chain such as N, N-dialkylaminoalkylene glycol). These polyols may be aromatic, alicyclic or fatty. Polyisocyanates such as tolylene diisocyanate, diphenylmethane diisocyanate, xylylene diisocyanate, dicyclohexylmethane diisocyanate, cyclohexylene diisocyanate, hexamethylene diisocyanate, and lysine diisocyanate. A polymer is emulsified and dispersed in an aqueous solution of a carboxylic acid such as alkyl sulfuric acid, formic acid or acetic acid, or an organic phosphonic acid, and subjected to a chain extension reaction using water or / and an amine compound such as ethyleneamine or melamine. Urethane resin or the like can be used.

  As the epoxy resin, a modified epoxy resin comprising an addition reaction between a bisphenol type, novolak type or alkylene type epoxy resin and a polyfunctional amine can be used. For example, bisphenol A-diglycidyl ether, bisphenol F-diglycidyl ether, novolac glycidyl ether, hexahydrophthalic acid glycidyl ester, dimer acid glycidyl ester, tetraglycidylaminodiphenylmethane, 3,4-epoxy-6-methylcyclohexyl methyl carboxylate , Triglycidyl isocyanurate, 3,4-epoxycyclohexylmethyl carboxylate, polypropylene diglycidyl ether, polybutadiene or polysulfide modified at both ends with diglycidyl ether, and polysulfide-modified epoxy resin.

  The polyfunctional amine described above is an amine having two or more active hydrogens in one molecule. Specifically, isopropanolamine, monopropanolamine, monobutanolamine, monoethanolamine, diethylenetriamine, ethylenediamine, butylamine, propylamine, isophoronediamine, tetrahydrofurfurylamine, xylenediamine, diaminediphenylmethane, diaminosulfone, octylamine, metaphenylene Examples include diamine, amylamine, hexylamine, nonylamine, decylamine, triethylenetetramine, tetramethylenepentamine, dimethylaminopropylamine, N-aminoethylpiperazine, metacenediamine, and diaminodiphenylsulfone. Alkanolamines are particularly preferred because of their good solubility in water.

  As the acrylic resin, a monomer in which at least one of the constituent monomers of the resin has a nitrogen-containing functional group selected from a primary to tertiary amino group, a quaternary ammonium group, and a primary to secondary amide group can be used. . Further, acrylamide is used as a part of the monomer component, and further aminated by Mannich reaction, Hoffman reaction or the like.

  As the above-mentioned acrylic monomer having a nitrogen-containing functional group, aminoalkyl acrylate such as aminomethyl acrylate, aminomethyl methacrylate, aminoethyl acrylate, aminoethyl methacrylate, aminopropyl acrylate, aminobutyl acrylate, etc. 8) Esters, (meth) acrylamide, methylol (meth) acrylamide, and the like.

  Examples of the polyolefin-based resin include cationic polyolefins such as polyvinylphenol-modified Mannich amine, polyvinyl imidazole, polyvinyl pyridine, and polyethyleneimine.

  Examples of the formalin condensation resin include cationic formalin condensation resins such as melamine resin, Mannich-modified aminated phenol resin, and Mannich-modified amination resin of aniline and formalin condensation resin.

  Examples of natural polysaccharides include cationic natural polysaccharides such as chitin and chitosan.

  Examples of the polyamide include cation-modified polyamides such as cationic nylon obtained by condensation polymerization of aminopiperazine and adipic acid.

  Examples of polyacrylamide include acrylamide homopolymers and copolymers with other monomers (acrylic acid, acrylate esters, etc.) copolymerizable with acrylamide.

  Each of these water-based resins has the nitrogen-containing functional group of any one of the structural formulas (1) to (8) described above. Therefore, one or more of these water-based resins are combined to form a metal surface treatment agent. It is preferable.

  The water-based resin constituting the metal surface treatment agent is water-soluble resin, water-based crosslinkable resin such as water-based dispersion, water-based emulsion, water-based emulsion forcedly emulsified by self-emulsification or emulsifier, regardless of whether it contains a nitrogen-containing functional group, Or a water-based polymer resin can be mentioned. These polymer resins may have a crosslinkable functional group as long as the effects of the present invention are not impaired.

