KR102043572B1 - Waterborne treatments, galvanized or galvanized steel and painted galvanized or galvanized steel - Google Patents

Abstract

Even if it does not contain chromium, the aqueous treatment agent which provides corrosion resistance, alkali resistance, acid resistance, and coating film adhesiveness of a molding process part can be provided. (A) Zirconium compound, (B) Epoxy resin, (C) The silanol group containing compound represented by following formula [I] and / or its condensate, XY (Z) _n Si (OH) _{3- n} (I), ( D) A phosphoric acid compound and (E) tetravalent vanadium compound are contained, and mass ratio [(B) / Zr] of the mass in Zr conversion of a zirconium compound (A) and the mass of an epoxy resin (B) is 0.7-1.5 , Mass ratio [SiO ₂ / Zr] of the silanol group-containing compound and / or its condensate (C) to the SiO ₂ equivalent mass is 0.15 to 1.5, and mass ratio of the P equivalent mass of the phosphoric acid compound (D) [P / Zr] The water treatment agent whose mass ratio [V / Zr] with the V conversion mass of this 0.025-0.1, tetravalent vanadium compound (E) is 0.02-0.05.

Description

Waterborne treatments, galvanized or galvanized steel and painted galvanized or galvanized steel

The present invention provides excellent corrosion resistance, chemical resistance (e.g., alkali resistance, acid resistance, etc.) and molding process for coated steel sheets (also called pre-coated steel sheets or post-coated steel sheets) and post-coated steels having zinc and zinc alloy plating layers. Galvanized steel, zinc alloy plated steel, painted galvanized steel, and painted zinc alloy plating having an aqueous treatment agent that gives coating film adhesion and a film obtained by the aqueous treatment agent, which has excellent corrosion resistance, chemical resistance, and coating film adhesion of a molded processing part. A steel material and a manufacturing method thereof.

BACKGROUND ART In industrial fields such as home appliances, building materials, automobiles, and the like, technologies for producing products by cutting, molding, and using steel sheets (precoat steel sheets) that have been applied in advance to steel sheets by manufacturers are widely used. Painted steel sheets that need to maintain designability require high coating film adhesion that can withstand rigorous subsequent processing by the end user. In addition, excellent corrosion resistance capable of withstanding long-term outdoor exposure, alkali resistance capable of withstanding an alkali concentrated environment derived from livestock powder, detergent, and the like, and acid resistance that can withstand acid rain or detergent, etc. are required.

Representative coated steel sheets include those coated with an organic coating film having a two-layer structure including a primer coating film and a top coating film on a plated steel sheet subjected to a treatment for providing coating film adhesion. In order to achieve the said corrosion-resistant performance, the coating material which provides this coating-film adhesiveness contains the chromate treatment, and the coating material which contained the chromium-type rustproof pigment also in the primer coating film is used conventionally. However, in recent years, chromate freeization of these coating films etc. is strongly requested | required from the problem of the environmental load of hexavalent chromium. In indoors used in mild conditions such as home appliance fields, chromate freeization is being progressed. However, in outdoor products used in harsh outdoor conditions such as building materials, it is difficult to satisfy all end user requirements, and chromate freeization does not proceed. There is a phenomenon.

Generally, the coating film adhesiveness of a coated steel plate is evaluated by the test by a bending process. However, the coating film adhesiveness in more stringent processing conditions, such as a test by drawing molding process, may be required. When the processing conditions are severe, if the coating film adhesiveness is insufficient, the coating film curls up and peels off from the side portions, end surface portions, scratches, and the like subjected to the processing load. About strict processing conditions, since the coating film adhesiveness of a very high process part and the processing followability of a coating film are calculated | required, the processing agent which has resin as a main component is applicable as chromate-free processing. However, since outdoor use also has a high level of alkali resistance, acid resistance and corrosion resistance, conventional treatment agents containing resins which cannot be deteriorated when exposed to a long-term corrosive environment must satisfy their required performance. no.

In the case where the coating layer composition in the coated steel sheet is zinc-based zinc main, when the processing is performed, the plating layer is ductile, so that cracks do not occur in the plating layer during processing, and a large stress is applied to the coating film formed on the plating layer. Since the stress causes a coating film peeling, in the coated steel plate based on a zinc and zinc alloy plated steel plate, it is more difficult to ensure the coating film adhesiveness after performing strict processing, such as said drawing molding process.

As the chromate-free coated steel sheet, for example, Patent Documents 1 to 3 include water-soluble resins such as a silane coupling agent and / or a hydrolytic condensate thereof, a non-chromate metal surface treatment agent containing a water dispersible silica, a zirconium compound, or an acrylic resin. A technology relating to a metal surface treatment agent is further disclosed. According to these techniques, excellent corrosion resistance etc. can be provided to steel materials.

Patent Document 4 discloses a surface treating agent containing water, a carbonate of a metal selected from Mg, Co, Zr, Ni, Zn, and Cu, a water dispersible silica, and a specific organic acid. According to this surface treating agent, the surface-treated steel sheet excellent in the processing adhesiveness and corrosion resistance of a coating film can be provided.

Japanese Patent Laid-Open No. 2001-240979 Japanese Patent Laid-Open No. 2001-316845 International Publication No. 2004/005579 Japanese Patent Laid-Open No. 2004-277849

INDUSTRIAL APPLICABILITY The present invention has excellent corrosion resistance and can form a coating having chemical resistance and coating film adhesion of a molded processed portion, a chromium-free water-based treatment agent, and a galvanized steel, zinc alloy plated steel, and galvanized zinc coating having the coating. An object of the present invention is to provide a steel material and a coated zinc alloy plated steel material and a manufacturing method thereof.

MEANS TO SOLVE THE PROBLEM As a result of earnestly examining in order to achieve the said objective, the present inventors included a specific zirconium compound, an epoxy resin, a specific silanol group containing compound, a phosphoric acid compound, and a vanadium compound, and it is specific about these containing components. By using an aqueous treatment agent that satisfies the composition ratio, it has been found that a coated galvanized steel and a coated zinc alloy plated steel can be obtained that have excellent corrosion resistance and are compatible with chemical resistance and coating film adhesion of a molded part in a high dimension. Has come to complete.

That is, this invention is as follows.

