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Functionalized phenol-formaldehyde resin and method for treating metallic surfaces

a functionalized, phenol-formaldehyde technology, applied in the direction of liquid surface applicators, anti-corrosion paints, coatings, etc., can solve the problems of phosphate waste accumulation in the phosphate step, high cost of pre-treatment plants, and inability to replace phosphate, etc., to achieve the effect of improving corrosion prevention and/or adhesion

Inactive Publication Date: 2007-01-25
HENKEL KGAA
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Benefits of technology

The present invention provides new, functionalized polymers that can be used for surface treatment of bare metal surfaces or metal surfaces carrying a conversion layer. These polymers improve corrosion prevention and adhesion, and can be applied in the form of an aqueous solution or emulsion. The polymers contain a phenolic component, an aromatic hydroxycarboxylic acid, and imidazole. The molar ratio of the phenolic component to the aromatic hydroxycarboxylic acid and imidazole is important, with a ratio of at least 1:1 to 10:1. The polymers can be produced using a process involving the addition of an aqueous aldehyde solution containing a phenol-aldehyde resin, followed by mixing for 10 to 100 hours at a temperature between 40 and the boiling point. The invention also provides an aqueous treatment solution containing the functionalized phenol polymers for improving the surface treatment of metal surfaces.

Problems solved by technology

Accordingly, the pre-treatment before painting requires several treatment steps which, in turn, necessitate a correspondingly extensive and hence expensive pre-treatment plant.
In addition, waste containing heavy metals accumulates in the phosphating step and has to be expensively disposed of.
However, none of these alternative processes has so far been able to replace phosphating as a pre-treatment before painting in car manufacture.

Method used

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Examples

Experimental program
Comparison scheme
Effect test

example 1

Conversion Process with Modified Resins

Substrate: CRS

Process Step Sequence (Dip Application)

[0107] 1. Cleaning: Ridoline 1570, 2%; Ridosol 1237, 0.3%; 5 mins.; 55° C. [0108] 2. Rinse: water [0109] 3. Rinse: DE water [0110] 4. Conversion treatment: 180 s; 30° C. with one of the following baths: [0111] ZrF62− corresponding to 150 mg / l Zr, polymer [0112] (Table 1, 37 mg / l solids content); pH 4.0 [0113] 5. Rinse: DE water [0114] 6. Drying: compressed air [0115] 7. Painting: Polyester PES 5807 / RAL 5009 GL (TIGC-free, from IGP); [0116] ca. 60-80 μm

Corrosion Test:

Neutral Salt Spray Test SS DIN 50021, 21d

[0117] Note on evaluation of the results: the creepage values at the cut were determined from one side of the cut (in accordance with the Standard). in some test series, Comparative Example 1b with Sokalan® HP 56 was used as the reference system. this corresponded to a relative corrosion protection of 1. These “reference sheets” were included in each corrosion test series in order...

example 3

Conversion Process with Modified Resins at Different pH Values

Polymer: Phenol-Salicyclic Acid-Formaldehyde Grafted with 0.5 Part Imidazole, Based on Phenol (Ration of Phenol to Salicylic Acid 1:1)

Substrate: CRS

Process Step Sequence (Dip Application)

[0141] 1. Cleaning: Ridoline 1570, 2%; Ridosol 1237, 0.3%; 5 mins.; 55° C. [0142] 2. Rinse: water [0143] 4. Conversion treatment: 180 s; 30° C. with one of the following baths: [0144] ZrF62− corresponding to 150 mg / l Zr, Table 4 (37 mg / l polymer solids content) [0145] 5. Rinse: DE water [0146] 6Drying: compressed air [0147] 7. Painting: Polyester PES 5807 / RAL 5009 GL (TIGC-free, from IGP);

[0148] ca. 60-80 μm

TABLE 4Example 3Corrosion protectionTestpH(DIN 50021 SS, 21 d) U / 2 in mm11.81.222.02.032.22.242.42.054.02.7

example 4

Conversion process with resin: phenol-formaldehyde grafted with 0.25 part imidazole, based on phenol; different pH values.

Substrate: CRS

Process Step Sequence (Dip Application)

[0149] 1. Cleaning: Ridoline 1570, 2%; Ridosol 1237, 0.3%; 5 mins.; 55° C. [0150] 2. Rinse: water [0151] 3. Rinse: DE water [0152] 4. Conversion treatment: 180 s; 30° C. with one of the following baths: [0153] ZrF62− corresponding to 150 mg / l Zr, Table 5 (37 mg / l polymer solids content) [phenol-formaldehyde resin×0.25 imidazole][0154] 5. Rinse: DE water [0155] 6. Drying: compressed air [0156] 7. Painting: Polyester PES 5807 / RAL 5009 GL (TIGC-free, from IGP);

[0157] ca. 60-80 μm

TABLE 5Example 4Corrosion protectionTestpH(DIN 50021 SS, 21 d) U / 2 in mm11.82.024.03.2

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Abstract

The invention relates to a functionalized phenol-aldehyde resin which comprises a phenol-aldehyde condensation product, having a phenol component with no carboxyl group, and an aromatic hydroxycarboxylic acid and imidazole as constituents which is useful for corrosion-inhibiting treatment of bare or conversion-coated metal surfaces is provided. Methods of making the functionalized phenol-aldehyde resin, processes for coating metal surfaces using compositions according to the invention and products coated thereby are also included in the invention.

Description

CROSS-REFERENCE TO RELATED APPLICATIONS [0001] This application is a continuation under 35 USC Sections 365(c) and 120 of International Application No. PCT / EP2004 / 012324, filed 30 Oct. 2004 and published 7 Jul. 2005 as WO 2005 / 061570, which claims priority from German Application No. 103 58 309.2, filed 11 Dec. 2003, each of which is incorporated herein by reference in its entirety.FIELD OF THE INVENTION [0002] This invention relates to a new functionalized phenol-aldehyde resin and to the use of this or related resins for the anti-corrosion treatment of metal surfaces. The metal surfaces may be bare, i.e. non-pre-treated, metal surfaces or metal surfaces which already have a corrosion-inhibiting conversion layer. A particular feature of the invention in this regard is that no toxic chromium has to be used. BACKGROUND OF THE INVENTION [0003] Structural elements fitted together from metal sheets, such as vehicle bodies, housings of domestic appliances or metal furniture items, can be...

Claims

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Application Information

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Patent Type & Authority Applications(United States)
IPC IPC(8): C23C22/06B05D7/16C08G8/18C08G8/28C09D5/00C09D5/08C09D5/12C23C22/34C23C22/36
CPCB05D7/16B05D2202/00C23C22/361C09D5/12C23C22/34C08G8/28
Inventor QUELLHORST, HEIKEDRONIOU, PATRICKKOCH, ALINA M.LAMMERSCHOP, OLAFKUX, MICHAEL
Owner HENKEL KGAA