  As described above, the water-based resin constituting the first and second metal surface treatment agents has a specific amount of the above-described nitrogen-containing functional groups, all or at least one or a part thereof, and as a result, It is sufficient that the mass ratio (N / C) of nitrogen and carbon contained in the obtained surface treatment film is adjusted to be 0.005 to 0.5. As a result, the surface treatment film formed with the metal surface treatment agent according to the present invention is improved in (a) the adhesion between the formed surface treatment film and the laminate film and the moldability is improved. As a result, the water resistance of the surface-treated film is improved to prevent a decrease in the corrosion resistance of the metal surface, the adhesion between the metal surface-treated film and the metal surface is improved, and the moldability is improved.

(Water-soluble metal compound)
In the first and second metal surface treatment agents, the water-soluble metal compound contained is one or more metals selected from Cr (III), Zr, Ti, V, Nb, Mo, W, and Ce. A water-soluble metal compound containing an element can be given. Note that Cr (III) means that hexavalent chromium is not included.

  The water-soluble metal compound is a salt, complex compound or coordination compound of the metal element described above. Specifically, for example, trivalent chromium compounds such as chromium fluoride, chromium nitrate, chromium sulfate, chromium oxalate, chromium acetate, and chromium biphosphate; zirconium hydrofluoric acid, zirconium zirconium hydrofluoride, zirconium fluoride Zirconium compounds such as sodium hydride, zirconyl nitrate, zirconyl sulfate, and zirconyl acetate; titanium hydrofluoric acid, potassium titanium hydrofluoride, sodium titanium hydrofluoride, titanyl sulfate, diisopropoxytitanium bisacetylacetone, lactic acid and titanium alkoxide And titanium compounds such as titanium lactate; pentavalent vanadium compounds such as vanadium pentoxide, metavanadate, ammonium metavanadate, sodium metavanadate, and vanadium oxytrichloride; vanadium trioxide Vanadium compounds having an oxidation number of pentavalent, tetravalent or trivalent vanadium such as vanadium oxide, vanadium dioxide, vanadium oxysulfate, vanadium oxyacetyl acetate, vanadium acetylacetate, vanadium trichloride and phosphovanadomolybdic acid; molybdic acid, molybdenum Molybdenum compounds such as ammonium acid, sodium molybdate, and molybdophosphoric acid compounds (eg, ammonium molybdate, sodium molybdophosphate, etc.); metatungsten, ammonium metatungstate, sodium metatungstate, paratungstic acid, ammonium paratungstate, And tungsten compounds such as sodium paratungstate; cerium compounds such as cerium acetate, cerium (III) or (IV) nitrate, and cerium chloride; And niobium compounds such as niobium fluoride and niobium phosphate;

  Among these, from the viewpoint of the corrosion resistance of the surface treatment film formed with the metal surface treatment agent and the adhesion to the metal surface and the laminate film, one or more selected from Cr (III), Zr, Ti and V are used. A water-soluble metal compound containing any of the above metal elements is preferred. Since the metal compound having these specific metal elements is a compound that can react with the metal surface, it has an effect of improving the adhesion between the metal surface and the surface treatment film.

  By including a predetermined amount of water-soluble metal compound in the metal surface treatment agent, adhesion between the metal surface and the obtained surface treatment film, and adhesion between the laminate film and the obtained surface treatment film Any of the properties can be enhanced, and by containing a predetermined amount, a film having sufficient flexibility can be formed. As a result, the adhesion between the surface treatment film and the laminate film can be maintained by subsequent processing.

  The water-soluble metal compound contained in the metal surface treatment agent is preferably contained in an amount of 1 to 50% by mass in terms of metal in the total solid content of the metal surface treatment agent. By adjusting the metal surface treatment agent that makes the content of the water-soluble metal compound within the above range in terms of metal, metal elements (Cr (III), Zr contained in the surface treatment film formed with the metal surface treatment agent) , Ti, V, Nb, Mo, W, and Ce) and the carbon mass ratio (TM / C) can be 0.01 to 1.3.

  When the mass ratio (TM / C) of the total of metal elements (TM) and carbon (C) contained in the surface treatment film formed with the metal surface treatment agent is within the above range, the metal surface and the obtained The surface treatment film obtained can prevent the deterioration of the adhesion between the surface treatment film and the corrosion resistance due to the entry of the corrosive medium into the metal surface. The surface treatment film can be prevented from being deteriorated, and the surface treatment film thus obtained is prevented from becoming brittle to improve the flexibility of the surface treatment film itself, and then the surface treatment obtained even when processing is added. There is an advantage that adhesion between the film and the laminate film is not lowered.

