JP2003313680A - Chromium-free metal surface treatment agent, chromium- free metal surface treatment method, and aluminum or aluminum alloy sheet - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a chromium-free metal surface treatment agent superior in stability, for imparting adequate adhesiveness to a laminated metallic material. <P>SOLUTION: The chromium-free metal surface treatment agent comprises a water-soluble zirconium compound and/or a water-soluble titanium compound, an organic phosphonate compound, and tannin, wherein the organic phosphonate compound has a phosphorus atom constituting a phosphonic group and boning to a carbon atom, a content of the above water-soluble zirconium compound and/or the above water-soluble titanium compound is 20-800 ppm in zirconium and/or titanium terms, a content of the above organic phosphonate compound is 10-500 ppm, and a content of the tannin is 200-4,000 ppm; has a pH of 1.6-4.0; and is used for manufacturing a thermoplastic polyester resin-coated metal sheet. <P>COPYRIGHT: (C)2004,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a non-chrome metal surface treatment agent, a non-chrome metal surface treatment method, and an aluminum or aluminum alloy plate.

[Prior art]

[0002] In recent years, as a method of coating a metal material, a polyester-based coating material is used from the viewpoints of improving the protective function of the coating material, improving the aesthetic appearance, and contributing to environmental protection without the emission of an organic solvent in the coating process. Resin film heat fusion,
The application of the laminating method by melt extrusion coating of polyester resin is expanding.

As an example of a thin plate material which is a material of a laminated metal material, a metal plate such as aluminum or aluminum alloy can be cited. Such a metal plate is usually preliminarily subjected to degreasing treatment and then surface treatment for providing adhesion.

Conventionally, a phosphoric acid chromate-based treating agent has been mainly used as a surface treating agent for laminated metal materials, but in recent years, there has been an increasing demand for adhesion of the coated film to a substrate. From the perspective of environmental protection
There is a need for a surface treatment agent that does not contain chromium and that can impart high adhesion.

JP-A-52-95546 discloses an aqueous solution containing, as main components, one or more selected from the group of tannin, tannic acid and decomposition products of tannic acid, and titanium salts or zirconium salts. A method for surface treatment of aluminum, magnesium, and alloys thereof, which is surface-treated in accordance with US Pat. This is a method carried out for the purpose of applying to aluminum, magnesium and alloys thereof for construction, automobiles, electric appliance materials, and has not been examined for laminated metal materials.

As the reactive chromium-free surface treatment agent,
For example, zirconium fluoride-based and zirconium phosphate-based treatment agents have been put to practical use for beverage can bodies and the like. However, such a conventional chrome-free surface treatment agent can give high adhesion to the paint used for the body of a beverage can, but the adhesion required for a laminated metal material. It wasn't something that could satisfy her.

[0007]

SUMMARY OF THE INVENTION In view of the above situation, it is an object of the present invention to provide a non-chromium metal surface treatment agent which provides a laminated metal material with sufficient adhesion and is excellent in stability. Is.

[0008]

The present invention provides a non-chromium metal surface treatment agent comprising a water-soluble zirconium compound and / or a water-soluble titanium compound (1), an organic phosphonic acid compound (2), and tannin (3). In the organic phosphonic acid compound (2), a phosphorus atom forming a phosphon group is bonded to a carbon atom, and the water-soluble zirconium compound and / or the water-soluble titanium compound (1)
Content of zirconium and / or titanium is 20 to 800 ppm on a mass basis, and the content of the organic phosphonic acid compound (2) is 10 to 500 on a mass basis.
ppm, the content of the tannin (3) is 200 to 4000 ppm on a mass basis as the amount of the tannin, and the non-chromium metal surface treatment agent has a pH of 1.6.
It is ~ 4.0, and is a non-chromium metal surface treatment agent characterized by being used for manufacturing a thermoplastic polyester resin-coated metal plate.

The present invention also provides a non-chrome metal surface treatment method, which comprises the step (A) of treating an object with the above-mentioned non-chrome metal surface treatment agent. It is preferable that a step of washing with an acid is performed before the step (A) is performed. It is preferable that a step of washing with an alkali and then a step of washing with an acid are performed before the step (A) is performed.

