Aqueous adhesive composition based on epoxy resin with improved adhesion and storage stability

Abstract

An aqueous adhesion composition comprising: a) at least one dispersed solid epoxy resin (EP); b) at least one amino silane (AS); c) at least one acid (HS); d) at least one amine hardener (AH); and e) water. According to the invention, the adhesion compositions substantially improve, particularly under humid conditions, the adhesion on different substrates. The compositions are storage stable for a longer period of time and have, even after different aging states of the components, essentially no impairment in the action thereof.

Claims

1. An aqueous adhesion promoter composition, the adhesion promoter composition being formulated as a two-component composition that comprises a first component KA and a second component KB; wherein the first component KA is separate from the second component KB; the first component KA comprises: a) at least one dispersed solid epoxy resin EP, b) at least one aminosilane AS, c) at least one acid HS, and e) water; and the second component KB comprises: a) at least one amine hardener AH, b) at least one inorganic base BA, and c) water.

2. The adhesion promoter composition as claimed in claim 1, wherein the acid HS and the inorganic base BA are selected such that when the two components KA and KB are combined, the acid HS and the inorganic base BA together in water form a low-solubility salt.

3. The adhesion promoter composition as claimed in claim 1, wherein the inorganic base BA comprises at least one alkali metal hydroxide and/or alkaline earth metal hydroxide.

4. The adhesion promoter composition as claimed in claim 1, wherein the acid HS comprises one or more acids from the group of H.sub.3PO.sub.4, H.sub.2SO.sub.4 or water-soluble carboxylic acids CHS.

5. The adhesion promoter composition as claimed in claim 4, wherein the water-soluble carboxylic acid CHS comprises acetic acid.

6. The adhesion promoter composition as claimed in claim 1, wherein the aminosilane AS comprises at least one aminosilane having at least one primary and/or at least one secondary amino group and also having at least one trimethoxysilane group.

7. The adhesion promoter composition as claimed in claim 1, wherein the dispersed solid epoxy resin EP is included with a content of 15 to 35 wt %, based on the overall adhesion promoter composition.

8. The adhesion promoter composition as claimed in claim 1, wherein the amine hardener AH is included with an amine hardener content of 0.5 to 30 wt %, based on the overall adhesion promoter composition.

9. The adhesion promoter composition as claimed in claim 1, wherein the first component KA is made of: a) 75 to 95 wt % of an aqueous dispersion of at least one solid epoxy resin EP having a solids content of 50 to 60%, based on the aqueous dispersion, b) 0.5 to 2 wt % of the at least one aminosilane AS, c) 0.5 to 5 wt % of the at least one acid HS, and d) sufficient water to make the sum of the weight percentages of the individual constituents a) to d) equal to 100 wt % of the first component KA; and the second component KB is made of: a) 5 to 35 wt % of an aqueous dispersion of the at least one amine hardener AH, the at least one amine hardener AH having a solids content of 75 to 85%, based on the aqueous dispersion, b) 0.5 to 10 wt % of the at least one inorganic base BA; c) 0 to 35 wt % of carbon black and/or pigments, d) 0 to 0.5 wt % of at least one silane catalyst, e) 0 to 2 wt % of at least one wetting agent, and f) sufficient water to make the sum of the weight percentages of the individual constituents a) to f) equal to 100 wt % of the second component KB.

10. A method comprising applying a primer for adhesives, sealants or coatings with an adhesion promoter composition as claimed in claim 1.

11. A method for employing an adhesion promoter composition as claimed claim 1, at least comprising the steps of: a) mixing components KA and KB by combining the two components, and subsequently stirring and/or shaking the resultant mixture; b) applying the mixture of components KA and KB to a surface to be bonded or coated; c) flashing off the applied adhesion promoter composition until the water present has undergone at least partial evaporation; d) applying an adhesive or sealant to the bonding surface pretreated by steps a) to c).

12. An article bonded or coated, or pretreated for bonding or coating, with the aid of an adhesion promoter composition as claimed in claim 1.

13. An adhesion promoter composition that consists of a single component KAB, the single component KAB being a composition that is made of: a) at least one dispersed solid epoxy resin EP; b) at least one aminosilane AS; c) 0.1 to 5 wt % of at least one acid HS, the at least one acid HS being an acid selected from the group consisting of water-soluble carboxylic acids CHS; d) at least one amine hardener AH; and e) water.

