SOLVENT-BASED PRETREATMENT AGENT HAVING IMPROVED ADHESION TO RESIDUAL ADHESIVE BEADS

Abstract

A pretreatment composition for adhesive bonds, including i) between 10 and 30 parts by weight of at least one polyurethane polymer PU containing isocyanate groups, obtained from the reaction of at least one poly(meth)acrylate polyol P and at least one polyisocyanate Il, with the proviso that the poly(meth)acrylate polyol P has an OH number of at least 35 and the polyurethane polymer PU has an NCO content of between 2.0% and 25.0% by weight, based on the polyurethane polymer PU; ii) 0.1 to 10 parts by weight of at least one organosilane OS; iii) 0 to 10 parts by weight of at least one further polyisocyanate I2; iv) 60 to 90 parts by weight of a solvent L; v) 0 to 15 parts by weight of an industrial carbon black; vi) 0 to 10 parts by weight of a fumed hydrophobic silica.

Claims

1. A pretreatment composition for adhesive bonds, comprising i) between 10 and 30 parts by weight of at least one polyurethane polymer PU containing isocyanate groups, obtained from the reaction of at least one poly(meth)acrylate polyol P and at least one polyisocyanate I1, with the proviso that the poly(meth)acrylate polyol P has an OH number of at least 35 and the polyurethane polymer PU has an NCO content of between 2.0% and 25.0% by weight, based on the polyurethane polymer PU; ii) 0.1 to 10 parts by weight of at least one organosilane OS; iii) 0 to 10 parts by weight of at least one further polyisocyanate I2; iv) 60 to 90 parts by weight of a solvent L; v) 0 to 15 parts by weight of an industrial carbon black; vi) 0 to 10 parts by weight of a fumed hydrophobic silica.

2. The pretreatment composition as claimed in claim 1, wherein the polyurethane polymer PU has a residual content of unreacted polyisocyanate I1 of <0.5% by weight, based on the polyurethane polymer PU.

3. The pretreatment composition as claimed in claim 1, wherein the poly(meth)acrylate polyol P has an average OH functionality of 3.5 to 4.5 and/or an average molecular weight M.sub.n, measured by GPC against polystyrene, of 1000 to 4000 g/mol.

4. The pretreatment composition as claimed in claim 1, wherein the organosilane OS comprises at least one hydrolyzable alkoxysilane group and is selected from the group comprising aminosilanes, hydroxysilanes, epoxysilanes, mercaptosilanes, isocyanuratosilanes, reaction products of amines and epoxysilanes, reaction products of aminosilanes and epoxides, reaction products of aminosilanes and epoxysilanes, reaction products of isocyanates and aminosilanes, reaction products of isocyanates and hydroxysilanes, and mixtures, hydrolyzates, partial hydrolyzates and/or condensates of these compounds.

5. The pretreatment composition as claimed in claim 1, wherein the polyisocyanate I1 is methylene diphenyl diisocyanate (MDI), oligomeric or polymeric MDI (PMDI) or tris(p-isocyanatophenyl) thiophosphate.

6. The pretreatment composition as claimed in claim 1, wherein the pretreatment composition is free of industrial carbon black and fumed hydrophobic silica.

7. The pretreatment composition as claimed in claim 1, wherein the polyisocyanate I2 is selected from the group consisting of methylene diphenyl diisocyanate (MDI), oligomeric or polymeric MDI (PMDI), tris(p-isocyanatophenyl) thiophosphate and oligomeric or polymeric hexamethylene 1,6-diisocyanate (PHDI), and is present in the pretreatment composition in an amount of 1 to 10 parts by weight.

8. The pretreatment composition as claimed in claim 1, wherein the organosilane OS is an aminotrialkoxysilane and/or the polyisocyanate I1 is tris(p-isocyanatophenyl) thiophosphate and/or the polyisocyanate I2 is tris(p-isocyanatophenyl) thiophosphate.