The present invention is an aluminum or aluminum alloy plate characterized by being obtained by the above-mentioned non-chromium metal surface treatment method. The above-mentioned aluminum or aluminum alloy plate has a water-soluble zirconium compound and / or a water-soluble titanium compound (1) of 2 to 100 in terms of zirconium and / or titanium atoms, after being dried.
25 mg / ^{m 2,} an organic phosphonic acid compound ⁽²⁾ 0.2~5mg / ^m 2 in terms of phosphorus atom, as well as, tannin (3) is formed coating that 3~75mg / ^{m 2} containing a carbon atom in terms It is preferable that The present invention will be described in detail below.

The chromium-free metal surface treatment agent of the present invention is used as a pretreatment agent in the production of a thermoplastic polyester resin-coated metal plate. That is, when the above-mentioned thermoplastic polyester-based resin is coated on a metal plate treated with the chromium-free metal surface-treating agent of the present invention, the resin can be coated with good adhesiveness, and the thermoplastic polyester-based resin coating having good properties is coated. A metal plate can be manufactured.

The non-chromium metal surface treatment agent of the present invention contains a water-soluble zirconium compound and / or a water-soluble titanium compound (1). The water-soluble zirconium compound is not particularly limited as long as it is a compound containing zirconium, but stability at the pH is good,
A water-soluble zirconium compound containing fluorine is preferable because it has excellent film forming properties.

The water-soluble zirconium compound containing fluorine is not particularly limited, and examples thereof include H ₂ Zr.
_{F 6, (NH 4) 2} ZrF 6, K 2 ZrF 6, Na 2 Z
Examples thereof include rF ₆ and Li ₂ ZrF ₆ . These may be used alone or in combination of two or more.

The water-soluble titanium compound is not particularly limited as long as it is a compound containing titanium.
It has good stability in H and excellent film formation,
Water-soluble titanium compounds containing fluorine are preferred.

The water-soluble titanium compound containing fluorine is not particularly limited, and examples thereof include H ₂ TiF ₆ ,
(NH ₄ ) ₂ TiF ₆ , K ₂ TiF ₆ , Na ₂ TiF ₆
Etc. can be mentioned. These may be used alone or in combination of two or more.

The content of the water-soluble zirconium compound and / or the water-soluble titanium compound (1) in the non-chromium metal surface-treating agent is 20 ppm in the lower limit and 20% in the upper limit on a mass basis as the amount of zirconium and / or titanium. Is 8
It is 00 ppm. If it is less than 20 ppm, a sufficient amount of zirconium or titanium coating cannot be obtained in a short time,
Adhesion decreases. When it exceeds 800 ppm, the adhesiveness is lowered, and the performance is not improved and the processing time is not shortened, and the cost may be increased. The lower limit is 100
ppm is preferable, and the upper limit is 300 pp
It is preferably m. The content of the water-soluble zirconium compound and / or the water-soluble titanium compound (1) is the total content of zirconium and titanium contained in the non-chrome metal surface treatment agent.

The non-chromium metal surface treating agent of the present invention is
Organic compound in which phosphon group () is bonded to carbon atom in compound
It is a thing. Containing an organic phosphonic acid compound (2)
Is. The organic phosphonic acid compound (2) is a compound
Phosphon group (-PO _ThreeH_Two) Combined
It is an organic compound.

The above organic phosphonic acid compound (2) is a compound
Phosphon group (-PO _ThreeH_Two) Combine
The compound is not particularly limited as long as it is
Aminotri (methylenephosphonic acid) represented by (a),
1-hydroxyethylidene represented by the following formula (b):
1,1-diphosphonic acid, 2-pho represented by the following formula (c)
Examples include sufobutanone 1,2,4-tricarboxylic acid
You can

[0019]

[Chemical 1]

Examples of the organic phosphonic acid compound (2) include ethylenediaminetetra (methylenephosphonic acid) represented by the following formula (d) and diethylenetriaminepenta (methylenephosphonic acid) represented by the following formula (e). Can be mentioned.

[0021]

[Chemical 2]

Among the above-mentioned organic phosphonic acid compounds (2), the aminotri (methylenephosphonic acid) represented by the above formula (a), the above-mentioned, since it is excellent in film deposition property, corrosion resistance after coating and film adhesion, 1-Hydroxyethylidene-1,1-diphosphonic acid represented by the formula (b) and 2-phosphobutanone 1,2,4-tricarboxylic acid represented by the formula (c) are preferable.

