Aqueous corrosion protection formulation based on silanes

Abstract

The present invention relates to a composition comprising —a specific binder containing at least one cocondensate based on at least one ω-glycidyloxyalkylalkoxysilane and a bis(alkoxyalkylsilyl)amine, —water, —alcohol in an amount of less than 3% by weight, based on the composition, —at least one addition selected from the group consisting of particulate metals, metal alloys and metal compounds and —optionally at least one additive, where the pH of the composition is from 1 to 14 and the dry residue of the binder is from 1 to 50% by weight, based on the binder used, a process for the production thereof and also the use thereof for coatings, in particular for the protection of metals against corrosion.

Claims

1. A method of protecting a substrate from corrosion, comprising applying a composition to a substrate surface and curing said composition in air, wherein said composition comprises: a binder, water, alcohol in a positive amount of less than 3% by weight, based on a total weight of the composition, at least one first additive selected from the group consisting of zinc powder, zinc flake, zinc dust, a powder or a flake or a dust of zinc alloys, a zinc-bismuth alloy, an aluminum powder, an aluminum flake, a powder or a flake or a dust of aluminum alloys, a magnesium powder, a magnesium flake, and a powder or a flake of magnesium alloys, an aqueous base pH adjuster, and optionally a further additive, wherein: said composition has a pH of 7.1 to 14, a dry residue of the binder is from 1% to 50% by weight, based on a total weight of the binder, the binder comprises: a cocondensate based on an ω-glycidyloxyalkylalkoxysilane of formula I
X—Si(R.sup.2).sub.x(OR.sup.1).sub.3-x  (I), wherein X is a 2-(3,4-epoxycyclohexyl)ethyl, 1-glycidyloxymethyl, 2-glycidyloxyethyl, 3-glycidyloxypropyl or 3-glycidyloxyisobutyl group, R.sup.1 and R.sup.2 each independently are a linear or branched alkyl group comprising from 1 to 4 C atoms, and x is 0 or 1, a bis(alkoxysilylalkyl)amine of formula II
(OR.sup.1).sub.3Si-A-Si(OR.sup.1).sub.3  (II), wherein each R.sup.1 independently is a linear or branched alkyl group comprising from 1 to 4 C atoms and A is a bis-amino-functional group of formula IIa
—(CH.sub.2).sub.i—[NH(CH.sub.2).sub.f].sub.gNH[(CH.sub.2).sub.f*NH].sub.g*—(CH.sub.2).sub.i*—  (IIa), wherein i and i* each independently are an integer of 1, 2, 3 or 4, f and f* each independently are an integer of 1 or 2, and g and g* each independently are an integer of 0 or 1, and optionally, at least one further silicon compound selected from the group consisting of tetraalkoxysilane, alkylalkoxysilane, mercaptoalkylalkoxysilane, carboxyalkylalkoxysilane, aminoalkylalkoxysilane, ureidoalkylalkoxysilane, thiocyanatoalkylalkoxysilane and a silica sob; and said substrate is at least one substrate selected from the group consisting of a metal and a metal alloy.

2. The method according to claim 1, wherein the binder is obtained by a process comprising: introducing water in a molar excess, based on silanes of the formulae I and II and, optionally, on the at least one further silicon compound and adjusting to an acidic pH with addition of an organic or inorganic acid, and an optional addition of a silica sol, metering in the w-glycidyloxyalkylalkoxysilane of formula I, thereby obtaining a mixture, heating the mixture, optionally metering in further acid, metering in the bis(alkoxysilylalkyl)amine of formula II and optionally at least one further silicon compound selected from the group consisting of tetraalkoxysilane, alkylalkoxysilane, mercaptoalkylalkoxysilane, carboxyalkylalkoxysilane, aminoalkylalkoxysilane, ureidoalkylalkoxysilane and thiocyanatoalkylalkoxysilane, thereby obtaining a reaction mixture, reacting the reaction mixture, subsequently removing at least proportionately a resultant hydrolysis alcohol from the reaction mixture under reduced pressure, thereby obtaining the binder, optionally diluting the binder with water, an aqueous acid, or both, and subsequently filtering the binder.

3. The method according to claim 1, wherein a dry residue is from 1% to 50% by weight, based on the total weight of the composition.

4. The method according to claim 1, wherein an amount of the at least one first additive in the composition is from 1% to 95% by weight.

5. The method according to claim 1, wherein the further additive is selected from the group consisting of a defoamer, a thickener, a rheological assistant, a dispersion assistant, an anti-settling agent, a rust inhibitor, a wetting agent, an organic pigment, a polymer, a polymer dispersion, and catalyst for condensation and curing.

6. The method according to claim 1, wherein, based on the total weight of the composition, the further additive is at least one of a thickener of from 0% to 5% by weight, an anti-settling agent of 0% to 5% by weight, a wetting agent of 0% to 3% by weight, and a corrosion inhibitor of 0% to 1% by weight.

7. The method according to claim 1, further comprising curing said coating in air at a temperature of 16 to 26° C.

8. The method according to claim 1, wherein the composition has a pH of from 7.3 to 14.

9. The method according to claim 1, wherein the at least first additive is zinc dust.

10. The method according to claim 1, wherein the composition has a pH of 7.5 to 14.

11. The method according to claim 1, wherein the composition has a pH of 7.1 to 12.

12. The method according to claim 1, wherein the composition has a pH of 7.1 to 7.3.

13. The method according to claim 1, wherein the composition has a pH of 8.0 to 14.

Description

EXAMPLES

(1) Chemicals and Abbreviations Used:

(2) TABLE-US-00001 Trade name Description Manufacturer Dynasylan ® 3-Glycidyloxypropyltrimethoxysilane Evonik Degussa GLYMO (GLYMO) Dynasylan ® Bis(triethoxysilylpropyl)amine Evonik Degussa 1122 (Bis-AMEO) Dynasylan ® 3-Aminopropyltriethoxysilane Evonik Degussa AMEO (AMEO) Dynasylan ® Propyltrimethoxysilane (PTMO) Evonik Degussa PTMO Dynasylan ® 3-Mercaptopropyltrimethoxysilane Evonik Degussa MTMO Dynasylan ® 3-Ureidopropyltriethoxysilane in Evonik Degussa 2201 EQ methanol Si 264 3-Isocyanatopropyltriethoxysilane Evonik Degussa Dynasylan ® Tetraethoxysilane (TEOS) Evonik Degussa A Dynasylan ® Solvent-containing sol-gel system Evonik Degussa AR Köstrosol ® Silica sol, 35 nm Chemische Werke 3550 Bad Köstritz Levasil ® Silica sol, 100 nm Akzo Nobel 100S/45 Chemicals GmbH HP 1535 Silica sol, 30 nm Silco International, USA HP 5540 Silica sol, 130 nm Silco International, USA
Additions:

(3) TABLE-US-00002 Additions Manufacturer/supplier Zinc dust 3 μm Numinor MIOX Micro 30 Kärtner Montanindustrie Bayferrox Red 130 BM Harold-Scholz & Co. GmbH Zinc oxide Red Seal (STD) Numinor Sibelco SiO.sub.2 M500 S.C.R.-Sibelco N.V Aerosil ® 300 Evonik Degussa
Analytical Investigations:
Determination of pH:

(4) The pH of the reaction mixtures was determined using pH paper (special-purpose indicator pH 2.5-4.5, Merck; pH-Fix 0.0-6.0, Machery-Nagel).

(5) The pH values in the binders and the compositions formulated from them were determined alternatively using a Metrohm 826 pH mobile pH meter. The formulations were diluted 1:1 with water prior to measurement.

