JP6043689B2 - Self-deposition type coating composition for various metal materials and method for producing the same, metal material having organic resin film and method for producing the same - Google Patents

Description

  The present invention relates to steel materials used in automobile bodies, automobile parts, heat exchangers, building materials, home appliances, beverage cans, aircraft bodies, aircraft parts, etc., cast products, sheet coils, galvanized materials, aluminum Self-deposition coating composition for multi-metallic materials that can have equivalent film deposition properties and film quality with the same auto-deposition coating composition for various metal materials such as alloy materials, a method for producing the same, and the multi-metal materials The present invention relates to a metal material having an organic resin film using a self-depositing film composition for use and a method for producing the same.

  An aqueous coating composition capable of forming an organic resin film on the surface of a metal material by bringing the surface of the metal material into contact with an acidic coating composition containing an organic resin is known as an autodeposition coating composition. For example, it is disclosed in Patent Documents 1 and 2. A characteristic of the conventional known coating composition is that an organic resin film whose thickness or weight increases with the immersion time can be formed by immersing a clean metal material surface in the coating composition. Furthermore, this film formation is achieved by the chemical action of the coating composition on the surface of the metal material (metal ions eluted from the surface of the metal material by etching act on the resin particles and precipitate on the surface of the metal material). Therefore, a resin film can be effectively formed on the surface of the metal material without using external electricity as in electrodeposition coating. Therefore, even with the throwing power that is not good with electrodeposition coating, it is possible to uniformly coat complex structures with autodeposition coating. In addition, since electrodeposition coating does not require pretreatment such as phosphate treatment, which is indispensable for ensuring adhesion, there is an advantage that the treatment process can be shortened as compared with the electrodeposition coating method.

In the conventional well-known self-deposition type coating composition, the target metal material includes iron, zinc, galvanizing, or aluminum. The film formed by the coating composition has good film deposition property and film. Appearance, corrosion resistance, adhesion, electrical insulation, and the like have been mainly limited to iron. For example, when the coating composition is used to treat a non-ferrous metal material such as aluminum, the coating amount is as low as several g / m ² and a pinhole is formed. It is not possible to ensure the same performance. That is, when different types of metal materials were treated with the same self-depositing coating composition, a film having the same precipitation properties and film quality could not be obtained. Thus, development has been carried out characterized by the above-mentioned performance being superior to metal materials other than iron.

For example, in Patent Document 3, a combination of an organic polymer compound having an acid group containing phosphorus, a Cr compound and a fluorine compound, or the organic polymer compound, Zn, Mn, Zr, Ti, Ni, Co, Fe, Ca A film formed by treating aluminum and other metal materials with a treatment agent in combination with one or more compounds selected from Mg, Al, Sn, W and Mo and a fluorine compound has excellent resistance. It is disclosed that it has an effect of suppressing boiling water, surface slipperiness, and odor generation. However, the adhesion amount of the film obtained by the treatment agent is as low as several g / m ^2, and the film deposition property and corrosion resistance are not sufficient.

In Patent Document 4, a water-dispersible or water-soluble organic film-forming resin, one or more ions selected from fluoride ions and complex fluoride ions, and tungstate ions and molybdate ions are used. An aluminum plate is treated with an autodeposition-type coating composition containing one or two selected ions and having a pH of 1.6 to 5, and a film of about 20 g / m ² Amount of adhesion is obtained. However, as a result of verification by the present inventors under the same conditions as in the patent document, the obtained coating amount is about 10 g / m ² , and the coating film has many coating defects such as pinholes. The reproducibility of the effects of the invention described in the patent document could not be found.

  Therefore, in the prior art, the same autodeposition-type coating composition cannot provide a coating performance equivalent to iron for metal materials other than iron such as aluminum alloys.

Japanese Patent Publication No. 47-17630 Japanese Patent Publication No.52-21006 JP-A-7-90612 JP-A-5-214266

  An object of the present invention is to solve the problems of the prior art. That is, an object of the present invention is to provide an autodeposition coating composition that can provide equivalent film deposition properties and film quality with the same autodeposition coating composition for various metal materials, a method for producing the same, and a method for producing such various metal materials. An object of the present invention is to provide a metal material having an organic resin film using a self-depositing film composition and a method for producing the metal material.

  As a result of intensive studies to solve the above-described problems of the prior art, the present inventors have at least a water-dispersible or water-soluble anionic organic resin, a soluble trivalent iron source, and a soluble fluorine source. And an organic component having at least one carboxyl group or a salt of a carboxyl group in the molecule, a soluble type for soluble trivalent iron dissolved in the aqueous solvent when added to the aqueous solvent Fluorine molar ratio ([mol of soluble fluorine]) / ([mol of soluble trivalent iron]) {where the organic component is an organic acid metal salt ( The number of moles of soluble fluorine]) / ([number of moles of soluble trivalent iron] + [number of moles of metal cation component derived from organic acid metal salt])} is set to 1.0 to 3.2. The present inventors have found that excellent film deposition properties can be obtained for various metal materials. The present invention has been completed by finding that the self-deposited film deposited and formed from the coating composition is uniform and free of significant film defects and has corrosion resistance and electrical insulation.