14. The adhesion promoter composition as claimed in claim 13, wherein the single component KAB consists of: a) 35 to 50 wt % of an aqueous dispersion of at least one solid epoxy resin EP having a solids content of 50 to 60%, based on the aqueous dispersion; b) 0.25 to 1 wt % of the at least one aminosilane AS; c) 0.25 to 2.5 wt % of the at least one acid HS selected from the group consisting of water-soluble carboxylic acids CHS; d) 1 to 10 wt % of the at least one amine hardener AH, the at least one amine hardener AH having a solids content of 75 to 85%, based on the aqueous dispersion; and e) sufficient water to make the sum of the weight percentages of the individual constituents a) to e) of the single component KAB equal to 100 wt % of the adhesion promoter composition.

Description

EXAMPLES

(1) Set out hereinbelow are working examples which are intended to elucidate in more detail the invention described. Of course, the invention is not confined to these working examples described.

(2) Raw Materials Used

(3) Common chemicals which are traded as pure substances under their chemical name, such as phosphoric acid, for example, were obtained from Sigma Aldrich Switzerland. The chemicals known by a trade name are listed below. The water used was always standard laboratory deionized water.

(4) TABLE-US-00001 A-1110 3-Aminopropyltrimethoxysilane Silquest ® A-1110, Momentive Performance Materials, Germany A-1120 N-(2-Aminoethyl)-3-aminopropyltrimethoxysilane Silquest ® A-1120, Momentive Performance Materials, Germany A-1130 Diethylenetriaminopropyltrimethoxysilane Silquest ® A-1130, Momentive Performance Materials, Germany A-1170 Bis(trimethoxysilylpropyl)amine Silquest ® A-1170, Momentive Performance Materials, Germany A-187 3-Glycidyloxypropyltrimethoxysilane Silquest ® A-187, Momentive Performance Materials, Germany A-189 3-Mercaptopropyltrimethoxysilane Silquest ® A-189, Momentive Performance Materials, Germany Hydropalat 3031 Surfactant, Hydropalat ® 3031, Cognis, Germany AR555 Aqueous dispersion of a solid epoxy resin with 55% solids fraction, Ancarez ® AR555, AirProducts, USA Beckopox 623 Aliphatic polyamine adduct, aqueous dispersion with 80% solids fraction, Beckopox ® EH 623 W, Allnex, Germany Carbon black Low color furnace black, Printex ® 25, Evonik Industries, Germany Dispersant Copolymer preparation, Disperbyk ®-191, Byk Chemie, Germany Defoamer Polymer preparation, Byk ®-014, Byk Chemie, Germany Catalyst Dibutyltin dilaurate (DBTL), TIB KAT ® 218, TIB Chemicals, Germany

(5) Production of the Adhesion Promoter Compositions

(6) Production of Components KA for Two-Component Adhesion Promoters

(7) A series of inventive (KA1 to KA3) and also two noninventive (KA4 and KA5) components KA were produced. The amounts of the individual ingredients are listed in wt % in table 1. KA4 is not inventive since it contains no aminosilane AS; KA5 is not inventive since it contains no acid HS or CHS.

(8) TABLE-US-00002 TABLE 1 Inventive and noninventive components KA produced for the corresponding example compositions. All quantities in wt % are based on the overall respective component KA. KA4 KA5 KA1 KA2 KA3 (Ref.) (Ref.) AR555 89 89 89 94  90 Water — — — 2 — Acetic acid  1  1  1 — — Silane mixture ES1 — — — 4 — Silane mixture AS1 10 — — — — Silane mixture AS2 — 10 — — — Silane mixture AS3 — — 10 — — Silane mixture AS4 — — — — 10 Total (wt %) 100  100  100  100  100 

(9) The production of components KA was identical in all cases. First, AR-555 was placed in a reactor and, with stirring, the acetic acid (glacial acetic acid; Sigma Aldrich Switzerland) or the additional water (in the case of KA4) was added. Thereafter, with vigorous stirring, the respective silane mixture was added slowly. The product in all cases was a milky fluid which was homogeneous but nontransparent.

(10) Production of the Silane Mixtures

(11) A series of silane mixtures for use in component KA were produced according to the compositions in wt % indicated in table 2, based on the respective silane mixtures. These silane mixtures then either were added as inventive aminosilanes AS to the corresponding components KA, or they served as an additive for reference compositions.