9. The pretreatment composition as claimed in claim 1, wherein the solvent L is selected from the group consisting of carboxylic esters, especially methyl acetate, ethyl acetate, butyl acetate, isopropyl acetate, 1-methoxy-2-propyl acetate and 3-methoxy-n-butyl acetate, ketones, especially acetone, butanone, methyl ethyl ketone and methyl isobutyl ketone, acetals, especially ethylal, and aromatic hydrocarbons, especially toluene and ethylbenzene, and from mixtures of these solvents.

10. The pretreatment composition as claimed in claim 1, wherein a bismuth catalyst is used in the preparation of the polyurethane polymer PU.

11. The pretreatment composition as claimed in claim 1, wherein the polyurethane polymer PU is obtained: —either from the reaction of tris(p-isocyanatophenyl) thiophosphate with a poly(meth)acrylate polyol, where the poly(meth)acrylate polyol has an average OH functionality of 3.5 to 4.5; or from the reaction of methylene diphenyl diisocyanate (MDI) with a poly(meth)acrylate polyol, where the poly(meth)acrylate polyol has an average OH functionality of 3.5 to 4.5, and where the molar ratio of isocyanate groups of polyisocyanate I1 to OH groups of the poly(meth)acrylate polyol P is between 3/1 and 10/1, and where the excess polyisocyanate I1 is removed by means of distillation after the reaction.

12. A method of adhesive bonding or of sealing, comprising the steps of i) applying a pretreatment composition according to claim 1 to a substrate S1 to be adhesively bonded or sealed; ii) flashing off the pretreatment composition applied, such that the pretreatment composition forms a film on the substrate S1; iii) applying an adhesive or sealant to the film that has been formed from the pretreatment composition and is present on the substrate S1; iv) contacting the adhesive or sealant with a second substrate S2, the second substrate optionally likewise having been treated beforehand with the same or a different pretreatment composition.

13. The method as claimed in claim 12, wherein the substrate S1 comprises the residual bead of a previously partly removed, old cured adhesive, metal or painted metal, and substrate S2 comprises glass, metal, painted metal or ceramic.

14. The method as claimed in claim 12, wherein the adhesive or sealant is a polyurethane adhesive containing at least one isocyanate-comprising polyurethane prepolymer or is an adhesive based on silane-functional polymers.

15. An article, an industrial good or a means of transport, the production of which involves performing a method as claimed in claim 12.

Description

EXAMPLES

[0152] The present invention is elucidated further hereinafter via experimental examples.

Polyols P Used for the Preparation of Polyurethane Polymer PU

[0153] The polyols in table 1 were used as polyol P for the production of the illustrative isocyanate-containing polyurethane polymers PU.

TABLE-US-00001 TABLE 1 Polyols P used. Name OH (manufacturer) Category number Joncryl 963 (BASF) Poly(meth)acrylate polyol 130 Arufon UH-2000 (Toagosei) Poly(meth)acrylate polyol 20 Synthalat A-TS 3737 (Synthopol) Poly(meth)acrylate polyol 100 Setalux D A 160 (Nuplex) Poly(meth)acrylate polyol 90 Arufon UH-2041 (Toagosei) Poly(meth)acrylate polyol 120 Arufon UH-2190 (Toagosei) Poly(meth)acrylate polyol 32 Desmophen 670 BA (Covestro) Polyester polyol 145 Baycoll AD 2047 (Covestro) Polyester polyol 55 Desmpohen C 1100 (Covestro) Polycarbonate polyol 109

TABLE-US-00002 TABLE 2 Further raw materials used. Name (manufacturer) Function Chemical name Silquest A1170 Organosilane OS Bis(trimethoxysilylpropyl)amine (Momentive) Coscat 83 Catalyst Bismuth carboxylate (Vertellus) Desmodur RFE Polyisocyanate 11 Tris(p-isocyanatophenyl) (Covestro) thiophosphate (27% by weight in ethyl acetate) Ethyl acetate Solvent L Ethyl acetate (Sigma Aldrich)

Further Raw Materials Used

[0154] The raw materials of table 2 were additionally used for the production of the example compositions.