(6) Determination of Dry Residue (Solids Content):

(7) The solids content (also referred to as dry residue) of the aqueous silane systems was determined as follows:

(8) 1 g of the sample was weighed out into a small porcelain dish and dried to constant weight in a drying oven at 105° C.

(9) Determination of SiO.sub.2 Content:

(10) 1.0 to 5.0 g of the sample in a 400 ml glass beaker were admixed with a Kjeldahl tablet and with 20 ml of sulphuric acid and heated slowly to start with. During the heating procedure, the glass beaker was covered with a watch glass. The temperature was raised until the sulphuric acid fumed substantially and all the organic constituents were destroyed, with the solution remaining clear and light. The cold digestion solution was diluted to approximately 200 ml with distilled water and briefly boiled (water at the edge of the glass beaker is allowed to flow under the acid). The residue was filtered through a white-band filter and washed with hot water until the washing water gave a pH of >4 (pH paper). The filter was dried in a platinum crucible, ashed and calcined at 800° C. for 1 hour in a muffle furnace. After having been weighed, the residue was smoked off with hydrofluoric acid, the crucible was calcined by means of a fan burner and optionally calcined again at 800° C., and, after it had cooled, was weighed. The difference between the two weighings gave the amount of SiO.sub.2.

(11) Evaluation: D×100/E=% by weight SiO2

(12) D=weight difference before and after heating with hydrofluoric acid, in mg

(13) 100=conversion to %

(14) E=initial mass in mg

(15) Determination of Free Methanol and Ethanol Content:

(16) The alcohol determination was carried out by means of GC.

(17) Column: RTX 200 (60 m)

(18) Temperature programme: 90-10-25-240-0

(19) Detector: FID

(20) Injection volume: 1.0 μl

(21) Internal standard: 2-butanol

Example 1

(22) A 2 l stirred apparatus with metering device and reflux condenser was charged under nitrogen atmosphere with 1328.26 g of water and 1 g of formic acid (HCOOH=85% by weight). 90.0 g of 3-glycidyloxypropyttrimethoxysilane (GLYMO) were metered in (pH determined after the addition=3.4) and the mixture was heated to 65° C. and stirred for 1 hour. 27.0 g of formic acid (HCOOH=85% by weight) were added, and 210.0 g of Dynasylan® 1122 were metered in via the metering device. At a pH of 4.94, stirring was carried out at 65° C. for 3 hours. Finally, at approximately 130 mbar, 362.93 g of alcohol/water mixture were removed by distillation. The gel-like batch was admixed with 400.0 g of water. The residue, cooled to room temperature, was filtered on a Seitz T-950 filter plate. The final mass of the residue was 1681.4 g.

(23) A clear, yellowish liquid having a pH of 5.6 was obtained. The product is stable on storage for at least 6 months.

(24) Dry residue: 11.82% by weight

(25) SiO.sub.2 content: n. d.

(26) Free methanol: 0.6% by weight

(27) Free ethanol: 1.5% by weight

Example 2

(28) A 2 l stirred apparatus with metering device and reflux condenser was charged under nitrogen atmosphere with 1336.0 g of water and 2 g of formic acid (HCOOH=85% by weight). 150.0 g of GLYMO were metered in (pH determined after the addition=3.0) and the mixture was heated to 65° C. and stirred for 1 hour. 19.0 g of formic acid (HCOOH=85% by weight) were added, and 150.0 g of Dynasylan® 1122 were metered in via the metering device. A further 2.94 g of formic acid (HCOOH=85% by weight) were metered in. At a pH of 3.82, stirring was carried out at 65° C. for 3 hours and a further 1.29 g of formic acid (HCOOH=85% by weight) were metered in. Finally, at a pH of 3.8 and at approximately 170 mbar, 318.07 g of alcohol/water mixture were removed by distillation. The batch was admixed with 27.67 g of water. The residue, cooled to room temperature, was filtered on a Seitz T-950 filter plate. The final mass of the residue was 1312.33 g.

(29) A clear, yellowish liquid having a pH of 4.3 was obtained. The product is stable on storage for at least 6 months.

(30) Dry residue: 14.9% by weight

(31) SiO.sub.2 content: 5.9% by weight

(32) Free methanol: 1.1% by weight

(33) Free ethanol: 1.1% by weight

Example 3

(34) A 2 l stirred apparatus with metering device and reflux condenser was charged under nitrogen atmosphere with 1338.3 g of water and 2 g of formic acid (HCOOH=85% by weight). 180.0 g of GLYMO were metered in (pH determined after the addition=2.5) and the mixture was heated to 65° C. and stirred for 1 hour. 16.7 g of formic acid (HCOOH=85% by weight) were added, and 120.0 g of bis-AMEO were metered in via the metering device. A further 1.5 g of formic acid (HCOOH=85% by weight) were metered in. At a pH of 3.8 to 4.0, stirring was carried out at 65° C. for 3 hours. Finally, at approximately 200 mbar, 342.12 g of alcohol/water mixture were removed by distillation. The batch was admixed with 74.79 g of water. The residue, cooled to room temperature, was filtered on a Seitz T-950 filter plate. The final mass of the residue was 1280.21 g.

(35) A clear, yellowish liquid having a pH of 5.0 was obtained. The product is stable on storage for at least 6 months.

(36) Dry residue: 15.7% by weight

(37) SiO.sub.2 content: 5.7% by weight

(38) Free methanol: 0.7% by weight

(39) Free ethanol: 0.5% by weight

Example 4

(40) A 2 l stirred apparatus with metering device and reflux condenser was charged under nitrogen atmosphere with 1329.2 g of water and 2 g of formic acid (HCOOH=85% by weight). 120.0 g of GLYMO were metered in (pH determined after the addition=2.5) and the mixture was heated to 65° C. and stirred for 1 hour. 25.9 g of formic acid (HCOOH=85% by weight) were added, and 180.0 g of bis-AMEO were metered in via the metering device. At a pH of 4.0, stirring was carried out at 65° C. for 3 hours. Finally, at approximately 200 mbar, 344.57 g of alcohol/water mixture were removed by distillation. The batch was admixed with 20.18 g of water. The residue, cooled to room temperature, was filtered on a Seitz T-950 filter plate. The final mass of the residue was 1304.82 g.

(41) A clear, yellowish liquid having a pH of 4.4 was obtained. The product is stable on storage for at least 6 months.

(42) Dry residue: 15.0% by weight

(43) SiO.sub.2 content: 6.1% by weight

(44) Free methanol: 0.7% by weight

(45) Free ethanol: 1.1% by weight

Example 5

(46) A 2 l stirred apparatus with metering device and reflux condenser was charged under nitrogen atmosphere with 1319.6 g of water and 2 g of formic acid (HCOOH=85% by weight). 60.0 g of GLYMO were metered in (pH determined after the addition=2.5) and the mixture was heated to 65° C. and stirred for 1 hour. 34.5 g of formic acid (HCOOH=85% by weight) were added, and 240.0 g of bis-AMEO were metered in via the metering device. At a pH of 3.8 to 4.0, stirring was carried out at 65° C. for 3 hours. Finally, at approximately 200 mbar, 356.64 g of alcohol/water mixture were removed by distillation. The batch was admixed with 95.71 g of water, in order to achieve the theoretical solids content of 15%. However, the viscosity was so high that dilution was carried out additionally with 272.2 g of water to a solids content of approximately 10%. The residue, cooled to room temperature, was filtered on a Seitz T-950 filter plate. The final mass of the residue was 1472.29 g.

(47) A clear, yellowish liquid having a pH of 4.4 was obtained. The product is stable on storage for at least 6 months.