(1) (A) zirconium compound selected from ammonium zirconium carbonate, potassium zirconium carbonate, basic zirconium carbonate and zirconium acetate,

(B) epoxy resin,

(C) a silanol group-containing compound represented by the following formula [I] and / or a condensate thereof,

(X represents a functional group derived from a glycidoxy group or a glycidoxy group, Y represents an alkyl group having 1 to 10 carbon atoms, Z represents a methoxy group, an ethoxy group or a methyl group, and n represents an integer of 0 to 2). )

(D) phosphoric acid compounds,

(E) Vanadium Compound

It is an aqueous treatment agent containing

Regarding the mass in terms of Zr of the zirconium compound (A),

Solid content mass ratio [(B) / Zr] of the mass of an epoxy resin (B) is 0.7-1.5,

The solid content mass ratio [SiO ₂ / Zr] in the SiO ₂ equivalent mass of the silanol group-containing compound and / or its condensate (C) is 0.15 to 1.5,

Solid content mass ratio [P / Zr] in P conversion mass of a phosphoric acid compound (D) is 0.025-0.1,

The water treatment agent whose solid content mass ratio [V / Zr] in the V conversion mass of a vanadium compound (E) is 0.02-0.05.

(2) The aqueous treatment agent according to the above (1), wherein the epoxy resin is a bisphenol A epoxy resin containing a carboxyl group, and the weight average molecular weight of polystyrene conversion by gel permeation chromatography is 30,000 to 150,000.

(3) 1-40 mg of Zr adhesion amount formed in the at least single side | surface of the galvanized steel plate or zinc alloy plated steel plate whose plating layer composition is Zn: 80 mass% or more using the water-based treatment agent as described in said (1) or (2). Galvanized steel or zinc alloy plated steel having a treated coating layer of / m < 2 >.

(4) A coated galvanized steel or a coated zinc alloy plate having a laminated coating film containing at least one layer on the treated coating layer of the galvanized steel or zinc alloy plated steel according to (3), having a total film thickness of 1 to 50 µm. Steel.

(5) The aqueous treatment agent according to the above (1) or (2) is applied to at least one surface of a galvanized steel sheet or a zinc alloy plated steel sheet having a plating layer composition of Zn: 80 mass% or more to form a treated coating layer,

A method for producing a galvanized steel or zinc alloy plated steel, wherein the treated film layer is heated to dry and a treated film layer of 1 to 40 mg / m 2 is formed as a Zr deposition amount.

(6) The aqueous treatment agent according to the above (1) or (2) is applied to at least one surface of a galvanized steel sheet or a zinc alloy plated steel sheet having a Zn: 80 mass% or more, thereby forming a treated coating layer.

Heat-drying the said processed coating layer, and forming a treated coating layer of 1-40 mg / m <2> as Zr adhesion amount,

Moreover, at least 1 layer of coating material for laminated coatings is apply | coated on the said process film layer,

Heat-drying the said at least 1 layer laminated coating film, and forming a laminated coating film with a total film thickness of 1-50 micrometers,

Process for producing painted galvanized steel or painted galvanized steel.

Although the water treatment agent of this invention does not contain chromium, it has the outstanding corrosion resistance and can form the film which has the chemical-resistance and the coating-film adhesiveness of a molding process part. For this reason, it becomes possible to remarkably reduce the environmental load of the coated steel plate used for outdoor use. Therefore, the water treatment agent of the present invention has a very large industrial value. The coated galvanized steel of the present invention and the coated zinc alloy plated steel are the water-based treatment agent of the present invention not only in the precoated steel sheet in which the laminated coating film is performed in advance in a steel sheet maker, but also in any of the post-coated steel sheets carried out on the user side after delivery. You can expect the effect of.

EMBODIMENT OF THE INVENTION Below, the detail of this invention is demonstrated. The aqueous treatment agent of this invention contains a zirconium compound (A), an epoxy resin (B), a silanol group containing compound and / or its condensate (C), a phosphoric acid compound (D), and a vanadium compound (E) . Hereinafter, each said component is demonstrated.

Zirconium compound (A) is selected from ammonium zirconium carbonate, potassium zirconium carbonate, basic zirconium carbonate and zirconium acetate. The zirconium compound (A) is a film forming component capable of forming a three-dimensional crosslinked zirconium oxide film by condensation accompanying hydrolysis and desorption of volatile acids such as carbonic acid or acetic acid in the film formation (baking) process. It contributes to the expression of processing adhesiveness, corrosion resistance, and chemical resistance. In addition, since zirconium activated by the desorption of the acid is firmly bonded through the surface of the plating layer and oxygen atoms, it contributes to the expression of adhesion. The effect of the zirconium compound (A) is not obtained from zirconic hydrofluoric acid, fluorozirconate, zirconium nitrate, zirconium sulfate, zirconium oxychloride, or the like, but is obtained only from a zirconium compound stabilized with volatile acids, carbonic acid and acetic acid.

Epoxy resin (B) is a film forming component, it is complicated with a zirconium compound (A), a silanol group containing compound, and / or its condensate (C), and expresses work adhesiveness by giving toughness and suitable processing followability to a process film. Contribute to. In addition, the formation of a dense coating structure having high hydrolysis resistance contributes to the development of processing adhesion, chemical resistance and corrosion resistance. In addition, the epoxy group and hydroxyl group in resin contribute to adhesive expression with an upper layer by reaction with the organic functional group of an upper laminated coating film, and a hydrogen bond effect. The effect of such an epoxy resin (B) is not obtained with resin types other than an epoxy resin. For example, acrylic resins have a hard coating and poor processing followability, and thus work adhesion is not obtained. Polyurethane resins have poor durability against moisture, ultraviolet rays, and heat, and thus long-term corrosion resistance is not obtained. It is easy to be decomposed and alkali resistance is not obtained.

The epoxy resin (B) to be contained in the aqueous treatment agent of the present invention can be obtained by a known production method and is not particularly limited. Epoxy resin (B) is composed of bisphenol A, bisphenol F, novolac resin, and the like, and epoxy compounds having two or more epihalohydrins or glycidyl groups, such as epichlorohydrin, which are usually used for producing an aqueous epoxy resin. It can obtain by water-oxidizing the epoxy resin obtained by repeat of addition reaction and condensation reaction, or repeat of addition reaction.

The epoxy resin (B) may be obtained by reacting a modifier with an epoxy group or a hydroxyl group in the resin. For example, an epoxy ester resin reacted with an unsaturated fatty acid, an acrylic modified epoxy resin reacted with (meth) acrylic acid or an ester thereof, a urethane modified epoxy resin reacted with an isocyanate compound, a silane modified epoxy resin reacted with a silane coupling agent, and phosphoric acid And phosphoric acid-modified epoxy resins reacted with the above compounds or esters thereof. The said epoxy resin (B) may be used independently and may be used in combination of 2 or more type.