The present invention (1) includes at least a water-dispersible or water-soluble anionic organic resin, a soluble trivalent iron source, a soluble fluorine source, and at least one carboxyl group or carboxyl in the molecule. Adding an organic component having a base salt to an aqueous solvent,
In the step, the molar ratio of soluble fluorine to soluble trivalent iron dissolved in the aqueous solvent ([number of moles of soluble fluorine]) / ([number of moles of soluble trivalent iron]. ]) {Here, when the organic component is an organic acid metal salt, ([mol number of soluble fluorine]) / ([mol number of soluble trivalent iron] + [organic acid metal salt] The number of moles of the derived metal cation component])} is set to 1.0 to 3.2. This is a method for producing a self-deposition type coating composition for various metal materials.

  Here, the organic component may have two or more carboxyl groups or salts of carboxyl groups in the molecule.

The cation forming the salt of the carboxyl group is a metal ion (that is, the organic component is an organic acid metal salt), and the metal ion is Al ³⁺ , Ti ⁴⁺ , Mn ⁴⁺ , Fe ³⁺ , Co More preferably, it is at least one selected from the group consisting of ²⁺ , Ni ²⁺ , Zn ²⁺ , Zr ⁴⁺ and Mg ²⁺ .

  In the step, the molar ratio of the soluble organic component derived from the organic component to the soluble trivalent iron dissolved in the aqueous solvent ([mol number of soluble organic component] / [soluble The number of moles of type trivalent iron]) may be 0.01 to 1.0.

  In the step, an oxidizing agent may be further added to the solvent.

  Further, the one of the various metal materials may be an aluminum-based material.

The present invention (2) is a self-precipitation type for multiple metals containing, in an aqueous solvent, at least a water-dispersible or water-soluble anionic organic resin, soluble trivalent iron, and soluble fluorine. In the coating composition:
It further contains a soluble organic component derived from an organic component having at least one carboxyl group or a carboxyl group salt in the molecule, and a molar ratio of soluble fluorine to soluble trivalent iron ([ Mole number of soluble type fluorine]) / ([Mole number of soluble type trivalent iron]) {wherein the composition contains Al ³⁺ , Ti ⁴⁺ , Mn ⁴⁺ , Co ²⁺ , Ni ²⁺ , Zn ²⁺ , When it further contains at least one soluble metal ion selected from the group consisting of Zr ⁴⁺ and Mg ²⁺ , ([mol number of soluble fluorine]) / ([soluble trivalent iron] The total number of moles of the soluble metal ions])} is 1.0 to 3.2, which is a self-deposition type coating composition for multi-metallic materials.

  Here, the organic component may have two or more carboxyl groups or salts of carboxyl groups in the molecule.

  Further, the molar ratio of the soluble organic component derived from the organic component to the soluble trivalent iron dissolved in the aqueous solvent ([mol number of soluble organic component] / [soluble trivalent iron] The number of moles]) may be from 0.01 to 1.0.

  Further, an oxidizing agent may be contained.

  Further, the one of the various metal materials may be an aluminum-based material.

  The present invention (3) is a method for producing a metal material having an organic resin coating, comprising the step of bringing the self-deposition coating composition for multiple metal materials into contact with a metal material.

  Here, the metal material may be an aluminum-based material.

  As described above, according to the present invention, excellent film deposition properties are provided for various metal materials, the obtained film is uniform and free of significant film defects, has excellent corrosion resistance, and further has electrical insulation properties. An excellent self-depositing film can be formed.

≪Method for producing this composition≫
Hereafter, the manufacturing method of the self-deposition type | mold coating composition for multiple metal materials based on this invention is explained in full detail. First, each raw material will be described, and then the manufacturing process will be described. The “self-deposition coating composition for various metal materials” according to the present invention includes not only a new solution but also an old solution (a composition resulting from the accumulation or consumption of some components by the use of the new solution). .

<Each raw material>
(Anionic organic resin)
The water-dispersed (including emulsion) or water-soluble anionic organic resin that is one raw material of the self-deposition coating composition for multi-metallic materials is not particularly limited. Examples of the anionic organic resin include acrylic resin, polyvinylidene chloride resin, epoxy resin, urethane resin, polyester resin, polyamide resin, polyimide resin, and phenol resin. These are materials that are widely used in autodeposition coating compositions and are available as commercial products.

(Soluble trivalent iron source, soluble fluorine source)
As a soluble trivalent iron source and a soluble fluorine source, which are one raw material of a self-deposition coating composition for various metal materials, soluble trivalent iron and soluble fluorine in the composition, respectively, Any component that can be released is not particularly limited. Examples of soluble trivalent iron sources include ferric fluoride, ferric sulfate, ferric nitrate, ferric citrate, ferric oxalate, and the like. Examples of these include ferric fluoride, titanium hydrofluoric acid, silicohydrofluoric acid, hydrofluoric acid, sodium fluoride, and the like. Ferric fluoride (trivalent iron ion source or fluoride ion) produced by soluble trivalent iron and soluble fluorine released from these soluble trivalent iron sources and soluble fluorine sources Including ferric fluoride added as a source) has the function of etching the metal material.