Production of Pretreatment Composition C1 (Noninventive)

[0155] To an initial charge of 57 parts by weight of Desmodur RFE in a vat was then added 43 parts by weight of Arufon UH-2000 while stirring. Thereafter, 0.01 part by weight of Coscat 83 was added. The mixture was heated to 60° C. and left to react over the course of 8 h. The reaction was stopped once the measurement of free NCO groups (determined via titration) remained stable. 34.26 parts by weight of the reaction mixture obtained was diluted with 65.74 parts by weight of ethyl acetate, and 5 parts by weight of Silquest A1170 was added to 95 parts by weight of this diluted mixture. The result was a homogeneous, clear pretreatment composition with solids content about 25%.

Production of Pretreatment Composition C2 (Inventive)

[0156] To an initial charge of 81.7 parts by weight of Desmodur RFE in a vat was then added 18.3 parts by weight of Synthalat A-TS 3737 (70% by weight in butyl acetate) while stirring. The mixture was heated to 60° C. and left to react over the course of 8 h. The reaction was stopped once the measurement of free NCO groups remained stable.

[0157] 57 parts by weight of the reaction mixture obtained was diluted with 38 parts by weight of ethyl acetate, and 5 parts by weight of Silquest A1170 was then added. The result was a homogeneous, clear pretreatment composition with solids content about 25%.

Production of Pretreatment Composition C3 (Inventive)

[0158] To an initial charge of 87 parts by weight of Desmodur RFE in a vat was then added 13 parts by weight of Setalux D A 160 (60% by weight in xylene) while stirring. The mixture was heated to 60° C. and left to react over the course of 8 h. The reaction was stopped once the measurement of free NCO groups remained stable.

[0159] 80 parts by weight of the reaction mixture obtained was diluted with 20 parts by weight of ethyl acetate. Then 5 parts by weight of Silquest A1170 was added to 95 parts by weight of this diluted mixture. The result was a homogeneous, clear pretreatment composition with solids content about 29.5%.

Production of Pretreatment Composition C4 (Inventive)

[0160] To an initial charge of 88.5 parts by weight of Desmodur RFE in a vat was then added 11.5 parts by weight of Arufon UH-2041 while stirring. The mixture was heated to 60° C. and left to react over the course of 8 h. The reaction was stopped once the measurement of free NCO groups remained stable. 56.5 parts by weight of the reaction mixture obtained was diluted with 43.5 parts by weight of ethyl acetate, and 5 parts by weight of Silquest A1170 was added to 95 parts by weight of this diluted mixture. The result was a homogeneous, clear pretreatment composition with solids content about 25%.

Production of Pretreatment Composition C5 (Noninventive)

[0161] To an initial charge of 68 parts by weight of Desmodur RFE in a vat was then added 32 parts by weight of Arufon UH-2190 while stirring. The mixture was heated to 60° C. and left to react over the course of 8 h. The reaction was stopped once the measurement of free NCO groups remained stable. 39.68 parts by weight of the reaction mixture obtained was diluted with 60.32 parts by weight of ethyl acetate, and 5 parts by weight of Silquest A1170 was added to 95 parts by weight of this diluted mixture. The result was a homogeneous, clear pretreatment composition with solids content about 25%.

Production of Pretreatment Composition C6 (Noninventive)

[0162] To an initial charge of 82 parts by weight of Desmodur RFE in a vat was then added 18 parts by weight of Desmophen 670 BA (80% by weight in butyl acetate) while stirring. The mixture was heated to 60° C. and left to react over the course of 8 h. The reaction was stopped once the measurement of free NCO groups remained stable.

[0163] 80.3 parts by weight of the reaction mixture obtained was diluted with 19.7 parts by weight of ethyl acetate, and 5 parts by weight of Silquest A1170 was added to 95 parts by weight of this diluted mixture. The result was a homogeneous, clear pretreatment composition with solids content about 30%.

Production of Pretreatment Composition C7 (Noninventive)

[0164] To an initial charge of 65 parts by weight of Desmodur RFE in a vat was then added 35 parts by weight of Baycoll AD 2047 while stirring. The mixture was heated to 60° C. and left to react over the course of 8 h. The reaction was stopped once the measurement of free NCO groups remained stable. 38.05 parts by weight of the reaction mixture obtained was diluted with 61.95 parts by weight of ethyl acetate, and 5 parts by weight of Silquest A1170 was added to 95 parts by weight of this diluted mixture. The result was a homogeneous, clear pretreatment composition with solids content about 42.5%.