  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 total metal elements (TM) and carbon (C) contained in the formed surface treatment film ( TM / C) may deviate from the above range, and as a result, the adhesion between the metal surface and the obtained surface treatment film may decrease, and the corrosion medium may enter the metal surface and the corrosion resistance may decrease. . In particular, the adhesion between the metal surface and the obtained surface treatment film tends to decrease in a high humidity environment.

  On the other hand, even when the content of the water-soluble metal compound contained in the metal surface treatment agent exceeds 50% by mass in terms of metal, the total of metal elements (TM) and carbon (C) contained in the formed surface treatment film The mass ratio (TM / C) may deviate from the above range, and as a result, the coating becomes brittle and the function of the laminate film as a base coating is unfavorable.

  In the present application, the “total solid content” means a solid content excluding volatile components such as a solvent to be described later among the components constituting the metal surface treatment agent, specifically, an aqueous resin and a water-soluble resin. It indicates the total amount with the metallic metal compound. Therefore, the water-soluble metal compound contained in the metal surface treatment agent is 1 to 50% by mass in terms of metal with respect to the total amount (total solid content) of the water-based resin and the water-soluble metal compound constituting the metal surface treatment agent. include. More preferably, it is 1-20 mass% in metal conversion.

(solvent)
The solvent constituting the metal surface treatment agent is mainly water, but does not hinder the combined use of an alcohol-based, ketone-based, or cellosolve-based water-soluble organic solvent as necessary, such as improvement of the drying property of the film.

(Other ingredients)
In addition, surfactants, antifoaming agents, leveling agents, antibacterial and antifungal agents, coloring agents, curing agents, and the like can be added within a range that does not impair the spirit and film performance of the present invention. Moreover, in order to improve the corrosion resistance of the film, organic cross-linking agents such as methylolated melamine, carbodiimide, and isocyanate, and γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropyltriethoxy for improving adhesion Silane coupling agents such as silane, [gamma] -aminopropyltriethoxysilane, and N- [beta] -aminoethyl- [gamma] -aminopropyltrimethoxysilane can be added within a range that does not impair the spirit and film performance of the present invention.

(Metal material)
As shown in FIG. 1, the metal surface treatment agent according to the present invention is applied to the surface of a metal material 1 that is an object to be processed to form a surface treatment film 2 according to the present invention. Here, the metal material 1 which is a to-be-processed object is not specifically limited, Various things can be applied. In particular, in the present invention, after the surface treatment film 2 is formed on the surface of the metal material 1, the resin film (3) is laminated or the resin film (3) is formed, and then deep drawing, ironing, or stretch drawing A metal material that can be subjected to severe molding such as is preferably used. In addition, in FIG. 1, although the example which formed the surface treatment film | membrane 2 and the resin film or the resin coating film (3) on one surface of the metal material 1 is shown, on both surfaces of the metal material 1, ie, the other surface Alternatively, a surface treatment film may be formed, and a resin film or a resin coating film may be further provided.

  As such a metal material, for example, a thin plate material made of aluminum or an aluminum alloy, a steel thin plate material, a stainless steel thin plate material, an aluminum foil for packaging, an aluminum alloy foil, or a stainless steel foil can be preferably exemplified. In the present application, the metal material 1 on which the surface treatment film 2 is not provided is referred to as “metal substrate 1”, and the metal material 10 on which the surface treatment film 2 is provided on the metal substrate 1 is referred to as “metal material 10”. May be called.

  Examples of the use of the metal material include, but are not limited to, a metal material applicable to a body or lid of a food can, a food container, a dry battery container, a secondary battery exterior material, and the like. Metal materials that can be applied to a wide range of applications can be given. Particularly recently, exterior materials for mobile lithium-ion secondary batteries used in mobile phones, electronic notebooks, notebook computers, video cameras, etc., and exterior materials for lithium-ion secondary batteries used as drive energy for electric vehicles or hybrid vehicles. Examples of usable metal materials include:

  As described above, according to the first and second metal surface treatment agents according to the present invention, a specific type of water-based resin having a specific type of nitrogen-containing functional group is contained, and a specific type of water-soluble metal compound is further included. Therefore, the surface treatment of the above-mentioned composition (N / C ratio and TM / C ratio) that can cause the water-based resin to be stably present in the metal surface treatment agent and provides high adhesion to the metal surface. A film can be formed. As a result, a surface treatment film formed by treatment with such a metal surface treatment agent is formed on a metal surface, and a resin film is laminated thereon or a resin coating film is formed by deep drawing, ironing or stretch drawing. Even when severe molding processing such as processing is performed, there is an effect that the laminate film or the resin coating film is hardly peeled off.

