JP2011184800A - Surface-treating agent comprising crystalline layered inorganic compound dispersed in nanosheet form - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a nanosheet-dispersed sol-type non-chromate surface-treating agent which shows excellent corrosion resistance and coating-adhesiveness at a processed part and can form a stiff film even used in the manufacture of a precoated metal plate which is applicable to an electric appliance, an automotive product or the like which is required to have a strictly machined shape. <P>SOLUTION: Disclosed is a surface-treating agent comprising a crystalline layered inorganic compound formed with an organic amine or an organic ammonium into a nanosheet, wherein the organic amine or organic ammonium is a polyfunctional organic amine or polyfunctional organic ammonium. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a surface treatment agent capable of forming a surface film excellent in corrosion resistance and paint adhesion, in which a crystalline layered inorganic compound is dispersed in a nanosheet. More specifically, for example, a non-chromium surface treatment agent as a temporary rust prevention or coating base used for a metal material, a surface treatment method using this surface treatment agent, and further treated with this surface treatment agent It relates to metal materials and metal products.

Recently, in order to create a material that is structurally and functionally superior, nanostructure control of the material surface interface has been vigorously promoted. Under such circumstances, there has been proposed a technique for obtaining a nanosheet-dispersed sol in which fine crystal flakes of the layered crystal metal compound are dispersed, which is obtained by subjecting the layered crystal metal compound to a predetermined treatment (Patent Documents 1 to 3). ). For example, layered titanate H _x Ti _{2-x / 4} O ₄ is mixed with an aqueous solution of an amine or ammonium compound (functioning as a release agent and a dispersant) and stirred to peel off the layer, and titanium oxide (TiO ₂ ) A method for preparing a sol solution in which fine crystal flakes are dispersed is known. However, even if conventional nanosheet dispersion sol is used as a surface treatment agent, there is a problem that a strong film (a film excellent in corrosion resistance and adhesion) is not formed, and the actual situation is that the surface treatment agent has not reached a practical level. is there.

  On the other hand, chromate treatment has been widely adopted in various fields such as steel, home appliances, building materials and automobiles in order to improve the corrosion resistance and coating film adhesion of various metal materials. However, the chromate treatment has a lot of environment-related problems associated with pollution measures, such as the toxicity of hexavalent chromium and the need for wastewater treatment facilities. Yes. For example, when producing a pre-coated metal plate to be applied to products such as home appliances and automobiles with severe processing shapes, various non-chromium surface treatment agents and treatment methods have been proposed (Patent Documents 4 to 6). However, there remains a problem that the corrosion resistance and paint adhesion at the processed part cannot be ensured.

Therefore, the present invention forms a strong film excellent in corrosion resistance and paint adhesion at the processed part even when, for example, a pre-coated metal plate to be applied to products with severely processed shapes such as home appliances and automobiles is produced. An object of the present invention is to provide a nanosheet-dispersed sol-type non-chromium surface treatment agent to be obtained.
Japanese Patent Laid-Open No. 2005-220001 JP 2005-290369 A JP 2004-315347 A JP-A-53-9238 JP 59-116381 A JP 2002-36364 A

  As a result of diligent research to solve the above problems, the present inventor does not crosslink and fix alkylamine or alkylammonium salt that functions as a delamination agent and nanosheet dispersant in a conventional nanosheet-dispersed sol type composition. The present invention has been completed by finding that it remains in the coated and dried film and adversely affects the film-forming property.

  The present invention (1) is a surface treatment agent obtained by nano-sheeting a crystalline layered inorganic compound with an organic amine or organic ammonium, wherein the organic amine or organic ammonium is a polyfunctional organic amine or a polyfunctional organic ammonium. It is a surface treating agent characterized by this.

  This invention (2) is the surface treating agent of the said invention (1) whose said polyfunctional organic amine or polyfunctional organic ammonium is a polyvalent amine compound, an amino acid, aminosilane, chitosan, and a polyfunctional amino polymer. is there.

  The present invention (3) is the surface treatment agent according to the invention (1) or (2), wherein the crystalline layered inorganic compound is a phosphate or oxide of zirconium, titanium, vanadium, silicon or aluminum.

  In the present invention (4), the ratio of the polyfunctional organic amine or polyfunctional organic ammonium to the crystalline layered inorganic compound is 0.1 to 2 moles per mole of the crystalline layered inorganic compound. The surface treatment agent according to any one of the inventions (1) to (3).

  The invention (5) is any one of the inventions (1) to (4), wherein the amount of the crystalline layered inorganic compound (solid content) is 5 to 95 wt% with respect to the total solid content of the surface treatment agent. One surface treatment agent.

  The present invention (6) further comprises at least one component selected from the group consisting of an inorganic component selected from the group consisting of silicon, cerium, lithium, zinc, magnesium, calcium and manganese and a water-soluble polymer. It is a surface treatment agent according to any one of the inventions (1) to (5).

