KR20020015272A - Conversion treatment composition and process therefor - Google Patents

Abstract

PURPOSE: To provide a technique for forming a substrate treatment film showing an excellent anticorrosive property and adhesion to top coatings and adhesive films. CONSTITUTION: The substrate-treating agent contains a water-soluble vanadium compound (A), a water-soluble titanium or zirconium complex fluoride (B) and a resin (C).

Description

Treatment agent and disposal method {CONVERSION TREATMENT COMPOSITION AND PROCESS THEREFOR}

The present invention relates to a ground treatment agent and a ground treatment method. In more detail, it is possible to improve the rust resistance without using a chromium compound as a coating material of an aluminum sheet or an aluminum alloy sheet used in the fields of automobiles, home appliances, building materials, food containers, etc. The present invention relates to a coating type antirust agent and an antirust agent which can form an organic-inorganic composite film having excellent adhesion with a top coat or a film.

For example, a treatment agent containing chromic acid, dichromic acid, or chromate as an antirust treatment method for aluminum or aluminum alloy (hereinafter, simply referred to as aluminum alloy) plate that has been used in a wide range of fields such as home appliances, building materials, and food containers. A chromate treatment using is known. This chromate treatment is performed for the purpose of the improvement of antirust property with respect to the aluminum alloy surface, and the adhesiveness with a top coat or an adhesive film. The chromate-treated surface-treated aluminum alloy sheet material is excellent in terms of high productivity, uniformity of surface treatment, and the like, and has been widely used as a method of surface treatment after processing.

The chromate treatment is roughly classified into three types: reactive chromate, coated chromate and electrolytic chromate.

Due to the characteristics of the treatment method, the coated chromate is less waste of the treatment liquid than the reaction type or the electrolytic chromate, and it does not need to be washed after treatment, so the waste liquid treatment load is light, the productivity is excellent, and moreover, the hexavalent chromium is applied to the coating. It has been widely used because it has a feature of imparting a so-called self-repair function to act on exposed portions of material metal present in a defective portion or a wound portion formed after treatment to form a passive film.

However, there is a problem that hexavalent chromium, which is harmful to the human body contained in the treatment liquid, is eluted by contact with water and is associated with environmental pollution or adverse effects on the human body.

The film formed by the reactive chromate treatment and the electrolytic chromate treatment is mainly composed of trivalent chromium, and has almost no elution of chromium from the treated metal plate material, which is excellent in environmental pollution and human safety.

However, it does not have the above self-repair function, and its corrosion resistance is insufficient depending on the use. In addition, in some treatment methods, in order to keep the treatment liquid in a state suitable for surface treatment, it may be necessary to periodically change the liquid or overflow by a predetermined amount. Moreover, since the washing water or the like containing hexavalent chromium cannot be avoided, the processing load of the waste liquid is large.

Therefore, there is a desire in the industry to establish an antirust treatment method, that is, a coating treatment solution or a treatment method containing no hexavalent chromium, which avoids the harmful effects of using a treatment liquid containing hexavalent chromium.

As a representative technique of non-chromate type surface treatment without chromium, Japanese Patent Laid-Open No. 56-136978 discloses an aqueous solution containing a vanadium compound and at least one compound selected from the group consisting of titanium salts, zirconium salts and zinc salts. A chemical conversion treatment liquid is disclosed.

However, this chemical conversion treatment liquid is used in a treatment method in which an aluminum alloy is immersed therein for 1 to 20 minutes, preferably 3 to 5 minutes, and thus, it cannot be said that it is reasonable as a surface treatment of a metal plate material.

Japanese Unexamined Patent Publication No. Hei 1-246370 discloses degreasing with a degreasing agent containing PO ₄ ions, an aluminum chelating agent and a surfactant adjusted to pH 11-13 with alkali metal hydroxides, and then the pH is set to 1.5-4.0. The chemical conversion treatment agent containing the adjusted V ion, Zr ion, PO ₄ ion, and effective F ion, and the chemical conversion treatment method to apply the same are disclosed.

This method is excellent in that it does not contain chromium and can perform degreasing, washing, and chemical conversion at high speed while maintaining the quality level. However, since it is a chemical treatment method, water washing is required after treatment, and there is a limit in the amount of the coating film obtained, and the corrosion resistance is insufficient depending on the use.