[Metal surface treatment method]
The metal surface treatment method according to the present invention is a method in which the above-described metal surface treatment agent is applied to a metal surface and then heated and dried at a temperature of 60 to 250 ° C. Here, the “metal surface” is a surface of a metal material that is a target for forming a surface treatment film. The surface of the metal material is degreased and cleaned as necessary. The degreasing agent can be selected from various types suitable for metal substrates. The cleaning liquid is usually water, but it may be a water-soluble solvent or a surfactant aqueous solution. Further, the degreasing means and the cleaning means are not particularly limited, and a spray method or a dipping method is preferably used.

  The metal surface treatment agent is the metal surface treatment agent according to the present invention described above, and may be either the first or second metal surface treatment agent. The liquid temperature of the metal surface treatment agent is usually in the range of 10 to 50 ° C. The means for applying the metal surface treatment agent is not particularly limited, and a spray method, a dipping method, or the like is preferably used. The contact time of the metal surface treatment agent to the metal surface is usually about 0.5 to 180 seconds. The metal surface treatment agent according to the present invention is a coating-type treatment agent. Therefore, after contacting with the metal surface treatment agent, the metal surface treatment film is formed by performing the drying described below without washing.

  The formed surface treatment film is heat-dried at a temperature of 60 to 250 ° C. Although this temperature range can be changed arbitrarily depending on the type of the resin component within the range, 80 to 200 ° C. is more preferable.

  The method of heating and drying is not specified, and a batch type or continuous hot air circulation drying furnace, a conveyor type hot air drying furnace, or an electromagnetic induction heating furnace using an IH heater can be applied. Set to

  Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples. The present invention is not limited by the following examples. In addition, the following “parts” means “parts by mass”.

[Water-based resin]
(Urethane resin: Symbol a)
The monomer composition was changed to polyol component “200 parts of polyester polyol (number average molecular weight: 2000) of isophthalic acid and 1,6 hexanediol, 5 parts of trimethylolpropane (molecular weight: 134), N-methyl-diethanolamine (molecular weight: 119) 32 Parts ”, isocyanate component“ 118 parts of isophorone diisocyanate (molecular weight: 222) ”and chain extender“ 5 parts of ethylenediamine (molecular weight: 60) ”.

  For the synthesis of the urethane resin a, the polyol component and the isocyanate component were reacted in a methyl ethyl ketone solvent at 80 ° C. to obtain a urethane prepolymer. The urethane prepolymer was emulsified in an aqueous solution of dimethyl sulfate (30 parts) and then reacted in a 10% aqueous solution of a chain extender, and then the solvent was removed to obtain a urethane resin a.

(Epoxy resin: Symbol b1)
Component 1 "Bisphenol A-based epoxy resin (Opika Shell Epoxy, Epicoat 828) (epoxy equivalent: 187 g) 235.7 parts", Component 2 "Bisphenol A 59.4 parts", Component 3 "Reaction catalyst (salt Lithium) 0.1 part ”and component 4“ diethanolamine 14 parts ”.

  The epoxy resin b1 was synthesized by reacting at 140 ° C. with stirring while introducing nitrogen gas in a four-necked flask containing the above components 1 to 3 and 125 parts of propylene glycol monomethyl ether acetate. A solution was obtained. Next, 343.3 parts of propylene glycol monomethyl ether acetate and 8.2 parts of hexamethylene diisocyanate were added and 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 reacted at 65 ° C. with stirring. After completion of the reaction, 154.7 parts of propylene glycol monomethyl ether acetate was added, and the amine-modified epoxy resin b1 An aqueous solution was obtained.

(Epoxy resin: Symbol b2)
Component 1 “bisphenol A-diglycidyl ether epoxy resin (Mitsui Chemicals, Epomic R302) (epoxy equivalent: 475 g) 1000 parts” and component 2 “3-aminopropanol 118.4 parts” were used.