  This invention (7) includes the process of forming a film | membrane by apply | coating and drying any one surface treating agent of said invention (1)-(6) on the metal material surface, The metal material characterized by the above-mentioned. This is a surface treatment method.

  The present invention (8) is the method according to the invention (7), wherein the film is an inorganic / organic nanohybrid film containing an inorganic nanosheet.

This invention (9) is the method of the said invention (7) or (8) whose film | membrane mass of the said film | membrane is 0.01-5 g / m < ² >.

As for this invention (10), the coating-film mass 0.01- formed in the said metal material surface by apply | coating and drying any one surface treatment agent of said invention (1)-(6) on the metal material surface. It is a surface-treated metal material characterized by having a film of 5 g / m ² .

  The present invention (11) is the surface-treated metal material according to the invention (10), wherein the metal material is at least one selected from an iron-based substrate, a zinc-based substrate, and an aluminum-based substrate.

  According to the present invention, the organic amine or organic ammonium functioning as a delamination agent and nanosheet dispersant is left in the film in a cross-linked and fixed state, so that the film is as in the case of using a conventional alkyl amine or alkyl ammonium salt. In addition to having no adverse effect on the water resistance, there is an effect that the corrosion resistance and coating film adhesion can be dramatically improved.

  The best mode of the present invention will be described below. However, the following description is only the best mode and is not limited to the description. For example, although the upper limit and lower limit of the numerical range are described as preferred ranges, even if the upper limit and lower limit are exceeded, as long as the constituent requirements of the present invention are satisfied, they are within the technical scope of the present invention. .

  First, the nanosheet-dispersed sol type surface treating agent according to the best mode will be described. Here, the surface treatment agent is in the form of an aqueous solution at the time of use, but a concentrated type that is diluted with water at the time of use is also included in the concept of the surface treatment agent. Hereinafter, a liquid coating type surface treatment agent (treatment liquid) will be described as an example. Here, the “coating type” refers to a type in which a liquid surface treatment agent is applied to a metal material and then dried to form a film.

  The surface treatment agent is a surface treatment agent obtained by nano-sheeting a crystalline layered inorganic compound with an organic amine or organic ammonium, wherein the organic amine or organic ammonium is a polyfunctional organic amine or a polyfunctional organic ammonium. And Hereinafter, first, each component of this surface treating agent is explained in full detail.

First, the “crystalline layered inorganic compound” used as a raw material is a cation exchangeable crystalline layered inorganic compound, for example, a phosphate or an oxide of zirconium, titanium, vanadium, silicon or aluminum ( Hereinafter, “component A”). Here, “phosphoric acid” means phosphoric acid, polyphosphoric acid, hypophosphorous acid, tripolyphosphoric acid, hexametaphosphoric acid, primary phosphoric acid, secondary phosphoric acid, tertiary phosphoric acid, polymetaphosphoric acid, heavy phosphoric acid, organic It means phosphonic acid and the like. Specifically, examples of the crystalline layered phosphate include zirconium phosphate, zirconium phosphonate, titanium phosphate, vanadium phosphate, and aluminum dihydrogen triphosphate. Examples of the crystalline layered oxide include silicon dioxide, titanium oxide, cesium titanate, potassium titanate, vanadium pentoxide, vanadium oxide {M _x V _y O _z · nH ₂ O (where M is an alkali A metal or an alkaline earth metal)}. Here, the layered structure of the layered phosphate and the layered oxide is usually an inorganic compound in which sheets having a thickness of about 1 nm are superimposed, and can be confirmed from a diffraction pattern by a powder X-ray diffraction method. For example, layered zirconium phosphate α-Zr (O ₃ POH) ₂ · nH ₂ O (α-ZrP) forms a sheet with Zr being a plane square type unit, and tetragonal HPO ₄ ^2- Groups are coordinated alternately to form a layered structure. Of the four oxygen atoms bonded to the phosphorus atom, three are bonded to Zr and the other is bonded to hydrogen. As a whole, a polymacroanion such as [Zr (PO ₄ ) _2n ] ²⁻ is formed, and oxygen ions are neutralized with protons to form POH groups. The proton serves as an ion exchange point and an acid point, the former contributes to intercalation, and the latter functions as a solid acid catalyst. This zirconium phosphate has a feature that various functional groups can be introduced between ZrP layers by using phosphonic acid (O ₃ PR R = functional group) instead of phosphoric acid (O ₃ POH). The thickness of the nanosheet consisting of these delaminations corresponds to the thickness of the single layer of the mother crystal, for example, zirconium phosphate 0.76 nm, titanium phosphate 0.76 nm, tripolyaluminum dihydrogen phosphate 0.79 nm, Titanium oxide is 0.75 nm. On the other hand, the lateral size basically depends on the size of the layered crystal before peeling. In general, the thickness is from 200 nm to 100 μm, but considering the dispersion of the treatment liquid and the baking of the film, it is appropriate to use a nanosheet of 1 μm or less. As these layered phosphate and layered oxide, those produced by a known method can be used. For example, a hydrothermal precipitation method, a fluoride complex method, a reflux method, an autoclave method, and the like are known as methods for producing a layered phosphate such as zirconium phosphate and titanium phosphate. It can be easily produced in the presence of water vapor based on the description in Japanese Patent No. 150214.