(48) Dry residue: 10.4% by weight

(49) SiO.sub.2 content: 4.3% by weight

(50) Free methanol: 0.2% by weight

(51) Free ethanol: 0.6% by weight

Example 6

(52) A 2 l stirred apparatus with metering device and reflux condenser was charged under nitrogen atmosphere with 1346.3 g of water and 2 g of formic acid (HCOOH=85% by weight). 210.0 g of GLYMO were metered in (pH determined after the addition=2.5) and the mixture was heated to 65° C. and stirred for 1 hour. 11.73 g of formic acid (HCOOH=85% by weight) were added, and 90.0 g of bis-AMEO were metered in via the metering device. At a pH of 4.0, stirring was carried out at 65° C. for 3 hours. Finally, at approximately 180 mbar, 335.16 g of alcohol/water mixture were removed by distillation. The batch was admixed with 72.14 g of water. The residue, cooled to room temperature, was filtered on a Seitz T-950 filter plate. The final mass of the residue was 1299.86 g.

(53) A clear, yellowish liquid having a pH of 4.2 was obtained. The product is stable on storage for at least 6 months.

(54) Dry residue: 15.6% by weight

(55) SiO.sub.2 content: 5.8% by weight

(56) Free methanol: 1.1% by weight

(57) Free ethanol: 0.5% by weight

Example 7

(58) A 2 l stirred apparatus with metering device and reflux condenser was charged under nitrogen atmosphere with 1347.9 g of water and 2 g of formic acid (HCOOH=85% by weight). 240.0 g of GLYMO were metered in (pH determined after the addition=2.5) and the mixture was heated to 65° C. and stirred for 1 hour. 7.1 g of formic acid (HCOOH=85% by weight) were added, and 60 g of bis-AMEO were metered in via the metering device. At a pH of 4.0 to 4.5, stirring was carried out at 65° C. for 3 hours. In between, 3.0 g of formic acid (HCOOH=85% by weight) were metered in, to give a pH of 3.5. Finally, at approximately 180 mbar, 295.81 g of alcohol/water mixture were removed by distillation. The batch was admixed with 50.62 g of water. The residue, cooled to room temperature, was filtered on a Seitz T-950 filter plate. The final mass of the residue was 1333.38 g.

(59) A clear, yellowish liquid having a pH of 5.2 was obtained. The product is stable on storage for at least 6 months.

(60) Dry residue: 16.2% by weight

(61) SiO.sub.2 content: 5.6% by weight

(62) Free methanol: 1.4% by weight

(63) Free ethanol: 0.4% by weight

Example 8

(64) A 2 l stirred apparatus with metering device and reflux condenser was charged under nitrogen atmosphere with 1353.2 g of water and 2 g of formic acid (HCOOH=85% by weight). 270 g of GLYMO were metered in (pH determined after the addition=2.5) and the mixture was heated to 65° C. and stirred for 1 hour. 2.6 g of formic acid (HCOOH=85% by weight) were added, and 30.0 g of Dynasylan® 1122 were metered in via the metering device. At a pH of 4.3, stirring was carried out at 65° C. for 3 hours. In between, 1.1 g of formic acid (HCOOH=85% by weight) were metered in, to give a pH of 4.0. Finally, at approximately 180 mbar, 289.82 g of alcohol/water mixture were removed by distillation. The batch was admixed with 43.64 g of water and with a further 0.5 g of formic acid (HCOOH=85% by weight). The residue, cooled to room temperature, was filtered on a Seitz T-950 filter plate. The final mass of the residue was 1355.06 g.

(65) A clear, yellowish liquid having a pH of 4.8 was obtained. The product is stable on storage for at least 6 months.

(66) Dry residue: 16.2% by weight

(67) SiO.sub.2 content: 5.3% by weight

(68) Free methanol: 1.7% by weight

(69) Free ethanol: 0.2% by weight

Example 9

(70) A 2 l stirred apparatus with metering device and reflux condenser was charged under nitrogen atmosphere with 1524.8 g of water and 2 g of formic acid (HCOOH=85% by weight). 180.0 g of GLYMO were metered in (pH determined after the addition=2.0) and the mixture was heated to 65° C. and stirred for 1 hour. 15.0 g of formic acid (HCOOH=85% by weight) were added, and 105.0 g of Dynasylan® 1122 were metered in via the metering device. At a pH of 4.0, 15.0 g of n-propyltrimethoxysilane (PTMO) were added, followed by stirring at 65° C. for 3 hours. Finally, at approximately 130 mbar, 585.35 g of alcohol/water mixture were removed by distillation. The batch was admixed with 4.83 g of water and with a further 0.90 g of formic acid (HCOOH=85% by weight). The residue, cooled to room temperature, was filtered on a Seitz T-950 filter plate. The final mass of the residue was 1235.30 g. A clear, yellowish liquid having a pH of 4.5 was obtained. The product is stable on storage for at least 6 months.

(71) Dry residue: 16.8% by weight

(72) SiO.sub.2 content: 6.3% by weight

(73) Free methanol: 0.3% by weight

(74) Free ethanol: 0.1% by weight

Example 10

(75) A 2 l stirred apparatus with metering device and reflux condenser was charged under nitrogen atmosphere with 1220.0 g of water and 2 g of formic acid (HCOOH=85% by weight). 165.10 g of GLYMO were metered in (pH determined after the addition=2.5) and the mixture was heated to 65° C. and stirred for 1 hour. 15.0 g of formic acid (HCOOH=85% by weight) were added, and 105.0 g of bis-AMEO were metered in via the metering device. At a pH of 4.0, 30.0 g of PTMO were added, followed by stirring at 65° C. for 3 hours. Finally, at approximately 130 mbar, 323.13 g of alcohol/water mixture were removed by distillation. The batch was admixed with 158.76 g of water. The residue, cooled to room temperature, was filtered on a Seitz T-950 filter plate. The final mass of the residue was 1196.54 g.

(76) A clear, yellowish liquid having a pH of 4.5 was obtained. The product is stable on storage for at least 6 months.

(77) Dry residue: 15.2% by weight

(78) SiO.sub.2 content: 6.0% by weight

(79) Free methanol: 1.4% by weight

(80) Free ethanol: 0.7% by weight

Example 11

(81) A 2 l stirred apparatus with metering device and reflux condenser was charged under nitrogen atmosphere with 1193.8 g of water and 2 g of formic acid (HCOOH=85% by weight). 152.6 g of Levasil 100S/45 and subsequently 210 g of GLYMO were metered in (pH determined after the addition=3.8) and the mixture was heated to 65° C. and stirred for 1 hour. 11.75 g of formic acid (HCOOH=85% by weight) were added, and 90 g of Dynasylan® 1122 were metered in via the metering device. All in all it was necessary to add a further 4.93 g of formic acid (HCOOH=85% by weight) in order to reach a pH of 3.8. This was followed by further stirring at 65° C. for 3 hours. Finally, at approximately 180 mbar, 374.22 g of alcohol/water mixture were removed by distillation. The batch was admixed with 92 g of water. The residue, cooled to room temperature, was filtered on a paint filter. The final mass of the residue was 1279.92 g.

(82) A milkily cloudy, slightly orange liquid having a pH of 4.0 was obtained. The product is stable on storage for at least 6 months.