  For the synthesis of the epoxy resin b2, the above component 1 and ethylene glycol dimethyl ether (479.3 g) were placed in a three-necked flask and dissolved by heating to 60 ° C. Next, Component 2 was added, the temperature was raised to 85 ° C., and the viscosity was measured by sampling after 4 hours and after 5 hours, respectively. After confirming that the viscosity became constant, the mixture was cooled to 70 ° C., 284.0 parts of lactic acid was added and mixed for 30 minutes, and 2591.9 parts of ion-exchanged water was added while stirring, and the solid content was 25%. And a colloidal dispersion solution of amine epoxy resin b2 having a viscosity of 520 cps was obtained.

(Acrylic resin: Symbol c)
As the monomer composition, “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, N, 20 parts of N-dimethylaminopropyl methacrylate (molecular weight: 175) ”was used.

  The synthesis of the acrylic resin c was carried out using a 10% by weight aqueous emulsifier solution in which a reactive emulsifier “Adeka Resorb NE-20” (manufactured by ADEKA Corporation) and a nonionic emulsifier “Emulgen 840S” (manufactured by Kao Corporation) were mixed at 6: 4 S-1) 100 parts of the above monomer was mixed and emulsified with a homogenizer at 5000 rpm for 10 minutes to obtain a monomer emulsion (ER). Next, 150 parts of the emulsifier aqueous solution (S-1) was added to a four-necked flask equipped with a stirrer, a reflux condenser, a thermometer, and a monomer supply pump, and kept at 40 to 50 ° C., 5 mass of ammonium persulfate. % Aqueous solution (50 parts) and the above monomer emulsion (ER) were placed in a dropping funnel, attached to another mouth of the flask, dropped over about 2 hours, and the temperature was raised to 60 ° C. Stir for 1 hour. The mixture was cooled to room temperature with stirring to obtain an emulsion solution of acrylic resin c.

(Phenolic resin: symbol d)
A bisphenol-type cation-modified phenol resin having the following structural formula was used. In the following structural formula, the degree of polymerization (m + n) is 10-15, and n / m is 40/60.

(Polyacrylamide: symbol e)
A copolymer (average molecular weight: 20000) of acrylamide (80% by mass) and methacrylic acid (20% by mass) was used.

(Natural polysaccharide: symbol f)
Glycerylated chitosan (number average molecular weight: 1 to 100,000, glycerylated 1.1) having the following structural formula was used.

(Polyacrylic acid: symbol g)
Polyacrylic acid (number average molecular weight: 30000) was used.

(Polyethyleneimine: Symbol h)
Polyethyleneimine (number average molecular weight: 1600) was used.

(Acrylic resin: Symbol i)
As a monomer composition, “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, 5 parts of N-dimethylaminopropyl methacrylate (molecular weight: 175) ”was used. The synthesis of the acrylic resin i was performed in the same manner as the acrylic resin c.

(Polyethyleneimine: Symbol j)
Polyethyleneimine (number average molecular weight: 10,000) was used.

(Epoxy resin: Symbol k)
Component 1 "Bisphenol A-based epoxy resin (Opika Shell Epoxy, Epicoat 828) (epoxy equivalent: 187 g) 235.7 parts", Component 2 "Bisphenol A 59.4 parts", Component 3 "Reaction catalyst (salt Lithium) 0.1 part ”and component 4“ diethanolamine 7 parts ”. The epoxy resin k was synthesized in the same manner as the epoxy resin b.

  The prepared aqueous resin is summarized in Table 1. As shown in Table 1, aqueous resins a, b1, b2, and c are classified as aqueous resins (P1), and aqueous resins d, e, and f are classified as aqueous resins (P2). The water-based resins g, i, and k are classified as a water-based resin (P1), and the water-based resins h and j are classified as a water-based resin (P2).

[Water-soluble metal compound]
The water-soluble metal compound (M) used is shown below.
M1: Chromium diphosphate Cr (H ₂ PO ₄ ) ₃
M2: chromium fluoride CrF ₃ · _3H 2 O
M3: zirconium hydrofluoric acid H ₂ ZrF ₆
M4: Titanium hydrofluoric acid H ₂ TiF ₆
M5: Vanadium acetylacetonate VO (C ₅ H ₇ O ₂ ) ₂

[Metal surface treatment agent]
The above-described aqueous resin and a water-soluble metal compound were combined to prepare metal surface treatment agents of Examples 1 to 39 and Comparative Examples 1 to 11 shown in Tables 2 to 4.