Production of Pretreatment Composition C8 (Inventive)

[0165] To an initial charge of 89.12 parts by weight of Desmodur RFE in a vat was then added 10.87 parts by weight of Joncryl 963 while stirring. Thereafter, 0.01 part by weight of Coscat 83 was added. The mixture was heated to 60° C. and left to react over the course of 8 h. The reaction was stopped once the measurement of free NCO groups remained stable. 57.24 parts by weight of the reaction mixture obtained was diluted with 42.76 parts by weight of ethyl acetate, and 5 parts by weight of Silquest A1170 was added to 95 parts by weight of this diluted mixture. The result was a homogeneous, clear pretreatment composition with solids content about 23.5%.

Production of Pretreatment Composition C9 (Inventive)

[0166] 460 g of Joncryl® 963 and 540 g of diphenylmethane 4,4′-diisocyanate (Desmodur® 44 MC L, from Covestro) were reacted by a known method at 80° C. to give a poly(meth)acrylate urethane polymer having an NCO content of 14.0% by weight, a viscosity of 14.7 Pa.Math.s at 20° C. and a monomeric diphenylmethane 4,4′-diisocyanate content of about 33% by weight. Subsequently, the volatile constituents, especially the majority of the monomeric diphenylmethane 4,4′-diisocyanate, were removed by distillation in a short-path evaporator (jacket temperature 180° C., pressure 0.1 to 0.005 mbar, condensation temperature 47° C.). The poly(meth)acrylate urethane polymer thus obtained had an NCO content of 4.8% by weight, a viscosity of 50.7 Pa.Math.s at 60° C. and a monomeric diphenylmethane 4,4′-diisocyanate content of 0.12% by weight.

[0167] 15.0 parts by weight of the reaction mixture obtained was diluted with 85.0 parts by weight of ethyl acetate, and 5 parts by weight of Silquest A1170 was added to 95 parts by weight of this diluted mixture. The result was a homogeneous, clear pretreatment composition with solids content about 37%.

Production of Pretreatment Composition C10 (Noninventive)

[0168] To an initial charge of 89.12 parts by weight of Desmodur RFE in a vat was then added 10.87 parts by weight of Joncryl 963 while stirring. Thereafter, 0.01 part by weight of Coscat 83 was added. The mixture was heated to 60° C. and left to react over the course of 8 h. The reaction was stopped once the measurement of free NCO groups remained stable. 57.24 parts by weight of the reaction mixture obtained was diluted with 42.76 parts by weight of ethyl acetate. The result was a homogeneous, clear pretreatment composition with solids content about 20%.

[0169] Pretreatment compositions C1 to C10 were placed into tightly sealable glass bottles and, after storage at room temperature for 1 day, used for the adhesion tests.

Production of Pretreatment Composition C11 (Noninventive)

[0170] To an initial charge of 80 parts by weight of Desmodur RFE in a vat was then added 20 parts by weight of Desmophen C 1100 while stirring. Thereafter, 0.01 part by weight of Coscat 83 was added. The mixture was heated to 60° C. and left to react over the course of 8 h. The reaction was stopped once the measurement of free NCO groups remained stable. 96 parts by weight of the reaction mixture obtained was diluted with 55 parts by weight of ethyl acetate. The result was a homogeneous, clear pretreatment composition with solids content about 29%.

Production of Pretreatment Composition C12 (Noninventive)

[0171] To an initial charge of 88 parts by weight of Desmodur RFE in a vat was then added 12 parts by weight of Desmophen C 1100 while stirring. Thereafter, 0.01 part by weight of Coscat 83 was added. The mixture was heated to 60° C. and left to react over the course of 8 h. The reaction was stopped once the measurement of free NCO groups remained stable. 96 parts by weight of the reaction mixture obtained was diluted with 37 parts by weight of ethyl acetate. The result was a homogeneous, clear pretreatment composition with solids content about 28%.