(83) Dry residue: 20.3% by weight

(84) SiO.sub.2 content: 9.7% by weight

(85) Free methanol: 0.8% by weight

(86) Free ethanol: 0.4% by weight

Example 12

(87) A 2 l stirred apparatus with metering device and reflux condenser was charged under nitrogen atmosphere with 1041.7 g of water and 3.63 g of formic acid (HCOOH=85% by weight). 305.0 g of Levasil® 100S/45 and subsequently 210 g of GLYMO were metered in (pH determined after the addition=3.5) and the mixture was heated to 65° C. and stirred for 1 hour. 11.79 g of formic acid (HCOOH=85% by weight) were added, and 90 g of bis-AMEO were metered in via the metering device. All in all it was necessary to add a further 6.67 g of formic acid (HCOOH=85% by weight) in order to reach a pH of 3.8. This was followed by further stirring at 65° C. for 3 hours. Finally, at approximately 120 mbar, 320.71 g of alcohol/water mixture were removed by distillation. The batch was admixed with 55.38 g of water. The residue, cooled to room temperature, was filtered on a paint filter. The final mass of the residue was 1316.62 g.

(88) A milkily cloudy liquid having a pH of 3.9 was obtained. The product is stable on storage for at least 6 months.

(89) Dry residue: 25.4% by weight

(90) SiO.sub.2 content: 13.9% by weight

(91) Free methanol: 1.0% by weight

(92) Free ethanol: 0.5% by weight

Example 13

(93) A 2 l stirred apparatus with metering device and reflux condenser was charged under nitrogen atmosphere with 954.9 g of water and 2.16 g of formic acid (HCOOH=85% by weight). 392 g of HP 1535 and subsequently 210.8 g of GLYMO were metered in (pH determined after the addition=3.0) and the mixture was heated to 65° C. and stirred for 1 hour. 11.79 g of formic acid (HCOOH=85% by weight) were added, and 90 g of bis-AMEO were metered in via the metering device. All in all it was necessary to add a further 2.58 g of formic acid (HCOOH=85% by weight) in order to reach a pH of 4.0. This was followed by further stirring at 65° C. for 3 hours. Finally, at approximately 160 mbar, 291.96 g of alcohol/water mixture were removed by distillation. The batch was admixed with 12.23 g of water and also with 1.04 g of formic acid (HCOOH=85% by weight). The residue, cooled to room temperature, was filtered on a paint filter. The final mass of the residue was 1359.80 g.

(94) A slightly yellow, milkily cloudy liquid having a pH of 4.2 was obtained. The product is stable on storage for at least 6 months.

(95) Dry residue: 25.8% by weight

(96) SiO.sub.2 content: 15.6% by weight

(97) Free methanol: 1.5% by weight

(98) Free ethanol: 0.7% by weight

Example 14

(99) A 2 l stirred apparatus with metering device and reflux condenser was charged under nitrogen atmosphere with 501.8 g of water and 1.5 g of formic acid (HCOOH=85% by weight). 171.6 g of HP 5540 and subsequently 105.7 g of GLYMO were metered in (pH determined after the addition=2.0) and the mixture was heated to 65° C. and stirred for 1 hour. 5.88 g of formic acid (HCOOH=85% by weight) were added, and 44.45 g of Dynasylan® 1122 were metered in via the metering device. It was necessary to add a further 0.98 g of formic acid (HCOOH=85% by weight) in order to reach a pH of 3.8. This was followed by further stirring at 65° C. for 3 hours. Finally, at approximately 120 mbar, 159.4 g of alcohol/water mixture were removed by distillation. The batch was admixed with 24.57 g of water and also with 0.92 g of formic acid (HCOOH=85% by weight). The residue, cooled to room temperature, was filtered on a paint filter. The final mass of the residue was 661.44 g.

(100) A milkily cloudy liquid having a pH of 4.0 was obtained. The product is stable on storage for at least 6 months.

(101) Dry residue: 25.8% by weight

(102) SiO.sub.2 content: 15.5% by weight

(103) Free methanol: 1.1% by weight

(104) Free ethanol: 0.5% by weight

Example 15

(105) A 2 l stirred apparatus with metering device and reflux condenser was charged under nitrogen atmosphere with 1150.7 g of water and 2.0 g of formic acid (HCOOH=85% by weight). 196 g of HP 1535 and subsequently 210 g of GLYMO were metered in (pH determined after the addition=2.5) and the mixture was heated to 65° C. and stirred for 1 hour. 11.73 g of formic acid (HCOOH=85% by weight) were added, and 90 g of bis-AMEO were metered in via the metering device. It was necessary to add a further 2.6 g of formic acid (HCOOH=85% by weight) in order to reach a pH of 4.0. This was followed by further stirring at 65° C. for 3 hours. Finally, at approximately 230 mbar, 321.52 g of alcohol/water mixture were removed by distillation. The batch was admixed with 42.85 g of water and also with 1.0 g of formic acid (HCOOH=85% by weight). The residue, cooled to room temperature, was filtered on a paint filter. The final mass of the residue was 1329.12 g.

(106) A milkily cloudy liquid having a pH of 4.3 was obtained. The product is stable on storage for at least 6 months.

(107) Dry residue: 20.7% by weight

(108) SiO.sub.2 content: 10.7% by weight

(109) Free methanol: 1.1% by weight

(110) Free ethanol: 0.6% by weight

Example 16

(111) A 2 l stirred apparatus with metering device and reflux condenser was charged under nitrogen atmosphere with 758.8 g of water and 2.13 g of formic acid (HCOOH=85% by weight). 588 g of HP 1535 and subsequently 210 g of GLYMO were metered in (pH determined after the addition=2.5) and the mixture was heated to 65° C. and stirred for 1 hour. 11.73 g of formic acid (HCOOH=85% by weight) were added, and 90 g of Dynasylan® 1122 were metered in via the metering device. This was followed by further stirring at 65° C. for 3 hours. Finally, at approximately 300 mbar, 306.17 g of alcohol/water mixture were removed by distillation. The batch was admixed with 25.15 g of water. The residue, cooled to room temperature, was filtered on a paint filter. The final mass of the residue was 1346.94 g.

(112) A milkily cloudy liquid having a pH of 4.2 was obtained. The product is stable on storage for at least 6 months.

(113) Dry residue: 30.8% by weight

(114) SiO.sub.2 content: 20.5% by weight

(115) Free methanol: 1.3% by weight

(116) Free ethanol: 0.6% by weight

Example 17

(117) A 2 l stirred apparatus with metering device and reflux condenser was charged under nitrogen atmosphere with 831.9 g of water and 3.0 g of formic acid (HCOOH=85% by weight). 514.5 g of HP 5540 and subsequently 210 g of GLYMO were metered in (pH determined after the addition=2.0) and the mixture was heated to 65° C. and stirred for 1 hour. 11.74 g of formic acid (HCOOH=85% by weight) were added, and 90 g of Dynasylan® 1122 were metered in via the metering device. It was necessary to add a further 1.77 g in total of formic acid (HCOOH=85% by weight) in order to reach a pH of 4.0. This was followed by further stirring at 65° C. for 3 hours. In between, 1.1 g of formic acid (HCOOH=85% by weight) were metered in, to give a pH of 4.0. Finally, at approximately 180 mbar, 314.63 g of alcohol/water mixture were removed by distillation. The batch was admixed with 38.02 g of water. The residue, cooled to room temperature, was filtered on a paint filter. The final mass of the residue was 1334.02 g.

(118) A milkily cloudy liquid having a pH of 4.3 was obtained. The product is stable on storage for at least 6 months.

