JP2771110B2 - Surface treatment composition for aluminum-containing metal material and surface treatment method - Google Patents

Abstract

A surface of aluminiferous metal is brought into contact at 30 DEG C to 65 DEG C for 5 to 60 seconds with a surface treatment bath with a pH of 2.0 to 6.5 that contains phosphate ion, condensed phosphate ion, and a water soluble polymer in the following weight proportions: 1 - 30 : 0.1 - 10 : 0.2 - 20. This is followed by a water rinse and drying by heating. The water soluble polymer has a chemical structure conforming with formula (I), in which (i) each of X<1> and X<2> represents a hydrogen atom, a C1 to C5 alkyl group, or a C1 to C5 hydroxyalkyl group; (ii) each of Y<1> and Y<2> represents a hydrogen atom or a moiety "Z" that conforms to formula (II) or (III), wherein each of R<1>, R<2>, R<3>, R<4>, and R<5> represents a C1 to C10 alkyl group or a C1 to C10 hydroxyalkyl group; (iii) the average value for the number of Z moieties substituted on each phenyl ring in the polymer molecule is from 0.2 to 1.0; (iv) n is an integer with a value from 2 to 50; and (v) each polymer molecule contains at least one Z moiety.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel surface-treating composition for aluminum-containing metal materials and a method of treating the surfaces of the aluminum-containing metal materials, which impart excellent corrosion resistance and paint adhesion to the surfaces of the aluminum-containing metal materials before painting. Things. One area where the present invention is effectively applied is in the surface treatment of aluminum DI cans. Prior to painting and printing on an aluminum DI can formed by drawing and ironing an aluminum alloy plate, the surface of the can is imparted with excellent corrosion resistance and paint adhesion, and The surface treatment composition and the surface treatment method of the present invention, in order to also provide excellent slipperiness (hereinafter simply referred to as slipperiness) necessary for smoothing the conveyor transfer,
It is particularly effective.

[0002]

2. Description of the Related Art Aluminum-containing metallic materials,
Table of metallic materials made of aluminum or aluminum alloy
Surface treatment liquid available in chromate and non-chromate types
They can be roughly classified. Chromate type surface treatment liquid
A typical example is a chromate chromate conversion treatment solution.
And chromate phosphate conversion solution.
The chemical conversion solution was put into practical use around 1950 and is still hot.
Widely used for surface treatment such as fin materials for exchangers
You. Chromic acid chromate conversion treatment solution is chromic acid (Cr
O_Three) And hydrofluoric acid (HF) as main components,
In addition, an accelerator is added to the
Can form a film containing dry hexavalent chromium
You. Phosphate chromate conversion solution was purchased in the United States in 1945
According to the invention described in Japanese Patent No. 2,438,877.
This chemical conversion treatment solution is chromic acid (CrO_Three)
Phosphoric acid (H_ThreePO_Four), And hydrofluoric acid (HF)
As a component, the resulting film is hydrated
Chromium phosphate (CrPO_Four・ 4H _TwoO) as the main component
Things. This conversion coating contains hexavalent chromium
Not to be coated on the body and lid of a beverage can
It is still widely used for processing.

As a typical non-chromate type chemical conversion treatment solution, there is a treatment solution disclosed in Japanese Patent Application Laid-Open No. 52-131937. The treatment solution is an acidic aqueous coating solution containing zirconium, titanium, or a compound thereof, phosphate and fluoride, and having a pH of about 1.0 to 4.0. When the treatment is performed using this chemical conversion treatment liquid, a chemical conversion film containing zirconium and / or titanium oxide as a main component is formed on the surface of the aluminum-containing metal material. Such a non-chromate type chemical conversion treatment solution has the advantage of not containing hexavalent chromium, but has the disadvantage that the resulting chemical conversion film has poorer corrosion resistance and paint adhesion than the chromate type chemical conversion treatment solution. have. Both the chromate-type and non-chromate-type chemical conversion treatment solutions contain fluorine, but in recent years, practical use of non-fluorine-type surface treatment solutions has been desired due to environmental problems.

On the other hand, a surface treatment solution or a treatment method for imparting corrosion resistance and paint adhesion to an aluminum-containing metal material using a water-soluble resin is disclosed in Japanese Unexamined Patent Publication No. Sho.
JP-A-1-91369, JP-A-1-172406, JP-A-1-177379, JP-A-1-177
It is disclosed in JP-A-380, JP-A-2-608, JP-A-2-609, and the like. In these conventional surface treatment solutions and surface treatment methods, a metal surface is treated with a solution containing a derivative of a polyhydric phenol compound. However, with these conventional methods, it is difficult to form a sufficiently stable resin-containing film on the surface of the aluminum-containing metal material, and sufficient performance (corrosion resistance) has not been obtained. Japanese Patent Application Laid-Open No. 4-66671 discloses a method for improving a treatment method containing a derivative of the polyhydric phenol compound.
The invention of Japanese Patent Application Laid-Open No. H10-15095 also has a problem that sufficient adhesion may not be obtained.