As an epoxy resin (B), the bisphenol-A epoxy resin containing a carboxyl group is preferable. Rigidity and moderate flexibility derived from the structural unit of bisphenol A type in this resin contribute to the improvement of the work adhesiveness of the coating film. Moreover, the structure which is hard to hydrolyze contributes to the improvement of chemical-resistance and corrosion resistance. The carboxyl group in an epoxy resin bonds strongly with a plated metal surface by its polarity, and contributes to the improvement of adhesiveness with a plated metal surface. Moreover, in the formation process of a process film, the carboxyl group in an epoxy resin crosslinks with the said zirconium compound and silanol group containing compound, and the toughness of a process film is improved and it contributes to the improvement of chemical resistance and corrosion resistance. It is preferable that the carboxyl group in resin is neutralized with a basic neutralizing agent from a viewpoint of maintaining miscibility with the zirconium compound (A) in a processing agent. As a basic neutralizing agent, since it is hard to remain in a film formation process, it is more preferable to use volatile amine or ammonia.

It is preferable that the weight average molecular weights of polystyrene conversion by the gel permeation chromatography of an epoxy resin (B) are 30,000-150,000. By defining a weight average molecular weight in the said range, it contributes to the expression of the outstanding chemical-resistance, and contributes to the expression of process adhesiveness and corrosion resistance.

Although the acid value of an epoxy resin (B) is not specifically limited, It is preferable that it is 10-40. By specifying an acid value within the said range, while improving the process adhesiveness and liquid stability of a process film, chemical-resistance can be improved.

In the aqueous treatment agent of the present invention, the solid content mass ratio [(B) / Zr] of the mass of the epoxy resin (B) to the mass in terms of Zr of the zirconium compound (A) is 0.7 to 1.5, preferably 1.0 to 1.5. to be. When less than 0.7, sufficient processing adhesiveness and corrosion resistance are not obtained, while when exceeding 1.5, sufficient processing adhesiveness, chemical resistance, and corrosion resistance are not obtained.

The silanol group-containing compound as component (C) is represented by the following formula [I].

In formula [I], X represents a functional group derived from glycidoxy group or glycidoxy group, Y represents a C1-C10 alkylene group, Z represents a methoxy group, an ethoxy group, or a methyl group, n is 0 The integer of 2 is shown.

The silanol group containing compound used for this invention is a compound obtained by hydrolyzing the organosilicon compound which has glycidoxy group. Hydrolysis of an organosilicon compound is generally performed by adding a hydrolysis adjuvant in water or the water-soluble organic solvent of a ketone, a cellosolve system containing water. The hydrolysis aid is used to bring the pH value of the solvent into the range of 3 to 5, and known ones are used without particular limitation. Examples of the hydrolysis aid include carboxylic acids such as inorganic acids such as hydrochloric acid, sulfuric acid and nitric acid, acetic acid, lactic acid, tartaric acid and citric acid. Among them, acetic acid is particularly preferred in that it volatilizes during the film forming process and is difficult to remain in the treated film.

As an organosilicon compound which has the said glycidoxy group, 3-glycidoxy propyl trimethoxysilane, 3-glycidoxy propyl triethoxy silane, 3-glycidoxy propylmethyl diethoxysilane, 3-glycol, for example Cidoxy propylmethyl diethoxysilane, etc. are mentioned. These compounds may be used independently and may be used in combination of 2 or more type.

The silanol group-containing compound and / or its condensate (C) used in the present invention is a film forming component, which is intricately intertwined with a zirconium compound (A) and an epoxy resin (B), thereby providing toughness and suitable processing followability to the treated film. Contributes to the expression of processing adhesion of the treated film. In addition, the formation of a dense coat structure also contributes to the development of chemical resistance. In addition, the silanol group (-Si-OH) contributes to the improvement of adhesion with the plated metal surface because -Si-O-M forms a strong chemical bond through the plated metal surface and the oxygen atom. The functional group derived from glycidoxy group or glycidoxy group has a role which maintains the miscibility of the zirconium compound (A) and an epoxy resin (B) in a processing agent. When a silanol group containing compound has functional groups, such as an amino group, a vinyl group, and a methacryl group with high activity at the terminal, since the miscibility of the zirconium compound (A) and epoxy resin (B) in a processing agent is not maintained, these The functional group of is not applicable.

In the aqueous treatment agent of the present invention, the solid content mass ratio [SiO ₂ / Zr] in terms of the silanol group-containing compound and / or its condensate (C) in terms of SiO ₂ to the mass in terms of Zr of the zirconium compound (A) is 0.15 to 1.5, preferably 0.2 to 1.0. When it is less than 0.15, sufficient processing adhesiveness and corrosion resistance are not obtained. On the other hand, when it exceeds 1.5, sufficient processing adhesiveness, chemical resistance, and corrosion resistance are not obtained.

Phosphoric acid compound (D) and vanadium compound (E) contribute to corrosion resistance as an elutable inhibitor (corrosion inhibiting substance). In the corrosion of the cut end surface portion or the scratched portion of the coated steel sheet, first, the anode dissolution reaction of the plating layer occurs due to the sacrificial anticorrosive action, but at that time, the phosphoric acid compound and the vanadium compound contained in the treated coating layer elute, and the zinc eluted from the plating layer. Corrosion is suppressed by forming a corrosion product and passivating the plating layer surface. When both a phosphoric acid compound (D) and a vanadium compound (E) are contained, since the corrosion product which has higher electrical insulation is formed and it is immobilized on the plating layer surface, a corrosion inhibitory effect becomes remarkably high.

Although it does not specifically limit as a phosphoric acid compound (D), For example, phosphoric acid, the ammonium salt of phosphoric acid, the alkali metal salt of phosphoric acid, the alkaline earth metal salt of phosphoric acid, etc. are mentioned.

In the aqueous treatment agent of the present invention, the solid content mass ratio [P / Zr] of the P equivalent mass of the phosphoric acid compound (D) to the mass in terms of Zr of the zirconium compound (A) is 0.025 to 0.1, preferably 0.03 to 0.07 to be. If it is less than 0.025, the effect on chemical resistance and corrosion resistance does not appear. On the other hand, when it exceeds 0.1, sufficient corrosion resistance is not obtained.

Although it does not specifically limit as a vanadium compound (E), For example, vanadium pentoxide, HVO ₃ metavanadate, ammonium metavanadate, vanadium trioxide VOCl ₃ , vanadium trioxide V ₂ O ₃ , vanadium dioxide, vanadium oxysulphate VOSO ₄ , vanadiumoxyacetylacetonate VO (OC (= CH ₂ ) CH ₂ COCH ₃ ) ₃ , vanadiumacetylacetonate V (OC (= CH ₂ ) CH ₂ COCH ₃ ) ₃ , vanadium trichloride VCl ₃ , and the like. .