The organic phosphonic acid compound (2) is preferably water-soluble. When it is a water-soluble compound, it is not necessary to use an organic solvent, and the load on the environment can be reduced.

The above organic phosphonic acid compound (2) may be used alone or in combination of two or more kinds. In addition, it is not preferable to include an organic phosphonic acid compound salt in which a hydrogen atom contained in a phosphon group is substituted with an alkali metal, ammonium or the like in the non-chrome metal surface treatment agent because the corrosion resistance of the formed film is reduced.

The content of the organic phosphonic acid compound (2) in the non-chromium metal surface treating agent is 10 ppm by mass and 500 ppm by mass. If it is less than 10 ppm, an appropriate amount of phosphorus film may not be obtained in the formed film, and the adhesion may be deteriorated.
If it exceeds, the adhesion may not be improved and the cost may be increased. The lower limit is preferably 50 ppm and the upper limit is preferably 200 ppm.

The non-chromium metal surface treating agent of the present invention contains tannin (3). The above tannin is
Also called tannic acid, it is a general term for aromatic compounds having a complex structure having a large number of phenolic hydroxyl groups widely distributed in the plant kingdom. The tannin may be hydrolyzable tannin or condensed tannin.

Examples of the tannin (3) include hamamelitannin, oyster tannin, tea tannin, quintet tannin, gallic tannin, myrobalan tannin, dividibi tannin, argarovillatannin, valonia tannin and catechin tannin. Further, the tannin (3) may be a tannin decomposition product obtained by decomposing tannin existing in a plant by a method such as hydrolysis.

The above-mentioned tannin (3) is commercially available, for example, "tannic acid extract A", "B tannic acid", "N tannic acid", "industrial tannic acid", "purified tannic acid", "Hi". "Tannic acid", "F tannic acid", "local tannic acid" (all manufactured by Dainippon Pharmaceutical Co., Ltd.),
"Tannic acid: AL" (manufactured by Fuji Chemical Industry Co., Ltd.) or the like can also be used. The tannin may be used alone,
You may use 2 or more types together.

The tannin (3) has a number average molecular weight of 2
It is preferably 00 or more. When a tannin decomposition product is used as the tannin (3), if it is a low molecular weight compound having a molecular weight of less than 200 due to excessive progress of decomposition, it does not have the property of tannin and thus adheres to a laminate film. Does not improve.

The above-mentioned tannin (3) is contained in the chromium-free metal surface-treating agent at a lower limit of 200 ppm and an upper limit of 40 on a mass basis.
It is in the range of 00 ppm. 200 tannins (3) above
If it is less than ppm, the film adhesiveness will decrease, and
Even if blended in excess of 000 ppm, the adhesion will not be improved, which is not desirable in terms of cost. The above lower limit is 500 pp
m is preferable, and the upper limit is 1600 ppm.
Is preferred.

The non-chromium metal surface treatment agent of the present invention is p
H is in the range of the lower limit of 1.6 and the upper limit of 4.0. When the pH is less than 1.6, the etching of the metal surface is promoted too much, so that the appearance of the coating becomes poor and the corrosion resistance of the obtained coating also deteriorates. When the pH exceeds 4.0, the chemical conversion reaction does not proceed satisfactorily, and the chemical conversion film becomes difficult to form. The lower limit is more preferably 1.8,
More preferably, it is 2.2. The upper limit is 3.4.
Is more preferable, and 2.8 is more preferable.

In addition to the above components, the non-chromium metal surface treatment agent of the present invention may further contain an etching aid, a chelating agent, and a pH adjusting agent, if necessary. Examples of the etching aids include hydrofluoric acid, hydrofluoric acid salts, and fluoroboric acid. When the water-soluble zirconium compound or the zirconium or titanium complex mentioned as the water-soluble titanium compound is used as a source of fluorine ions, the amount of fluorine ions produced is insufficient, and thus the fluorine compound is used. Is preferably used in combination.

Examples of the chelating agent include citric acid, tartaric acid, gluconic acid, and other acids that form a complex with aluminum, and metal salts thereof.