[0005] At present, the above-mentioned non-chromate type surface treatment solution of phosphoric acid chromate and zirconium is mainly used for the surface treatment of aluminum DI cans. In an aluminum DI can, the bottom outer surface is sterilized at a high temperature without being painted. However, if the corrosion resistance is insufficient at this time, there is a problem that aluminum is oxidized and the appearance changes to black. This phenomenon is generally called blackening.
In order to prevent this blackening, the coating itself (unpainted) formed by the surface treatment is required to have high corrosion resistance.

In the can manufacturing process, a high coefficient of friction on the outer surface of the can causes a slippage of the can surface when the can is transported on the conveyor, causing the can to roll over and causing a problem of transfer obstruction. In particular, the transportability of the can becomes a problem when trying to transport it to a printer. Therefore, in the canning industry,
It is necessary to reduce the coefficient of static friction of the outer surface of the can without adversely affecting the adhesion of the paint or ink applied to the can. As a method for improving the slipperiness, there is an invention described in JP-A-64-85292. The present invention relates to a surface treatment agent for metal cans containing a water-soluble organic substance selected from phosphates, alcohols, mono- or polyhydric fatty acids, fatty acid derivatives and mixtures thereof. This method is effective for improving the slipperiness of an aluminum can, but has a problem that no improvement in corrosion resistance and paint adhesion is observed.

As a method for improving the slipperiness of an aluminum can, the invention of Japanese Patent Application Laid-Open No. Hei 5-239434 is known which uses a phosphate ester. Although the improvement is recognized, there is a problem that the corrosion resistance and the paint adhesion are not improved.

[0008]

DISCLOSURE OF THE INVENTION The present invention has been made to solve the above-mentioned problems of the prior art, and specifically, provides excellent corrosion resistance and paint adhesion to the surface of an aluminum-containing metal material, In particular, an object of the present invention is to provide a surface treatment composition and a surface treatment method for an aluminum-containing metal material, which can provide excellent sliding properties when applied to an aluminum DI can.

[0009]

Means for Solving the Problems The present inventors diligently studied means for solving the above-mentioned problems of the prior art. As a result, a specific surface treatment liquid was prepared using a surface treatment composition containing a specific phosphate ion, a condensed phosphate ion, and a water-soluble polymer having a specific structure, and this was treated with an aluminum-containing metal. By contacting the material surface, it has excellent corrosion resistance and paint adhesion,
In addition, they have found that a fat-containing film that improves the slipperiness when applied to an aluminum DI can can be formed on the surface of the metal material, and the present invention has been completed.

The surface treatment composition for an aluminum-containing metal material according to the present invention comprises 1 to 30 parts by weight of a phosphate ion,
0.1 to 10 parts by weight of condensed phosphate ion, 0.1 to 2 parts by weight
0 parts by weight of a water-soluble polymer of the following general formula (I):

Embedded image [However, in the formula (I), X ¹ and X ² each independently represent a hydrogen atom, a C ₁ -C ₅ alkyl group or a C ₁ -C ₅ hydroxyalkyl group, and Y ¹ and Y ² is each independently a hydrogen atom, or the following formulas (II) and (III):

Embedded image

Embedded image (However, in the formulas (II) and (III), R ¹ , R ² ,
R ³ , R ⁴ and R ⁵ are each independently of the other
_{1 to} C ₁₀ alkyl group and C _{1 to} C ₁₀ hydroxyalkyl group), and each of the Z groups bonded to the benzene ring of the polymer molecule. May be different from each other, or may be the same as the other, and the average value of the number of Z group substitution of each benzene ring in the polymer molecule is 0.2 to 1.0. And n
Represents an average degree of polymerization of 2 to 50. ] Are included.

The surface treatment method for an aluminum-containing metal material according to the present invention is characterized in that the surface treatment solution containing the surface treatment composition according to the present invention and adjusted to a pH of 6.5 or less is coated with the surface of the aluminum-containing metal material. At a temperature of 30 to 65 [deg.] C. for a total of 5 to 60 seconds, washing the contact surface with water and drying by heating.

[0012] In the above method of the present invention, the surface treatment solution may contain 1 to 30 g / liter of phosphate ions and 0.1 to 30 g / liter.
10 g / liter of condensed phosphate ions and 0.1 to 20
g / liter of a water-soluble polymer of formula (I),
It is preferably water-soluble and has a pH of 2.0 to 6.5.

[0013] In the surface treatment method of the present invention, the aluminum-containing metal material is added to the surface treatment solution in an amount of 5 to 5 wt.
You may soak for 60 seconds.

Further, in the surface treatment method of the present invention, the surface treatment liquid is sprayed on the surface of the aluminum-containing metal material two or more times at intervals of 2 to 5 seconds, and the total time of the spraying operation and the interval is reduced. It may be 5 to 60 seconds.

[0015]

The surface treatment composition of the present invention is an acidic aqueous solution containing, as essential components, a phosphate ion, a condensed phosphate ion and a water-soluble polymer having a specific chemical structure.