  Since ferric fluoride has strong oxidizing power, it is possible to accelerate the dissolution reaction of the metal substrate, and compared with the case of using an inorganic acid such as hydrofluoric acid as an etching agent for etching the metal material. Thus, it is possible to form a film that is more uniform and has fewer defects. For example, when Al or Fe is used as the metal material, hydrogen is generated when an inorganic acid such as hydrofluoric acid is used as the etchant. The hydrogen generated in this manner causes defects such as pinholes in the organic resin coating formed using the self-depositing coating composition. On the other hand, when ferric fluoride is used as an etching agent, metal materials such as Al and Fe can be etched without generating hydrogen unnecessarily, thereby suppressing the occurrence of defects such as pinholes. be able to.

(Organic component having a carboxyl group)
The organic component which is one raw material of the self-deposition type coating composition for multi-metallic materials is an organic component having at least one carboxyl group or a carboxyl group salt in the molecule. Specifically, an organic acid having at least one carboxyl group in the molecule, an organic acid salt having at least one carboxyl group in the molecule (for example, an organic acid metal salt), at least one in the molecule And organic acid salts having a carboxyl group salt. Due to the presence of the component, it is possible to avoid the presence of soluble trivalent iron and soluble fluorine in a form that adversely affects film deposition properties and film quality, so that excellent film deposition properties and film quality can be achieved. .

  Here, the organic acid is not particularly limited as long as it has at least one or more carboxyl groups in the molecule, but preferably has two or more, more preferably carboxyl groups. An organic acid having three or more groups. Specific examples include formic acid, acetic acid, citric acid, malic acid, malonic acid, tartaric acid, oxalic acid, glutamic acid, aspartic acid, maleic acid, fumaric acid, succinic acid, phthalic acid, itaconic acid, melittic acid, trimellitic acid, trimesin Acid, pyromellitic acid, naphthalenetetracarboxylic acid, propanedicarboxylic acid, butanedicarboxylic acid, pentanedicarboxylic acid, hexanedicarboxylic acid, heptanedicarboxylic acid, butanetricarboxylic acid, butanetetracarboxylic acid, cyclohexanetetracarboxylic acid, hexanetricarboxylic acid, 2- Phosphonobutane-1,2,4-tricarboxylic acid, ethylenediaminetetraacetic acid, trinitroacetic acid, cyclohexanediaminetetraacetic acid, diethylenetriaminepentaacetic acid, hydroxyethylenediaminetriacetic acid, glycol etherdiaminetetraacetic acid, tri Chirentetoramin hexaacetic acid, iminodiacetic acid, ethylenediamine diacetic acid, diaminopropanol tetraacetic acid, propylenediamine tetraacetic acid, hydroxyethyliminodiacetic acid, ethylenediamine dipropionate acid, bis aminophenyl ethylene glycol tetraacetic acid.

Next, as an organic acid salt, the salt (organic acid metal salt) of the said organic acid anion and a metal cation can be mentioned, for example. Here, as the metal cation, those which complex with organic acid anions or soluble fluorine in the composition and dissolve are suitable. For example, Al ³⁺ , Ti ⁴⁺ , Mn ⁴⁺ , Fe ³⁺ , Co ²⁺ , Ni There may be mentioned at least one selected from the group consisting of ²⁺ , Zn ²⁺ , Zr ⁴⁺ and Mg ²⁺ . These metal cations may be added in a form separately added to the composition after the addition of the organic acid salt, and the form of addition in that case may not be the organic acid salt.

  The “soluble trivalent iron source”, “soluble fluorine source”, and “organic component having a carboxyl group” may be the same component in some or all combinations even if they are separate components. It may be. For example, as an example in which some combinations are the same component, ferric fluoride can be cited as an example in which the “soluble trivalent iron source” and the “soluble fluorine source” are the same component. In addition, examples of the "soluble trivalent iron source" and the "organic component having a carboxyl group" that are the same component include ferric citrate and ferric oxalate.

(Oxidant)
In the case of a system in which reduced metal ions (for example, Fe ²⁺ ) can be generated in the reaction process, for example, an oxidizing agent is preferably added to the self-deposition coating composition for multi-metallic materials. Here, the oxidizing agent is preferably at least one selected from perchloric acid, hypochlorous acid, dissolved oxygen, ozone, permanganic acid, and hydrogen peroxide. Hydrogen peroxide is a suitable oxidizing agent for the present invention, since it is not necessary to consider the influence on the autodeposition treatment bath because the by-product of the reduction reaction is water.

(Other additive ingredients)
As an optional additive component that may be used in the self-depositing type coating composition used in the present invention, a film-forming auxiliary, for example, a tri-layering agent for lowering the minimum film-forming temperature and facilitating fusion of the precipitated resin particles. Alkylpentanediol isobutyrate, alkyl carbitol, etc. may be added, and pigments for coloring the film, such as carbon black, phthalocyanine blue, phthalocyanine green, quinacridone red, Hansa yellow, benzidine yellow, etc. may be added. It may be.

(Aqueous solvent)
The aqueous solvent used in the autodeposition coating composition for multi-metallic materials is preferably water. In addition, you may contain other aqueous solvents, such as alcohol. Here, the water-based solvent is preferably 50% by volume or more, preferably 80% by volume or more, more preferably water based on the total volume of liquid components used in the self-deposition coating composition for multi-metallic materials. Contains 90% by volume or more.