[Production of test materials]
An aluminum alloy plate (JIS A3004, plate thickness 0.26 mm) was spray degreased with a 2% aqueous solution of fine cleaner 4377K (an alkaline degreasing agent manufactured by Nihon Parkerizing Co., Ltd.) at 50 ° C. for 10 seconds, and then washed with water to clean the surface. . Then, in order to evaporate the water | moisture content on the surface of an aluminum alloy plate, it heat-dried at 80 degreeC for 1 minute. A 5% by mass aqueous solution of the metal surface treatment agents of Examples 1 to 39 and Comparative Examples 1 to 11 shown in Table 2 was applied to the surface of the degreased and washed aluminum alloy plate by bar coating (# 3 bar), and hot air circulation was performed. A surface treatment film was formed on the surface of the aluminum alloy plate by drying at 200 ° C. for 1 minute in an oven. The aluminum alloy plate on which the surface treatment film was formed was heat laminated to a polyester film (film thickness 16 μm) at 250 ° C. for 5 seconds (180 ° C. at the ultimate plate temperature) so that the surface pressure was 50 kg / cm ^2. A coated metal plate was produced.

  A coated metal plate formed by laminating a resin film was deep drawn by a drawing ironing test. The coated metal plate punched to a diameter of 160 mm was drawn (first time) to produce a cup having a diameter of 100 mm. Subsequently, the cup was again drawn to a diameter of 75 mm (second time), and further drawn to a diameter of 65 mm (third time) to prepare a can as a test material. Note that the ironing (thinning) ratios in the first drawing, the second drawing, and the third drawing were 5%, 15%, and 15%, respectively.

[Performance evaluation]
The initial adhesion, durability adhesion, and acid resistance adhesion after deep drawing of the coated metal plate were evaluated as follows. Furthermore, drug stability was also evaluated as follows. The results are shown in Table 5.

(Initial adhesion)
The initial adhesion of the specimen after deep drawing was evaluated. The case where the can was prepared and the film was not peeled was marked with “◯”, the can was made but the film was partially peeled off was marked with “Δ”, and the case where the can was broken and could not be made was marked with “X”. In addition, among “◯”, those which did not peel at all and were particularly excellent in appearance were designated as “◎”.

(Durable adhesion)
About the test material after deep drawing, the retort test was implemented in the atmosphere of heating-pressurization steam. The retort test was conducted at 125 ° C. for 1 hour using a commercially available sterilizer (autoclave). About the test material after a test, what did not peel of a film was set to "(circle)", that from which the film partly peeled was set to "(triangle | delta)", and the thing from which the film peeled entirely was set to "x". In addition, among “◯”, those which did not peel at all and were particularly excellent in appearance were designated as “◎”.

(Acid resistance adhesion)
The specimens after deep drawing were evaluated for adhesion after being immersed in a 0.5% HF aqueous solution at 50 ° C. for 16 hours. The case where the film was not peeled was designated as “◯”, the case where a part of the film was peeled was designated as “Δ”, and the case where the film was peeled off was designated as “X”. In addition, among “◯”, those which did not peel at all and were particularly excellent in appearance were designated as “◎”.

(Drug stability)
After 200 cc of each of the metal surface treatment agents (chemicals) of Examples 1 to 39 and Comparative Examples 1 to 11 shown in Tables 2 to 4 was sealed in a 300 cc plastic container and allowed to stand in an atmosphere of 20 ° C. for 2 weeks. The state of the drug was evaluated. The sample without solidification, separation and precipitation was marked with “◯”, the sample without solidification and separation but with precipitation was marked with “Δ”, and the sample with solidification and separation was marked with “X”. In addition, among “◯”, solidification, separation and precipitation were not observed at all, and particularly excellent stability was designated as “◎”.

  As shown in Table 5, the metal surface treatment agents of Examples 1 to 39 can form a surface treatment film having excellent adhesion to the laminate film on the surface of the metal material.