Japanese Patent Application Laid-Open No. Hei 13128181 discloses an rust preventive pigment having both an oxidizer function and a deposition function of chromic acid ions and excellent corrosion resistance. The use of 0.1-50 parts of the total solid content of the coating allows coating type antirust treatment without chromium. However, it is not a technology in mind to use it as a base treatment such as coating or film laminate. Was difficult.

Therefore, the problem to be solved by the present invention is a problem with the above-described conventional technology, that is, to provide a technology capable of forming a base treatment film excellent in anti-rust properties and adhesion to the top coating and adhesive film.

MEANS TO SOLVE THE PROBLEM As a result of earnestly examining the means for solving the said subject, it is borne in mind that the composition containing a vanadium compound and a specific complex fluoride can provide the outstanding antirust property to the surface of an aluminum alloy, For example, an aqueous polymer By compounding the compounds, it has been found that excellent antirust properties can be imparted to the aluminum alloy surface as a coating type.

Furthermore, it has also been found that by specifying the kind of the complexed fluoride and the aqueous high molecular compound, it can be used as a coating type antirust base treatment agent for forming a base treatment film having excellent adhesion to a top coat and an adhesive film.

In view of the above, the present invention has been achieved, and the above problems are a water-soluble vanadium compound (A),

Titanium or zirconium-based water-soluble complex fluoride (B),

It is solved by the base treatment agent containing resin (C).

As a water-soluble vanadium compound (A) used by this invention, the inorganic or organic compound containing the vanadium of a valence which can be taken can be applied. Especially preferably, it is a compound which produces | generates water-soluble V containing ion in presence of water. For example, metavanadium acid, vanadium acid, and salts thereof (e.g., sodium, potassium, ammonium, etc.), vanadium oxide such as vanadium pentoxide, vanadium halide such as vanadium pentachloride and vanadium pentafluoride, vanadium sulfate, sulfuric acid Organic vanadium compounds, such as vanadium, vanadium nitrate, vanadium phosphate, vanadium heavy acid, vanadium acetate, and vanadium acetylacetonate and vanadil acetylacetonate, are mentioned as a preferable thing. Further, as a means for containing the vanadium compound in the treatment agent of the present invention, the vanadium compound and the reducing agent may be used in combination to contain a partially reduced or fully reduced vanadium compound. In this case, the reducing agent used for the reduction of the vanadium compound is not particularly limited.

The titanium- or zirconium-based water-soluble complex fluoride (B) used in the present invention is particularly preferably a complex in which F is bonded to a number exceeding the valence of titanium or zirconium. And compounds capable of releasing protons in the presence of water. Or it is a compound which can produce hydrofluoric acid in presence of water. For example, the zirconic hydrofluoric acid and the hydrofluoric acid titanium are exemplified.

Resin (C) used by this invention becomes like this. Especially preferably, it is resin of polyacrylic acid type, polyacrylamide type, polyamide type, polyurethane type, polyester type, phenol resin type, or epoxy resin type. Especially, it is water-soluble or water dispersible (aqueous) thing. And it is preferable to be able to exist stably in liquid with said (A) and (B), and to show uniform wettability when it is apply | coated to the surface of plate materials, such as aluminum alloy. In particular, at least one water-soluble resin selected from the group consisting of polyacrylic acid, polyacrylamide, polyurethane, polyester, or phenol resins is preferably volatilized or baked to lose water solubility after drying.

And the ratio of the water-soluble vanadium compound (A), the water-soluble complex fluoride (B) and the resin (C) of the titanium-based or zirconium-based compound is the titanium in the vanadium (V) and the complexed fluoride (B) in the vanadium compound (A). (Ti) and / or zirconium (Zr) and the weight ratio of the resin (C),

V: (Zr + Ti) = 1: 5000 to 5000: 1

{V + (Zr + Ti)}: (C) = 10: 1-1: 100

Is preferably.

That is, when V: (Zr + Ti) = (less than 1): 5000, the antirust property of the formed base treatment film tends to be insufficient, and conversely, V: (Zr + Ti) = 5000: (less than 1). This is because the adhesiveness to the surface of the aluminum alloy material of the formed base treatment film tends to deteriorate in the case of). And when {V + (Zr + Ti)}: (C) = 10: (less than 1), when coating a base treatment agent, coating defects generate | occur | produce or aluminum alloy of the base treatment film formed. This is because the adhesion to the ash surface tends to deteriorate. And when {V + (Zr + Ti)}: (C) = (less than 1): 100, the antirust property of the formed base treatment film will become inadequate, or the adhesiveness with a top coat film or an adhesive film will deteriorate. Because of this.