(119) Dry residue: 31.0% by weight

(120) SiO.sub.2 content: 20.7% by weight

(121) Free methanol: 1.1% by weight

(122) Free ethanol: 0.5% by weight

Example 18

(123) A 2 l stirred apparatus with metering device and reflux condenser was charged under nitrogen atmosphere with 1003.7 g of water and 3.0 g of formic acid (HCOOH=85% by weight). 343 g of HP 5540 and subsequently 210 g of GLYMO were metered in (pH determined after the addition=3.0) and the mixture was heated to 65° C. and stirred for 1 hour. 11.88 g of formic acid (HCOOH=85% by weight) were added, and 90 g of bis-AMEO were metered in via the metering device. It was necessary to add a further 2.32 g of formic acid (HCOOH=85% by weight) in order to reach a pH of 4.0. This was followed by further stirring at 65° C. for 3 hours. Finally, at approximately 200 mbar, 311.97 g of alcohol/water mixture were removed by distillation. The batch was admixed with 28.71 g of water. The residue, cooled to room temperature, was filtered on a paint filter. The final mass of the residue was 1343.39 g.

(124) A milkily cloudy liquid having a pH of 4.2 was obtained. The product is stable on storage for at least 6 months.

(125) Dry residue: 25.9% by weight

(126) SiO.sub.2 content: 15.7% by weight

(127) Free methanol: 1.1% by weight

(128) Free ethanol: 0.5% by weight

Example 19

(129) A 2 l stirred apparatus with metering device and reflux condenser was charged under nitrogen atmosphere with 1175.1 g of water and 3.0 g of formic acid (HCOOH=85% by weight). 171.5 g of HP 5540 and subsequently 210 g of GLYMO were metered in (pH determined after the addition=2.0) and the mixture was heated to 65° C. and stirred for 1 hour. 11.73 g of formic acid (HCOOH=85% by weight) were added, and 90 g of bis-AMEO were metered in via the metering device. It was necessary to add a further 0.91 g of formic acid (HCOOH=85% by weight) in order to reach a pH of 4.0. This was followed by further stirring at 65° C. for 3 hours. Finally, at approximately 190 mbar, 336.96 g of alcohol/water mixture were removed by distillation. The batch was admixed with 58.03 g of water. The residue, cooled to room temperature, was filtered on a paint filter. The final mass of the residue was 1314.02 g.

(130) A cloudy, pale beige liquid having a pH of 5.0 was obtained. The product is stable on storage for at least 6 months.

(131) Dry residue: 21.2% by weight

(132) SiO.sub.2 content: 10.7% by weight

(133) Free methanol: 0.9% by weight

(134) Free ethanol: 0.5% by weight

Example 20

(135) A 2 l stirred apparatus with metering device and reflux condenser was charged under nitrogen atmosphere with 1336.11 g of water and 2.07 g of formic acid (HCOOH=85% by weight). 150 g of GLYMO were metered in and the mixture was heated to 65° C. and stirred for 1 hour. 18.21 g of formic acid (HCOOH=85% by weight) were added, and 30 g of Dynasylan® A and 120 g of Dynasylan® 1122 were metered in via the metering device. This was followed by further stirring at 65° C. for 3 hours. Finally, at approximately 140 mbar, 332.97 g of alcohol/water mixture were removed by distillation. The batch was admixed with 13.65 g of water. The residue, cooled to room temperature, was filtered on a Seitz T-950 filter plate. The final mass of the residue was 1311.58 g.

(136) A clear, yellowish liquid having a pH of 4.5 was obtained. The product is stable on storage for at least 6 months.

(137) Dry residue: 14.7% by weight

(138) SiO.sub.2 content: 6.1% by weight

(139) Free methanol: 1.3% by weight

(140) Free ethanol: 1.1% by weight

Example 21

(141) A 2 l stirred apparatus with metering device and reflux condenser was charged under nitrogen atmosphere with 1419.98 g of water and 2.04 g of formic acid (HCOOH=85% by weight). 150 g of GLYMO were metered in and the mixture was heated to 65° C. and stirred for 1 hour. 11.80 g of formic acid (HCOOH=85% by weight) were added, and 60 g of Dynasylan® A and 90 g of Dynasylan® 1122 were metered in via the metering device. This was followed by further stirring at 65° C. for 3 hours. Finally, at approximately 150 mbar, 417.63 g of alcohol/water mixture were removed by distillation. The batch was admixed with 81.99 g of water. The residue, cooled to room temperature, was filtered on a Seitz T-950 filter plate. The final mass of the residue was 1306.34 g.

(142) A clear, yellowish liquid having a pH of 4.5 was obtained. The product is stable on storage for at least 6 months.

(143) Dry residue: 13.4% by weight

(144) SiO.sub.2 content: 5.8% by weight

(145) Free methanol: 0.8% by weight

(146) Free ethanol: 0.7% by weight

Example 22

(147) A 2 l stirred apparatus with metering device and reflux condenser was charged under nitrogen atmosphere with 1525.36 g of water and 2.06 g of formic acid (HCOOH=85% by weight). 180 g of GLYMO were metered in and the mixture was heated to 65° C. and stirred for 1 hour. 15.00 g of formic acid (HCOOH=85% by weight) were added, and 15 g of Si 264 and 105 g of Dynasylan® 1122 and were metered in via the metering device. This was followed by further stirring at 65° C. for 3 hours. Finally, at approximately 130 mbar, 408.08 g of alcohol/water mixture were removed by distillation. The batch was admixed with 124.11 g of water. The residue, cooled to room temperature, was filtered on a Seitz T-950 filter plate. The final mass of the residue was 1417.98 g.

(148) A clear, yellowish liquid having a pH of 4.5 was obtained. The product is stable on storage for at least 6 months.

(149) Dry residue: 13.4% by weight

(150) SiO.sub.2 content: 5.1% by weight

(151) Free methanol: 0.9% by weight

(152) Free ethanol: 0.5% by weight

Example 23

(153) A 2 l stirred apparatus with metering device and reflux condenser was charged under nitrogen atmosphere with 1540.21 g of water and 2.06 g of formic acid (HCOOH=85% by weight). 180 g of GLYMO were metered in and the mixture was heated to 65° C. and stirred for 1 hour. 15.01 g of formic acid (HCOOH=85% by weight) were added, and 30 g of Dynasylan® 2201 and 105 g of Dynasylan® 1122 were metered in via the metering device. This was followed by further stirring at 65° C. for 3 hours. Finally, at approximately 150 mbar, 424.56 g of alcohol/water mixture were removed by distillation. The batch was admixed with 123.63 g of water. The residue, cooled to room temperature, was filtered on a Seitz T-950 filter plate. The final mass of the residue was 1433.42 g.

(154) A yellowish liquid having a pH of 4.5 was obtained. The product is stable on storage for at least 6 months.

(155) Dry residue: 13.5% by weight

(156) SiO.sub.2 content: 5.1% by weight

(157) Free methanol: 0.8% by weight

(158) Free ethanol: 0.4% by weight

Example 24

(159) A 2 l stirred apparatus with metering device and reflux condenser was charged under nitrogen atmosphere with 1525.28 g of water and 2.02 g of formic acid (HCOOH=85% by weight). 179.91 g of GLYMO were metered in and the mixture was heated to 65° C. and stirred for 1 hour. 15.01 g of formic acid (HCOOH=85% by weight) were added, and 15.84 g of Dynasylan® MTMO and 105.23 g of DS 1127 were metered in via the metering device. This was followed by further stirring at 65° C. for 3 hours. Finally, at approximately 200 mbar, 335.83 g of alcohol/water mixture were removed by distillation. The batch was admixed with 52.39 g of water. The residue, cooled to room temperature, was filtered on a Seitz T-950 filter plate. The final mass of the residue was 1491.77 g.

(160) A clear, colourless liquid having a pH of 4.5 was obtained. The product is stable on storage for at least 6 months.

