EP0760870A1

EP0760870A1 - Iron phosphatisation using substituted monocarboxilic acids

Info

Publication number: EP0760870A1
Application number: EP95922451A
Authority: EP
Inventors: Karl-Dieter Brands; Melita Krause; Bernd Mayer; Thomas Molz; Annette Willer
Original assignee: Henkel AG and Co KGaA
Current assignee: Henkel AG and Co KGaA
Priority date: 1994-05-21
Filing date: 1995-05-12
Publication date: 1997-03-12
Anticipated expiration: 2015-05-12
Also published as: ES2124558T3; DK0760870T3; EP0760870B1; JPH10500452A; CA2190991A1; ATE172757T1; US5919318A; DE4417965A1; DE59504085D1; WO1995032319A1

Abstract

PCT No. PCT/EP95/01815 Sec. 371 Date Sep. 9, 1997 Sec. 102(e) Date Sep. 9, 1997 PCT Filed May 12, 1995 PCT Pub. No. WO95/32319 PCT Pub. Date Nov. 30, 1995Described are a concentrate, a working solution and a process for iron phosphating of metals, in which the solution contains nitrobenzene sulfonic acid and substituted short-chain monocarboxylic acids of the amino acid and/or hydroxycarboxylic acid type as the accelerators.

Description

"Iron Phosphating Using Substituted Monocarboxylic Acids"

The invention relates to a new phosphating solution for the so-called non-layer-forming phosphating of reactive metal surfaces, in particular surfaces made of steel, aluminum, zinc or alloys, the main component of which is at least one of the metals iron, aluminum or zinc. In the case of non-layer-forming phosphating, the metal surfaces are treated with acidic solutions (pH range between 3.5 and 6) of phosphates, as a result of which a layer of phosphates and / or oxides is formed on the metal surface, the cations of which from the metal surface and do not come from other components of the phosphating bath. This distinguishes the "non-layer-forming" iron phosphating from a "layer-forming" zinc phosphating, in which cations of the phosphating bath are built into the phosphate layer. Processes for iron phosphating are known in the prior art. They are used, for example, as a pre-treatment process before painting in those cases in which the components are not expected to be too corrosive.

In order to meet the corrosion protection requirements, it is desirable that the iron phosphate layers have a mass per unit area (layer weight) of above about 0.2 g / m * -. In principle, the corrosion protection effect increases with increasing layer weight. At higher layer weights, for example above about 0.8 g / m * - *, however, there is a risk that the layers become powdery and do not adhere firmly to the metal surface. This leads to an unacceptably poor paint adhesion. Efforts are therefore made to produce iron phosphate layers which, on the one hand, achieve a layer weight that is as high as possible, for example in the range between approximately 0.5 and approximately 1 g / m * - *, the coverings being said to simultaneously form firmly adhering layers.

It is known that the layer formation is very strongly influenced by the presence of so-called "accelerators". Such accelerators are inorganic or organic substances with an oxidizing, more rarely with a reducing effect. Inorganic accelerators are, for example Nitrates, chlorates, bromates, molybdates and tungstates. Known organic accelerators are aromatic nitro compounds such as nitrobenzenesulfonic acid, especially m-nitrobenzenesulfonic acid ("NBS"). An example of an inorganic substance with a rather reducing effect and with good accelerator properties is hydroxylamine and its salts. Phosphating baths containing such accelerator systems are known, for example, from US Pat. No. 5,137,589 and WO93 / 09266. According to the last-mentioned document, particularly good layers are produced when oxidizing and reductive accelerators are combined with one another, here, for example, hydroxylamine with organic nitro compounds, with molybdate or tungsten.

When using a molybdate accelerator, relatively thin layers (0.2 to 0.5 g / m * -) are obtained, which usually have a bluish tinge. With organic accelerators, thicker layers of up to 1 g / m * can be achieved, which generally offer significantly better corrosion protection against the penetration of rust. With phosphate layer weights over 0.5 / * ^ one speaks of a thick-layer iron phosphating, with layer weights under 0.5 g / π.2 from a thin-layer iron phosphating.

Furthermore, it is known that the formation of iron phosphate layers is favorably influenced if the phosphating solution contains chelating complexing agents for iron. According to US Pat. No. 5,137,589, gluconic acid is particularly suitable for this. CA-874944 further recommends the use of ethylenediaminetetraacetic acid, nitrilotriacetic acid, diethylenetriapentaacetic acid, citric acid, tartaric acid and glucoheptonic acid. The complexing agents mentioned have in common that they represent chelating carboxylic acids with at least 4 C atoms and with at least 3 substituents selected from carboxyl and hydroxyl groups.