The base treatment agent of this invention can add various well-known additives, such as a leveling agent, an antifoamer, and a thickener, as needed.

The base treatment agent of the present invention is particularly used as a base treatment agent for rust prevention of aluminum or aluminum alloy material.

The mechanism of the effect of the organic-inorganic composite coating formed by the base treatment agent of the present invention is not necessarily clear at this stage, but is assumed to be as follows.

The vanadium compound contained in the base treatment agent of the present invention generates water-soluble V-containing ions such as vanadil ions when the formed undercoat is exposed to a corrosive environment accompanied by the presence of moisture, which oxidizes and stabilizes the surface of the base material. It is thought to have the effect of forming and preventing corrosion.

Titanium or zirconium-based water-soluble complex fluoride releases a small amount of fluorine ions in an aqueous solution, and it is thought that it is to etch the surface of the aluminum alloy material to secure the adhesion between the rust-proof film and the substrate by the anchoring effect. Furthermore, after treatment and drying, the complex fluoride is thought to exhibit an effect as a rust preventive film which inhibits corrosion of aluminum by depositing metal salts including zirconium oxide and titanium oxide on the aluminum surface.

It is considered that the resin exhibits a barrier effect against corrosion factors such as oxygen, water, and the like, in which the film formed after the treatment is dried from the corrosive environment.

By treatment with a treatment agent in which these compounds coexist, an organic-inorganic composite film made of an inorganic solid such as Zr and Ti, a fluoride, and an aqueous organic high molecular compound is formed on the surface to be treated, whereby the corrosion of the film The action of water-soluble V-containing ions, such as vanadium ions, in which the vanadium compound is formed on the surface of the aluminum alloy substrate exposed from the defects of the coating or the defects generated after the formation of the coating, while improving the barrier property (shielding force) to the environment. By oxidative stabilization gradually, it is thought that the inductor can be formed to give an effect of preventing corrosion.

And the said subject is solved by the ground treatment method characterized by apply | coating and drying the said ground treatment agent on a ash surface so that the total adhesion amount of V, Zr, and Ti may be 0.05-100 mg / m <^2> .

In addition, when the total adhesion amount of V, Zr and Ti is less than 0.05 mg / m ^2, the antirust property of the formed base coating is insufficient, and conversely, when the total adhesion amount of V, Zr and Ti exceeds 100 mg / m ² . This is because the rust-preventing effect is saturated and uneconomical, and tends to deteriorate the adhesion to the surface of the aluminum alloy material, the top coat film or the adhesive film formed on the base treatment film.

Embodiment of this invention is described.

The ground treatment agent according to the present invention contains a water-soluble vanadium compound (A), a titanium-based or zirconium-based water-soluble complex fluoride (B), and a resin (C).

As a water-soluble vanadium compound (A) used by this invention, the inorganic or organic compound containing the vanadium of a valence which can be taken can be applied. In particular, it is a compound which produces | generates water-soluble V containing ion in presence of water. For example, metavanadium acid, vanadium acid, and salts thereof (e.g., sodium, potassium, ammonium, etc.), vanadium oxide such as vanadium pentoxide, vanadium halide such as vanadium pentachloride and vanadium pentafluoride, vanadium sulfate, sulfuric acid And organic vanadium compounds such as vanadium, vanadium nitrate, vanadium phosphate, vanadium heavy acid, vanadium acetate, and vanadium acetylacetonate and vanadil acetylacetonate. Further, as a means for containing the vanadium compound in the treatment agent of the present invention, the vanadium compound and the reducing agent may be used in combination to contain a partially reduced or fully reduced vanadium compound. In this case, the reducing agent used for the reduction of the vanadium compound is not particularly limited.

The titanium-based or zirconium-based water-soluble complex fluoride (B) used in the present invention is particularly a complex in which F in excess of the valence of titanium or zirconium is bonded. And compounds capable of releasing protons in the presence of water. Or it is a compound which can produce hydrofluoric acid in presence of water. For example, a zirconic hydrofluoric acid and a hydrofluoric acid titanium are mentioned.