[0016] Phosphate ions are added to the surface treatment composition of the present invention.
Phosphoric acid (H_ThreePO _Four), Sodium phosphate
Um (Na_ThreePO_Four) Can be used. R
The content of sulphate ion is 1 to 3 in the above mixing ratio.
0 parts by weight, particularly 1 to 5 parts by weight
Preferably, there is. Phosphate ion
When the content of the component is less than 1 part by weight,
Insufficient reactivity with the surface of the metal material and sufficient film formation
Not done. When it exceeds 30 parts by weight, good
A film is formed, but the cost of the processing solution is high and economical
Disadvantaged.

The condensed phosphate ion used in the present invention is:
It includes pyrophosphate ions, tripolyphosphate ions, tetrapolyphosphate ions and the like, and includes one or more of these. To make the surface treatment composition of the present invention contain condensed phosphate ions, condensed phosphoric acid or a salt thereof can be used. For example, pyrophosphate (H ₄ P ₂ O ₇ ) or sodium pyrophosphate (Na ₄ P ₂ O ₇ ) can be used to contain pyrophosphate ions. In the above composition ratio of the surface treatment composition of the present invention, the content of condensed phosphate ions is 0.1
It is preferably in the range of 10 to 10 parts by weight, particularly preferably in the range of 0.5 to 3.0 parts by weight. When the content of the condensed phosphate ion is less than 1 part by weight in the above-mentioned component mixing ratio, the etching effect of the surface treatment liquid obtained therefrom is weak and a film cannot be formed sufficiently. On the other hand, if it exceeds 10 parts by weight, the etching effect of the obtained surface treatment liquid is too strong, and the film forming reaction is hindered.

The water-soluble polymer used in the present invention is a polymer containing an oligomer represented by the following general formula, wherein the water-soluble polymer represented by the general formula (I) (including the oligomer) is:

Embedded image In the formula (I), n represents a positive number of 2 to 50, which represents the average degree of polymerization of the polymer. X ¹ and X ² are
Each independently represents a C ₁ -C ₅ alkyl group or a C ₁ -C ₅ hydroxyalkyl group. Y ¹ and Y ² each independently represent a hydrogen atom or a Z group, and the Z group is an amino group and an ammonium group represented by the following formulas (II) and (III).

Embedded image

Embedded image In the formulas (II) and (III), R ¹ , R ² , R ³ ,
R ⁴ and R ⁵ each independently represent a C ₁ -C ₁₀ alkyl group or a C ₁ -C ₁₀ hydroxyalkyl group.

In the polymer molecule of the formula (I), the Y ¹ and Y ² groups contained in each polymerized unit may be the same or different from each other. May be different from each other or may be the same. However, the polymer molecule of the formula (I) necessarily contains a benzene ring substituted by a Z group, and the average number of Z group substitutions in each benzene ring is 0.2 to 1.0. The average value of the number of substituted Z groups is hereinafter referred to as “average Z group substitution number”.

In the polymer of the formula (I), when n is less than 2, the effect of improving the corrosion resistance of the obtained surface coating becomes unsatisfactory, and when it exceeds 50, the resulting surface treatment composition, And the stability of the surface treatment liquid becomes insufficient,
This causes practical inconvenience.

The alkyl or hydroxyalkyl group represented by X ¹ and / or X ² has the number of carbon atoms
If the number is 6 or more, the obtained polymer molecule becomes bulky, causing steric hindrance, making it difficult to form a dense and excellent corrosion resistant film.

Y ¹ and / or Y ² are a hydrogen atom or a Z group of formulas (II) and (III). The polymer of the formula (I) contains a Z group as a substituent, and the average Z group substitution rate in each benzene ring of the polymer molecule is from 0.2 to 0.2.
1.0. For example, a polymer with n = 10 contains 20 benzene rings and one of the 20 benzene rings.
When only 0 groups are each substituted with one Z group, the average number of Z group substitutions of this polymer is [(1 × 10) + (0 × 10 ′)] / 20 = 0.5. is there. When the average number of Z group substitution is less than 0.2, the resulting polymer has insufficient water solubility, and the resulting surface treatment composition and surface treatment solution have insufficient stability. Also,
When the average number of Z group substitution exceeds 1.0 (two or more Z
In the case of containing a benzene ring substituted by a group), the water solubility of the obtained polymer becomes excessively high, and it becomes difficult to form a surface film.

In the formulas (II) and (III), R ¹ ,
The alkyl group or hydroxyalkyl group represented by R ² , R ³ , R ⁴ , and R ⁵ has 1 to 10 carbon atoms. When the number of carbon atoms is 11 or more, the obtained polymer molecule becomes excessively bulky, the density of the obtained film becomes coarse, and the effect of improving the corrosion resistance becomes insufficient.

In the above composition ratio of the surface treatment composition of the present invention, the content of the water-soluble polymer of the formula (I) is as follows:
0.1 to 20 parts by weight, preferably 0.5 to 5 parts by weight. If the content of the water-soluble polymer is less than 0.1 part by weight in the above-mentioned component mixing ratio, it becomes difficult to form a film on the surface of the metal material by the obtained surface treatment liquid, If the amount is more than 10 parts by weight, the cost of the obtained surface treatment composition and the cost of the surface treatment method increase, which is economically problematic.