(Preferred combination)
Here, particularly suitable combinations of raw materials in the case of including an Al-based substrate as one of various metal materials for forming an organic coating include anionic resins, ferric fluoride, hydrofluoric acid, citric acid. The combination of an acid or its salt (especially ferric citrate) is mentioned. This is because when the agent according to the combination is used, particularly excellent film deposition properties and film quality can be achieved. In addition, it is preferable to add an oxidizing agent as an essential component (particularly hydrogen peroxide is more preferable). This is because the liquid stability is excellent in the case of the system when an oxidizing agent is present. Incidentally, the “soluble trivalent iron source” in the above preferred examples is ferric fluoride and ferric citrate, and the “soluble fluorine source” is ferric fluoride and hydrofluoric acid. It is.

<Addition amount>
(Anionic organic resin)
The amount of water-dispersed or water-soluble anionic organic resin used in the production of the self-depositing coating composition used in the present invention is not particularly limited as long as the desired coating can be obtained sufficiently, but the coating can be efficiently performed. Is preferably from 5 to 550 g / L, more preferably from 20 to 200 g / L, and particularly preferably from 40 to 100 g / L. When the resin solid content concentration is less than 5 g / L, sufficient film deposition cannot be obtained, and when it exceeds 550 g / L, the storage stability of the treatment liquid is lowered.

(Soluble trivalent iron source, soluble fluorine source)
The total addition amount of the soluble trivalent iron source and the soluble fluorine source in producing the autodeposition coating composition used in the present invention is preferably 0.1 to 15 g / L, more preferably 0. 0.5 to 10 g / L, more preferably 1.0 to 5 g / L. When the total addition amount of the soluble trivalent iron source and the soluble fluorine source is less than 0.1 g / L, the etching reactivity with respect to the target metal material decreases, and the metal ions necessary for the aggregation of the organic resin May not be sufficiently supplied, and film deposition may be insufficient. On the other hand, when the total addition amount of the soluble trivalent iron source and the soluble fluorine source exceeds 15 g / L, the concentration of metal ions taken into the deposited film increases, and the amount of moisture taken into the film accordingly. Therefore, the autodeposition film may be peeled off in the subsequent water washing step. In addition, unless otherwise specified, the amount of the component in the present specification including the soluble trivalent iron source and the soluble fluorine source means that the component in the solution is a solution (for example, an aqueous solution) unless otherwise specified. Refers to dissolved mass (for example, HF in solution in the case of hydrofluoric acid).

(Oxidant)
As described above, in the case where an Al-based material is included in the various metal materials to be coated, it is preferable to add an oxidizing agent. The amount of the oxidant added when producing the self-depositing coating composition used in the present invention is preferably 0.01 to 5 g / L, more preferably 0.05 to 4 g / L, still more preferably 0. .1-3 g / L. When the addition amount of the oxidizing agent is less than 0.01 g / L, the liquid stability may be insufficient. On the other hand, when the addition amount of the oxidizing agent is more than 5 g / L, the film deposition property is lowered. There is a case.

≪Ingredients of this composition≫
Each component of the self-depositing coating composition according to the present invention produced as described above will be described.

The self-precipitation type coating composition according to the present invention comprises at least a water-dispersible or water-soluble anionic organic resin, soluble trivalent iron, soluble fluorine, and at least in the molecule in an aqueous solvent. Soluble organic components derived from organic components having one or more carboxyl groups or salts of carboxyl groups (organic components having at least one carboxyl group in the molecule, at least one carboxyl group in the molecule or An organic component having a carboxyl group salt or an anion of the organic component). Further, the molar ratio of soluble fluorine to soluble trivalent iron dissolved in the aqueous solvent ([mol number of soluble fluorine]) / ([mol number of soluble trivalent iron]) { Here, the composition further comprises at least one or more soluble metal ions selected from the group consisting of Al ³⁺ , Ti ⁴⁺ , Mn ⁴⁺ , Co ²⁺ , Ni ²⁺ , Zn ²⁺ , Zr ⁴⁺ and Mg ^2+. When contained, ([mol number of soluble fluorine]) / ([mol number of soluble trivalent iron] + [total number of moles of soluble metal ions])} is 1.0 to 3.2.

The soluble trivalent iron in the self-deposited coating composition is a component supplied from the soluble trivalent iron source described above, and the soluble fluorine is supplied from the soluble fluorine source described above. It is an ingredient. In addition, the organic component having a carboxyl group or the like described above exists as a soluble organic component {for example, an acid state where protons are not dissociated (R-COOH), an anion state where protons are dissociated (R-COO) ^- ), And a state where a complex is formed with other components in the agent (R-COOH · M, R-COOM, etc.)}. The other components of the autodeposition-type coating composition are the same as described above, and a detailed description thereof is omitted here.