Resin (C) used by this invention is resin of polyacrylic acid type, polyacrylamide type, polyamide type, polyurethane type, polyester type, phenol resin type, or epoxy resin type, for example. Especially, it is water-soluble or water dispersible (aqueous) thing. And it is preferable to be able to exist stably in liquid with said (A) and (B), and to show uniform wettability when it is apply | coated to the surface of plate materials, such as aluminum alloy. In particular, at least one water-soluble resin selected from the group consisting of polyacrylic acid, polyacrylamide, polyurethane, polyester, or phenol resins is preferably volatilized or baked to lose water solubility after drying.

And the ratio of the water-soluble vanadium compound (A), the water-soluble complex fluoride (B) and the resin (C) of the titanium-based or zirconium-based compound is the titanium in the vanadium (V) and the complexed fluoride (B) in the vanadium compound (A). (Ti) and / or zirconium (Zr) and the weight ratio of the resin (C),

V: (Zr + Ti) = 1: 5000 to 5000: 1,

In particular, 1: 100-100: 1,

{V + (Zr + Ti)}: (C) = 10: 1-1: 100,

Especially 10: 1-1:10

Is preferably.

The base treatment agent of this invention can add various well-known additives, such as a leveling agent, an antifoamer, and a thickener, as needed.

The base treatment agent of the present invention is particularly used as a base treatment agent for rust prevention of aluminum or aluminum alloy material.

According to the present invention, the method for treating the organic-inorganic composite coating formed by the substrate treating agent of the present invention may be carried out so that the total amount of adhesion of V, Zr and Ti is 0.05 to 100 mg / m ^2. Iii) It is a method of coating and drying on the surface.

Next, the method of forming the base treatment agent of this invention as a film on the surface of an aluminum alloy material is demonstrated.

The base treatment agent of the present invention is applied to the surface of the object to be cleaned by a solvent cleaner, an alkali or an acidic water cleaner, by spraying, dipping, roller coating, shower coating, or the like, and dried to form a film. The treatment temperature and the treatment time are not particularly limited, but in general, the treatment temperature is 10 to 40 ° C and the treatment time is 0.1 to several minutes. The drying temperature after application is not particularly limited as long as the drying temperature is at least room temperature (usually 20 ° C. or more) and in which the moisture can be volatilized. However, drying at 150 ° C to 250 ° C is particularly preferred in view of the rust resistance of the present invention and the adhesion to the aluminum surface, the top coat film, or the adhesive film of the formed base treatment film. And on the surface treatment material in which the base treatment film of this invention was formed, various top coat films and film laminate layers are formed, The kind is not specifically limited. For example, as a top coat, a hydrophilic film layer, a lubricated organic film layer, an anti-fog film, etc. are mentioned, As a laminated film, PET film, a polyamide film, a polyethylene film, etc. are mentioned. None of the organic, inorganic or organic inorganic composites is of any kind. And depending on the antirust level desired, it can be used also for the use which does not form a top coat film or a film laminate layer on the surface treatment material in which the base treatment film of this invention was formed.

Hereinafter, although an Example and a comparative example are given and this invention is demonstrated further more concretely, this invention is not limited by these Examples and a comparative example.

EXAMPLE

<Notice>

As the aluminum alloy material, two kinds of JIS A1000 equivalent (for top coating) and JIS A3004 equivalent (for film bonding), which are commercially available aluminum alloy thin plate commercial products having a thickness of 0.3 mm, a width of 200 mm, and a length of 300 mm, were suitably used.

<Cleaning Method of Test Materials>

The surface of the aluminum alloy sheet was subjected to dry cleaning of a strong alkali degreasing agent "Fine Cleaner 4377" (trademark; Nippon Parkarizing Agent) at a chemical concentration of 20 g / L under a treatment temperature of 60 캜 and a treatment time of 7 seconds. Sprayed.

In this way, dust and oil adhering to the surface were removed, and the alkali residue remaining on the surface was washed with tap water and dried at 80 ° C.

<The composition of antirust processing agent>

The composition of the antirust base treatment agent of this invention used in the Example and the comparative example is shown in Table 1. The solvents were all water, and the addition amount was the weight (g) contained in 1 L of the treatment agent, and was expressed as g / L.