Modern iron phosphating baths are expected to be able to treat not only iron surfaces but also surfaces made of zinc, aluminum and their alloys. Although no or at most very thin phosphate layers are formed on aluminum and zinc, the paint adhesion is somewhat improved by acid pickling. The influence of this so-called mixed driving style is disadvantageous of the aluminum ions going into solution, which lead to a disturbance in the formation of the iron phosphate layer even from a very low concentration. By adding fluorides to the phosphating baths, this "bath poison" can be complexed and thus rendered harmless. Adding fluoride also improves the pickling effect on aluminum surfaces. It has proven to be advantageous if the treatment solutions contain free and / or complex-bound fluoride (W093 / 09266).

EP-A-398203 shows that iron phosphating solutions can contain anionic titanium compounds, preferably in a concentration of between 0.05 and 0.2 g / l of dissolved titanium, instead of the usual accelerators.

Iron phosphating can be carried out by first cleaning the metal parts in a cleaning solution and then treating the cleaned parts in a phosphating bath. In this case, the phosphating bath itself does not have to have a cleaning effect. This procedure provides the better cleaning and phosphating results, but requires a higher number of treatment baths. Alternatively, it is possible to clean and phosphate contaminated metal parts in a bath at the same time. In this case it is necessary to add surfactants, preferably non-ionic ones, to the phosphating bath. According to WO93 / 09266, for example, ethoxylated alcohols having 12 to 22 carbon atoms, other modified aromatic or aliphatic polyethers and salts of complex organic phosphoric acid esters are suitable for this.

The object of the invention is to provide an iron phosphating solution with an accelerator system which is ecologically favorable. It was found that ecologically harmless substituted monocarboxylic acids in combination with the co-accelerator nitrobenzenesulfonic acid lead to phosphate layers which meet the technical requirements.

The invention accordingly relates to an aqueous solution for phosphating metals with a pH in the range from 3.5 to 6, containing a) 1 to 20 g / 1 of dissolved phosphate, b) 0.02 to 2 g / 1 of nitrobenzenesulfonic acid, c) water and, if desired, further auxiliaries, characterized in that the solution furthermore d) 0.01 to 2 g / 1 of one or several organic monocarboxylic acids of the general formula (I)

H

R - C - (CH) _n - C00H (I)

contains, where

R = H, CH ₃ , CH ₂ Y, C ₂ H ₅ , C ₂ H ₄ Y, C ₆ H ₅ , C ₆ H ₄ Y or C ₆ H ₃ Y ₂ ,

X and Y are independently NH or 0H and n = 0, 1 or 2.

Depending on the choice of the substituent X, the above formula (I) describes either amino acids (X = NH ₂ ) or hydroxycarboxylic acids (X = 0H). When choosing amino acids, α-amino acids are preferred. They are described by the general formula (1) in that the index n = 0. The amino acids are preferably selected from glycine, alanine, serine, phenylalanine, (hydroxyphenyl) alanine and (dihydroxyphenyl) alanine, with glycine, alanine and serine being particularly preferred.

The hydroxycarboxylic acids of the general formula (I) characterized by X = 0H are preferably selected from glycolic acid and lactic acid.

Phosphating solutions are preferably used which contain 0.1 to 0.8 g / 1, preferably 0.2 to 0.4 g / 1, of one or more carboxylic acids of the general formula (I). Particularly favorable phosphating results are achieved with phosphating solutions which contain 0.2 to 0.5 g / 1 nitrobenzenesulfonic acid. The nitrobenzenesulfonic acid ("NBS") is preferably used.

The substituted carboxylic acids described by the general formula (I) are generally optically active. For the use according to the invention, it is immaterial whether the acids are in the form of a racemate or in the R or L form.

The acids mentioned, including phosphoric acid, can be used as such or as alkali or ammonium salts. The pH of the phosphating solution must be adjusted to the effective range between about 3.5 and about 6.0. This can optionally be done by adding acid, preferably phosphoric acid, or lye, preferably sodium hydroxide solution. Under these pH conditions, the acids mentioned are in some cases in undissociated form according to their respective pK values.