Adhesion Test of Adhesion Promoter Compositions

[0172] The pretreatment compositions produced were then respectively applied to an air side and a tin side of a float glass substrate, and to the ceramic substrates specified below, by means of a cellulose cloth soaked therewith (Tela®, Tela-Kimberly Switzerland GmbH).

Ceramic Substrates Used:

[0173]

TABLE-US-00003 “JM 1PBL3020” Johnson Matthey 1PBL3020 automotive glass enamel frit “Ferro 14303” Ferro 14 303 IR-7134 high durable windshield enamel frit “Ferro 14316” Ferro 14 316 IR-7363 high durable windshield enamel frit “JM IL5350” Johnson Matthey IL5350-WF734 automotive enamel frit “Ferro 14633” Ferro 14 633 IR-7355 automotive glass enamel frit “Ferro 14531” Ferro 14 531 IR-7344 automotive glass enamel frit “Ferro 14251” Ferro 14 251 automotive glass enamel frit

[0174] All float glass and ceramic substrates were sourced from Rocholl AG, Germany.

[0175] All substrates were cleaned immediately prior to application of the adhesion promoter composition by wiping using a cellulose cloth (Tela®) that had been soaked with an isopropanol/water mixture (2:1) and flashed off for at least 2 minutes prior to the application of the pretreatment composition.

[0176] After application according to the conditions in the tables (time, temperature, relative air humidity), the respective pretreatment composition was flashed off, and then a round bead of a SikaTack® Drive adhesive was applied by means of expression cartridge and nozzle. SikaTack® Drive is a one-component moisture-curable polyurethane adhesive which contains polyurethane prepolymers having isocyanate groups but no adhesion promoters and is commercially available from Sika Schweiz AG. SikaTack® Drive is an adhesive specifically used for glazing replacement bonds in vehicles.

[0177] The adhesive was tested for adhesion after a curing time of 7 days of storage in a room under standard climatic conditions (23° C., 50% rel. humidity) (“7d NC”), and after subsequent exposure to water (“7d H.sub.2O”) in water at 23° C. for 7 days, and after subsequent exposure to heat for one day at 80° C. in an oven (“1d 80° C.”), and after subsequent exposure to hot and humid conditions (“7d KPL”) for 7 days at 70° C., 100% rel. humidity.

[0178] The adhesion of the adhesive was tested using the ‘bead adhesion test’. This involves cutting into the bead at its end just above the adhesive bonding surface. The cut end of the bead is held with round-nose pliers and pulled away from the substrate. This is done by carefully rolling up the bead onto the tip of the pliers, and making a cut at right angles to the bead pulling direction down to the bare substrate. The bead pulling speed should be chosen such that a cut has to be made about every 3 seconds. The test distance must correspond to at least 8 cm. What is assessed is the adhesive remaining on the substrate after the bead has been pulled away (cohesion fracture). The adhesion properties are assessed by visual determination of the cohesive fraction of the bonding area.

[0179] The higher the proportion of cohesive failure the better the adhesive bonding. Test results with cohesion fractures of less than 70% are typically considered to be inadequate. The results are summarized in tables 3 to 7. The numbers shown in the tables describe the percentage of cohesive fracture.

[0180] Adhesion to residual adhesive beads was determined on cured and aged adhesive layers as bonding substrate. For this purpose, in each case, a commercially available polyurethane adhesive for bonding of panes (Sikaflex®-250 SV-3, from Sika Automotive Hamburg GmbH, and also Sikaflex®-250 DM-6, from Sika Automotive Hamburg GmbH, and also SikaTack® PRO, from Sika Schweiz AG) was applied in the form of a triangular bead of width about 8 mm and height about 10 mm to a glass body, covered with a silicone-coated release paper, pressed to a layer thickness of about 5 mm and cured under standard climatic conditions for 7 days, the release paper was removed and the compressed adhesive bead was aged at 80° C. for 14 days. Some substrates were additionally subjected to hot and humid conditions for 7 days. Subsequently, the cured and aged adhesive bead was cut away from the glass body down to a layer thickness of about 1 mm. In addition, an automotive paint substrate was used.

[0181] Thereafter, under standard climatic conditions, the respective pretreatment composition, as described above for the adhesion tests, was applied to the respective residual bead substrate (or automotive paint substrate) and flashed off.