(161) Dry residue: 13.5% by weight

(162) SiO.sub.2 content: 5.1% by weight

(163) Free methanol: 1.1% by weight

(164) Free ethanol: 0.6% by weight

Example 25

(165) A 2 l stirred apparatus with metering device and reflux condenser was charged under nitrogen atmosphere with 1525.68 g of water and 2.02 g of formic acid (HCOOH=85% by weight). 180.15 g of GLYMO were metered in and the mixture was heated to 65° C. and stirred for 1 hour. 15.01 g of formic acid (HCOOH=85% by weight) were added, and 29.98 g of Si 264 in methanol (1:1) and 105 g of Dynasylan® 1122 were metered in via the metering device. This was followed by further stirring at 65° C. for 3 hours. Finally, at approximately 130 mbar, 370.58 g of alcohol/water mixture were removed by distillation. The batch was admixed with 67.71 g of water. The residue, cooled to room temperature, was filtered on a Seitz T-950 filter plate. The final mass of the residue was 1474.32 g.

(166) A clear, colourless liquid having a pH of 4.5 was obtained. The product is stable on storage for at least 6 months.

(167) Dry residue: 13.6% by weight

(168) SiO.sub.2 content: 5.1% by weight

(169) Free methanol: 1.3% by weight

(170) Free ethanol: 0.6% by weight

Example 26

(171) A 2 l stirred apparatus with metering device and reflux condenser was charged under a nitrogen atmosphere with 1203.89 g of water and 3.00 g of formic acid (HCOOH=85% by weight). Then 135.68 g of Köstrosol 3550 were added rapidly and 180 g of Dynasylan® GLYMO were metered in via a metering device. The batch was heated to 65° C. and stirred at that temperature for 1 hour. 17.7 g of formic acid (HCOOH=85% by weight) were added, and 120 g of Dynasylan® 1122 were metered in via the metering device. After this, stirring was continued at 65° C. for 3 hours and an additional 1.11 g of formic acid (HCOOH=85% by weight) were added. Finally, at about 180 mbar, 340.64 g of alcohol/water were removed by distillation. The batch was admixed with 38.80 g of fully deionized (DI) water.

(172) The final mass of the residue was 1347.82 g.

(173) The batch was again distilled at approximately 180 mbar to remove 36.19 g of alcohol/water mixture, and was admixed with 51.22 g of DI water. The cooled residue was filtered on a Seitz T-950 filter plate.

(174) The final mass of the residue was 1347.82 g.

(175) A milky white liquid having a pH of approximately 4.3 was obtained.

(176) The product is stable on storage for at least 6 months.

(177) Dry residue: 20.6% by weight

(178) SiO.sub.2 content: 10.8% by weight

(179) Free methanol: 0.4% by weight

(180) Free ethanol: 0.7% by weight

Example 27

(181) A 2 l stirred apparatus with metering device and reflux condenser was charged under a nitrogen atmosphere with 1067.61 g of water and 3.00 g of formic acid (HCOOH=85% by weight). Then 271.09 g of Köstrosol 3550 were added rapidly and 180.16 g of GLYMO were metered in via a metering device. The batch was heated to 65° C. and stirred at that temperature for 1 hour.

(182) After stirring at 65° C. for 1 hour, the batch was adjusted to a pH of 3.0 with an additional 2.79 g of formic acid (HCOOH=85% by weight) and stirred again at 65° C. for 0.5 hour. Then 17.71 g of formic acid (HCOOH=85% by weight) were added and 120.06 g of Dynasylan® 1122 were metered in. After this, stirring of the batch was continued at 65° C. for 3 hours and an additional 3.21 g of formic acid (HCOOH=85% by weight) were added. Finally, at about 160 mbar, 343.80 g of alcohol/water mixture were removed by distillation. The batch was admixed with 48.91 g of fully deionized (DI) water.

(183) The cooled residue was filtered on a Seitz T-950 filter plate.

(184) The final mass of the residue was 1308.51 g.

(185) A milky white liquid having a pH of approximately 4.0 was obtained.

(186) The product is stable on storage for at least 6 months.

(187) Dry residue: 26.0% by weight

(188) SiO.sub.2 content: 15.8% by weight

(189) Free methanol: 1.0% by weight

(190) Free ethanol: 0.5% by weight

Example 28

(191) A 2 l stirred apparatus with metering device and reflux condenser was charged under a nitrogen atmosphere with 1203.54 g of water and 2.99 g of formic acid (HCOOH=85% by weight). Then 135.59 g of Köstrosol 3550 were added rapidly and 165 g of GLYMO were metered in via a metering device. The batch was heated to 65° C. and stirred at that temperature for 2 hours.

(192) Dry residue: 20.4% by weight

(193) SiO.sub.2 content: 13.6% by weight

(194) Free methanol: 1.2% by weight

(195) Free ethanol: 0.5% by weight

Example 29

(196) A 2 l stirred apparatus with metering device and reflux condenser was charged under a nitrogen atmosphere with 1203.16 g of water and 3.00 g of formic acid (HCOOH=85% by weight). Then 135.55 g of Köstrosol 3550 were added rapidly and 165 g of GLYMO were metered in via a metering device. The batch was heated to 65° C. and stirred at that temperature for 2 hours.

(197) Dry residue: 20.5% by weight

(198) SiO.sub.2 content: 11.0% by weight

(199) Free methanol: 1.5% by weight

(200) Free ethanol: 0.6% by weight

Example 30

(201) A 2 l stirred apparatus with metering device and reflux condenser was charged under a nitrogen atmosphere with 1112.88 g of water and 1.01 g of formic acid (HCOOH=85% by weight). First of all 225.49 g of Köstrosol K 1530 (pH after the addition=3.5), then 180 g of GLYMO, were metered in, and the batch was heated to 65° C. and stirred for 1 hour. Then 18.71 g of formic acid (HCOOH=85% by weight) were added, and 120 g of bis-AMEO were metered in via the metering device. At a pH of 4.0, the batch was stirred at 65° C. for 3 hours. Finally, at about 130 mbar, 321.56 g of alcohol/water mixture were removed by distillation. The batch was admixed with 20.23 g of water. The residue, cooled to RT, was filtered on a Seitz T-950 filter plate. The final mass of the residue was 1334.77 g.

(202) A liquid having a pH of 4.0 was obtained. The product is stable on storage for at least 6 months.

(203) Dry residue: 20.9% by weight

(204) SiO.sub.2 content: 10.5% by weight

(205) Free methanol: 1.2% by weight

(206) Free ethanol: 0.8% by weight

Example 31

(207) A 2 l stirred apparatus with metering device and reflux condenser was charged under nitrogen atmosphere with 1220.56 g of water and 2.02 g of formic acid (HCOOH=85% by weight). 180 g of GLYMO were metered in and the mixture was heated to 65° C. and stirred for 1 hour. 15.00 g of formic acid (HCOOH=85% by weight) were added, and 90 g of bis-AMEO were metered in via the metering device. After 15 minutes, 30.0 g of PTMO were added. At a pH of 4.0, the batch was stirred at 65° C. for 3 hours. Finally, at approximately 130 mbar, 316.39 g of alcohol/water mixture were removed by distillation. The batch was admixed with 18.68 g of water. The residue, cooled to RT, was filtered on a Seitz T-950 filter plate. The final mass of the residue was 1212.58 g.

(208) A clear, yellowish liquid having a pH of 4.0 was obtained. The product is stable on storage for at least 6 months.