Examples of the pH adjuster include nitric acid,
Examples thereof include acids or bases such as perchloric acid, sulfuric acid, sodium nitrate, ammonium hydroxide, sodium hydroxide and ammonia, which do not adversely affect the surface treatment.

The non-chrome metal surface treating agent of the present invention is used for producing a thermoplastic polyester resin-coated metal plate. That is, the metal plate surface-treated with the chromium-free metal surface treatment agent of the present invention is used as a thermoplastic polyester resin-coated metal plate after a step of coating the thermoplastic polyester resin. The thermoplastic polyester resin coated metal plate is a laminate of a polyester resin on a metal plate, which is to protect the surface by the polyester resin layer, for metal cans, aluminum foil containers, home appliances, home building materials. It can be used for metal materials and the like.

The thermoplastic polyester resin is not particularly limited, and is composed of constitutional units such as ethylene terephthalate unit, ethylene naphthalate unit, ethylene isophthalate unit, butylene terephthalate unit, 1,4 cyclohexanedimethanol terephthalate unit. A thermoplastic polyester resin can be mentioned. It may be a copolymerized thermoplastic polyester resin having two or more of the above structural units. A polyethylene terephthalate resin comprising ethylene terephthalate units or a polyethylene naphthalate resin comprising naphthalene terephthalate units is more preferred.

The above thermoplastic polyester resin, even if it is laminated on a metal after forming a film,
The thermoplastic polyester resin that has been heated and melted may be extruded in a film shape by a slit having a narrow extruding width of an extrusion molding machine and directly laminated on a metal plate by direct lamination. When the film is laminated after being formed, the film is not particularly limited, and may be, for example, an unstretched film, a uniaxially stretched film, or a biaxially stretched film.

The non-chromium metal surface treatment method of the present invention comprises:
It comprises the step (A) of treating an object to be treated with the non-chromium metal surface treating agent. By performing the step (A), excellent corrosion resistance and adhesion can be imparted to the object to be treated.

Examples of the object to be treated include a metal base material, and aluminum or aluminum alloy is preferable. For example, aluminum alloy 5182 material, aluminum alloy 5021 material, aluminum alloy 5022 material,
Aluminum alloy 5052 material, aluminum alloy 300
4, aluminum alloy 3005 material, aluminum alloy 1050 material, aluminum alloy 1100 material and the like are preferably used. The use of the material to be treated is not particularly limited, and examples thereof include home appliances, food and drink containers, and housing building materials.

The method of treating the object to be treated in the above-mentioned chromium-free metal treatment method is not particularly limited, and for example, a roll coating method, a dipping method, a spray method or the like can be used. A spray processing method is preferred. The treatment by the chromium-free metal surface treatment method of the present invention needs to be performed on the surface of the metal plate to be coated with the thermoplastic resin. Therefore, when the thermoplastic resin is coated on both sides, it is necessary to coat both sides.

In the step (A), the lower limit is 30 ° C. and the upper limit is 80.
It is preferably carried out in the temperature range of ° C. If the temperature is lower than 30 ° C., the reaction rate decreases and the film deposition property deteriorates.
In order to obtain a sufficient amount of film, it is necessary to extend the processing time, which lowers productivity. If it exceeds 80 ° C, energy loss may increase. The lower limit is 50 ° C
Is more preferable. The upper limit is more preferably 70 ° C.

When the step (A) is carried out by the spray method, the processing time is preferably within the range of the lower limit of 1 second and the upper limit of 20 seconds. If it is less than 1 second, the amount of film formed is not sufficient, and corrosion resistance and adhesion may be deteriorated. If it exceeds 20 seconds, etching during film formation may proceed excessively, resulting in poor adhesion and corrosion resistance. It may decrease. The lower limit is more preferably 3 seconds. The upper limit is more preferably 8 seconds.

After the step (A), a water washing treatment can be carried out if necessary. The above-mentioned water washing treatment is performed once or more times so as not to adversely affect the appearance of the coating film and the like. In this case, the final washing with water is suitably performed with pure water. The above-mentioned water washing treatment may be either spray water washing or immersion water washing, and it is also possible to perform water washing by combining these methods.