In the aqueous treatment agent of the present invention, the solid content mass ratio [V / Zr] in the V-converted mass of the vanadium compound (E) to the mass in the Zr equivalent of the zirconium compound (A) is 0.02 to 0.05, preferably 0.02 to 0.05. 0.03. If it is less than 0.02, the effect on chemical resistance and corrosion resistance does not appear. On the other hand, when it exceeds 0.05, sufficient acid resistance is not obtained.

It is preferable that the aqueous treatment agent of this invention does not contain the metal component (F) which is inert rather than zinc. As such a metal component (F), Fe, Co, Ni, Sn, Pb, Bi, Cu, etc. are mentioned, for example. It is preferable that solid content mass ratio [F / Zr] in the metal element conversion mass of a metal component (F) with respect to the mass in Zr conversion of a zirconium compound (A) is 0.01 or less. This is because, after the metal component (F) is eluted from the treated coating layer under a corrosive environment, it is substituted and precipitated in the zinc plating layer and promotes corrosion of zinc in the plating layer, and therefore, alkali resistance, acid resistance and corrosion resistance tend to be lowered. to be.

The aqueous treatment agent of the present invention can be produced by dissolving or dispersing the above components (A), (B), (C), (D) and (E) in water or an aqueous solvent. Each component is adjusted so that it may become a prescribed composition ratio in the non volatile matter (in a process film) except a solvent and a volatile component. Although a solvent is water normally, you may use together a small amount (for example, 10 volume% or less of the whole aqueous medium) alcohol, a ketone, and a cellosolve type water-soluble organic solvent for the purpose of improving the dryness of the process film layer obtained. . Moreover, in order to form a more uniform process layer, the additive normally used by the coating agent, such as surfactant which improves wettability, an antifoamer which suppresses foaming, can be mix | blended in the range which does not impair the effect of this invention.

The pH of the aqueous treatment agent of the present invention is not particularly limited as long as the effect of the present invention can be achieved, but is preferably in the range of 7 to 10. By adjusting pH to this range, in addition to improving storage stability, corrosion resistance can be improved. In addition, for adjustment of pH, volatile alkali components, such as ammonia, or volatile acid components, such as acetic acid and formic acid, can also be used.

The solid content concentration of the aqueous treatment agent of the present invention is not particularly limited as long as the effect of the present invention can be achieved, but is preferably in the range of 1 to 20% by mass. When a solid content concentration of an aqueous treatment agent is this range, a film can be formed efficiently and the storage stability of this aqueous treatment composition can be improved.

By using the water-based treatment agent of the present invention, the reason for obtaining a treated coating layer excellent in chemical resistance and coating film adhesion of a molded processing portion is estimated below. However, this estimation and the effect of this invention should not be interpreted limitedly.

The water treatment agent of this invention contains a specific zirconium compound, an epoxy resin, a specific silanol group containing compound, and / or its condensate as a main component.

As the zirconium compound, a zirconium compound (A) stabilized with a volatile acid is applied, and in the process of forming a coating film (baking), the zirconium oxide crosslinked three-dimensionally by condensation accompanying hydrolysis or desorption of volatile acids. To form a film. Such a film containing zirconium oxide has very high chemical resistance, and is difficult to elute under a dark acid or alkali environment. However, since it is hard and has brittle physical properties, at the time of forming processing, the coating is not completely followed and coating film adhesion is not obtained by itself.

Therefore, the inventors found out that the epoxy resin (B) is optimal as a component that gives toughness to the film. Epoxy resins have rigidity and flexibility in structure, and have high hydrolyzability. Moreover, it contributes to adhesive expression with a laminated coating film by reaction with the organic functional group of the top coat film of an epoxy group and a hydroxyl group in an epoxy resin, or a hydrogen bonding effect. In addition, it forms a dense structure by crosslinking with the zirconium compound. Therefore, it is estimated that by mix | blending an epoxy resin with a suitable ratio with respect to a zirconium compound, toughness was provided to a film, without reducing the high chemical resistance of a zirconium oxide film.

Moreover, in order to provide the adhesiveness which can endure shaping | molding process, it is necessary to mix a silanol-group containing compound and / or its condensate. As a silanol group containing compound, the compound called a silane coupling agent is generally known, The silanol group (-Si-OH) of a molecular terminal is oriented in the vicinity of a raw material, and -Si-OM is firm through the plating metal surface and oxygen atom. Since it forms a chemical bond, it adheres firmly. The inverse terminal organic functional group contributes to adhesive expression with the laminated coating film. However, when the silane coupling agent used generally is applied, the reactivity of the terminal organic functional group is very high, and it cannot maintain the miscibility with the zirconium compound (A) and epoxy resin (B) in a processing agent. Thus, the inventors have found that the most effective action for imparting miscibility and adhesion is silanol group-containing compound and / or its condensate (C) containing an organic functional group derived from glycidoxy group or glycidoxy group. Glycidoxy group was inferior in reactivity, so that it was possible to maintain miscibility, and also to provide adhesion to the laminated coating film through hydrogen bonding, moderate flexibility derived from organic groups, and adhesion to plated metal surfaces derived from silanol groups.

The proportion of the zirconium compound and the silanol group-containing compound is also important. The silanol group-containing compound itself is easily eluted in a dark acid and alkaline environment, and if the blending amount of the silanol group-containing compound is excessive, the chemical resistance is lowered, but the silanol group is blended by blending the silanol group-containing compound in an appropriate ratio with respect to the zirconium compound. It is estimated that and zirconium crosslink three-dimensionally, and elution of a silanol group-containing compound is suppressed.

As described above, it is estimated that by treating the specific zirconium compound, the epoxy resin, the specific silanol group-containing compound and / or its condensate in a specific ratio, the treated film layer excellent in chemical resistance and coating film adhesion of the molded processing part could be formed.

Next, the galvanized steel material and zinc alloy plated steel material which have a process film layer formed using the water-based treatment agent of this invention are demonstrated.

The aqueous treatment agent of the present invention can be applied to a galvanized steel sheet or a zinc alloy plated steel sheet having a Zn: 80 mass% or more. As said galvanized steel and zinc alloy plated steel, a well-known galvanized steel plate and a zinc alloy plated steel plate can be used. For example, a hot dip galvanized steel plate, an alloyed hot dip galvanized steel sheet, an electrogalvanized steel sheet, a hot dip Zn-Al plated steel sheet, a hot dip Zn-Al-Mg plated steel sheet, an electric Zn-Ni plated steel sheet, etc. are mentioned.

Prior to forming the treated coating layer using the aqueous treatment agent of the present invention, it is not essential, but usually, cleaning with degreasing agent, washing with hot water, pickling, alkali washing, solvent cleaning to remove oil and contamination adhered to the metal material to be treated. Etc. can be combined suitably. In the washing | cleaning of the metal material surface, it is preferable to wash with water after washing | cleaning so that a washing | cleaning agent may not remain on the metal material surface.