With respect to the pH of the surface treatment composition of the present invention,
Although there is no particular limitation, it is generally preferred that the adjustment be made to 6.5 or less.

In the method of the present invention, a surface treatment liquid is prepared using the above surface treatment composition (generally, diluted with water). At this time, the pH of the surface treatment solution is adjusted to 6.5 or less, preferably 2.0 to 6.5. When the pH of the surface treatment solution is higher than 6.5, the polymer of the formula (I) tends to precipitate and precipitate in the resulting surface treatment solution,
Insufficient stability and service life of the processing solution. Also,
When the pH is less than 2.0, the etching property of the surface treatment liquid on the surface of the metal material may be excessively high, and thus it may be difficult to form a surface film. The pH of the surface treatment solution can be adjusted by using an acid such as phosphoric acid, nitric acid or hydrochloric acid and an alkali such as sodium hydroxide, sodium carbonate or ammonium hydroxide. If wastewater treatment is not a problem, hydrofluoric acid may be used for pH adjustment.

In the method of the present invention, the surface treatment liquid is preferably
30 g / l of phosphate ions and 0.1 to 10 g /
1 liter of condensed phosphate ion and 0.1 to 20 g / liter of a water-soluble polymer of the formula (I), and
It preferably has a pH of ~ 6.5. As described above, if the phosphate ion concentration in the surface treatment solution is less than 1 g / liter, the formation of the surface film may be insufficient. May result in disadvantages. If the concentration of the condensed phosphate ions is less than 0.1 g / liter, the etching properties of the obtained surface treatment solution may be excessively weak and the formation of the surface film may be insufficient. When the amount exceeds the above range, the etching property of the obtained surface treatment liquid becomes excessively strong, and the film forming reaction may be inhibited. Further, the concentration of the water-soluble polymer of the formula (I) is 0.1 g.
If the amount is less than 1 g / liter, the film forming property of the obtained surface treatment liquid may be insufficient. If the amount exceeds 20 g / l, the cost may be increased, which is economically disadvantageous.

When aluminum ions eluted from the aluminum-containing metal material are mixed in the surface treatment solution, the polymer of the formula (I) and the metal ions form a complex,
Precipitation may occur. In such a case, an aluminum sequestering agent may be added to the treatment liquid. Examples of the aluminum sequestering agent include EDTA, Cy-DTA, triethanolamine, gluconic acid, heptogluconic acid,
Oxalic acid, tartaric acid, malic acid and organic phosphonic acids are useful, and there is no particular limitation on these types. If hydrofluoric acid does not pose a problem in wastewater treatment, it may be used as a blocking agent.

In the method of the present invention, the surface treatment solution prepared as described above is brought into contact with the surface of the aluminum-containing metal material at a concentration of 30 to 65 ° C. for a total of 5 to 60 seconds. Next, the film formed on the surface of the metal material is washed with water,
Heat and dry. At this time, as the contact operation, an aluminum-containing metal material is placed in a surface treatment solution at 30 to 65 ° C.
, May be immersed for 5 to 60 seconds. Alternatively, as the contact operation, a surface treatment liquid is sprayed on the surface of the aluminum-containing metal material at 30 to 65 ° C., and the total contact time between the surface treatment liquid and the aluminum-containing metal material is 5
It may be up to 60 seconds. At this time, at intervals of 2 to 5 seconds,
It is preferable that two or more sprays are applied, and the total of the spray time and the interval time is 5 to 60 seconds.

When the spray treatment is performed, the surface treatment liquid foams, which may cause a problem in a film formed. The presence and degree of foaming greatly depends on the spraying device and conditions. If foaming cannot be sufficiently solved by changing the spraying device and conditions, an antifoaming agent may be added to the surface treatment liquid. There are no restrictions on the type and amount of the defoaming agent, and it is sufficient that the defoaming agent does not impair the paint adhesion of the resulting film.

Next, the method for producing the surface treatment composition of the present invention will be outlined. The phosphate ion and the condensed phosphate ion are collected in the above-mentioned mixing ratio, dissolved in water in a predetermined amount as required, and sufficiently stirred. If the pH of this solution is not 7 or less, adjust the pH to 7 or less with the appropriate acid described above. Next, while stirring, the water-soluble resin defined in the present invention is added and completely dissolved, and the pH is adjusted to 6.5 or less by the method described above.