  Next, the “organic amine or organic ammonium” that penetrates between the layers of the crystalline layered inorganic compound (intercalation) and performs delamination and also functions as a dispersant is a polyfunctional organic amine or polyfunctional organic ammonium. (Hereinafter, “component B”). Here, “polyfunctionality” means having one or more reactive groups in addition to an amine group (for example, an amino group, an ammonium group, or an imino group). , Carboxyl group, hydroxyl group and the like. Here, the reactive group functions so as to react with other functional groups to be chemically crosslinked. Accordingly, an appropriate reactive group is determined in relation to the other side of the cross-linking (for example, when cross-linking with the nanosheet, a reactive group capable of cross-linking with the functional group of the nanosheet; other additives described later) When cross-linking with a functional group possessed by the additive, a reactive group capable of cross-linking with the functional group possessed by the additive; when a cross-linking agent is added, a reactive group capable of reacting with the cross-linking agent; In the case of crosslinking with a reactive group, a reactive group capable of crosslinking with another functional group of the organic amine or the like).

Here, a mechanism for forming a strong film by using a cation-exchangeable crystalline layered inorganic compound and a polyfunctional organic amine or polyfunctional organic ammonium will be described with reference to FIG. However, the following description is mainly aimed at facilitating understanding of the invention, and the present invention is not limited to the mechanism, the cross-linked structure, the bonding form, and the like. Hereinafter, a polyfunctional amine having a structure represented by the general formula: NH ₂ R (NH ₂ ) COOH is taken as an example (for example, asparagine). In the figure, for the sake of easy understanding, an example in which OH groups that are cation exchange groups are alternately substituted is shown, but the present invention is not limited thereto. For convenience of explanation, the case where a trifunctional amine is used will be described, but the number of functional groups is not limited thereto.

First, FIG. 1 (a) shows a state in which an amine group of a polyfunctional amine is bonded to a cation exchange group on the surface of a metal compound layer before drying (in a state where water is present). In the presence of water, a proton of the OH groups are cation exchange groups, positively charged amine group and the results for ion exchange multifunctional amine, as shown in the figure, the cation exchange group O ^- and —NH ₃ ⁺ is electrically coupled. Although not shown, another —NH ₃ ⁺ of the polyfunctional amine is an vacant cation exchange group (OH) of a metal compound layer different from the metal compound layer to which the polyfunctional amine is bonded. When the group is approached, it is electrically bound to the vacant cation exchange group.

Next, FIG.1 (b) and FIG.1 (c) show a mode that both metal compound layers were couple | bonded firmly via the said polyfunctional organic amine or organic ammonium after drying (especially after a heating process). It is a thing. First, FIG. 1B is an example in which one polyfunctional organic amine or the like crosslinks both metal compound layers. Here, the first point is that a dehydration condensation reaction occurs between the cation exchange group on the surface of the metal compound layer and the amine group of the polyfunctional amine during drying, and as a result, the dotted box in FIG. As shown in A, a covalent bond of —NH— is formed. The second point is that a functional group (for example, —COOH) of the polyfunctional organic amine that is not bonded to the metal compound layer at a position close to the cation exchange group (OH group) on the surface of the metal compound layer. Is present, as a result of a dehydration condensation reaction between the cation exchange group and the functional group, a covalent bond of —COO— is formed as shown by a dotted box B in FIG. Is a point. Next, FIG. 1C is an example in which two (or more) polyfunctional organic amines and the like cross-link both metal compound layers. Here, as in FIG. 1B, the first point is that a dehydration condensation reaction occurs between the cation exchange group on the surface of the metal compound layer and the amine group of the polyfunctional amine during drying. As indicated by a dotted box A in FIG. 1 (c), a covalent bond of —NH— is formed. The second point is that the polyfunctional organic amine bonded to one metal compound layer has a free functional group (for example, —NH ₂ ) bonded to the other metal compound layer during drying. When a free functional group (for example, —COOH) of the organic organic amine is close, a dehydration condensation reaction occurs between both functional groups. As a result, as shown by a dotted line C in FIG. A covalent bond is formed.

  The functional group other than the amine group may be bonded to the cation exchange group of the metal compound layer as shown in FIG. 1 (b), but other organic groups as shown in FIG. 1 (c). It may be bonded to an amine or organic ammonium functional group, or may be bonded to both of them. In addition, by selecting the type and number of functional groups as appropriate, a more complicated cross-linked structure can be adopted, and as a result, a stronger film can be formed.