The treated film layer of the galvanized steel or zinc alloy plated steel of the present invention is formed on the surface by heating and drying without washing with water after contacting the plated steel sheet with the aqueous treatment agent of the present invention.

There is no restriction | limiting in particular as a contact method of the aqueous treatment agent of this invention, For example, well-known methods, such as a roll coater method, an immersion method, a spray method, are mentioned. Although there is no restriction | limiting in particular as a heat-drying method, The heat drying by a hot stove, an induction heating furnace, an electric furnace, etc. is preferable. Moreover, there is no restriction | limiting in particular as reached steel plate temperature at the time of drying, 50-150 degreeC is preferable.

By the contact of the aqueous treatment agent of the present invention, the coating amount of the treated coating layer formed on the galvanized steel or the zinc alloy plated steel is 1 to 40 mg / m 2 as the Zr deposition amount, and preferably 5 to 30 mg / m 2. If the amount of Zr deposition is less than 1 mg / m 2, the effect of the treated film layer cannot be obtained. If the amount of Zr is exceeded, the formed film tends to cause cohesive failure, resulting in poor work adhesiveness.

The coated galvanized steel or the coated zinc alloy plated steel of the present invention has a laminated coating including at least one layer on the treated coating layer of the galvanized steel or the zinc alloy plated steel, and is generally a precoated steel sheet and a postcoated steel sheet. It refers to the coated steel plate called. The total film thickness of the laminated coating film of the coated galvanized steel or the coated zinc alloy plated steel of the present invention is 1 to 50 µm. By adjusting a film thickness in this range, chemical-resistance, corrosion resistance, and work adhesiveness can be improved.

Although there is no restriction | limiting in particular as a structure of the said laminated | multilayer coating film, In the outdoor use used in severe conditions, the intermediate | middle coating layer which mix | blended the antirust pigment for the purpose of improving corrosion resistance is laminated | stacked on the said processed coating layer, and it aims at providing designability on it again. The thing of the structure which laminated | stacked the top coat film layer which mix | blended the coloring pigment can be applied. In indoors used under relatively mild conditions, functional pigments such as those having a structure in which a top coat layer is formed for the purpose of providing designability without passing through a middle coat layer containing a rust preventive pigment on the treated coating layer. The thing of the structure which formed the coating film which mix | blended them is also applicable. As a rust preventive pigment, a well-known chromate-free pigment can be used, For example, phosphate antirust pigments, such as zinc phosphate, iron phosphate, aluminum phosphate, and magnesium phosphate, molybdenum, such as calcium molybdate, aluminum molybdate, and barium molybdate Rustproof pigments such as acid rust preventive pigments, vanadium oxide and calcium vanadate, and fine silica rust preventive pigments such as water-dispersible silica and fumed silica.

As the coloring pigment, known inorganic and organic coloring pigments can be used. For example, as the inorganic coloring pigment, titanium oxide (TiO ₂ ), zinc oxide (ZnO), zirconium oxide (ZrO ₂ ), calcium carbonate (CaCO ₃ ), Barium sulfate (BaSO ₄ ), alumina (Al ₂ O ₃ ), kaolin clay, carbon black, iron oxides (Fe ₂ O ₃ , Fe ₃ O ₄ ), and the like as the organic colored pigments Chinese characters yellow, pyrazolone orange, azo pigments Etc. can be mentioned.

There is no restriction | limiting in particular about the formation method of a laminated coating film. For example, the formation method which repeats the process of heat-drying by well-known methods, such as a hot stove, an induction heating furnace, an electric furnace, after contacting paint by well-known methods, such as a roll coater method, an immersion method, and a spray method, Can be mentioned. There is no restriction | limiting in particular as reached steel plate temperature at the time of drying, 80-250 degreeC is preferable.

Example

The present invention will be described in detail by the following examples, but the present invention is not limited to these examples.

<Production of Aqueous Treatment Agent>

Preparation of Aqueous Treatment Agent 1 (Nos. 1 to 31 and 35 to 39)

Each component (A) to (F) selected from the following is sequentially added to the deionized water by the combination of the raw materials shown in Table 1, and the mixing | blending ratio, and the aqueous treatment agent (No. 1-14, 35-38) for an Example, and a comparison The aqueous aqueous treatment agent (Nos. 15-31, 39) was obtained. Deionized water was added and adjusted so that a non volatile matter might be 7 mass%.

<Zirconium Compound (A)>

A1: zirconium ammonium carbonate

A2: zirconium acetate

a1: ammonium zircon fluoride

<Epoxy Resin (B)>

B1: carboxyl group-containing bisphenol type epoxy resin

200 mass parts of bisphenol-A liquid epoxy resin, 30 mass parts of polyethyleneglycol diglycidyl ether, and 80 mass parts of butyl cellosolves were put into the reaction container, and it heated and dissolved at 100 degreeC under nitrogen reflux and stirring, 3 mass parts of ethylamines were added, and it was made to react at 120 degreeC for 5 hours. Subsequently, 30 mass parts of butyl acrylate, 10 mass parts of acrylic acid, 10 mass parts of methyl methacrylate, 25 mass parts of styrene, and 30 mass parts of butyl cellosolves were dripped over 2 hours using the dropping funnel. After completion of the dropwise addition, heating, nitrogen reflux and stirring were continued for 4 hours. After cooling to 80 ° C, 10 parts by mass of triethylamine and 580 parts by mass of deionized water were mixed. The molecular weight of 61,000 and the acid value of the obtained carboxyl group-containing bisphenol-A epoxy resin (B1) were 20 mgKOH / g.

B2: Bisphenol-type epoxy resin containing no carboxyl group

200 mass parts of bisphenol-A liquid epoxy resin, 30 mass parts of polyethyleneglycol diglycidyl ether, and 80 mass parts of butyl cellosolves were put into the reaction container, and it heated and dissolved at 100 degreeC under nitrogen reflux and stirring, 5 mass parts of ethylamines were added, and it was made to react at 120 degreeC for 5 hours. Subsequently, 100 mass parts of bisphenol-A liquid epoxy resins and 80 mass parts of methyl isobutyl diketamine were added, and heating, nitrogen reflux, and stirring were continued for 4 hours. Then, after adding 50 mass parts of methyl isobutyl diketimines, and cooling at 80 degreeC, 10 mass parts of triethylamines and 550 mass parts of deionized water were mixed. The weight average molecular weight of the obtained carboxyl group-free bisphenol-type epoxy resin (B2) was 18,000, and the acid value was 25 mgKOH / g.