Next, a film formed on the surface of the aluminum-containing metal material will be outlined. The film formed by the surface treatment liquid of the present invention is an organic-inorganic composite film containing phosphate and the polymer of the formula (I) as main components. The surface of the metal material is etched by the phosphate ions and the condensed phosphate ions. At this time, a local increase in pH occurs at the interface, and phosphate deposits on the surface of the metal material. In addition, the amino group of the polymer of the formula (I) has a chelating effect, and forms a kind of coordination compound with a new surface of a substrate generated by etching. Basically, an organic-inorganic composite film is formed by the above two actions. However, when condensed phosphate ions coexist in the surface treatment solution, a polymer-metal coordination compound is more easily formed. As a result, it is possible to stably form an organic-inorganic composite film on the surface over a wide pH range. Further, it is possible to further polymerize the polymer on the surface by heating the formed surface film. When particularly high corrosion resistance is required, it is preferable to heat the film to further polymerize the polymer on the surface. As the heating condition at this time, 200 ° C. for 1 minute or more is appropriate.

The aluminum-containing metal material used in the method of the present invention is aluminum and a material composed of an aluminum-containing alloy such as an aluminum-manganese alloy, an aluminum-magnesium alloy, an aluminum-silicon alloy, for example, a plate, a rod, a tube, And wire rods. There are no restrictions on the size and shape of this metal material.

A preservative or a fungicide may be mixed with the polymer composition of the present invention. These are effective to prevent spoilage or mold from occurring during use or storage of the surface treatment liquid at a low temperature. A specific example is hydrogen peroxide.

Next, an outline of a surface treatment process for an aluminum-containing metal material to which the surface treatment solution of the present invention is applied will be described. The surface treatment liquid of the present invention is applied in a process described below as a preferred example. (1) Surface cleaning: degreasing (any of acid type, alkali type, solvent type) (2) Rinsing with water (3) Film formation treatment (surface treatment method of the present invention) Treatment temperature: 30 to 65 ° C Treatment method: immersion Or spraying treatment time: 5 to 60 seconds (4) Rinse with water (5) Rinse with deionized water (6) Dry

The surface treating solution of the present invention is used after being heated to 30 to 65 ° C. If the temperature is lower than 30 ° C., the reactivity is insufficient and a good film is not formed. If the temperature exceeds 65 ° C., a good film is formed, but the energy cost for heating increases, which is not economically preferable. The immersion treatment time is 5 to 60 seconds. If the immersion treatment time is less than 5 seconds, the film does not react sufficiently and a film having excellent corrosion resistance is not formed. Further, even if it is longer than 60 seconds, the effect of improving performance is saturated. On the other hand, in the case of spraying, when the liquid is continuously sprayed, the pH near the surface interface
Elevation does not easily occur, and a film may not be formed sufficiently. For this reason, it is preferable to spray intermittently. The intermittent time is preferably 2 to 5 seconds, and the total processing time is preferably in the range of 5 to 60 seconds. If the total contact time is less than 5 seconds, it does not react sufficiently, making it impossible to form a film having excellent corrosion resistance, and if it is longer than 60 seconds, the effect of improving performance is saturated.

[0037]

EXAMPLES The present invention will be further described below with reference to examples. In addition, regarding the composition of the surface treatment solution and the surface treatment method,
Examples and comparative examples are individually described. Evaluation method (1) Corrosion resistance The corrosion resistance (blackening resistance to boiling water) of the aluminum DI can was evaluated by the degree of discoloration (blackening) after immersing the treated aluminum DI can in boiling tap water for 30 minutes. No blackening is "○", partial blackening is "△", and all blackening is "x"
Indicated by

(2) Paint Adhesion The paint adhesion was tested as follows. Epoxyurea-based paint for cans on the surface of treated cans
And bake at 215 ° C for 4 minutes.
The sample was cut into strips of 0 mm and hot-pressed with a polyamide-based film to obtain test pieces, which were peeled by a 180-degree peel test method, and the peel strength at that time was evaluated. Therefore, the higher the peel strength, the better the paint adhesion. Generally, it is practically good if the peel strength is 4.0 kgf / 5 mm width or more.

(3) Slipperiness The slipperiness was evaluated by measuring the static friction coefficient of the outer surface of the can. Therefore, the lower the coefficient of static friction, the better the slipperiness. In general, it is good if it has a static friction coefficient of 1.0 or less.

Example 1 An aluminum DI can prepared by DI working an aluminum alloy plate (A3004) was mixed with an acidic degreasing agent (trade name:
An 8% aqueous solution of Palclean 500 (manufactured by Nippon Parkerizing Co., Ltd.) was degreased by spraying at 75 ° C. for 60 seconds, then washed with water and cleaned. A surface treatment liquid 1 having the following composition was heated to 60 ° C. on the clean surface, and sprayed for 5 seconds three times at intervals of 5 seconds (total of 25 seconds).
Release, then rinse with tap water, then 3,000,000 more
After spraying deionized water of Ωcm or more for 10 seconds,
It was dried in a hot air drying oven at 0 ° C. for 2 minutes.