The phosphating solution according to the invention can contain further auxiliaries known in the prior art. Examples include:

e) 0.05 to 3 g / 1 free and / or complex-bound fluoride. According to W093 / 09266, it is recommended that the solution contain both free and complex-bound fluoride. Examples of possible sources of free fluoride are hydrofluoric acid and alkali metal and / or ammonium fluorides, and sources of complex-bound fluoride are, for example, tetrafluoroborates, hexafluorotitanates, hexafluorozirconates, hexafluorosilicates or in each case their acids.

f) 0.1 to 6 g / 1 of a chelating carboxylic acid with at least 4 carbon atoms and at least 3 substituents selected from carboxyl and hydroxyl groups. Examples of such chelating carboxylic acids are sugar acids such as gluconic acid, polybasic hydroxycarboxylic acids such as tartaric acid and citric acid and carboxylic acids derived from tertiary amines such as ethylenediaminetetraacetic acid, Diethylenetriaminepentaacetic acid or nitrilotriacetic acid. Gluconic acid is particularly preferred, g) 0.02 to 20 mmol / l molybdate and / or tungstate. In the simplest case, these can be salts of the molybdenum acid H MoO 4 and / or the tungsten acid H ₂ WO. The anions containing tungsten or molybdenum can also be present in condensed form and can be described for molybdenum, for example, by the general formula [Mo _n 0 (3 _{n +} ι)] 2 ~.

h) 0.02 to 1 g / 1 of an anionic titanium compound according to the teaching of EP-A-398203, and / or a corresponding amount of an anionic zirconium compound, in each case based on the amount of the anions. Hexafluorotitanic acid, hexafluorozirconic acid or their alkali metal or ammonium ions are particularly suitable for this. The concentrations of the anions are preferably selected in the range from 0.05 to 0.5 g / l.

i) up to 40 g / 1, preferably 0.2 to 1 g / 1 and in particular 0.3 to 0.5 g / 1 of surfactants, preferably nonionic surfactants of the fatty alcohol ethoxylate type. Such surfactants are particularly necessary if the phosphating solution is to have a cleaning effect at the same time. Depending on the tendency of the surfactants to foam, which should preferably be as low as possible, it may be necessary to use, together with the surfactants, defoaming substances such as block copolymers of ethylene oxide and propylene oxide. Furthermore, it may be necessary, particularly in the case of higher surfactant contents, to use so-called hydrotropes for the formulation of homogeneous concentrates of the treatment solutions. Toluene, xylene or cumene sulfonates, for example, are suitable for this, the hydrotropic effect of which can be supported by the addition of water-soluble complex organic phosphoric acid esters.

k) 0.05 to 5 g / 1 nitrate.

When incorporated, the iron phosphating baths usually have iron (II) contents of up to about 25 ppm, which have a positive effect on the bathing properties. When it comes to new phosphating solutions, it is it is recommended to add iron (II) ions in the ppm range, for example by adding about 20-50 ppm iron (II) sulfate.

Phosphating solutions are further characterized by their "total acid" content, expressed in points. The total acid number is understood to mean the consumption in milliliters of 0.1 N sodium hydroxide solution in order to titrate 10 ml of the solution to the point of transition of phenolphthalein or to a pH of 8.5. Technically customary ranges of total acid are between about 3 and about 7 points, preferably between about 4 and about 6 points.

The temperatures of the treatment solutions are usually between about 30 and 70 ° C. In baths with a cleaning action, the bath temperature depends on the type and amount of soiling and on the treatment time provided. The minimum temperature depends on the foam behavior of the wetting agents used and is preferably selected above the cloud point of the wetting agents. The temperature is usually between 50 and 60 ° C. The workpieces to be treated can be sprayed with the solution or immersed in the solution. Higher layer weights are generally obtained using immersion processes. Depending on the type of application and the substrate, the required treatment times can be between 15 seconds and 10 minutes, although in practice treatment times rarely fall below 60 seconds and rarely exceed 5 minutes.

Accordingly, the invention also relates to a method for phosphating metal surfaces, preferably surfaces made of steel, zinc, aluminum or alloys, the main component of which is at least one of the metals iron, zinc or aluminum, by preferably, the surfaces with the solutions described above with a temperature between 30 and 70 ° C, for a time between 15 seconds and 10 minutes, preferably one to 5 minutes, by immersion in the solution and / or by spraying with the solution. The process parameters are preferably chosen so that phosphate layers with a layer weight in the range from 0.2 to 1 g / m * -, preferably 0.4 to 0.9 g / m * ^ and in particular 0.4 to 0.7 g / m * - can be obtained. The process can be used in particular for pretreating metal surfaces before applying an organic coating, preferably selected from the group of paints and varnishes and natural or synthetic rubbers and rubbers.