The film obtained in the above step (A) is preferably dried after washing with water. As a method for drying the film, heat drying is preferable, and examples thereof include oven drying and / or heat drying by forced circulation of hot air. These heat drying is usually 40 to 1
It is carried out at 20 ° C. for 6 seconds to 60 seconds.

The non-chromium metal surface treatment method of the present invention comprises:
It is preferable that a step of washing with an acid is performed before the treatment of the step (A). Further, it is preferable that a step of washing with alkali is performed before the step of washing with acid.
The most preferred embodiment is a method in which the steps of alkali washing, water washing, acid washing, water washing, non-chromium metal surface treatment, water washing, and drying are sequentially performed.

The alkali cleaning treatment is not particularly limited, and for example, the alkali cleaning conventionally used for alkali cleaning treatment of metals such as aluminum and aluminum alloys can be performed. In the case of applying the metal surface treating agent of the present invention, in the above alkali cleaning treatment, alkali cleaning is usually performed using an alkaline cleaner from the viewpoint of improving the adhesion to coating materials and the anticorrosion property. The acid cleaning is performed using an acid cleaner.

The above alkaline cleaner is not particularly limited, and for example, those which are used for usual alkaline cleaning can be used, and examples include "Surf Cleaner 360" manufactured by Nippon Paint Co., Ltd. The acid cleaner is not particularly limited, and examples thereof include inorganic acids such as sulfuric acid, nitric acid, hydrochloric acid; "Surf Cleaner ST160" manufactured by Nippon Paint Co., Ltd., and the like.

The above acid cleaning and alkali cleaning treatments are usually carried out by a spray method. After performing the above-mentioned acid cleaning or alkali cleaning treatment, water cleaning treatment is performed in order to remove the acid cleaning liquid or the alkali cleaning agent remaining on the surface of the base material.

The coating film by the non-chromium metal surface treatment method of the present invention has a lower limit of 2 mg / molar amount of the water-soluble zirconium compound and / or the water-soluble titanium compound (1) in terms of zirconium and / or titanium atom in terms of mass per one surface after drying. m
² , the upper limit of which is 25 mg / m ² , and the organic phosphonic acid compound (2) has a lower limit of 0.2 mg / in terms of phosphorus atom.
m ² , the upper limit of 5 mg / m ² , and the tannin (3) in terms of carbon atoms, the lower limit is 3 mg / m ² , and the upper limit is 75.
It is preferably contained within the range of mg / m ² . In addition,
The amount of zirconium and titanium in the water-soluble zirconium compound and / or the water-soluble titanium compound (1) and the amount of phosphorus in the organic phosphonic acid compound (2) in the film can be measured by a fluorescent X-ray analyzer. The amount of (3) can be measured by the amount of organic carbon measured by the carbon / moisture analyzer according to form.

In the film obtained by the above-mentioned non-chrome metal surface treatment method, the film amount of each component can be obtained by appropriately setting the composition of the non-chrome metal surface treatment agent, the treatment temperature and the treatment time. .

The aluminum or aluminum alloy of the present invention is obtained by the above-mentioned chromium-free metal surface treatment method. The aluminum or aluminum alloy thus obtained has excellent corrosion resistance and adhesiveness, and thus can be suitably used for applications such as food and drink containers, home appliances, and building materials.

The method of adhering the film to the surface-treated metal plate thus obtained is not particularly limited, and, for example, a method usually used for lamination can be used. For example, the film is attached to the surface-treated metal plate. And place it on a heating roller, etc.
A method of bonding by thermocompression bonding for 0.1 to 10 seconds can be mentioned. Further, if necessary, after the film is pressure-bonded, it may be reheated (remelt, 5 seconds to 60 seconds) up to near the softening point (180 to 260 ° C.) of the film.

The non-chrome metal surface treatment agent of the present invention is excellent in workability and stability during treatment, and the obtained polyester resin-coated metal plate has sufficient adhesion. Therefore, the non-chrome metal surface treating agent of the present invention can be suitably used for producing a polyester resin-coated metal plate.

[0054]

EXAMPLES The present invention will be described in more detail with reference to examples below, but the present invention is not limited to these examples. In the examples, "parts" means "parts by mass" unless otherwise specified.