  The existence form of “component B” may be a polyfunctional organic amine or polyfunctional organic ammonium monomer, a polyfunctional organic amino polymer, or a mixture thereof. Alternatively, a polymerizable organic monomer or a low molecular weight polymer may be first introduced between the layers of the layered metal compound, and polymerization may be performed by polymerization using this interlayer space as a reaction field. As the polymer becomes more polymerized, the distance between layers expands and the layers are peeled off. Specific examples include interlayer synthesis of polyaniline as a polyfunctional organic amine. A zirconium phosphate / polyaniline hybrid can be generated by adding ammonium persulfate used as an oxidative polymerization agent using aniline hydrochloride and layered zirconium phosphate as monomers.

  Here, specific examples of “Component B” include, for example, polyvalent amine compounds, amino acids, aminosilanes (which generate hydroxyl groups by hydrolysis), chitosan compounds, polyfunctional amino polymers, and the like. Examples of the polyvalent amine compound include alkylene diamines such as ethylene diamine, octamethylene diamine, m-xylylenediamine, hexamethylenetetramine, polyallylamine, and melamine. In addition, among the above, the carbon number of the alkylene diamine is not particularly limited, but 2 to 20 is preferable. This is because if the carbon number is too large, it is difficult to incorporate between layers, and if it is too small, delamination occurs and slows. Examples of amino acids include valine, leucine, isoleucine, alanine, arginine, glutamine, lysine, aspartic acid, threonine, methionine, histidine, phenylalanine, glycine and the like. Examples of the aminosilane compound include N-2 (aminoethyl) 3-aminopropylmethyldimethoxysilane, N-2 (aminoethyl) 3-aminopropyltrimethoxysilane, and N-2 (aminoethyl) 3-aminopropyl. Triethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N- (1,3-dimethyl-butylidene) propylamine, N- (vinylbenzyl) -2-amino Examples thereof include ethyl-3-aminopropyltrimethoxysilane and N, N-bis [3- (trimethoxysilyl) propyl] ethylenediamine. Examples of the chitosan compound include chitosan, chitosan PCA, chitosan succinamide, carboxymethyl chitin, humanoxyethyl chitosan, carboxymethyl chitosan succinamide, and the like. Examples of the polyfunctional amino polymer include polyallylamine, polyaniline, nylon, melamine resin, amino-modified aqueous phenol resin, cationic aqueous urethane resin, and cationic aqueous epoxy resin. Examples of the polyfunctional organic ammonium include tetramethylammonium hydroxide.

  Next, the surface treatment agent according to the best mode further includes at least one inorganic component selected from the group consisting of silicon, cerium, lithium, zinc, magnesium, calcium and manganese (hereinafter referred to as “component C”) and It is preferable to contain at least one component selected from the group consisting of water-soluble polymers (hereinafter referred to as “component D”). By containing these components, corrosion resistance and coating adhesion can be further improved. Further, the existence form of the component C and the component D may be an ionic state, a fine particle dispersed state, or a mixture thereof.

  Here, the inorganic component serving as a supply source of “component C” is not particularly limited, and examples thereof include water-dispersed oxides, hydroxides, phosphates, carbonates, and silicates. Specifically, for example, for silicon compounds, silica such as water-dispersible silica, water-soluble silicate compounds such as sodium silicate, potassium silicate, and lithium silicate, silicate esters, alkyl silicates such as diethyl silicate Examples thereof include silicates such as clay mineral montmorillonite having a crystalline layered structure and silane coupling agents. The water-dispersible silica is not particularly limited, and examples thereof include “Snowtex” type (all manufactured by Nissan Chemical Industries, Ltd.), fumed silica such as “Aerosil” (manufactured by Nippon Aerogi Co., Ltd.), and the like. Can be mentioned. The silicate having the crystal layer structure is not particularly limited, and examples thereof include purified bentonite mainly composed of clay mineral montmorillonite of “Bengel” series (manufactured by Hojun Co., Ltd.). For example, regarding a magnesium compound, magnesium oxide, magnesium hydroxide, magnesium phosphate, magnesium silicate, etc. can be mentioned. Further, the water-soluble polymer as “component D” is not particularly limited, and examples thereof include various water-soluble or water-soluble resins. Of these, polyacrylic acid polymers, water-soluble phenol resins, water-soluble urethane resins, water-soluble epoxy resins, and the like are suitable. When component D is added to component A and component B, component A and component B may be added as a special dispersion pigment (additive) and component D may be added as an organic binder.