The ready-to-use phosphating solutions can be prepared on site by dissolving the individual components in the required concentration in water. However, the usual procedure is to prepare concentrates of the phosphating solutions which are diluted to the application concentration on site. Aqueous concentrates are usually adjusted so that the application concentration can be adjusted by dilution with water by a factor between 5 and 200, preferably between 20 and 100. Accordingly, the invention also includes aqueous concentrates from which the phosphating solutions described above can be obtained by appropriate dilution with water.

As an alternative to liquid-aqueous concentrates, powdered concentrates can be used. Their composition is chosen so that when the powders are dissolved in water in a concentration between 0.2 and 5% by weight, preferably between 0.5 and 3% by weight, the phosphating solutions described above are obtained.

Iron phosphating baths can be controlled and regulated on the basis of the pH value, the electrical conductivity or the total acid score.

To increase the corrosion protection of iron phosphate layers, these can be subjected to a passivating aftertreatment. Chromium-containing and chromium-free post-passivation agents are available for this. A prerequisite for the good quality of the subsequent painting is the thorough rinsing of the phosphated parts, regardless of whether they have been passivated or not. For this purpose, the parts are rinsed once or twice with process water and finally with deionized water. Examples

To check the phosphating baths, steel sheets (Stl405) were treated according to the following procedure:

1. alkaline cleaning (spraying)

Ridoline ^R 1250 E (Henkel KGaA), 70 ° C, 2 min, 1 bar, 20 g / 1

2. Rinse

3. Iron phosphating (spraying) 50 ° C, 2.5 min, 1 bar

Bath composition: see individual examples

4. Rinse

5. Rinse, demineralized water

6. Drying

7. For corrosion testing: powder coating with powder coating PE / EP 400 from Herberts, hardened at 180 ° C for 10 min.

Layer weights were determined by detaching the phosphate layer with triethanolamine in accordance with DIN 50942. A three-week salt spray test in accordance with DIN 53167 was carried out to test the corrosion resistance. The paint infiltration was measured on a cut after 21 days of testing.

Examples 1 to 6. Comparative Examples 1 to 3

The phosphating baths had the composition: 0.79% H3PO4, 85% 0.38% NaOH, 50% 0.014% Na gluconate 0.005% FeS04 x 7 H ₂ 0

Accelerator according to table 1

After adding the accelerator, the pH was adjusted to the value given in Tab. 1 with 50% sodium hydroxide solution. Examples 7 to 10

The phosphating baths had the composition

400 ppm m-nitrobenzenesulfonic acid 240 ppm lactic acid 125 ppm gluconic acid 10 ppm iron (II)

Phosphoric acid, sodium hydroxide solution: Table 2; pH: 4.5

Table 1: Quantity variation of the NBS / lactic acid accelerator system

Test ppm NBS ¹ ) ppm lactic acid pH GS2) layer weight Appearance of paint thickness

No. in the bathroom in the bathroom g / m ² (μ) hike (mm)

Cf. 1 - - 4.5 5.3 0.22 gray

Cf. 2,300 - 4.5 5.3 ^• 1.0 powder

Cf. 3 - 300 4.5 5.3 0.18 gray

Ex. 1 500 300 4.5 5.3 0.67 bluish 48 3.9

Ex. 2 400 240 4.2 3.1 0.77 bluish 52 4.5

Ex. 3 300 240 4.5 3.1 0.86 bluish 45 5.1

Ex. 4 300 180 4.5 3.1 0.68 bluish

Ex. 5 200 960 4.5 5.3 0.52 somewhat powdery

Ex. 6 400 960 4.5 3.2 1.17 powdery

1) NBS = m-nitrobenzenesulfonic acid • * -) GS = total acid (points)

Table 2: Variation of phosphate and total acid

Trial - H3PO485% NaOH 50% GS layer weight Appearance no. G / ig / ig / m ²

Ex. 7 4.6 2.2 2.5 0.77 gray-blue, firm

Ex. 8 7.9 3.8 3.7 0.84 bluish iridescent solid

Ex. 9 6.2 3.0 4.2 0.84 bluish iridescent solid

Example 10 9.3 4.47 7.2 0.59 gray little wipeable

Examples 11 to 14. Comparative Examples 4 to 6

The phosphating baths had the following composition:

0.5% phosphoric acid 75% 0.02% gluconic acid 50%

0.1% Na cumene sulfonate

0.1% P3-Tensopon ^R 0555 (nonionic surfactant mixture based on fatty alcohol ethoxylate propoxylate, 30% aqueous solution; Henkel KGaA, Düsseldorf)

0.005% FeS04 ^x ? H ₂ 0 Accelerator according to table 3

adjusted to pH = 5.0 with 50% sodium hydroxide solution.