B3: carboxyl group-containing bisphenol type epoxy resin

200 mass parts of bisphenol-A liquid epoxy resin, 30 mass parts of polyethyleneglycol diglycidyl ether, and 80 mass parts of butyl cellosolves were put into the reaction container, and it heated and dissolved at 100 degreeC under nitrogen reflux and stirring, 5 mass parts of ethylamines were added, and it was made to react at 120 degreeC for 5 hours. Subsequently, 30 mass parts of butyl acrylate, 20 mass parts of acrylic acid, 10 mass parts of methyl methacrylate, 25 mass parts of styrene, and 30 mass parts of butyl cellosolves were dripped over 2 hours using the dropping funnel. After completion of the dropwise addition, heating, nitrogen reflux and stirring were continued for 4 hours. After cooling to 80 ° C, 10 parts by mass of triethylamine and 560 parts by mass of deionized water were mixed. The weight average molecular weight of the obtained carboxyl group-containing bisphenol-A epoxy resin (B3) was 84,000, and the acid value was 41 mgKOH / g.

B4: carboxyl group-containing bisphenol type epoxy resin

200 mass parts of bisphenol-A liquid epoxy resin, 30 mass parts of polyethyleneglycol diglycidyl ether, and 80 mass parts of butyl cellosolves were put into the reaction container, and it heated and dissolved at 100 degreeC under nitrogen reflux and stirring, 0.5 mass part of ethylamine was added, and it was made to react at 120 degreeC for 5 hours. Subsequently, 30 mass parts of butyl acrylate, 10 mass parts of acrylic acid, 10 mass parts of methyl methacrylate, 25 mass parts of styrene, and 30 mass parts of butyl cellosolves were dripped over 2 hours using the dropping funnel. After completion of the dropwise addition, heating, nitrogen reflux and stirring were continued for 4 hours. After cooling to 80 ° C, 10 parts by mass of triethylamine and 580 parts by mass of deionized water were mixed. The molecular weight 22,000 and the acid value of the obtained carboxyl group-containing bisphenol-A epoxy resin (B4) were 26 mgKOH / g.

B5: carboxyl group-containing novolak type epoxy resin

After 200 mass parts of novolak-type liquid epoxy resin, 30 mass parts of polyethyleneglycol diglycidyl ether, and 80 mass parts of butyl cellosolves were put into a reaction container, it heated and dissolved at 100 degreeC under nitrogen reflux and stirring, 3 mass parts of ethylamines were added, and it was made to react at 120 degreeC for 5 hours. Subsequently, 30 mass parts of butyl acrylate, 10 mass parts of acrylic acid, 10 mass parts of methyl methacrylate, 25 mass parts of styrene, and 30 mass parts of butyl cellosolves were dripped over 2 hours using the dropping funnel. After completion of the dropwise addition, heating, nitrogen reflux and stirring were continued for 4 hours. After cooling to 80 ° C, 10 parts by mass of triethylamine and 580 parts by mass of deionized water were mixed. The molecular weight 33,000 and the acid value of the obtained carboxyl group-containing novolak-type epoxy resin (B5) were 28 mgKOH / g.

b1: polyurethane resin

66 parts by mass of polyester polyol obtained by reacting 1,6-hexanediol, adipic acid and terephthalic acid in a reaction vessel, 44 parts by mass of dicyclohexylmethane 4,4'-diisocyanato, 6 parts by mass of dimethylolpropionic acid, N 4 parts by mass of triethylamine are added to the urethane prepolymer obtained by adding 30 parts by mass of methyl-2-pyrrolidone and reacting for 5 hours while maintaining the temperature at 70 ° C. under nitrogen reflux and stirring, and reacting at 30 ° C. for 30 minutes. Anionic urethane prepolymers were obtained. Subsequently, after adding and dispersing 110 mass parts of deionized water and emulsifying and dispersing, stirring was continued at 40 degreeC for 10 hours, and the anionic polyurethane resin emulsion was obtained.

b2: acrylic resin

100 parts by mass of deionized water, 3 parts by mass of a reactive surfactant (manufactured by Aquaron KH-10, Daiichi Kogyo Seiyaku Co., Ltd.), and nitrogen reflux and stirring were heated to 50 ° C. Then, 20 mass parts of butyl acrylates, 2 mass parts of acrylic acid, 15 mass parts of methyl methacrylate, and 13 mass parts of styrene mixed monomer liquids, 0.2 mass parts of ammonium persulfate, and 4 mass parts of ion-exchange water are dripped respectively. It was dripped over 2 hours using the funnel. After completion of the dropwise addition, heating, nitrogen reflux and stirring were continued for 3 hours. It cooled to 30 degreeC, and continued stirring for 5 hours, and obtained the acrylic resin emulsion (b2).

b3: polyester resin

In the reaction vessel, 1 mol of all acid components including terephthalic acid (41 mol%), isophthalic acid (40 mol%), isophthalic acid dimethyl-5-sulfonic acid sodium (2 mol%) and trimellitic anhydride (17 mol%), and ethylene glycol ( 2 mol total alcohol components including 90 mol%) and trimethylolpropane (10 mol%), 0.25 g of calcium acetate and 0.1 g of N-butyl titanate were added as a catalyst, and the system was refluxed and stirred under nitrogen and heated to 180 ° C. To melt the contents. Then, after heating to 200 degreeC, stirring was continued for about 2 hours and esterification or transesterification reaction was performed. Subsequently, it heated at 260 degreeC, pressure-reduced the system to 0.5 mmHg after about 15 minutes, and made it polycondensate for about 3 hours. After the reaction was completed, the mixture was allowed to cool under nitrogen introduction, and the contents were taken out. To the extracted contents, an appropriate amount of ammonia water and deionized water having a final pH of 6 to 7 was added, and the mixture was heated and stirred at 100 ° C for 2 hours in an autoclave, and finally the poly of the aqueous emulsion in which the solid content was adjusted to 30% with deionized water. Ester resin (b3) was obtained.

<Silanol group-containing compound (C)>

C1: The silanol-group containing compound (C1) was obtained by adding 0.02 mass part of acetic acid and 25 mass parts of 3-glycidoxy propyl trimethoxysilane to 80 mass parts of deionized water, and stirring at 25 degreeC for 2 hours.

C2: The silanol-group containing compound (C2) was obtained by adding 0.02 mass part of acetic acid, 20 mass parts of ethanol, and 25 mass parts of 3-glycidoxy propyl triethoxysilanes to 60 mass parts of deionized water, and stirring at 60 degreeC for 2 hours. .

C3: silanol-group containing compound (C3) by adding 0.02 mass part of acetic acid, 20 mass parts of isopropyl alcohol, and 25 mass parts of 3-glycidoxy propylmethyldimethoxysilane to 60 mass parts of deionized water, and stirring at 60 degreeC for 2 hours. Got.

c1: The silanol-group containing compound (c1) was obtained by adding 30 mass parts of N-2- (aminoethyl) -3-aminopropyl triethoxysilane to 70 mass parts of deionized water, and stirring at 25 degreeC for 2 hours.