(Preparation of Non-Chromium Metal Surface Treatment Agent) Example 1 9994.5 parts of ion-exchanged water was placed in a vessel equipped with a stirrer. While stirring at room temperature, 1.2 parts of "Zirconium hydrofluoric acid" (containing 17.6% as Zr) manufactured by Nippon Light Metal Co., Ltd. was gradually added. Furthermore, while stirring
"1-Hydroxyethylidene-1,1" manufactured by Morita Chemical Industries, Ltd.
0.3 parts of "diphosphonic acid" was gradually added. Then
While stirring, Dainippon Pharmaceutical Co., Ltd. "Tannic acid extract A"
4 parts (50% non-volatile content) were gradually added. Then, while stirring, the free fluorine concentration is 12 p with respect to the treatment agent.
After blending hydrofluoric acid so as to be pm, ammonia was added to adjust the pH of the treating agent to 2.6. Stirring was continued for 10 minutes, and zirconium hydrofluoric acid was used as zirconium to obtain 21 ppm, 1-hydroxyethylidene-1,
10 ppm of 1-diphosphonic acid as phosphorus, tannin 2
A slightly brown aqueous solution containing 00 ppm was obtained.

Examples 2 to 12 and Comparative Examples 1 to 4 Non-chromium metal surface treatments of Examples 2 to 12 and Comparative Examples 1 to 4 by the same method as in Example 1 with the compounding ratios shown in Tables 1 and 2. The agent was prepared.

Example 13 9995 parts of ion-exchanged water was placed in a vessel equipped with a stirrer. "Titanium hydrofluoride" manufactured by Morita Chemical Industries, Ltd. (containing 29.3% of Ti) while stirring at room temperature 0.7
Parts were added slowly. Furthermore, 0.3 part of "1-hydroxyethylidene-1,1-diphosphonic acid" manufactured by Morita Chemical Industries, Ltd. was gradually added while stirring. Next, 4 parts of "tannic acid extract A" (nonvolatile content 50%) manufactured by Dainippon Pharmaceutical Co., Ltd. was gradually added with stirring. Subsequently, while stirring, hydrofluoric acid was added to the treating agent so that the free fluorine concentration was 12 ppm, and then ammonia was added to adjust the pH of the treating agent to 2.6. Stirring is continued for 10 minutes, and 20 ppm of titanium hydrofluoric acid is used as titanium.
A slightly brown aqueous solution containing 1 ppm of 1-hydroxyethylidene-1,1-diphosphonic acid as phosphorus and 200 ppm of tannin was obtained.

Examples 14 to 21 and Comparative Examples 5 to 8 Non-chromium metal surface treatments of Examples 14 to 21 and Comparative Examples 5 to 8 by the same method as in Example 13 with the compounding ratios shown in Tables 1 and 2. The agent was prepared.

Example 22 9987.9 parts of ion-exchanged water was placed in a vessel equipped with a stirrer. With stirring at room temperature, 1.7 parts of zirconium hydrofluoric acid and then 1.0 part of hydrofluoric titanium titanate were gradually added. Further, 1.4 parts of 1-hydroxyethylidene-1,1-diphosphonic acid was gradually added with stirring. Next, 8 parts of "tannic acid extract A" (nonvolatile content 50%) manufactured by Dainippon Pharmaceutical Co., Ltd. was gradually added with stirring. Subsequently, while stirring, hydrofluoric acid was added to the treating agent so that the free fluorine concentration was 12 ppm, and then ammonia was added to adjust the pH of the treating agent to 2.6. Stirring is continued for 10 minutes, and zirconium hydrofluoric acid is used as zirconium at 30 ppm, titanium hydrofluoric acid is used as titanium at 30 ppm, and 1-hydroxyethylidene-1,1-diphosphonic acid is used as phosphorus at 40 ppm.
A slightly brown aqueous solution containing 400 ppm of tannin was obtained.

Examples 23 to 25 The chromium-free metal surface treating agents of Examples 2 to 12 and Comparative Examples 1 to 4 were prepared by the same method as in Example 1 with the compounding ratios shown in Tables 1 and 2.