The coating and testing was carried out as in Examples 1 to 3. The coating thickness was approximately 50 μm. Results are shown in Table 3.

Table 3: Accelerators and phosphating results

Experiment accelerator layer weight Paint infiltration,

No. g / m ² mm

Compare 4 300 ppm NBS

200 ppm hydroxylamine 0.64 2.1

Compare 5 300 ppm NBS 0.61 5.5

Compare 6 400 ppm NBS 0.64 6.5

Ex. 11 300 ppm NBS 0.56 2.1 300 ppm glycine

Ex. 12 400 ppm NBS 0.58 1.7 200 ppm glycine

Ex. 13 300 ppm NBS

200 ppm lactic acid 0.56 1.9

Ex. 14 300 ppm NBS

300 ppm lactic acid 0.58 1.7

Claims

1. Aqueous solution for phosphating metals with a pH in the range from 3.5 to 6, containing a) 1 to 20 g / 1 of dissolved phosphate, b) 0.02 to 2 g / 1 of nitrobenzenesulfonic acid, c) water and If desired, further auxiliaries, characterized in that the solution furthermore d) 0.01 to 2 g / 1 of one or more organic monocarboxylic acids of the general formula (I)

contains, where

R = H, CH ₃ , CH ₂ Y, C ₂ H ₅ , C ₂ H ₄ Y, C ₆ H ₅ , C ₆ HY or C ₆ H ₃ Y ₂ ,

X and Y are independently NH or 0H and n = 0, 1 or 2.

2. Phosphating solution according to claim 1, characterized in that in the general formula (I) n = 0 and X = NH ₂ and the alpha-amino acids characterized thereby are preferably selected from glycine, alanine, serine, phenylalanine, (hydroxyphenyl ) alanine and (dihydroxyphenyl) alanine, with glycine, alanine and serine being particularly preferred.

3. Phosphating solution according to claim 1, characterized in that in the general formula (I) X = 0H and the hydroxycarboxylic acids characterized thereby are preferably selected from glycolic acid and lactic acid. 4. phosphating solution according to one or more of claims 1 to 3, da¬ characterized in that it 0.1 to 0.8 g / 1, preferably 0.2 to 0,

4 g / 1 of one or more carboxylic acids of the general formula (I) contains.

5. phosphating solution according to one or more of claims 1 to 4, da¬ characterized in that it contains 0.2 to 0.5 g / 1 nitrobenzenesulfonic acid.

6. Phosphating solution according to one or more of claims 1 to 5, characterized in that it contains -Nitrobenzenesulfonic acid as nitrobenzenesulfonic acid.

7. phosphating solution according to one or more of claims 1 to 6, characterized in that it contains one or more of the following auxiliary substances: e) 0.05 to 3 g / 1 free and / or complex-bound fluoride, f) 0.1 to 6 g / 1 of a chelating carboxylic acid with at least four carbon atoms and at least three substituents selected from carboxyl and hydroxyl groups, g) 0.02 to 20 mmol / 1 molybdate and / or tungstate, h) 0, 02 to 1 g / 1 of an anionic titanium or zirconium compound, i) up to 40 g / 1, preferably 0.2 to 1 g / 1, in particular 0.3 to

0.5 g / 1 surfactant, k) 0.05 to 5 g / 1 nitrate.

8. Process for phosphating metal surfaces, preferably surfaces made of steel, zinc, aluminum or alloys, the main component of which is at least one of the metals iron, zinc or aluminum, by treating the surfaces with solutions according to one or more of claims 1 to 7 , preferably at a temperature between 30 and 70 ° C, for a time between 15 seconds and 10 minutes, preferably 1 to 5 minutes by immersion in the solution and / or by spraying with the solution. 9. The method according to claim 8, characterized in that phosphate layers with a layer weight in the range 0.2 to 1 g / m ² , preferably 0.4 to 0,

9 g / m ² generated.

10. The method according to one or both of claims 8 and 9 for pretreating metal surfaces before applying an organic coating, preferably selected from the group of paints and varnishes and natural or synthetic rubbers and rubbers.

11. Aqueous concentrate which, when diluted with water by a factor between 5 and 200, preferably between 20 and 100, results in a phosphate solution according to one or more of claims 1 to 7.

12. Powdery agent which, when dissolved in water in a concentration between 0.2 and 5% by weight, preferably between 0.5 and 3% by weight, gives a phosphating solution according to one or more of Claims 1 to 7 .