Two effects can be expected by using a layered inorganic compound. The first is barrier properties and flexibility of the peeled nanosheet or inorganic / organic nanohybrid film, and excellent workability and corrosion resistance by taking advantage of these characteristics, that is, defects are not easily generated. The second is the “storing and sustained release” due to the interlayer space and intercalation of the layered inorganic compound, and the functional anticorrosive effect using these characteristics, that is, pH reduction and Self-repair can suppress the occurrence and progression of corrosion. Specifically, for example, intercalation of metal cations (cation ion exchange) such as organic amine or organic ammonium is possible with respect to the proton ion exchange point of layered zirconium phosphate. This intercalation remains in the intercalation between the layers of the parent layered zirconium phosphate, and does not go through the delamination. For example, nanosheets peeled off by organic amine or organic ammonium overlap again after film formation to form a new interlayer space, and in some cases, metal cations (for example, alkali metal ions such as Li) present in the treatment liquid are taken in between layers ( Intercalation). In this way, the metal cation is intercalated between layers of layered zirconium phosphate, so that the metal cation is “stored” in a (very narrow) interlayer space instead of proton ions. . The “stored” alkali metal ions are gradually released from the (narrow) interlayer space and neutralize the surrounding acidity by exchanging with the surrounding proton ions again (pH relaxation). Since metal corrosion basically occurs and progresses due to the polarization of the anode (acidic) and cathode (alkaline), reducing the pH, that is, suppressing the acidity on the anode side or alkalinity on the cathode side, suppresses the occurrence and progression of corrosion. It leads to. In addition, instead of alkali metal ions, polyvalent metal ions with oxidizing power (eg, V, Ce, Mn) are intercalated into the interlayer space, making use of the “storing and sustained release” oxidizing power Can be expected to keep long. It is also possible to demonstrate the “self-repair function” of Cr ⁶⁺ like conventional chromate treatment. Thus, “component C” can intercalate between the layers of the crystalline layered inorganic compound (component A), and can have storage properties and sustained release properties using the interlayer space.

  In addition, this surface treating agent can add well-known various additives, such as a wetting agent, a leveling agent, an antifoamer, and a thickener, as needed.

  Next, the content of each component in the surface treatment agent according to the best mode will be described. First, the ratio between the crystalline layered inorganic compound (component A) and the organic amine or organic ammonium (component B) is a molar ratio, and the organic amine or organic ammonium is 1 mol of the crystalline layered inorganic compound (component A). (Component B) is preferably from 0.1 to 2 mol, more preferably from 0.3 to 1.5 mol. When the amount of organic amine or organic ammonium (component B) is less than 0.1 mol relative to 1 mol of the crystalline layered inorganic compound (component A), delamination may not occur or stable dispersion may not occur. On the other hand, when there are more than 2 moles of organic amine or organic ammonium (component B) per mole of crystalline layered inorganic compound (component A), excess organic amine or organic ammonium (component B) that is not intercalated between layers is present. In some cases, the film-forming property is lowered, and the composite characteristics with the layered phosphate and the layered oxide cannot be utilized.

  Next, the amount (solid content) of the crystalline layered inorganic compound (component A) is preferably 0.5 to 95 wt% with respect to the total solid content of the surface treatment agent. This is because if the addition amount is less than 0.5 wt%, the corrosion resistance of the metal compound is small and the adhesion after coating may be insufficient, and if it exceeds 95 wt%, delamination and nanosheet dispersion may occur. This is because it becomes insufficient, the stability of the treatment liquid is lowered, and the performance of the film may not be achieved. Here, regarding a lower limit, 5 wt% or more is more suitable, and 30 wt% or more is especially suitable. Regarding the upper limit value, 70 wt% or less is more preferable, and 50 wt% or less is particularly preferable.

  Next, the addition amount of Component C is preferably 5 to 9900 parts by weight with respect to 100 parts by weight of the crystalline layered inorganic compound (solid content) serving as the supply source of Component A. Here, regarding a lower limit, 50 weight part or more is more suitable, and 100 weight part or more is especially suitable. With respect to the upper limit, 5000 parts by weight or less is more preferable, and 2500 parts by weight or less is particularly preferable. Moreover, it is suitable that the addition amount of the component D is 5-9900 weight part with respect to 100 weight part of crystalline layered inorganic compounds (solid content) used as the supply source of the component A. Here, regarding a lower limit, 50 weight part or more is more suitable, and 100 weight part or more is especially suitable. The upper limit is more preferably 5000 parts by weight or less, and particularly preferably 2500 parts by weight or less.

  The physical properties of the surface treatment agent are not particularly limited. Either an acidic treatment liquid containing a cationic polymer or an alkaline treatment liquid containing an anionic polymer can be used for pharmaceutical preparation.