(209) Dry residue: 16.9% by weight

(210) SiO.sub.2 content: 6.7% by weight

(211) Free methanol: 1.6% by weight

(212) Free ethanol: 0.6% by weight

Example 32

(213) A 2 l stirred apparatus with metering device and reflux condenser was charged under nitrogen atmosphere with 1333.02 g of water and 1.98 g of formic acid (HCOOH=85% by weight). 135.69 g of GLYMO were metered in (pH after the addition=3.0) and the mixture was heated to 65° C. and stirred for 1 hour. 20.09 g of formic acid (HCOOH=85% by weight) were then added, and 120.01 g of bis-AMEO were metered in via the metering device. After 15 minutes, 44.96 g of PTMO were added. At a pH of 3.9, the batch was stirred at 65° C. for 3 hours. Finally, at approximately 130 mbar, 344.63 g of alcohol/water mixture were removed by distillation. The batch was admixed with 45.51 g of water. The residue, cooled to RT, was filtered on a Seitz K-900 filter plate. The final mass of the residue was 1340.46 g.

(214) A clear, yellowish liquid having a pH of 3.9 was obtained. The product is stable on storage for at least 6 months.

(215) Dry residue: 14.7% by weight

(216) SiO.sub.2 content: 6.9% by weight

(217) Free methanol: 1.0% by weight

(218) Free ethanol: 0.6% by weight

Example 33

(219) A 2 l stirred apparatus with metering device and reflux condenser was charged under nitrogen atmosphere with 1324.50 g of water and 2.01 g of formic acid (HCOOH=85% by weight). 120.27 g of GLYMO were metered in (pH after the addition=3.0) and the mixture was heated to 65° C. and stirred for 1 hour. 22.01 g of formic acid (HCOOH=85% by weight) were then added, and 119.75 g of bis-AMEO were metered in via the metering device. After 15 minutes, 60.35 g of PTMO were added. At a pH of 3.9, the batch was stirred at 65° C. for 3 hours. Finally, at approximately 130 mbar, 314.81 g of alcohol/water mixture were removed by distillation. The batch was admixed with 3.59 g of water. The residue, cooled to RT, was filtered on a Seitz K-900 filter plate. The final mass of the residue was 1329.04 g.

(220) A clear, yellowish liquid having a pH of 3.9 was obtained. The product is stable on storage for at least 6 months.

(221) Dry residue: 14.8% by weight

(222) SiO.sub.2 content: 6.0% by weight

(223) Free methanol: 1.4% by weight

(224) Free ethanol: 0.8% by weight

Example 34

(225) A 2 l stirred apparatus with metering device and reflux condenser was charged under nitrogen atmosphere with 1265.70 g of water and 3.05 g of formic acid (HCOOH=85% by weight). First 133.43 g of Köstrosol 3550 were metered in (pH after the addition=3.0), then 134.93 g of GLYMO, and the mixture was heated to 65° C. and stirred for 1 hour. 21.08 g of formic acid (HCOOH=85% by weight) were added, and 119.97 g of bis-AMEO were metered in via the metering device. After 15 minutes of stirring, 44.99 g of PTMO were added. At a pH of 3.9, the batch was stirred at 65° C. for 3 hours. Finally, at approximately 130 mbar, 370.09 g of alcohol/water mixture were removed by distillation. The batch was admixed with 32.57 g of water. The residue, cooled to RT, was filtered on a Seitz K-900 filter plate. The final mass of the residue was 1340.09 g.

(226) A milkily cloudy liquid having a pH of 3.9 was obtained. The product is stable on storage for at least 6 months.

(227) Dry residue: 19.8% by weight

(228) SiO.sub.2 content: 11.0% by weight

(229) Free methanol: 1.3% by weight

(230) Free ethanol: 1.1% by weight

Example 35

(231) A 2 l stirred apparatus with metering device and reflux condenser was charged under nitrogen atmosphere with 1275.04 g of water and 1.96 g of formic acid (HCOOH=85% by weight). 120.23 g of GLYMO were metered in (pH after the addition=3.0) and the mixture was heated to 65° C. and stirred for 1 hour. 18.03 g of formic acid (HCOOH=85% by weight) were added, and first 30.12 g of Dynasylan® A were added via the metering device, and the batch was stirred until it turned from slightly cloudy to clear. Then 119.98 g of bis-AMEO were metered in. After 15 minutes, 30.08 g of PTMO were added. At a pH of 3.9, the batch was stirred at 65° C. for 3 hours. Finally, at approximately 130 mbar, 340.64 g of alcohol/water mixture were removed by distillation. The residue, cooled to RT, was filtered on a Seitz K-900 filter plate. The final mass of the residue was 1259.89 g.

(232) A clear, yellowish liquid having a pH of 3.9 was obtained. The product is stable on storage for at least 6 months.

(233) Dry residue: 17.4% by weight (for the application tests, the product was diluted with DI water to a solids content of 15% by weight)

(234) SiO.sub.2 content: 6.2% by weight

(235) Free methanol: 1.2% by weight

(236) Free ethanol: 1.2% by weight

(237) Experiments on the Stability of Aqueous Binders in the Alkaline Range

(238) TABLE-US-00003 Solids content (% pH adjusted Assessment of Binder by weight) after with aqueous stability of from addition of aqueous KOH KOH to alkalified binder Example 8 10 12 stable Example 7 10 12 stable Example 6 10 12 stable Example 3 10 12 stable Example 2 10 12 stable The pH of samples of the acidic aqueous binders from Examples 2, 3, 6, 7 and 8 was adjusted to pH 12 using a 10% strength aqueous KOH solution. For this, alkali solution was added rapidly. The examples marked in the table as “stable” were stable at the stated pH for at least 1 week.

APPLICATION EXAMPLES

(239) 1. Cleaning of the R-36 Steel Test Panels Made of DC01 C290, 152×76×0.8 mm (Rocholl)

(240) The steel test panels were cleaned with an organic solvent (ethyl acetate) and then placed into an alkaline cleaning bath (composition: 10.0 g/l S 5610 (Chemetal), pH 11.5, 60° C., 35 seconds). Following alkaline cleaning, the metal substrates were rinsed with DI water. The excess water was blown from the surface using a compressed-air gun.

(241) 2. Corrosion Investigations

(242) The corrosion tests (also referred to for short as NSS) were carried out in a salt spray mist (testing according to DIN 50021-SS).

(243) The cross-cut tests were carried out in accordance with EN ISO 2409.

(244) 3. Additions Used for the Application Examples

(245) Zinc dust “superfine” 3 micron (Numinor) (zinc powder) MIOX MICRO 30 (Kärntner Montanindustrie) (natural micaceous iron ore) Bayferrox Red 130 BM (Harald-Scholz Co. & GmbH) (org. colourant with Fe.sub.2O.sub.3) Zinc Oxide Red Seal (NUMINOR) (zinc oxide) Sikron M500 (SIBELCO, Benelux) (crystalline silica dust, SiO.sub.2 powder)
4. Binders Used for the Comparative Application Examples

(246) Binders used for the application examples were as follows:

(247) TABLE-US-00004 Binder 1 reproduced according to Example 3 from WO2006/079516 (comparative composition) dry residue 16.2% by weight Binder 2 Dynasylan ® AR (comparative composition, solvent-containing) dry residue 27.3% by weight Binder 3 from Example 6 (70% GLYMO) dry residue 15.6% by weight Binder 4 from Example 2 (50% GLYMO) dry residue 14.9% by weight Binder 5 from Example 9 (60% GLYMO) dry residue 16.8% by weight Binder 6 from Example 30 dry residue 20.9% by weight Binder 7 from Example 31 dry residue 15.0% by weight Binder 8 from Example 35 dry residue 17.4% by weight
5. Additions and preparation of additions B and C in an AM 501 T universal mixing machine from Hauschild Addition mixture B: 12.06% by weight Zinc Oxide Red Seal, 12.08% by weight Bayferrox Red 130 BM, 35.86% by weight MIOX MICRO 30, 40.00% by weight zinc dust 3 micron Addition mixture C: 43.13% by weight Sikron M500, 43.13% by weight zinc dust 3 micron, 13.74% by weight MIOX MICRO 30 Addition M: Sikron M500 Addition D: Aerosil® 300

(248) Additions B and C were prepared in a universal mixing machine (type AM 501 T from Hauschild). Addition mixtures B and C were each mixed in the universal mixing machine at 3000 rpm for 3×30 seconds.