[0182] The adhesive used for testing of adhesion was again SikaTack® Drive as described above. The adhesive was applied in the form of a triangular bead of width about 8 mm and height about 10 mm to strips of silicone-coated release paper. Subsequently, the triangular beads applied to the release paper were upturned and placed onto the residual adhesive bead remaining on the glass body in such a way that the release paper was on top and the composition was in contact with the residual adhesive bead. Subsequently, the composition was pressed to a layer thickness of about 5 mm and cured under standard climatic conditions for 7 d, then the release paper was removed and the adhesion of the cured composition on the residual adhesive bead was tested by making an incision into the cured composition at the narrow end just above the bond surface, holding the incised end of the composition with rounded tweezers and attempting to pull the composition away from the substrate (=residual adhesive bead). Then the composition was incised again down to the substrate, the part that had been cut away was rolled up with the rounded tweezers and an attempt was again made to pull the composition away from the substrate. In this way, the composition was cut away from the substrate by pulling. Subsequently, the fracture profile was used to assess the adhesion as described further up for the other adhesion tests.

[0183] The results of the adhesion tests of residual adhesive beads and automotive paint are shown in table 8. A datum “n/m” in the table means that this value was not measured.

TABLE-US-00004 TABLE 3 Adhesion tests on float glass and ceramic substrates. Pretreatment composition C1 (ref.) C2 C3 C2 C3 Flashoff conditions (time, temperature, rel. air humidity) 5 min, 23° C., 3 min, 23° C., Substrate Storage 50% r. h. 50% r. h. 3 min, −10° C. Float glass 7 d NC 0 100 100 100 100 (tin side) 7 d H.sub.2O 0 100 100 100 100 1 d 80° C. 0 100 100 100 100 7 d KPL 0 100 100 100 100 Float glass 7 d NC 0 100 100 100 100 (air side) 7 d H.sub.2O 0 90 100 100 100 1 d 80° C. 0 100 100 100 100 7 d KPL 0 100 100 100 100 JM 1PBL3020 7 d NC 0 100 100 100 100 7 d H.sub.2O 0 100 100 100 100 1 d 80° C. 0 100 100 100 100 7 d KPL 0 100 100 100 100 Ferro 14303 7 d NC 0 100 100 100 100 7 d H.sub.2O 0 100 100 100 100 1 d 80° C. 0 100 100 100 100 7 d KPL 0 100 100 100 100

TABLE-US-00005 TABLE 4 Adhesion tests on ceramic substrates. Pretreatment composition C1 (ref.) C2 C3 C2 C3 Flashoff conditions (time, temperature, rel. air humidity) 5 min, 23° C., 3 min, 23° C., Substrate Storage 50% r. h. 50% r. h. 3 min, −10° C. Ferro 14316 7 d NC 0 100 100 100 100 7 d H.sub.2O 0 100 100 100 100 1 d 80° C. 0 100 100 100 100 7 d KPL 0 100 100 100 100 JM IL5350 7 d NC 0 100 100 100 100 7 d H.sub.2O 0 100 100 100 100 1 d 80° C. 0 100 100 100 100 7 d KPL 0 100 100 100 100 Ferro 14633 7 d NC 0 100 100 100 100 7 d H.sub.2O 0 100 100 100 100 1 d 80° C. 0 100 100 100 100 7 d KPL 0 100 100 100 100 Ferro 14531 7 d NC 0 100 100 100 100 7 d H.sub.2O 0 100 100 100 100 1 d 80° C. 0 100 100 100 100 7 d KPL 0 100 100 100 100