Next, the manufacturing method of the surface treating agent which concerns on this best form is demonstrated. First, the liquid medium of the surface treatment agent is preferably an inorganic polar medium such as water, or an organic polar solvent such as dimethylformamide or alcohol, such as dimethyl sulfoxide, acetonitrile, methyl alcohol, or ethyl alcohol. . The liquid medium mainly used is an inorganic polar medium such as water, or an organic polar solvent such as a small amount of alcohol added to water. And this surface treating agent is, for example, a layered crystalline metal compound (component A: for example, in the case of titanium oxide, tetratitanate K ₂ Ti ₄ O ₉ , pentatitanate Cs _{2 in the} liquid medium. Ti ₅ O ₁₁ , lipidocrocite-type titanate Cs _0.7 Ti _1.825 O ₄ , K _0.8 Ti _1.73 Li _0.27 O _4, etc.) are added, and then an acid treatment is applied to the interlayer. After once synthesizing a hydrogen-type substance in which the alkali metal ions in the above are replaced with hydrogen ions, a polyfunctional organic amine or polyfunctional organic ammonium (component B) that functions as a “stripping agent” and “dispersing agent” is further added. Thereafter, it can be obtained by appropriately controlling the reaction conditions, for example, by applying a shearing force. As a result of performing the treatment, the layered inorganic compound is peeled off to be separated into one host layer or overlapped by several or several tens of sheets (nanosheet formation). As a result, the nanosheet is in a liquid medium. A colloidal solution dispersed in is formed. The application of the shearing force is performed by ultrasonic treatment, heat treatment, stirring using a stirrer, vibration, or the like. Among these, ultrasonic treatment and heat treatment are particularly preferable because the reaction time can be shortened.

  Next, the usage method (surface treatment method of a metal material) of this surface treating agent is demonstrated. The said method includes the process of apply | coating to a metal surface, and the process of drying after application | coating. In general, the method includes a degreasing step and a water washing step before the coating step.

  First, the coating process will be described. As a coating method, a conventional method can be applied as it is, and for example, roll coating, curtain flow coating, air spray, airless spray, dipping, bar coating, brush coating, and the like can be performed.

  Next, the drying process will be described. First, as a drying method, a conventional method can be applied as it is, and examples thereof include heat drying and air drying. Therefore, the processing drying temperature (maximum reached plate temperature, PMT) is preferably 60 to 300 ° C, and more preferably 100 to 250 ° C. There is no particular limitation as long as moisture can be evaporated and dried. However, drying at 100 ° C. to 250 is particularly preferable from the viewpoints of the corrosion resistance and adhesion, which are the objects of the present invention.

  The target metal materials are cold-rolled steel sheet, hot-rolled steel sheet, hot-dip galvanized steel sheet, electrogalvanized steel sheet, hot-dip galvanized steel sheet, aluminized steel sheet, aluminum-zinc alloyed steel sheet, stainless steel sheet, aluminum It can be applied to generally known metal materials and plated plates such as plates, copper plates, titanium plates, magnesium plates and the like. Furthermore, it is possible to deal with mixed processing of multiple kinds of materials. These metal plates may be subjected to ordinary treatments such as hot water washing and alkaline degreasing before treatment.

Next, the metal material on which a film is formed by the surface treatment will be described. First, the film mass of the formed film is preferably 0.01 to 5 g / m ² (dry mass). If the coating mass is less than 0.01 g / m ² , the corrosion resistance may be insufficient because the coating mass is small. Conversely, if it exceeds 5 g / m ² , the film-forming property may be deteriorated. Furthermore, the adhesiveness is insufficient and the cost is disadvantageous. A more preferable range is 0.05 g / ^{m 2} or more and 1.5 g / ^{m 2} or less.

  Here, it is presumed that the film to be formed is a nano-scale hybrid film of an inorganic nanosheet of phosphate or oxide and a polyfunctional organic amine or polyfunctional organic ammonium. Specifically, during the drying (baking) of the treated film, the hybrid coating is, for example, crosslinked by reaction with a hydroxyl group of the crystal layer (nanosheet) (nanosheet and polyfunctional organic amine or polyfunctional organic ammonium). Cross-linking), polyfunctional organic amines, or polyfunctional organic ammonium itself. Since this hybrid film is an extremely strong film having a very fine structure, it is estimated that it provides excellent corrosion resistance and adhesion.

  Next, the utilization method (use) of the metal material in which the film was formed with this surface treating agent will be described. First, various metal products can be obtained by processing the metal material into a desired shape. Examples of the metal product include fingerprint-resistant galvanized steel sheets for home appliances, pre-coated steel sheets for residential use for buildings, aluminum fin materials for air conditioners, and various metal parts for automobiles. In addition, the topcoat film provided on the film is not particularly limited, and examples of the topcoat film include electrodeposition coating, solvent coating, powder coating, and special coatings such as hydrophilic coatings, lubricating organic coatings, and antifouling coatings. Examples thereof include antibacterial films. Further, depending on the level of rust prevention, it is not necessary to provide a top coat (for example, temporary rust prevention).

  Hereinafter, the present invention will be described with specific examples. The present invention is not limited by these examples.