<Content ratio>
(Content ratio of soluble fluorine / soluble trivalent iron)
The content ratio (molar ratio) of soluble fluorine to soluble trivalent iron dissolved in an aqueous solvent when producing the autodeposition-type coating composition used in the present invention, ie, ([soluble Mole number of type fluorine]) / ([Mole number of soluble trivalent iron]) {wherein the composition contains Al ³⁺ , Ti ⁴⁺ , Mn ⁴⁺ , Co ²⁺ , Ni ²⁺ , Zn ²⁺ , Zr ⁴⁺ And at least one or more soluble metal ions selected from the group consisting of Mg ²⁺ and ([mol number of soluble fluorine]) / ([mol of soluble trivalent iron] Number] + [total number of moles of soluble metal ions])} is required to be 1.0 to 3.2. When the content ratio is less than 1.0, the dissolving power with respect to the material is weakened, so that the metal component for aggregating the resin becomes insufficient, and the depositability of the film is lowered. Further, when the content ratio exceeds 3.2, the dissolving power with respect to the material is increased, so that the film depositability is reduced due to excessive etching, or the appearance of the film is deteriorated due to the occurrence of pinholes and the film performance is deteriorated. The content ratio is preferably 1.5 to 3.0, more preferably 2.0 to 3.0 in order to further improve the depositability of the film and more reliably suppress the occurrence of pinholes and the like. More preferably. Here, the content of the soluble trivalent iron content in the agent is a value quantified by appropriately selecting ICP emission spectroscopic analysis, chelate titration, etc. depending on the compound used. Further, the content of soluble fluorine is a value quantified by appropriately selecting capillary electrophoresis (CE), ion chromatography (IC) or the like depending on the compound used.

(Content ratio of soluble organic component / soluble trivalent iron)
Molar ratio of soluble organic component derived from organic component (organic component having at least one carboxyl group or carboxyl group salt in the molecule) to soluble trivalent iron dissolved in aqueous solvent ( [Mole number of soluble organic component] / [Mole number of soluble trivalent iron]) is preferably 0.01 to 1.0, and more preferably 0.01 to 0.8. And more preferably 0.01 to 0.6. When the molar ratio is less than 0.01, the coating appearance may be deteriorated or the coating deposition may be deteriorated. On the other hand, when the molar ratio is more than 1.0, the coating appearance is deteriorated or The film depositability may be reduced. Here, the content of the soluble organic component in the agent is a value quantified by appropriately selecting capillary electrophoresis (CE), ion chromatography (IC), etc. depending on the compound used.

  Here, when the self-precipitation type coating composition of the present invention is brought into contact with a metal material, the presence forms of soluble trivalent iron and soluble fluorine are changed by etching reaction of the metal material with ferric fluoride or the like. Specifically, the concentration of trivalent iron ions or fluoride ions changes. For example, if the trivalent iron ion concentration becomes excessively high, a film containing trivalent iron ions (a film that is not etched by ferric fluoride or the like) is formed on the surface of the metal material, and the film deposition property may be reduced. . Also, if the fluoride ion concentration becomes excessively high, this fluoride ion combines with protons present in the autodeposition coating composition to produce hydrofluoric acid, and this hydrofluoric acid etches the metal. Hydrogen is generated, causing pinholes and the like. Since the organic component which has the carboxyl group etc. which were mentioned above as a raw material of the self-precipitation type coating composition which concerns on this invention at this time is included, this organic component stabilizes trivalent iron ion and fluoride ion ( (It can be made not to contribute to the etching reaction of the metal material and the deposition reaction of the film). Due to the action of such an organic component, the content ratio can be maintained in the range of 1.0 to 3.2 in the autodeposition-type coating composition of the present invention. The ion concentration or fluoride ion concentration does not increase. Therefore, when the self-depositing coating composition of the present invention is brought into contact with a metal material, defects such as pinholes hardly occur in the film, and good film deposition properties can be maintained.

≪Use of this composition≫
The self-depositing type coating composition according to the present invention can be applied to various metal materials. Examples of the metal material include aluminum-based materials (such as aluminum and aluminum alloys), iron-based materials (such as iron and steel), and zinc-based materials (such as zinc and galvanized materials). In particular, the autodeposition-type coating composition according to the present invention is characteristic in that it can be applied to various metal materials including aluminum-based materials (particularly applicable to both aluminum-based materials and iron-based materials).

  More specifically, the objects of the present invention are widely used for automobile bodies, automobile parts, heat exchangers, building materials, home appliances, beverage cans, aircraft bodies, molded products such as aircraft parts, cast products, sheet coils, etc. It is a metal material used in various fields. The present invention provides equivalent film quality for various metal materials.

≪How to use this composition≫
The self-deposition coating composition for multi-metallic materials according to the present invention is used for self-depositing an organic resin film on a metal material. Specifically, the resin coating method on the metal material using the self-deposition coating composition for multi-metallic materials according to the present invention (method for producing a metal material with an organic coating) is the self-deposition type according to the present invention. In this method, the coating composition is brought into contact with the surface of the metal material, an organic resin film is formed on the surface of the metal material, and the organic resin film is fixed to the surface of the metal material by heating and drying it. More specifically, in the resin coating method, the surface of the metal material is previously degreased and cleaned with water as necessary, and then contacted with the self-deposition type coating composition of the present invention. A film is formed by removing excess self-depositing composition adhering to the surface of the metal material and then drying. The drying temperature in a drying process will not be specifically limited if the water | moisture content which the deposited self-deposition type film contains evaporates. Furthermore, you may make it contact with a post-processing agent before drying as needed. Hereinafter, each process is explained in full detail.