  On the other hand, the metal surface treatment agents of Comparative Example 1 and Comparative Example 2 that do not contain a water-soluble metal compound and the metal surface treatment agent of Comparative Example 3 that has an aqueous resin that does not contain a nitrogen-containing functional group are all poor in adhesion. A surface treatment film was formed. In particular, the durability adhesion and the acid resistance adhesion were remarkably inferior. This cause is thought to be due to insufficient corrosion resistance.

  In addition, Comparative Examples 3, 8, and 9 in which N / C is out of the range of 0.005 to 0.5, and Comparative Examples 1, 2, 6, and in which TM / C is out of 0.01 to 1.3, 9-11 were inferior to initial stage adhesiveness, durable adhesiveness, and acid-resistant adhesiveness. In addition, Comparative Examples 4, 5, 6, 7, 8, 9, 10, 11 using only water-based resins h, i, j, and k whose number average molecular weight per nitrogen-containing functional group deviated from 50 to 3000. In addition to initial adhesion, durable adhesion and acid resistance adhesion, the drug stability was remarkably inferior.

DESCRIPTION OF SYMBOLS 1 Metal material 2 Surface treatment film 3 Laminate film or resin coating film 10 Metal material which has a surface treatment film

Claims (4)

A metal surface treatment agent for applying and forming a surface treatment film on the surface of a metal material,
One or more water-based resins selected from epoxy resins, acrylic resins, polyolefin resins, formalin condensation resins, natural polysaccharides, polyamides and polyacrylamides, and Cr (III), Zr, Ti, V, Nb, Mo A water-soluble metal compound containing one or more metal elements selected from W and Ce,
At least one of the aqueous resins has one or more nitrogen-containing functional groups selected from the following structural formulas (1) to (8),
The mass ratio (N / C) of nitrogen and carbon contained in the surface treatment film formed by coating is 0.008 to 0.343, and Cr (III), Zr, Ti, V, Nb, Mo, A metal surface treating agent, wherein a total mass of metal elements selected from W and Ce and a mass ratio of carbon (TM / C) is 0.01 to 1.3.
(In Structural Formulas (1) to (8), R ₁ , R ₂ and R ₃ are each independently hydrogen, a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms, an alkenyl group, A hydroxyalkyl group, a hydroxyalkenyl group, an aryl group, an arylalkyl group, a hydroxyaryl group or a hydroxyarylalkyl group, where X is a hydroxide ion, a halogen ion, a sulfate ion, a sulfonate ion, a phosphate ion and a phosphonate ion; 1 type or 2 types or more selected from

A metal surface treatment agent for applying and forming a surface treatment film on the surface of a metal material,
One or more first aqueous resins selected from epoxy resins and acrylic resins, and one or two or more second aqueous systems selected from polyolefin resins, formalin condensation resins, natural polysaccharides, polyamides and polyacrylamides. Containing a resin and a water-soluble metal compound containing one or more metal elements selected from Cr (III), Zr, Ti, V, Nb, Mo, W and Ce;
At least one of the first aqueous resin and the second aqueous resin has one or more nitrogen-containing functional groups selected from the following structural formulas (1) to (8),
The mass ratio (N / C) of nitrogen and carbon contained in the surface treatment film formed by coating is 0.008 to 0.343, and Cr (III), Zr, Ti, V, Nb, Mo, A metal surface treating agent, wherein a total mass of metal elements selected from W and Ce and a mass ratio of carbon (TM / C) is 0.01 to 1.3.
(In Structural Formulas (1) to (8), R ₁ , R ₂ and R ₃ are each independently hydrogen, a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms, an alkenyl group, A hydroxyalkyl group, a hydroxyalkenyl group, an aryl group, an arylalkyl group, a hydroxyaryl group or a hydroxyarylalkyl group, where X is a hydroxide ion, a halogen ion, a sulfate ion, a sulfonate ion, a phosphate ion and a phosphonate ion; At least one selected from

  The number average molecular weight per nitrogen-containing functional group of the water-based resin containing the nitrogen-containing functional group is 50 to 3000, and the water-soluble metal compound relative to the total solid content in the metal surface treatment agent is converted to metal. The metal surface treating agent according to claim 1 or 2, which is contained in an amount of 1 to 50% by mass.   After apply | coating the metal surface treating agent of any one of Claims 1-3 to the surface of a metal material, it heat-drys at the temperature of 60-250 degreeC, The metal surface treatment method characterized by the above-mentioned.

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