TABLE 1

sign (A) Vanadium Compound (B) complex fluoride (C) organic polymer compound Ingredient ratio Source Addition amount [g / L] Source and amount added [g / L] Zr + Ti conversion [g / L] Source (* Note) Addition amount [g / L] V: (Zr + Ti) (V + Zr + Ti): (C) Source V conversion end Sodium metavanadate 24 10.0 Hydrogen zirconium fluoride acid: 20 Hydrogen titanic acid fluoride: 0 8.8 Acrylic① 3 10: 8.8 18.8: 3 I Ammonium Metavanadate 0.02 0.009 Hydrogen zirconium fluoride: 50 Hydrogen titanic acid: 50 37.0 Acrylic② 10 0.009: 37 37.009: 10 All Vanadilacetylacetonate 170 32.7 Zirconium Hydrofluoric Acid: 0 Titanium Fluoric Acid: 0.03 0.009 Acrylamide 100 32.7: 0.009 32.709: 100 la Potassium metavanadate 6 2.2 Zirconium Hydrofluoric Acid: 0 Titanium Fluoric Acid: 7 2.0 Polyurethane 350 2.2: 2 4.2: 350 hemp Ammonium Metavanadate 2.3 1.0 Zirconium Hydrofluoric Acid: 2.5 Titanium Fluoric Acid: 0 1.1 Polyester 190 1: 1.1 2.1: 190 bar Vanadilacetylacetonate 5.2 One Hydrogen Zirconium Fluoride: 45 Hydrogen Titanium Fluoride: 0 19.8 phenol 20 1: 19.8 20.8: 20 four Sodium metavanadate 12 5.0 Zirconium Hydrofluoric Acid: 6Titanium Fluoric Acid: 6 4.4 amides 50 5: 4.4 9.4: 50 Ah Potassium metavanadate 6 2.2 Zirconium Hydrofluoric Acid: 0 Titanium Fluoric Acid: 11 3.2 Epoxy 7 2.2: 3.2 5.4: 7 character - - 0 Zirconium Hydrofluoric Acid: 0 Titanium Fluoric Acid: 35 10.2 Acrylic① 50 0: 10.2 10.2: 50 car Ammonium Metavanadate 23 10.0 - 0 Acrylamide 20 10: 0 10:20 Ka Sodium metavanadate 24 10.0 Hydrogen zirconium fluoride acid: 20 Hydrogen titanic acid fluoride: 0 8.8 - 0 10: 8.8 18.8: 0

(* Note): Breakdown of each resin supply source,

Acrylic ① --- acrylic acid homopolymer, number average molecular weight 20,000

Acrylic② --- acrylic acid homopolymer, number average molecular weight 200,000

Acrylamide-acrylamide homopolymer, number average molecular weight 70,000

Polyurethane --- "Yuko UWS-145" (trademark; Japan Chemical Industry Co., Ltd., solid content 35 wt.%)

Polyester --- "Pyronaru MD1100" (trademark; made in Japan's Toyo Spinning Co., Ltd., solid content 30 wt.%)

Phenol --- "Vitanoru 7102" (trademark; Nippon Chemical Co., Ltd., solid content 43 wt.%)

Amide --- Block polymer of adipic acid, aminoethylpiperazine and ε-caprolactam, number average molecular weight 10,000

Epoxy --- "Epomic WR942030" (trademark; Sanji Chemical Co., Ltd., solid content 28 wt.%)

<Listening method of rust prevention>

It carried out by the following method using the processing agent of Table 1.

Example 1

The treatment agent (A) was applied to one side by means of an air spray coat so that the total adhesion amount of V, Zr, and Ti became 50 mg / m ² , followed by drying at 200 ° C. for 0.5 minutes using an electric oven.

Example 2

The treatment agent (B) was applied on one side by a roller coat so that the total adhesion amount of V, Zr, and Ti became 100 mg / m ² , and then dried at 180 ° C. for 0.2 minutes using an electric oven.

Example 3

The treatment agent (C) was coated on one side by bar coat so that the total adhesion amount of V, Zr, and Ti became 0.05 mg / m ² , and then dried at 200 ° C. for 0.2 minutes using an electric oven.

Example 4

The treatment agent (d) was applied by one side so that the total adhesion amount of V, Zr, and Ti was 10 mg / m ² by the immersion coat, and 200 degreeC x 0.5 minute drying was performed using the electric oven.