(Degreasing process / washing process)
If oil, dirt or the like is adhered to the surface of the metal material to be treated, it is preferable to perform this in advance to clean the surface. The degreasing treatment is not particularly limited as long as the surface can be cleaned, and for example, solvent degreasing, alkaline degreasing, etc. can be used, and neutral washing, hot water washing, etc. can be used depending on the degree of dirt adhesion. The construction method is not particularly limited as long as the surface can be cleaned, such as pouring, spraying or dipping. Moreover, there is no limitation in particular also about the water-washing processing method performed after a degreasing process and an autodeposition type | mold coating process, It can select from pouring, spraying, immersion, etc. Although there is no particular restriction on the quality of water used for washing, ion-exchanged water is used from the viewpoint of preventing liquid deterioration due to the introduction of trace components into the self-deposition type coating treatment bath and preventing performance deterioration due to remaining in the coating. desirable.

(Pickling process)
A pickling step can be added depending on the surface state of the metal material to be treated. This process has the function of improving the adhesion of the resin to the metal material in the next autodeposition coating process by removing rust or oxide on the metal surface. The pickling treatment is not particularly limited as long as rust or oxide on the metal surface can be removed, and nitric acid, sulfuric acid, hydrofluoric acid and the like can be used, and the degreasing treatment can be performed by adding a solvent or a surfactant. It can also be made to serve the purpose of. The construction method is not particularly limited as long as it can remove rust or oxide on the surface, such as pouring, spraying or dipping. Moreover, there is no limitation in particular also about the water-washing processing method performed after a pickling process and an autodeposition type | mold coating process, It can select from pouring, spraying, immersion, etc. Although there is no particular restriction on the quality of water used for washing, ion-exchanged water is used from the viewpoint of preventing liquid deterioration due to the introduction of trace components into the self-deposition type coating treatment bath and preventing performance deterioration due to remaining in the coating. desirable.

(Self-precipitation type coating treatment)
The autodeposition type coating treatment of the present invention is preferably performed by an immersion method in which an object to be processed is immersed in a treatment bath. With respect to the treatment bath in which the dipping method is performed, it is only necessary to have an agitation effect that is equal to or higher than the level at which the component concentration in the treatment bath is kept uniform. The treatment time is preferably 10 to 500 seconds, and more preferably 20 to 300 seconds. If it is less than 10 seconds, a sufficient film may not be formed due to insufficient precipitation reaction. On the other hand, if it exceeds 500 seconds, the metal ion concentration in the coating film may become too high due to the dissolution of the object to be processed, which may cause poor appearance and reduced corrosion resistance. The treatment temperature is preferably 5 to 50 ° C, more preferably 10 to 40 ° C. If the treatment temperature is less than 5 ° C, the deposition efficiency may be low and a sufficient coating amount may not be obtained. If the treatment temperature exceeds 50 ° C, the coating surface appearance may be deteriorated due to excessive reaction.

(Post-processing process)
The self-deposited organic coating can optionally be post-treated. Since the self-deposited organic film is a wet film containing a large amount of water, the post-treatment agent penetrates and diffuses into the film using this water as a medium, and removes the solvent to improve surface hardness, solvent resistance, and corrosion resistance. There is an effect. The post-treating agent does not distribute the entire autodeposited organic coating uniformly, but the concentration near the coating surface is higher than the interface with the metal and its action is great, so it has excellent surface hardness without hindering adhesion to the material Solvent resistance and corrosion resistance can be imparted.

  Raw materials used for the post-treatment agent are organic raw materials such as amino resins such as melamine resins, guanamine resins and urea resins, phenol resins, epoxy resins and isocyanate compounds, and inorganic raw materials such as zircon hydrofluoric acid and titanium hydrofluoric acid. It is preferably at least one selected from

  As the post-treatment agent concentration, for example, a solid content concentration of 5 to 300 g / L can be used, and preferably 10 to 200 g / L. When the solid content concentration is less than 5 g / L, the content of the post-treatment agent in the film is not sufficient, and the degree of crosslinking of the film is not improved so much, so the effect of improving the film performance such as corrosion resistance, solvent resistance, surface hardness, etc. I can't expect it. On the other hand, when the solid content concentration exceeds 300 g / L, the surface hardness is increased, but at the same time, the coating becomes brittle, and further the appearance of the coating may be deteriorated.

(Solvent removal treatment process / film formation treatment process)
Examples of the heating means in the solvent removal and film formation process include a hot-air circulating drying furnace using electricity or petroleum fuel as an energy source, a heating furnace using far infrared rays, high-frequency heating, induction heating, and the like. The temperature is not particularly limited as long as moisture in the wet film can be evaporated.

  By the resin coating method described above, the metal material with an organic coating of the present invention can be obtained.

  EXAMPLES Next, although an Example and a comparative example demonstrate this invention, this Example is only a mere example and does not limit this invention.