(249) 6. Preparation of the Compositions for the Comparative Application Examples in the Universal Mixing Machine (Type AM 501 T from Hauschild)

(250) The addition or addition mixture in question was dispersed into the respective binder at 3000 rpm for 3×20 seconds; see Tables 1 and 2.

(251) TABLE-US-00005 TABLE 1 Compositions prepared for comparative examples (the pH of the compositions was measured in each case 30 minutes following preparation): Compar- Mass of Mass of Binder:addi- ative binder addition tion weight examples Binder Addition [g] [g] ratio pH 1 1 75 wt % B, 4.0 8.0 1:2 7.1 25 wt % M 2 2 75 wt % B, 5.0 16.0 .sup. 1:3.2 7.2 25 wt % M 3 1 C 4.0 8.0 1:2 7.2 4 2 C 4.0 16.0 1:4 7.1 5 1 75 wt % B, 4.0 8.0 1:2 7.3 25 wt % M

(252) TABLE-US-00006 TABLE 2 Compositions prepared for inventive application examples (the pH of the compositions was measured in each case 30 minutes following preparation): Appli- cation Mass of Mass of Binder:addi- exam- binder addition tion weight ples Binder Addition [g] [g] ratio pH 1 3 75 wt % B, 4.0 8.0 1:2 7.1 25 wt % M 2 4 C 4.0 8.0 1:2 7.2 3 5 75 wt % B, 4.0 8.0 1:2 7.1 25 wt % M 4 4 72.5 wt % B, 4.0 8.0 1:2 7.3 22.5 wt % M, 5 wt % D 5 6 75 wt % B, 4.0 10.0 .sup. 1:2.5 7.1 25 wt % M 6 7 75 wt % B, 4.0 10.0 .sup. 1:2.5 7.2 25 wt % M 7 8 75 wt % B, 4.0 10.0 .sup. 1:2.5 7.1 25 wt % M
7. Coating of the Cleaned Steel Test Panels

(253) The formulations or compositions prepared in accordance with Tables 1 and 2 were applied to the prepared steel test panels—cf. item 1—in a wet film thickness of 80 μm, using a four-way film applicator.

(254) After coating, the plates were dried at 20° C. for 24 hours and scribed.

(255) The adhesion of the coated substrates was tested by means of a cross-cut test.

(256) Results of cross-cut (EN ISO 2409) after 24 hours' curing at 20° C.:

(257) Comparative Example 1: 1

(258) Comparative Example 2: 1

(259) Application Example 1: 1

(260) Comparative Example 3: 0

(261) Comparative Example 4: 1

(262) Application Example 2: 1

(263) Comparative Example 5: 2

(264) Application Example 3: 0

(265) Application Example 4: 1

(266) In addition, the coated and scribed substrates were tested for corrosion resistance in a salt spray mist (DIN 50021-SS) and assessed.

(267) Results after 26 hours' salt spray testing (cf. also Table 3):

(268) Comparative Example 1: corrosion at the scribe and partially over the surface

(269) Comparative Example 2: largely corrosion-free

(270) Application Example 1: largely corrosion-free

(271) Comparative Example 3: corrosion at the scribe and over the surface

(272) Comparative Example 4: delaminations of the coating with corrosion

(273) Application Example 2: largely corrosion-free

(274) Results after 150 hours in the salt spray mist (cf. also Table 3):

(275) Comparative Example 5: corrosion at the scribe and partially over the surface

(276) Application Example 3: no corrosion at the scribe or over the surface

(277) Application Example 4: corrosion at the scribe and partially over the surface

(278) The sample from Application Example 3 was coated with a 2-component epoxy resin: Standox, EP primer-surfacer and Standox EP hardener. Mixing ratio 2:1 (according to specification). The coating system was applied using a bar applicator (80 μm wet film thickness, ˜30 μm dry film thickness) and cured at 20° C. for 24 hours. A comparative sample (steel panel cleaned only) was likewise coated.

(279) Cross-cut sample 1 (Application Example 3+epoxy resin coating): 0

(280) Cross-cut sample 2 (steel panel+epoxy resin coating): 0

(281) Both samples were scribed with a 1 mm scorer and investigated for corrosion in a salt spray mist. After 200 hours, sample 2 showed massive corrosion at the scribe and delaminations, while sample 1 was corrosion-free even at the scribe.

(282) The results from the application investigations are summarized once again in Table 3 below, since corresponding, suitable pictures can unfortunately not be reproduced in patent specifications.

(283) TABLE-US-00007 TABLE 3 Compilation of the results from the performance experiments before and after salt spray testing Corrosion test: Before neutral salt spray Appli- Compar- corrosion test test to DIN 50021-SS cation ative cross-cut to Evalu- Number Example Example Binder EN ISO 2409 .sup.1) ation .sup.2) of hours — 1 1 1 0 26 h — 2 2 1 + 26 h 1 — 3 1 + 26 h — 3 1 0 −− 26 h — 4 2 1 − 26 h 2 — 4 1 + 26 h — 5 1 2 0 150 h 3 — 5 0 ++ 150 h 4 — 4 1 0 150 h 5 — 6 1 + 150 h 6 — 7 4 0 250 h 7 — 8 3 0 135 h .sup.1) Cross-cut after 24 hours' curing at 20° C. of the coated sample panels .sup.2) Evaluation: ++ no corrosion at the scribe or over the surface. + largely corrosion-free at the scribe and over the surface. 0 corrosion at the scribe and partially over the surface. − delaminations of the coatings with corrosion. −− severe corrosion at the scribe and over the surface.
To Summarize:

(284) Comparative Examples 1 and 2 and Application Example 1 after 26 hours in the salt spray mist:

(285) Comparative Example 1 shows corrosion at the scribe and partially over the surface after just 26 hours. In contrast, Application Comparative Example 2 and Application Example 1 are without scribe corrosion.

(286) Comparative Examples 3 and 4 and Application Example 2 after 26 hours in the salt spray mist:

(287) Comparative Example 3 shows corrosion at the scribe and over the surface after 26 hours in the salt spray mist, whereas Application Comparative Example 4 exhibits only some corrosion at the scribe, although some instances of delamination can be observed. The best results are shown by Application Example 2. There is no determinable corrosion at the scribe.

(288) Comparative Example 5 and Application Examples 3 and 4 after 150 hours in the salt spray mist:

(289) Comparative Example 5 and Application Example 4 show corrosion at the scribe after 150 hours in the salt spray mist, whereas Application Example 3 is entirely corrosion-free at the scribe after 150 hours.

(290) Application Example 5 shows no scribe corrosion after 28, 90 or 150 hours. Over the surface, however, a slight discolouration can be observed.

(291) Application Example 6 shows no scribe corrosion after 17 hours, partial scribe corrosion after 150 hours and almost full-depth scribe corrosion after 250 hours. The surface, however, is corrosion-free.

(292) Application Example 7 shows no scribe corrosion after 19 hours in the salt spray mist. After 135 hours, however, full-depth corrosion at the scribe can be determined.