Surface treatment solution 1 75% phosphoric acid (H ₃ PO ₄ ) 10.0 g / liter (PO ₄ ion: 7.2 g / liter) Sodium pyrophosphate 3.0 g / liter (P ₂ O ₇ ion: ( Na ₄ P ₂ O ₇ · 10H ₂ O) 1.2 g / l) Water-soluble polymer 1 2.0 g / l (solid content) pH 4.0 (adjusted with sodium hydroxide) In (I), n = 5 X ¹ , X ² = hydrogen Z = —CH ₂ N (CH ₃ ) ₂ average number of Z group substitution = 0.25

Example 2 After cleaning the aluminum DI can under the same conditions as in Example 1, a surface treating solution 2 having the following composition was heated to 60 ° C. and immersed in the solution for 20 seconds. After the treatment, it was washed with water and dried under the same conditions as in Example 1. Surface treatment liquid 2 75% phosphoric acid (H ₃ PO ₄ ) 10.0 g / l (PO ₄ ion: 7.2 g / l) Sodium pyrophosphate 3.0 g / l (P ₂ O ₇ ion: (Na ₄ P ₂ O ₇ · 10H ₂ O) 1.2 g / l) Water-soluble polymer 1 0.4 g / l (solid content) pH 3.0 (adjusted with sodium carbonate) The above water-soluble polymer 1 is the same as in Example 1.

Example 3 After cleaning an aluminum DI can under the same conditions as in Example 1, a surface treating solution 3 having the following composition was heated to 35 ° C. and immersed in the solution for 60 seconds. After the treatment, it was washed with water and dried under the same conditions as in Example 1. Surface treatment solution 3 75% phosphoric acid (H ₃ PO ₄ ) 20.0 g / l (PO ₄ ion: 14.4 g / l) Sodium pyrophosphate 6.0 g / l (P ₂ O ₇ ion: (Na ₄ P _{2 O 7 · 10H 2 O)} 2.4g / liter) water-soluble polymer 1 8.0 g / liter (solids) pH 6.0 (adjusted with sodium hydroxide) the water-soluble polymer 1 same as example 1

Example 4 After cleaning an aluminum DI can under the same conditions as in Example 1, a surface treatment liquid 4 having the following composition was heated to 65 ° C., and sprayed 3 times at intervals of 2 seconds for 6 seconds. Went (total 2
2 seconds). After the treatment, it was washed with water and dried under the same conditions as in Example 1. Surface treatment solution 4 75% phosphoric acid (H ₃ PO ₄ ) 1.5 g / l (PO ₄ ion: 1.1 g / l) Sodium pyrophosphate 5.0 g / l (P ₂ O ₇ ion: (Na ₄ P ₂ O ₇ .10H ₂ O) 2.0 g / l) Water-soluble polymer 1 4.0 g / l (solid content) pH 2.5 (adjusted with nitric acid) The above water-soluble polymer 1 is the same as in Example 1.

Example 5 After cleaning an aluminum DI can under the same conditions as in Example 1, a surface treating solution 5 having the following composition was heated to 60 ° C. and immersed in the solution for 30 seconds. After the treatment, water washing under the same conditions as in Example 1,
Dried. Surface treatment liquid 5 75% phosphoric acid (H ₃ PO ₄ ) 30.0 g / l (PO ₄ ion: 21.6 g / l) Sodium tripolyphosphate 1.2 g / l (P ₃ O ₁₀ ion: (Na ₅ P ₃ O ₁₀ ) 0.8 g / liter) Water-soluble polymer 1 2.0 g / liter (solid content) pH 3.5 (adjusted with sodium hydroxide) The above water-soluble polymer 1 is the same as in Example 1.

Example 6 After cleaning an aluminum DI can under the same conditions as in Example 1, a surface treatment liquid 6 having the following composition was heated to 60 ° C., and sprayed twice at 5 second intervals for 5 seconds ( (15 seconds in total). After the treatment, it was washed with water and dried under the same conditions as in Example 1. Surface treatment solution 6 75% phosphoric acid (H ₃ PO ₄ ) 10.0 g / l (PO ₄ ion: 7.2 g / l) Sodium pyrophosphate 3.0 g / l (P ₂ O ₇ ion: (Na ₄ P ₂ O ₇ · 10H ₂ O) 1.2 g / l) Water-soluble polymer 2 2.0 g / l (solid content) pH 5.0 (adjusted with sodium hydroxide) However, the water-soluble polymer 2 is represented by the formula (I) ), N = 5 X ¹ , X ² = —C ₂ H ₅ Z = —CH ₂ N (CH ₂ CH ₂ OH) ₂ average Z group substitution number = 1.0

Example 7 After cleaning an aluminum DI can under the same conditions as in Example 1, a surface treating solution 7 having the following composition was heated to 60 ° C. and immersed in the solution for 30 seconds. After the treatment, water washing under the same conditions as in Example 1,
Dried. Surface treatment solution 7 75% phosphoric acid (H ₃ PO ₄ ) 10.0 g / l (PO ₄ ion: 7.2 g / l) Sodium pyrophosphate 3.0 g / l (P ₂ O ₇ ion: (Na ₄ P ₂ O ₇ .10H ₂ O) 1.2 g / l) Water-soluble polymer 3 2.0 g / l (solid content) pH 4.0 (adjusted with sodium hydroxide) However, the water-soluble polymer 3 is represented by the formula ( In I), n = 2 X ¹ , X ² = —C ₂ H ₅ Z = —CH ₂ N (CH ₂ CH ₂ CH ₂ OH) ₂ average Z group substitution number = 0.6