1. The sample materials used in the sample material examples and comparative examples are as follows.
I: Al aluminum alloy plate (JIS
A1000 series aluminum alloy)
II: Al aluminum alloy plate (JIS
A2000 series aluminum alloy)
III: Al aluminum alloy plate (JIS
A5000 series aluminum alloy)
IV: Al aluminum alloy plate (JIS
A6000 series aluminum alloy)
V: Al cast aluminum plate (AC4C)
VI: SPC Cold rolled steel sheet (JIS-G3141)
VII: GA double-sided alloyed hot-dip galvanized steel sheet (plating weight 45 g / m2)
VIII: EG Electrogalvanized steel sheet

2. Treatment liquid composition

Each component in Table 1 is as follows. In the table, F is the solid content concentration (g / L) of the organic resin, G is the total addition amount (g / L) of the soluble trivalent iron source and the soluble fluorine source, and H is [soluble fluorine. Number of moles] / ([number of moles of soluble trivalent iron] + [number of moles of metal cation component derived from organic acid metal salt]), I is [number of moles of soluble organic component] / [soluble Number of moles of type trivalent iron], J represents an oxidant addition amount (g / L), and K represents a post-treatment resin when post-treatment is performed. In addition, content measurement of soluble trivalent iron was performed using the ICP emission-spectral-analysis method (Shimadzu Corporation model number: ICPS-8100). Ion chromatography (Dionex model number: ICS-2000) was used to measure the amount of soluble fluorine, IonPacAS20 was used for the separation column, and IonPacAG20 was used for the guard column. The eluent was KOH 40 mmol / L, and the flow rate was 1.0 mL / min. Soluble organic components were subjected to capillary electrophoresis (Agilent model: Agilent 1600) using a fused silica capillary (inner diameter 75 μm, effective length 80.5 cm) as the capillary, and the injection method was the pressure injection method. The buffer is HP Organic Acids Buffer (HEWLETT PACKARD model number: PN8500-6785). The molar ratio was calculated based on the measured value.
・Water-dispersed or water-soluble organic resin (A)
A1: Saran latex L232A (polyvinylidene chloride resin, solid content concentration: 48% by weight, Asahi Kasei Chemicals)
A2: Primal WL-91 (acrylic resin, solid content concentration: 41.5% by weight, Rohm and Haas)
A3: F-2125D (urethane resin, solid content concentration: 30% by weight, Daiichi Kogyo Seiyaku)
A4: Vylonal MD-1500 (polyester resin, solid content concentration: 30% by weight, Toyobo)
A5: Epiletz 3522W60 (epoxy resin, solid content concentration: 60% by weight, oiled shell epoxy)
・Soluble trivalent iron source (B)
B1: Ferric fluoride B2: Ferric sulfate B3: Ferric nitrate B4: Ferric citrate, soluble fluorine source (C)
C1: Hydrofluoric acid C2: Titanium hydrofluoric acid C3: Sodium fluoride C4: Ferric fluoride / organic component (D)
D1: Ferric citrate
D2: ferric tartrate D3: magnesium malate D4: citric acid D5: aluminum oxalate D6: aluminum acetate D7: acetic acid D8: 4-sulfophthalic acid, oxidizing agent (E)
E1: Hydrogen peroxide and post - treatment resin (K)
K1: Melamine resin aqueous solution {Nippon Cytec Industries'"Cymel 385 (solid content concentration: 85% by weight)" diluted with ion-exchanged water to 100g / L}

3. Surface treatment method (1) Degreasing Spraying a solution obtained by heating a 20 g / L aqueous solution of an alkaline degreasing agent “Fine Cleaner L4460” (trade name, manufactured by Nihon Parkerizing Co., Ltd.) to 40 ° C. with a spray device. The surface of the test material after the degreasing treatment was washed with ion-exchanged water using a spray device.

(2) Treatment / Drying After immersing the test material whose surface has been degreased and washed in a treatment bath of various autodeposition coating compositions, it was washed with ion-exchanged water using a spray device, and then baked at 180 ° C. for 20 minutes. Went. In the case of carrying out post-treatment, after washing with the ion-exchanged water, it was immersed in post-treatment resin K for 10 seconds and then baked at 180 ° C. for 20 minutes. In the following evaluation, the film thickness was set to 20 μm for the film appearance, corrosion resistance, and electrical insulation.

4). Evaluation method The various surface-treated metal materials obtained were evaluated for coating appearance, coating deposition, corrosion resistance, and electrical insulation by the following methods.

(1) Appearance of coating The appearance of the treated plate samples prepared in Examples and Comparative Examples was visually determined.
Evaluation criteria: ◎ No abnormality, ○ Pinhole, bulge, crack failure less than 5 pieces, △ Pinhole, bulge, crack failure from 5 pieces to less than 20 pieces, × Pinhole, bulge, crack failure, 20 pieces or more

(2) Film deposition property The film thickness of the treated plate sample subjected to the film formation treatment at a treatment time of 300 seconds was measured using an eddy current type film thickness meter LZ-373 (manufactured by Kett Science Laboratory).
Evaluation criteria: ◎ 25 μm or more, ○ 15 μm or more and less than 25 μm, Δ5 μm or more and less than 15 μm, × 5 μm or less

(3) Corrosion resistance About the process board sample produced in the Example and the comparative example, the non-processed (plane part) corrosion resistance test was done. The evaluation method is as follows.