<Phosphate Compound (D)>

D1: phosphoric acid

D2: Ammonium Dihydrogen Phosphate

<Vanadium Compound (E)>

E1: Oxalic Acid Banadil

E2: Ammonium Metavanadate

<Metal Component (F)>

F1: Nickel Nitrate

Preparation of Aqueous Treatment Agent 2 (No. 32)

The aqueous treatment composition described in the Example of the said patent document 1 was manufactured as a comparative example.

To 1 liter of deionized water, 1.5 parts by mass of γ-aminopropyltriethoxysilane, 0.5 parts by mass of water dispersible silica (Snotex N; manufactured by Nissan Chemical Industries, Ltd.) and 0.02 parts by mass of zirconium ammonium carbonate in terms of zirconium ion were mixed. And the aqueous treatment agent (No. 32) were obtained.

Preparation of Aqueous Treatment Agent 3 (No. 33)

The aqueous treatment composition described in the Example of the said patent document 4 was manufactured as a comparative example.

100 parts by mass of deionized water, 25 parts by mass of zirconium ammonium carbonate, 25 parts by mass of water dispersible silica (Snotex N; manufactured by Nissan Chemical Industries, Ltd.), and 5 parts by mass of tartaric acid were mixed to obtain an aqueous treatment agent (No. 33).

Preparation of Aqueous Treatment Agent 4 (No. 34)

ZM-1300AN (made by Nippon Parkarizing Co., Ltd.) which is a coating chromate agent was used as a comparative example. This example is an example of the chromate treatment composition of the prior art.

<Production of Intermediate Paint>

S1: 70 mass parts of polyester resins, 10 mass parts of melamine resins, 5 mass parts of zinc phosphate antirust pigments, 5 mass parts of magnesium phosphate antirust pigments, 5 mass parts of tripolyaluminum dihydrogen phosphate, and 5 mass parts of modified silicas are mixed, A middle paint was obtained.

<Production of Top Coating>

T1: 60 mass parts of polyester resins, 15 mass parts of butylated melamine resins, 10 mass parts of titanium oxide, and 15 mass parts of carbon black were mixed, and the top coat was obtained.

<Production of trial version>

1. Material

M1: hot dip galvanized steel sheet

Plate thickness 0.6 mm, 40 g / m2 per plated coating weight (both sides plating)

M2: electro galvanized steel sheet

Plate thickness 0.6 mm, 20 g / m2 per plated coating weight (both sides plating)

M3: alloyed hot dip galvanized steel sheet

Plate thickness 0.6 mm, 45 g / m2 per plated coating weight (both sides plating)

M4: Molten Zn-11% Al-3% Mg-0.2% Si Alloy Plated Steel Sheet

Plate thickness 0.6 mm, 40 g / m2 per plated coating weight (both sides plating)

M5: electric Zn-Ni plated steel sheet

Plate thickness 0.6 mm, 20 g / m2 per plated coating weight (both sides plating)

2. Pretreatment

The above various steel sheets were sprayed for 10 seconds using FC-E6406 (manufactured by Nippon Parkerizing Co., Ltd.), which is an alkali degreasing agent, at a concentration of 20 g / L and a temperature of 60 deg. Then, after wash | cleaning with tap water, it throttled with the water removal roll and hot-air dried.

3. Formation of treated film layer

As shown in Table 2, each aqueous treatment agent was applied to the surface of various steel sheets after pretreatment so that the amount of Zr deposition (Cr represents Cr adhesion) was a predetermined amount. Then, it heat-dried so that the reaching board temperature might be 80 degreeC in the hot air drying furnace.

4. Formation of Intermediate Coating Layer

After forming a process coating layer, the said intermediate | middle coating material was apply | coated using the bar coater so that it might become a dry film thickness of 5 micrometers. Then, it heat-dried so that the reaching board temperature might be 210 degreeC in the hot air drying furnace.

5. Formation of Top Coating Layer

After the intermediate coating layer was formed, the top coat was applied using a bar coater so as to have a dry film thickness of 15 µm. Subsequently, it heat-dried so that the reaching board temperature might be 220 degreeC in the hot air drying furnace.

<Evaluation test>

1. Bending process adhesion

After each test plate was immersed in non-aqueous water for 2 hours, a 0T bending test without inserting the inner spacer plate was carried out at 20 ° C. in accordance with the test method of JIS-G3312 at 20 ° C., and the film peeling state after tape peeling was visually observed. Evaluation was performed according to the following criteria.

<Evaluation Criteria>

◎: no peeling

○: less than 10% of the peeling area

(Triangle | delta): Peeling area 10% or more and less than 50%

X: 50% or more of peeling area

2. Drawing processing adhesion

Drawing ratio: 2.0, wrinkle suppression pressure: 0.5t After deep drawing processing, the flaws which reach the metal base in the side part are put in the cutter with "X" type, and immersed in the non-water for 1 hour, and then the "X" type scratch part Attached tape to Then, the tape was peeled off and the coating film peeling state was observed visually, and evaluation was performed according to the following criteria.

<Evaluation Criteria>

◎: no peeling

(Circle): Peeling less than 2 mm from a cut part

(Triangle | delta): Peeling of 2 mm or more and less than 10 mm from a cut part

X: 10 mm or more peeling from a cut part

3. Alkali resistance

After immersing each test plate in 5 mass% sodium hydroxide aqueous solution at room temperature for 24 hours, the magnitude | size and the density | generation density of the blister which generate | occur | produced were visually observed, and the alkali resistance was evaluated according to the following criteria.

<Evaluation Criteria>

(Double-circle): No blister.

(Circle): one blister is less than 1.0 mm, and a density of generation is F. FIG.

(Triangle | delta): One blister is 1.0 mm or more, and generation density is F. FIG. Alternatively, the size of one blister is less than 1.0 mm and the density of generation is M.

X: The size of one blister is 1.0 mm or more, and generation density is M. FIG. Alternatively, the density of occurrence is D regardless of the size of the blister.

The generation density of a blister makes the evaluation prescribed | regulated to ASTMD 714, and the symbol used has the following meaning.

F: low blister density

M: Blister Density

D: Blister Density Mill

4. Acid resistance

(1) sulfuric acid resistant test

After immersing each test plate in 5 mass% sulfuric acid aqueous solution at room temperature for 24 hours, the magnitude | size and the density | generation density of the blister which generate | occur | produced were visually observed, and the evaluation criteria evaluated on the same alkali resistance.