Comparative Example 1 After cleaning an aluminum DI can under the same conditions as in Example 1, a surface treatment liquid 8 having the following composition was heated to 60 ° C., and sprayed 5 times at intervals of 5 seconds for 4 seconds 5 times ( (For a total of 40 seconds).
After the treatment, it was washed with water and dried under the same conditions as in the example. Surface treatment liquid 8 75% phosphoric acid (H ₃ PO ₄ ) 10.0 g / l (PO ₄ ion: 7.2 g / l) Water-soluble polymer 1 2.0 g / l (solid content) pH 3.0 (sodium carbonate) The above water-soluble polymer 1 is the same as in Example 1.

Comparative Example 2 After cleaning the aluminum DI can under the same conditions as in Example 1, a surface treating solution 9 having the following composition was heated to 60 ° C. and immersed in the solution for 30 seconds. After the treatment, it was washed with water and dried under the same conditions as in the example. Surface treatment liquid 9 75% phosphoric acid (H ₃ PO ₄ ) 1.0 g / l (PO ₄ ion: 0.72 g / l) Water-soluble polymer 1 2.0 g / l (solid content) pH 7.0 (hydroxylation The above water-soluble polymer 1 is the same as in Example 1.

Comparative Example 3 After cleaning the aluminum DI can under the same conditions as in Example 1, a surface treating solution 10 having the following composition was heated to 60 ° C. and immersed in the solution for 5 seconds. After the treatment, it was washed with water and dried under the same conditions as in the example. Surface treatment liquid 10 75% phosphoric acid (H ₃ PO ₄ ) 10.0 g / l (PO ₄ ion: 7.2 g / l) Sodium pyrophosphate 1.0 g / l (P ₂ O ₇ ion: (Na ₄ P _{2 O 7 · 10H 2 O)} 0.4g / liter) water-soluble polymer 1 0.05 g / l (solids) adjusted pH 4.0 (sodium carbonate) the water-soluble polymer 1 same as example 1

Comparative Example 4 After cleaning an aluminum DI can under the same conditions as in Example 1, a surface treatment liquid 11 having the following composition was heated to 60 ° C.
It was immersed for 2 seconds. After treatment, water washing under the same conditions as in the example,
Dried. Surface treatment liquid 11 95% sulfuric acid (H ₂ SO ₄ ) 2.0 g / l (SO ₄ ion: 1.9 g / l) Sodium pyrophosphate 1.0 g / l (P ₂ O ₇ ion: (Na ₄ P _{2 O 7 · 10H 2 O) 0.4g} / liter) water-soluble polymer 1 0.05 g / l (solids) adjusted pH 3.5 (sodium carbonate) the water-soluble polymer 1 same as example 1

COMPARATIVE EXAMPLE 5 After cleaning an aluminum DI can under the same conditions as in Example 1, a surface treating solution 12 having the following composition was heated to 60 ° C.
It was immersed for 2 seconds. After treatment, water washing under the same conditions as in the example,
Dried. Surface treatment liquid 12 75% phosphoric acid (H ₃ PO ₄ ) 1.0 g / l (PO ₄ ion: 0.72 g / l) Sodium pyrophosphate 1.0 g / l (P ₂ O ₇ ion: (Na ₄ P _{2 O 7 · 10H 2 O)} 0.4g / liter) water-soluble polymer 4 2.0 g / l (solids) pH 4.0 (adjusted with sodium hydroxide) However, the water-soluble polymer 4, formula (I ), N = 5 X ¹ , X ² = —C ₂ H ₅ Z = —CH ₂ SO ₃ H average—CH ₂ SO ₃ H group substitution number = 0.6

Comparative Example 6 After cleaning an aluminum DI can under the same conditions as in Example 1, a surface treating solution 13 having the following composition was heated to 60 ° C.
It was immersed for 2 seconds. After treatment, water washing under the same conditions as in the example,
Dried. Surface treatment liquid 13 (surface treatment bath described in Japanese Patent Laid-Open No. 4-66671) 75% phosphoric acid (H ₃ PO ₄₎ 1.0g / liter (PO ₄ ion: 0.72 g / l) Sodium pyrophosphate 1 .0G / l (P ₂ O _{7 ion: (Na 4 P 2 O 7} · 10H 2 O) 0.4g / liter) water-soluble polymer 5 2.0 g / l (solids) pH 4.0 (sodium hydroxide However, the water-soluble polymer 5 was a polymer represented by the following formula (IV).

Embedded image

Comparative Example 7 After cleaning an aluminum DI can under the same conditions as in Example 1, a surface treating solution 14 having the following composition was heated to 60 ° C.
It was immersed for 2 seconds. After treatment, water washing under the same conditions as in the example,
Dried. Surface treatment liquid 14 75% phosphoric acid (H ₃ PO ₄ ) 1.0 g / l (PO ₄ ion: 0.72 g / l) Sodium pyrophosphate 1.0 g / l (P ₂ O ₇ ion: (Na ₄ P ₂ O ₇ .10H ₂ O) 0.4 g / l) Water-soluble polymer 6 2.0 g / l (solid content) pH 4.0 (adjusted with sodium hydroxide) Water-soluble water-soluble polymer 6 No. 608) was a polymer represented by the following formula (V).