(Flat part)
According to the salt spray test method JIS-Z-2371, the white rust generation area after 480 hours of salt spray was determined and evaluated.
Evaluation criteria: White rust generation area ◎ <10%, ○ 10% to less than 30%, △ 30% to less than 60%, x60% or more

(4) Electrical insulation The processing plate samples produced in the examples and comparative examples were measured according to JIS-C2110 with the electrical insulation as a withstand voltage. With respect to the tester, a withstand voltage tester TOS5051 (manufactured by Kikusui Electronics Co., Ltd.), a brass φ25 mm cylindrical electrode having the same diameter was used. The initial voltage is set to 100 V, and after holding at each voltage for 20 seconds, the applied voltage is increased every 100 V. When the current value flowing through the film exceeds 10 mA, it is determined that the film has undergone dielectric breakdown. Withstand voltage. The maximum measurable voltage of the testing machine is 5,000V.
Evaluation criteria: Withstand voltage ◎ 3,000 V or more, ○ 1,500 V or more and less than 3,000 V, Δ500 V or more and less than 1,500 V, or less than × 500 V

(5) Storage stability After preparing the treatment liquids of Examples and Comparative Examples, the state after 1 month at room temperature was evaluated as storage stability as follows.
Evaluation criteria: ◎ No change, ○ Insoluble matter less than 5% by volume, ΔInsoluble matter 5% by volume or more and less than 20% by volume, X Insoluble matter 20% by volume or more

(6) Comprehensive evaluation The total score was calculated based on the score standard which prescribes | regulates the evaluation result of said (1) to (5) next.
Film appearance: ◎ 3pt, ○ 2pt, Δ1pt, × 0pt
Film deposition property: ◎ 6pt, ○ 4pt, Δ2pt, × 0pt
Corrosion resistance: ◎ 3pt, ○ 2pt, Δ1pt, × 0pt
Electrical insulation: ◎ 3pt, ○ 2pt, Δ1pt, × 0pt
Storage stability: ◎ 3pt, ○ 2pt, Δ1pt, × 0pt

Claims (12)

Organic component having at least one water-dispersible or water-soluble anionic organic resin, a soluble trivalent iron source, a soluble fluorine source, and at least one carboxyl group or carboxyl group salt in the molecule And adding to an aqueous solvent,
In the step, the molar ratio of soluble fluorine to soluble trivalent iron dissolved in the aqueous solvent ([number of moles of soluble fluorine]) / ([number of moles of soluble trivalent iron]. ]) {Here, when the organic component is an organic acid metal salt, ([mol number of soluble fluorine]) / ([mol number of soluble trivalent iron] + [organic acid metal salt] The number of moles of the derived metal cation component])} is set to 1.0 to 3.2. A method for producing a self-deposition coating composition for various metal materials.   The production method according to claim 1, wherein the organic component has two or more carboxyl groups or salts of carboxyl groups in the molecule.   In the step, the molar ratio of the soluble organic component derived from the organic component to the soluble trivalent iron dissolved in the aqueous solvent ([mol number of soluble organic component] / [soluble type 3] The manufacturing method of Claim 1 or 2 which makes 0.01-1.0 the number-of-moles of valence iron]).   The manufacturing method according to any one of claims 1 to 3, wherein an oxidizing agent is further added to the solvent in the step.   The manufacturing method according to any one of claims 1 to 4, wherein one kind of the multi-metallic material is an aluminum-based material. In an aqueous solvent, at least a water-dispersible or water-soluble anionic organic resin, soluble trivalent iron, and soluble fluorine, a self-deposition coating composition for multiple metals,
It further contains a soluble organic component derived from an organic component having at least one carboxyl group or a carboxyl group salt in the molecule, and a molar ratio of soluble fluorine to soluble trivalent iron ([ Mole number of soluble type fluorine]) / ([Mole number of soluble type trivalent iron]) {wherein the composition contains Al ³⁺ , Ti ⁴⁺ , Mn ⁴⁺ , Co ²⁺ , Ni ²⁺ , Zn ²⁺ , When it further contains at least one soluble metal ion selected from the group consisting of Zr ⁴⁺ and Mg ²⁺ , ([mol number of soluble fluorine]) / ([soluble trivalent iron] The total number of moles of the soluble metal ions])} is 1.0 to 3.2. A self-deposition coating composition for multi-metallic materials.   The self-deposition type coating composition for multi-metallic materials according to claim 6, wherein the organic component has two or more carboxyl groups or salts of carboxyl groups in the molecule.   Molar ratio of soluble organic component derived from the organic component to soluble trivalent iron dissolved in the aqueous solvent ([mol number of soluble organic component] / [mol of soluble trivalent iron] The number]) is 0.01 to 1.0, and the self-deposition coating composition for multi-metallic materials according to claim 6 or 7.   Furthermore, the self-deposition type | mold coating composition for multi-metallic materials as described in any one of Claims 6-8 containing an oxidizing agent.   The self-deposition coating composition for multi-metallic materials according to any one of claims 6 to 9, wherein one of the multi-metallic materials is an aluminum-based material.   A method for producing a metal material having an organic resin coating, comprising the step of bringing the self-deposition coating composition for multi-metallic materials according to any one of claims 6 to 10 into contact with a metal material.   The manufacturing method according to claim 11, wherein the metal material is an aluminum-based material.