TABLE-US-00006 TABLE 5 Adhesion tests on float glass and ceramic substrates. Pretreatment composition C5 C5 C5 C4 (ref.) C4 (ref.) C4 (ref.) Flashoff conditions (time, temperature, rel. air humidity) 3 min, 23° C., Substrate Storage 50% r. h. 3 min, −10° C. 10 min, −10° C. Float glass 7 d NC 100 100 100 95 100 0 (tin side) 7 d H.sub.2O 80 50 100 100 100 95 1 d 80° C. 100 100 100 100 100 100 7 d KPL 100 90 100 90 100 90 Float glass 7 d NC 100 100 100 100 100 100 (air side) 7 d H.sub.2O 80 95 100 100 100 100 1 d 80° C. 100 100 100 100 100 100 7 d KPL 100 95 100 90 100 100 JM 1PBL3020 7 d NC 100 100 100 70 100 20 7 d H.sub.2O 100 70 100 10 100 0 1 d 80° C. 100 100 100 100 100 20 7 d KPL 100 50 100 100 100 80 Ferro 14303 7 d NC 100 0 100 20 100 20 7 d H.sub.2O 100 20 100 10 100 20 1 d 80° C. 100 100 100 10 100 100 7 d KPL 100 100 100 10 100 30

TABLE-US-00007 TABLE 6 Adhesion tests on ceramic substrates. Pretreatment composition C5 C5 C5 C4 (ref.) C4 (ref.) C4 (ref.) Flashoff conditions (time, temperature, rel. air humidity) 3 min, 23° C., Substrate Storage 50% r. h. 3 min, −10° C. 10 min, −10° C. Ferro 14316 7 d NC 100 70 100 0 100 95 7 d H.sub.2O 100 0 100 0 100 90 1 d 80° C. 100 95 100 0 100 100 7 d KPL 100 70 100 10 100 100 JM IL5350 7 d NC 100 100 100 100 100 30 7 d H.sub.2O 100 100 100 100 100 0 1 d 80° C. 100 100 100 100 100 0 7 d KPL 100 100 100 100 100 0 Ferro 14633 7 d NC 100 80 100 0 100 30 7 d H.sub.2O 100 100 100 0 100 0 1 d 80° C. 100 100 100 30 100 0 7 d KPL 100 100 100 0 100 20 Ferro 14531 7 d NC 100 80 100 100 80 100 7 d H.sub.2O 90 70 100 80 100 95 1 d 80° C. 100 100 100 100 100 100 7 d KPL 100 90 100 100 100 80

TABLE-US-00008 TABLE 7 Adhesion tests on float glass and ceramic substrates. Pretreatment composition C6 C7 C7 C10 C11 C12 (ref.) (ref.) C8 (ref.) C8 (ref.) (ref.) (ref.) Flashoff conditions (time, temperature, rel. air humidity) 10 min, 18° C., 10 min, 5° C., 10 min, 23° C., Substrate Storage 25% r. h. 80% r. h. 25% r. h. Float glass 7 d NC 0 0 100 10 100 0 0 0 (tin side) 7 d H.sub.2O 0 80 100 100 100 0 0 0 1 d 80° C. 100 100 100 100 100 0 0 0 7 d KPL 100 100 100 100 100 0 0 0 Float glass 7 d NC 80 0 100 60 100 0 0 50 (air side) 7 d H.sub.2O 0 90 100 60 100 0 0 20 1 d 80° C. 100 100 100 100 100 0 0 90 7 d KPL 100 100 100 100 100 0 0 0 Ferro 14251 7 d NC 70 0 100 40 100 0 0 0 7 d H.sub.2O 30 90 100 100 100 0 0 0 1 d 80° C. 100 100 100 100 100 0 0 0 7 d KPL 100 100 100 100 100 0 0 0

TABLE-US-00009 TABLE 8 Adhesion tests on residual adhesive beads and automotive paint. Pretreatment composition C10 C2 C3 C8 C9 (ref.) Flashoff conditions (time, temperature, rel. air humidity) Residual 5 min, 23° C., adhesive bead Storage 50% r. h. Sikaflex-250 14 d 80° C. 100 100 100 100 100 SV-3 +7 d KPL 100 100 100 100 100 Sikaflex-250 14 d 80° C. 100 100 100 100 100 DM-6 +7 d KPL 100 100 100 100 70 SikaTack PRO 14 d 80° C. 100 100 100 100 100 +7 d KPL 100 100 100 100 100 Automotive 7 d NC 100 100 100 n/m n/m paint (without 7 d H.sub.2O 100 100 100 n/m n/m residual 1 d 80° C. 100 100 100 n/m n/m adhesive bead)