1. Preparation of test plate Cold rolled steel plate (SPCC-SD)
Alloyed hot-dip galvanized steel sheet (GA) plating coverage 45g / m ² per side (double-sided plating)
Electrogalvanized steel sheet (EG) Zinc adhesion amount 40g / m ² per side (double-sided plating)
Hot-dip galvanized steel sheet (GI) Zinc adhesion amount 60 g / m ² per side (double-sided plating)
55% aluminum galvanized steel sheet (GL) Zinc adhesion amount 60g / m ² per side (double-sided plating)
Aluminum plate (Al)
Dimensions of each test material 70mm x 150mm x 0.8mm

2. Pretreatment The test material was immersed in an aqueous solution having a concentration of 20 g / L and a temperature of 60 ° C. for 10 seconds using an alkaline degreasing agent Parculin N364S (manufactured by Nippon Parkerizing Co., Ltd.), washed with pure water and then dried. did.

3. surface treatment
<Examples 1 to 69, Comparative Examples 1 to 24>
For SPCC materials, GA materials, EG materials, GI materials, GL materials, or Al materials, as a bare rust-preventing bare plate (before painting) and / or as a ground-treating film for general-painted plates, and as a ground-treating film for pre-coated plates The surface treatment agent having the composition shown in Table 1 was applied by a bar coating method so as to have a predetermined film thickness, and dried in a drying furnace to a maximum plate temperature (PMT) of 120 ° C. Moreover, it apply | coated so that it might become a predetermined film thickness by the bar-coat method using the surface treating agent of the composition shown in Table 1 as a base-treatment film | membrane of a hydrophilic coating board with respect to Al material, and it dried to PMT180 degreeC with the drying furnace. . Here, a production example of the crystalline layered inorganic compound used in this example and the comparative example will be specifically described by taking crystalline layered zirconium phosphate [Zr (HPO ₄ ) ₂ .H ₂ O] as an example. . Other crystalline metal compounds can be produced according to the example.
ZrOCl ₂ , which is a water-soluble zirconium salt, was dissolved in 500 ml of 23.5 g of pure water, and 52.25 g of 75% phosphoric acid (P ₂ O ₅ / ZrO ₂ molar ratio 1.5) was gradually added thereto while stirring. It was dripped in. As a result, a white gel-like precipitate was obtained. After centrifuging this, 34 g of 75% phosphoric acid was further added, mixed, and then placed in an electric furnace whose temperature was set to 130 ° C. together with the crucible. Steam heated to 0 ° C. was blown in and reacted at 130 ° C. for 4 hours in the presence of steam. The obtained reaction product was white. The reaction product was washed with water, dehydrated, dried and then pulverized. As a result of X-ray diffraction measurement, this pulverized product was found to be zirconium phosphate [Zr (HPO ₄ ) ₂ .H ₂ O]. The interlayer distance of the zirconium phosphate was 7.6 mm (76 nm).

<Comparative Examples 25 to 28 (coating chromate treatment)>
Using EG material, GI material, GL material or Al material, using Zinchrome 1300AN (manufactured by Nihon Parkerizing Co., Ltd.) as the coating chromate agent, it is applied by the roll coating method so that the amount of adhesion is 40 mg / m ^2. And dried in a hot air drying oven to a PMT of 80 ° C.

4). Top coating General coating was performed under the following conditions (SPCC material, GA material, EG material, GI material, GL material, or Al material).
Paint: Amirac # 1000 (manufactured by Kansai Bainto)
Coating method: Bar coating method Baking: PMT 200 ° C. Film thickness: 20 μm
Pre-coating (primer + top) was performed under the following conditions (EG material, GI material, GL material or Al material).
Primer: TQ88 (manufactured by NOF Corporation)
Coating method: Bar coating method Baking: PMT 200 ° C. Film thickness: 7 μm
Top: SRF-05 (Nippon Yushi Co., Ltd.)
Coating method: Bar coating method Baking: PMT 225 ° C. Film thickness: 17 μm
Hydrophilic coating was performed under the following conditions (Al material).
Paint: Palen 5013 (Nippon Parkerizing hydrophilic paint)
Coating method: Bar coating method Baking: PMT 200 ° C. Coating amount: 0.8 g / m ²