Example 5

The treatment agent (e) was coated on one side by a roller coat so that the total adhesion amount of V, Zr, and Ti became 60 mg / m ² , and then dried at 200 ° C. × 0.3 minutes using an electric oven.

Example 6

The treatment agent (bar) was applied on one side by a roller coat so that the total adhesion amount of V, Zr, and Ti became 10 mg / m ² , followed by drying at 150 ° C. for 0.5 minutes using an electric oven.

Example 7

The treatment agent (g) was applied on one side by a roller coat so that the total adhesion amount of V, Zr, and Ti became 5 mg / m ² , and then dried at room temperature for 120 minutes using an electric oven.

Example 8

The treatment agent (a) was coated on one side by a roller coat so that the total adhesion amount of V, Zr, and Ti became 40 mg / m ² , followed by drying at 250 ° C. for 0.1 minutes using an electric oven.

Comparative Example 1

The treatment agent (co) was coated on one side by roller cout so that the total adhesion amount of V, Zr, and Ti became 50 mg / m ² , and then dried at 200 ° C. × 0.3 minutes using an electric oven.

Comparative Example 2

The treatment agent (tea) was coated on one side by a roller coat so that the total adhesion amount of V, Zr, and Ti became 50 mg / m ² , followed by drying at 200 ° C. for 0.2 minutes using an electric oven.

Comparative Example 3

The treatment agent (K) was coated on one side by a roller coat so that the total adhesion amount of V, Zr, and Ti became 5 mg / m ² , and then dried at 200 ° C. × 0.5 minutes using an electric oven.

Top coat or film adhesion method

(1) Top coat

Aqueous paint "Parene 5013" manufactured by Nippon Parkarizing Co., Ltd. was applied to a test piece treated with an antirust treatment with a roller coater so that the dry coating amount was 0.8 g / m ² , and dried by heating to 200 ° C at the plate temperature reached. It was.

(2) film adhesion

A 20 μm thick polyester resin film of 12 mol% polyethylene isophthalate and 88 mol% polyethylene terephthalate was melt-bonded at 250 ° C. and 100 kgf / cm ² , and then immersed and dried at room temperature. .

<Performance Evaluation Test Method>

The test shown below was carried out and judged according to the evaluation criteria.

(1) Evaluation of the top coat

(A) corrosion resistance

The appearance of white rust after 240 hours on the surface of the specimen was observed by the salt spray test (JIS Z2371).

-Evaluation standard-

◎: less than 1% of rust

○: White rust incidence 1% or more but less than 5%

△: white rust incidence 5% or more but less than 10%

×: more than 10% of white rust occurrence rate

(B) adhesiveness

A small amount of deionized water was attached to the surface of the test piece, and the surface condition after intensive rubbing with gauze 20 times was observed.

-Evaluation standard-

◎: Exposed body is less than 1% of test site

○: Exposed material is less than 1% and less than 5% of the test site

(Triangle | delta): Exposed 5% or more and less than 50% of a test site.

×: Possession of more than 50% of the test site

(2) Evaluation of film adhesive plate

(A) corrosion resistance

A 20 mm cut is orthogonal to the test piece surface with a sharp cutter and immersed in an aqueous solution (simulated juice) containing 1 wt.% Citric acid and 0.5 wt. Corrosion resistance was evaluated based on the following criteria by measuring the maximum bulging width of the film.

-Evaluation standard-

(Double-circle): The largest bulging width starting from a cut part is less than 0.1 mm

(Circle): The largest bulging width starting from a cut part is 0.1 mm or more and less than 0.5 mm

(Triangle | delta): The largest bulging width starting from a cut part is 0.5 mm or more and less than 1.0 mm

X: The largest bulging width starting from a cut part is 1.0 mm or more

(B) adhesiveness

Cut it with a sharp cutter on the back of the test piece, insert it for 30 minutes in an autoclave of 125 ° C × 0.8 MPa, shear the test piece in the cut part, and measure the width of the film from the front end of the evaluation surface. Evaluation was made according to the standard.

-Evaluation standard-

(Double-circle): The maximum blown-out width starting from a shear part is less than 0.1 mm.

(Circle): The largest blown-out width starting from a shear part is 0.1 mm or more and less than 0.2 mm

(Triangle | delta): The largest blown-out width starting from a shear part is 0.2 mm or more and less than 0.5 mm.