(Preparation of surface-treated plate) 1) Both sides of aluminum alloy 3004 plate material were washed with a 1% diluted solution of alkaline cleaner "Surf Cleaner 360" manufactured by Nippon Paint Co., Ltd. (65 ° C x 3 seconds). , Washed with water, then with a 1% diluted sulfuric acid solution (50 ° C. × 3 seconds), washed with water,
The aluminum material thus obtained is sprayed with a sprayer 5
The treatment with the non-chromium metal surface treating agent of the above-mentioned Examples and Comparative Examples was performed at 5 ° C. for 5 seconds, and the material temperature was 80 ° C.
After drying for 2 seconds, a surface-treated metal plate was obtained.

Comparative Example 15 Using "Alsurf 401/45" manufactured by Nippon Paint Co., Ltd., a phosphoric acid chromate-treated aluminum material was prepared.

(Measurement of coating amount) The masses of zirconium, titanium, phosphorus and chromium of the dried coating films obtained in Examples and Comparative Examples were measured by a fluorescent X-ray analyzer "XR" manufactured by Shimadzu Corporation.
F-1700 ". The mass of tannin in the dried chemical conversion film was determined by measuring the mass of carbon atoms derived from tannin using a carbon / water content analyzer “RC412” manufactured by LECO, USA. The carbon atom mass derived from tannin was measured by the following method.

[Measurement Method of Carbon Atom Mass Derived from Tannin] (1) A film consisting only of a water-soluble zirconium compound and / or a water-soluble titanium compound and an organic phosphonic acid compound was prepared, and carbon derived from the organic phosphonic acid compound was prepared. The mass and the phosphorus mass were measured, the mass ratio of the carbon mass derived from the organic phosphonic acid compound and the phosphorus was calculated, and a linear equation was prepared. (2) Next, a film made of a water-soluble zirconium compound and / or a water-soluble titanium compound, an organic phosphonic acid compound, and tannin was prepared, and the carbon mass and phosphorus mass were measured. (3) From the primary equation obtained in (1), the carbon mass derived from the organic phosphonic acid compound was calculated based on the phosphorus mass obtained in (2). (4) The carbon mass derived from tannin was calculated from the difference between the carbon mass (measured value) obtained in (2) and the phosphorus mass (calculated value) obtained in (3).

A carbon derived from tannin is obtained, where Zr is the mass of zirconium in the zirconium compound obtained by the above measurement, Ti is the mass of titanium in the titanium compound, and P is the mass of phosphorus derived from the organic phosphonic acid compound. It is shown in Tables 1 and 2 where C is the atomic mass.

[0066]

[Table 1]

[0067]

[Table 2]

(Preparation of Laminated Plate) A polyethylene terephthalate (PET) film was placed on the obtained base-treated plate and pressure-bonded using a heating roller at a roll temperature of 180 ° C. and a roll speed of 30 m / min, followed by a conveyor oven. Using, heat the material temperature 240 ℃ for 60 seconds,
It adhered and the laminated board was obtained.

(Evaluation method) The following evaluations were performed and the results are shown in Table 3.
And shown in Table 4. 1. Stability of chemical conversion agent The base treatment agent prepared as described above was stored at 40 ° C for 30 days, and the appearance of the treatment liquid was visually evaluated. In Tables 3 and 4, those having a good appearance without any abnormalities such as cloudiness, sedimentation and the presence or absence of aggregates were represented by “◯”, and those having abnormalities were represented by the state.

2. Appearance of coating film The surface of the surface-treated plate obtained as described above was visually evaluated. In Tables 3 and 4, those having a good appearance without repellency, unevenness, remarkable discoloration and the like were indicated by "◯", and those having an abnormality were indicated by the state.

3. Adhesion of Laminated Plate Regarding the laminated plate obtained as described above, the following (1) to
A tape peeling test was performed as in (6), and the adhesion was evaluated by the number of grids that were not peeled off by the tape among 100 grids before the tape was attached. (1) Plane / Untreated In accordance with JIS K 5400.8.5.1, PET
A cross-cut was cut on the surface to which the film was attached and a tape peeling test was performed. (2) Flat / Boiling Water Treatment The laminated plate was dipped in boiling water for 30 minutes, a cross-cut was cut on the surface on which the PET film was attached, and a tape peeling test was performed. (3) The flat / steam-treated laminated plate was placed in pressurized steam at 125 ° C. and 1.13 atm for 30 minutes, and a cross-cut was cut on the surface on which the PET film was attached, and a tape peeling test was performed. The absence of peeling points was regarded as a passing level.