5. Evaluation [film mass]
The film mass was determined by measuring the amount of metal (Zr, Ti, etc.) or phosphorus deposited using a fluorescent X-ray analyzer (FXA) and converting from the blended amount in the treating agent.
[Corrosion resistance]
[SST]
Flat part: The salt spray test prescribed in JIS-Z2371 was carried out for 240 hours on a bare plate (before painting) of EG material, GI material, GL material or Al material, and a hydrophilic coated plate of Al. The white rust resistance of the flat portion was visually measured and evaluated.
The evaluation criteria are as follows.
◎: White rust occurrence rate of less than 5% ○: White rust occurrence rate of 5% or more and less than 10% △: White rust occurrence rate of 10% or more and less than 50% X: White rust occurrence rate of 50% or more X cut part: SPCC material 480 hours of salt spray test stipulated in JIS-Z2371 for general coating plate of GA material, EG material, GI material, GL material or Al material, EG material, GI material, GL material or Al material pre-coated paint plate Carried out. The maximum swollen width was measured and evaluated.
The evaluation criteria are shown below.
◎: No swelling ○: Less than 6 mm △: 6 mm or more, less than 10 mm ×: 10 mm or more [Coating film adhesion]
[Primary adhesion]
SPCC material, GA material, EG material, GI material, GL material or Al material general coated plate is put on the painted surface with a 1mm square base with cutter life, and 5mm with Erichsen tester so that the painted surface becomes convex After extrusion, a tape peel test was performed. About the method of putting a base | substrate eye, the extrusion method of Erichsen, and the method of tape peeling, it implemented according to the method of JIS-K5400.88.2 and JIS-K5400.88.5. Evaluation was performed by the number of coating film peeling.
The evaluation criteria are shown below.
◎: No peeling ○: Number of peeled 1 or more, less than 10 △: Number of peeled 11 or more, less than 50 ×: Number of peeled 51 or more In addition, EG material, GI material, GL material or Al material pre-coated plate Was subjected to a bending test (2T), and was performed at the coating film peeling area after tape peeling.
The evaluation criteria are shown below.
◎: No peeling ○: Peeling area less than 10% △: Peeling area of 10% or more and less than 50% ×: Peeling area of 50% or more In addition, a small amount of deionized water is attached to the surface of an Al material hydrophilic coated plate. The appearance of the surface after rubbed strongly 20 times was observed.
The evaluation criteria are shown below.
◎: The substrate is exposed in less than 1% of the test site. ○: The substrate is exposed in 1% to less than 5% of the test site. △: The substrate is exposed in 5% to less than 50% of the test site. X: 50% or more of the test site. The substrate is exposed [secondary adhesion]
A general coated plate of SPCC material, GA material, EG material, GI material, GL material or Al material was immersed in boiling water for 2 hours, and then the same test as the primary adhesion was performed and evaluated. Moreover, after immersing the precoat coating board of EG material, GI material, GL material, or Al material for 2 hours in boiling water, it took out and evaluated by performing a test similar to the primary adhesion after 24 hours.

  The results are shown in Table 2. As is clear from the results in Table 2, in Examples using the coating surface treatment agent of the present invention, good coating adhesion and corrosion resistance were obtained.

FIG. 1 is a conceptual diagram of a mechanism for forming a strong film by using a cation-exchangeable crystalline layered inorganic compound and a polyfunctional organic amine or polyfunctional organic ammonium.

Claims (11)

  A surface treatment agent obtained by nano-sheeting a crystalline layered inorganic compound with an organic amine or organic ammonium, wherein the organic amine or organic ammonium is a polyfunctional organic amine or a polyfunctional organic ammonium. Agent.   The surface treatment agent according to claim 1, wherein the polyfunctional organic amine or polyfunctional organic ammonium is a polyvalent amine compound, an amino acid, an aminosilane, chitosan, or a polyfunctional amino polymer.   The surface treating agent according to claim 1 or 2, wherein the crystalline layered inorganic compound is a phosphate or oxide of zirconium, titanium, vanadium, silicon, or aluminum.   The ratio of the polyfunctional organic amine or polyfunctional organic ammonium to the crystalline layered inorganic compound is 0.1 to 2 moles per mole of the crystalline layered inorganic compound. The surface treating agent according to any one of 3.   The surface treatment agent according to any one of claims 1 to 4, wherein the amount of the crystalline layered inorganic compound (solid content) is 5 to 95 wt% with respect to the total solid content of the surface treatment agent.   Furthermore, it contains at least one component selected from the group consisting of an inorganic component selected from the group consisting of silicon, cerium, lithium, zinc, magnesium, calcium and manganese and a water-soluble polymer. The surface treating agent according to any one of 5.   A surface treatment method for a metal material, comprising a step of forming a film by applying and drying the surface treatment agent according to any one of claims 1 to 6 on the surface of the metal material.   The method according to claim 7, wherein the coating is an inorganic / organic nanohybrid coating containing inorganic nanosheets. The method of Claim 7 or 8 whose film | membrane mass of the said film | membrane is 0.01-5 g / m < ² >. It has a film | membrane with a film | membrane mass of 0.01-5 g / m < ² > formed on the said metal material surface by apply | coating and drying the surface treating agent as described in any one of Claims 1-6 on the metal material surface. A surface-treated metal material characterized by   The surface-treated metal material according to claim 10, wherein the metal material is at least one selected from an iron-based substrate, a zinc-based substrate, and an aluminum-based substrate.

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