Embedded image

Comparative Example 8 After cleaning the aluminum DI can under the same conditions as in Example 1, a 2% aqueous solution of a non-chromate surface treatment agent (trade name: Alodine 404, manufactured by Nippon Parkerizing Co., Ltd.) was heated to 40 ° C. Was sprayed three times at 5-second intervals for 5 seconds (25 seconds in total). After the treatment, it was washed with water and dried under the same conditions as in Example 1.

Table 1 shows the evaluation results of Examples 1 to 7 and Comparative Examples 1 to 8.

[0057]

[Table 1]

As is clear from the results shown in Table 1, Examples 1 to 3 using the surface treatment composition and the surface treatment method of the present invention were used.
In No. 7, the corrosion resistance, adhesion, and slipperiness of the surface-treated metal material were excellent. On the other hand, in Comparative Examples 1 to 8 using surface treatment liquids other than the present invention, it can be seen that all of the corrosion resistance, paint adhesion and slipperiness of the surface-treated metal material cannot be satisfied.

[0059]

As is apparent from the above description, the surface treatment composition and the surface treatment method according to the present invention allow the surface of the aluminum-containing metal material before coating to have excellent corrosion resistance and paint adhesion. A film can be formed. In addition, the surface treatment composition of the present invention is made of aluminum DI
By applying to can processing, it imparts excellent corrosion resistance and paint adhesion to the aluminum DI can surface before painting and printing, and also provides the excellent slipperiness required for smooth transfer of the can conveyor. A film can be formed. Furthermore, since the surface treatment composition used in the present invention and the surface treatment liquid used in the method of the present invention are of a non-chromium / non-fluorine type, they have an excellent effect that the load of wastewater treatment can be reduced.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁶ Identification code FI C08L 61/14 C08L 61/14 C23C 22/23 C23C 22/23 (56) References JP-A-4-66671 (JP, A) JP-A-1-177380 (JP, A) JP-A-2-282486 (JP, A) JP-A-5-117869 (JP, A) JP-A-5-186737 (JP, A) JP-A-1-177379 (JP, A) JP-A-7-278410 (JP, A) JP-A-62-260866 (JP, A) JP-A-60-248779 (JP, A) JP-A-57-149365 (JP, A) ( 58) Field surveyed (Int.Cl. ⁶ , DB name) C23C 22/00-22/86 B05D 3/10 B05D 7/14 101 B05D 7/24 302 C08G 8/04 C08L 61/14

Claims (5)

(57) [Claims] 1 to 30 parts by weight of a phosphate ion, 0.1 to 10 parts by weight of a condensed phosphate ion, and 0.1 to 20 parts by weight of a water-soluble polymer of the following general formula (I): Embedded image [However, in the formula (I), X ¹ and X ² each independently represent a hydrogen atom, a C ₁ -C ₅ alkyl group or a C ₁ -C ₅ hydroxyalkyl group, and Y ¹ and Y ² is each independently a hydrogen atom or a Z group represented by the following formulas (II) and (III): Embedded image (However, in the formulas (II) and (III), R ¹ , R ² ,
R ³ , R ⁴ and R ⁵ are each independently of the other
₁ -C ₁₀ alkyl groups, and C ₁ -C ₁₀ represents a hydroxyalkyl represents a member selected from the group), each of Z groups attached to the benzene ring of the polymer molecules, each other from the other It may be different or may be the same as the other, the average value of the Z group substitution number of each benzene ring in the polymer molecule is 0.2 to 1.0, and n is It represents an average degree of polymerization of 2 to 50. And a surface treatment composition for an aluminum-containing metal material. 2. A surface treatment liquid containing the surface treatment composition according to claim 1 and adjusted to a pH of 6.5 or less is applied to the surface of the aluminum-containing metal material at a temperature of 30 to 65 ° C. for a total of 5 times. Contact for ~ 60 seconds, rinse this contact surface with water,
A method for surface-treating an aluminum-containing metal material, comprising heating and drying. 3. The surface treatment liquid comprises 1 to 30 g / l of phosphate ions, 0.1 to 10 g / l of condensed phosphate ions, and 0.1 to 20 g / l of the above formula (I). The surface treatment method according to claim 2, comprising a water-soluble polymer and being water-soluble having a pH of 2.0 to 6.5. 4. The surface treatment method according to claim 2, wherein, in the contacting step, the aluminum-containing metal material is immersed in the surface treatment liquid for 5 to 60 seconds. 5. In the contacting step, the surface treatment liquid is sprayed twice or more at intervals of 2 to 5 seconds on the surface of the aluminum-containing metal material, and the total time of the spraying operation and the interval is 5 to 60. The surface treatment method according to claim 2 or 3, wherein the time is set to seconds.