X: The width of the largest bulge from the front end is 0.5 mm or more

Table 2 shows the results obtained by the above test procedure.

TABLE 2

Antirust treatment Top coat Film adhesive Corrosion resistance Adhesion Corrosion resistance Adhesion Example 1 ◎ ◎ ◎ ◎ Example 2 ◎ ◎ ◎ ◎ Example 3 ◎ ◎ ◎ ◎ Example 4 ◎ ◎ ◎ ◎ Example 5 ◎ ◎ ◎ ◎ Example 6 ◎ ◎ ◎ ◎ Example 7 ◎ ◎ ◎ ◎ Example 8 ◎ ◎ ◎ ◎ Comparative Example 1 △ ◎ × △ Comparative Example 2 ◎ △ △ × Comparative Example 3 ○ × △ ×

As apparent from Table 2, Examples 1-8 using the base treatment agent of this invention are excellent in both corrosion resistance and adhesiveness at the time of top coat and film adhesion.

On the other hand, in Comparative Example 1, since the addition of the vanadium compound of the present invention was omitted, the corrosion resistance was lowered, and in the film adhesion, a decrease in adhesion due to corrosion also occurred.

In Comparative Example 2, since the addition of the complex fluoride of the present invention was omitted, although the corrosion resistance of the top coat was good due to the action of the vanadium compound, the adhesion was poor, and the deterioration of the adhesion was remarkable also in the film adhesion. Deteriorated.

In the comparative example 3, since the addition of the resin of this invention was abbreviate | omitted, adhesive performance falls.

The substrate treatment agent of the present invention can provide a plate material excellent in corrosion resistance, top coat, or adhesion with an adhesive film with good productivity, and has a great effect in practical use, and does not use chromium at all. Since it does not generate waste water, it is extremely effective in terms of environmental conservation and waste liquid treatment cost reduction.

Claims (10)

A water treatment vanadium compound (A), a titanium-based or zirconium-based water-soluble complex fluoride (B) and a resin (C). The base treatment agent according to claim 1, wherein the water-soluble vanadium compound (A) is a compound which produces a water-soluble V-containing ion in the presence of water. The water-soluble vanadium compound (A) according to claim 1 or 2, wherein the water-soluble vanadium compound (A) is metavanadium acid, vanadium acid, and salts thereof, vanadium oxide, vanadium halide, vanadium sulfate, vanadium sulfate, vanadium nitrate, vanadium phosphate, and heavy acid. A base treatment agent characterized in that it is at least one or two or more compounds selected from the group consisting of vanadium, vanadium acetate, and an organic vanadium compound. The base treatment agent according to claim 1, wherein the titanium-based or zirconium-based water-soluble complex fluoride (B) is a compound capable of releasing protons in the presence of water. The base treatment agent according to claim 1 or 4, wherein the titanium or zirconium-based water-soluble complex fluoride (B) is a compound capable of producing hydrofluoric acid in the presence of water. The water-soluble complex fluoride (B) according to claim 1, 4 or 5, wherein the water-soluble complex fluoride (B) is at least one compound selected from the group consisting of zirconic hydrofluoric acid and salts thereof, and titanium hydrofluoric acid and salts thereof. Characterized as a lower extremity treatment agent. The resin (C) is at least one compound selected from the group consisting of polyacrylic acid, polyacrylamide, polyamide, polyurethane, polyester, phenol resin, and epoxy resin. Characterized as a lower extremity treatment agent. The ratio of the water-soluble vanadium compound (A), the titanium-based or zirconium-based water-soluble complex fluoride (B), and the resin (C) is vanadium in the vanadium compound (A). The weight ratio of (V) and titanium (Ti) and / or zirconium (Zr) and the resin (C) in the complex fluoride (B), V: (Zr + Ti) = 1: 5000 to 5000: 1 {V + (Zr + Ti)}: (C) = 10: 1-1: 100 A lower extremity treatment agent characterized in that. The base treatment agent according to any one of claims 1 to 8, wherein the base treatment agent is a base treatment agent for rust prevention of aluminum or an aluminum alloy material. The base treatment agent according to any one of claims 1 to 9 is applied and dried on the surface of ash such that the total adhesion amount of V, Zr, and Ti is 0.05 to 100 mg / m ^2. Not disposal method.