(4) An Erichsen processed / untreated laminate sheet was cross-cut with a cross-cut on the PET film-attached surface, and the cut surface was extruded by 4 mm with an Erichsen extrusion tester to perform a tape peeling test. (5) Erichsen processing / boiling water treatment A laminated plate was immersed in boiling water for 30 minutes, a cross-cut was cut on the surface on which the PET film was attached, and the cut surface was extruded by 4 mm with an Erichsen extrusion tester to perform a tape peeling test. . (6) Erichsen processing / steam treatment Laminated plate was placed in pressurized steam at 125 ° C and 1.13 atm for 30 minutes, put a cross cross cut on the PET film pasting surface, and cut the surface with an Erichsen extrusion tester to 4 mm. Extrusion and tape peeling tests were performed.

[0073]

[Table 3]

[0074]

[Table 4]

The polyester resin-coated metal sheet of the example which has been surface-treated with the non-chromium metal surface-treating agent of the present invention is excellent in all the properties such as stability of the treating agent, film appearance, and physical properties of the laminate material. A polyester resin-coated metal plate having excellent adhesion without using chromium metal has been obtained.

On the other hand, the content of any one of the water-soluble zirconium compound and / or the water-soluble titanium compound (1), the organic phosphonic acid compound (2) and the tannin (3) is included in the scope of the present invention. None of Comparative Examples 1 to 10 which cannot be subjected to the desired metal surface treatment, the resulting thermoplastic polyester resin-coated metal plate is inferior in adhesiveness, adhesion after boiling water treatment, adhesion after steam treatment The decrease in sex is also large.

[0077]

The metal plate treated with the non-chromium metal surface treatment agent of the present invention is suitable for use in a thermoplastic polyester resin-coated metal plate, and the thermoplastic polyester resin-coated metal plate has a film-metal plate adhesion property. It has excellent properties.

Continued front page    (72) Inventor Masayuki Kamimura             4-1-1 Minami-Shinagawa, Shinagawa-ku, Tokyo Japan             Within Paint Co., Ltd. (72) Inventor Minoru Inoue             4-1-1 Minami-Shinagawa, Shinagawa-ku, Tokyo Japan             Within Paint Co., Ltd. F term (reference) 4K026 AA09 BA09 BB07 BB08 CA13                       CA17 CA28 CA32 CA33 CA34                       CA36 CA38 DA03 DA06 EA11                       EB06

Claims (6)

[Claims] 1. A non-chromium metal surface treatment agent comprising a water-soluble zirconium compound and / or a water-soluble titanium compound (1), an organic phosphonic acid compound (2), and tannin (3), said organic phosphonic acid compound (2) is one in which a phosphorus atom constituting a phosphon group is bonded to a carbon atom, and the content of the water-soluble zirconium compound and / or the water-soluble titanium compound (1) is the amount of zirconium and / or titanium. As mass standard 20
To 800 ppm, the content of the organic phosphonic acid compound (2) is 10 to 500 ppm on a mass basis, and the content of the tannin (3) is 200 to 4000 ppm on a mass basis as the amount of the tannin. The non-chromium metal surface-treating agent has a pH of 1.6 to 4.0 and is used for producing a thermoplastic polyester resin-coated metal plate. 2. A non-chrome metal surface treatment method comprising the step (A) of treating an object with the non-chrome metal surface treatment agent according to claim 1. 3. The non-chromium metal surface treatment method according to claim 2, wherein a step of washing with an acid is carried out before the step (A) is carried out. 4. The non-chromium metal surface treatment method according to claim 2, wherein a step of washing with an alkali and then a step of washing with an acid are performed before the step (A). 5. An aluminum or aluminum alloy plate obtained by the non-chrome metal surface treatment method according to claim 2, 3 or 4. 6. A water-soluble zirconium compound and / or a water-soluble titanium compound (1) in terms of mass per one side after drying.
2 to 25 m in terms of zirconium and / or titanium atoms
g / ^{m 2,} an organic phosphonic acid compound ⁽²⁾ 0.2~5mg / ^m 2 in terms of phosphorus atom, as well as, tannin (3) is formed coating that 3~75mg / ^{m 2} containing a carbon atom in terms 7. The aluminum or aluminum alloy plate according to claim 6.