(2) hydrochloric acid test

After immersing each test plate in 5 mass% hydrochloric acid aqueous solution at room temperature for 24 hours, the magnitude | size and the density | generation density of the blister which generate | occur | produced were visually observed, and the evaluation criteria evaluated on the same alkali resistance.

5. Corrosion resistance

About each test board cut | disconnected to 150 mm x 70 mm, 200 cycles of the compound cycle test prescribed | regulated to JASO M609-91 were performed, exposing the cut end surface of a length part. The coating film expansion width (maximum value) from a cut end surface part was measured, and evaluation was performed based on the following criteria.

<Evaluation Criteria>

◎: less than 2 mm

○: 2 mm or more and less than 5 mm

Δ: 5 mm or more and less than 10 mm

×: 10 mm or more

6. Storage stability

Each water treatment agent shown in Table 1 was left to stand at 40 degreeC for 30 days. Then, each water treatment agent was evaluated in accordance with the following evaluation criteria.

<Evaluation Criteria>

◎: no change

(Circle): A trace amount of precipitation was seen.

(Triangle | delta): A trace amount of precipitation was seen and the viscosity became high.

X: A large amount of precipitation was seen or gelled.

<Evaluation result>

As shown in Table 2, Examples 1 to 24, which are coated zinc and zinc alloy plated steel sheets having a treated coating layer of the present invention, have work adhesion (bending work adhesion, drawing work adhesion, etc.), chemical resistance (alkali resistance, acid resistance, etc.). And all the performances of the corrosion resistance were excellent, and the performance equivalent to that of Comparative Example 21 which is a chromate system was shown. In addition, all the aqueous treatment agents used in Examples 1 to 24 were excellent also in storage stability.

Comparative Example 1, which does not contain a zirconium compound (A), is significantly inferior in processing adhesion, corrosion resistance, and chemical resistance. In addition, the comparative example 2 which contains the zirconium compound outside the scope of the present invention instead of the zirconium compound (A) was inferior in work adhesiveness and corrosion resistance.

In Comparative Example 3, which does not contain an epoxy resin (B), all performance is insufficient. In addition, Comparative Examples 4 and 5 containing resins outside the scope of the present invention had insufficient processing adhesiveness, corrosion resistance, chemical resistance, and the like.

The comparative example 6 which does not contain a silanol group containing compound (C) is inferior to work adhesiveness remarkably. In addition, Comparative Example 7 containing a silanol group-containing compound outside the scope of the present invention had insufficient processing adhesiveness and corrosion resistance.

The comparative example 8 which does not contain a phosphoric acid compound (D), and the comparative example 9 which does not contain a vanadium compound (E) had insufficient corrosion resistance.

Comparative Examples 10 and 11, in which the compounding ratio of the epoxy resin (B) was outside the range of the present invention, had insufficient work adhesiveness and corrosion resistance.

Comparative Examples 12 and 13 in which the blending ratio of the silanol group-containing compound (C) were outside the range of the present invention were insufficient in processing adhesiveness and corrosion resistance.

Corrosion resistance was remarkably inferior in Comparative Examples 14 and 15 in which the compounding ratio of the phosphoric acid compound (D) was outside the range of the present invention.

Corrosion resistance was remarkably inferior in the comparative examples 16 and 17 whose compounding ratio of a vanadium compound (E) is outside the range of this invention.

In Comparative Example 18 in which the amount of Zr deposition was outside the range of the present invention, work adhesiveness and corrosion resistance were remarkably inferior.

In Comparative Examples 19 and 20 according to Patent Documents 1 and 4, which became the prior art, any of work adhesiveness, corrosion resistance, and chemical resistance was insufficient.

Claims (6)

(A) zirconium compound selected from ammonium zirconium carbonate, potassium zirconium carbonate, basic zirconium carbonate and zirconium acetate,
(B) epoxy resin,
(C) a silanol group-containing compound represented by the following formula [I] and / or a condensate thereof,

(X represents a functional group derived from glycidoxy group or glycidoxy group, Y represents an alkylene group having 1 to 10 carbon atoms, Z represents a methoxy group, an ethoxy group or a methyl group, n represents an integer of 0 to 2) Indicates)
(D) phosphoric acid compounds,
(E) Vanadium Compound
It is an aqueous treatment agent containing
Regarding the mass in terms of Zr of the zirconium compound (A),
Solid content mass ratio [(B) / Zr] of the mass of an epoxy resin (B) is 0.7-1.5,
The solid content mass ratio [SiO ₂ / Zr] in the SiO ₂ equivalent mass of the silanol group-containing compound and / or its condensate (C) is 0.15 to 1.5,
Solid content mass ratio [P / Zr] in P conversion mass of a phosphoric acid compound (D) is 0.025-0.1,
Solid content mass ratio [V / Zr] in V conversion mass of a vanadium compound (E) is 0.02-0.05,
Aqueous treatment for galvanized steel or zinc alloy plated steel. The galvanized steel or zinc alloy plating according to claim 1, wherein the epoxy resin (B) is a bisphenol A epoxy resin containing a carboxyl group, and the weight average molecular weight of polystyrene conversion by gel permeation chromatography is 30,000 to 150,000. Aqueous treatment for steels. Treatment of 1-40 mg / m <2> as Zr adhesion amount formed in the at least single side | surface of the galvanized steel plate or zinc alloy plated steel plate whose plating layer composition is Zn: 80 mass% or more using the water-based treatment agent of Claim 1 or 2. Galvanized steel or zinc alloy plated steel with a coating layer. A coated galvanized steel or a coated zinc alloy plated steel having a laminated coating film including at least one layer on the treated coating layer of the galvanized steel or zinc alloy plated steel according to claim 3 having a total film thickness of 1 to 50 µm. The aqueous treatment agent of Claim 1 or 2 is apply | coated to the at least single side | surface of the galvanized steel plate or zinc alloy plated steel plate whose plating layer composition is Zn: 80 mass% or more, and forms a process film layer,
A method for producing a galvanized steel or zinc alloy plated steel, wherein the treated film layer is heated to dry and a treated film layer of 1 to 40 mg / m 2 is formed as a Zr deposition amount. The aqueous treatment agent of Claim 1 or 2 is apply | coated to the at least single side | surface of the galvanized steel plate or zinc alloy plated steel plate whose plating layer composition is Zn: 80 mass% or more, and forms a process film layer,
Heat-drying the said processed coating layer, and forming a treated coating layer of 1-40 mg / m <2> as Zr adhesion amount,
Moreover, at least 1 layer of coating material for laminated coatings is apply | coated on the said process film layer,
Heat-drying the said at least 1 layer laminated coating film, and forming a laminated coating film with a total film thickness of 1-50 micrometers,
Process for producing painted galvanized steel or painted galvanized steel.