(12) TABLE-US-00003 TABLE 2 Exemplary silane mixtures used in components KA. All quantities in wt % are based on the overall respective silane mixture. ES1 AS1 AS2 AS3 AS4 Water 55 70 77.5 77.5 80 H.sub.3PO.sub.4  5 15 10 — — H.sub.2SO.sub.4 — — — 10 — Potassium hydroxide — — — — 10 Hydropalat 3031 — 5 2.5 2.5 — A-1110 — 2.22 2.86 2.86 2.86 A-1120 — 2.22 2.86 2.86 2.86 A-1170 — 2.22 2.86 2.86 2.86 A-189 — 1.11 1.43 1.43 1.43 A-187 40 — — — — A-1130 — 2.22 — — — Total (wt %) 100  100 100 100 100

(13) The silane mixtures AS1 to AS4 were produced according to an identical scheme: First of all, the acid or base (where present), Hydropalat 3031, and water were premixed. The individual silanes were added slowly dropwise with stirring to this mixture at 23° C. under a nitrogen atmosphere. During the dropwise addition, care was taken to ensure that the silanes were added slowly and the solution remained clear. After all the silanes had been added, the solution was stirred for an hour. In all cases, a clear, colorless mixture was obtained. In the case of ES1, A-187 was added as the final raw material.

(14) Production of Components KB for Two-Component Adhesion Promoters

(15) A series of inventive (KB1 to KB5) and also one noninventive (KB6) components KB were produced. The amounts of the individual ingredients are listed in wt % in table 3. KB6 is not inventive since it contains no organic base BA.

(16) TABLE-US-00004 TABLE 3 Inventive and noninventive components KB produced for the corresponding example compositions. All quantities in wt % are based on the overall respective component KB. KB6 KB1 KB2 KB3 KB4 KB5 (Ref.) Beckopox 623 27.8 7.7 7.7 7.7 7.7 30.76 Water 67.7 78.15 66.75 90.64 71.4 69.24 Ca(OH).sub.2 4.5 1.15 1 — — — Ba(OH).sub.2 — — — 1.66 — — Mg(OH).sub.2 — — — — 0.8 — Carbon black — 12 24 — 20 — Dispersant — 1 0.5 — — — Defoamer — — 0.03 — 0.05 — Catalyst — — 0.02 — 0.05 — Total (wt %) 100 100 100 100 100 100

(17) The example components KB were always produced according to the following scheme: First, the amine hardener AH (Beckopox 623) was mixed with approximately half the water in a reactor, resulting in a decrease in viscosity and a greater ease in stirring. Thereafter the remainder of the water was added slowly with stirring, with the inorganic base BA dissolved therein, and also, where present, carbon black, dispersant, defoamer and catalyst dispersed therein. The mixture was subsequently stirred further for around 15 minutes until the resulting mixture was homogeneous and colorless or, if containing carbon black, was black.

(18) Production of Components KAB for One-Component Adhesion Promoters

(19) An inventive single component KAB1 and a noninventive single component KAB2 were produced. The fractions in wt % of the individual components KAB1 and KAB2 are set out in table 4. KAB2 is not inventive since no water-soluble carboxylic acid CHS is included.

(20) TABLE-US-00005 TABLE 4 Inventive and noninventive components KAB produced for the corresponding example adhesion promoter compositions. All quantities in wt % are based on the overall respective component KAB. KAB1 KAB2 (Ref.) AR555 61 61 A-1110 0.45 0.45 A-1120 0.45 0.45 A-1170 0.45 0.45 A-189 0.15 0.15 Beckopox 623 6 6 Water 29.5 31.5 Acetic acid 2 — Total (wt %) 100 100

(21) KAB1 was produced in a number of steps. First of all, approximately half of the water used was introduced with half of the acetic acid in a glass flask. The silanes were then added slowly and the mixture was shaken. Thereafter AR555 was charged to a reactor and the silane mixture was added. With stirring, all of the ingredients were mixed. In a second reactor, Beckopox 623 was likewise diluted with the remainder of the water and stirred for several minutes. Thereafter the remainder of the acetic acid was admixed, and stirring was continued. The contents of the second reactor were subsequently added with the amine hardener to the contents of the first reactor. The mixture was stirred for one hour more until a milky, homogeneous mixture was obtained.

(22) KAB2 was produced in an almost identical process, except that the acetic acid was replaced by water. Again a milky, homogeneous mixture was obtained. This mixture, however, underwent gelling within four weeks after production, and could only be used in fresh form.

(23) Production of the Ready-to-Use One- or Two-Component Adhesion Promoter Compositions

(24) For the production of the two-component adhesion promoter compositions, the respective components KA and KB were mixed in a suitable volume ratio. Unless otherwise indicated in the adhesion results, this ratio is always 1:1. Mixing was accomplished by conjoint pouring and subsequent shaking for 5 minutes. The single component KAB was shaken only for 5 minutes prior to use. The completed adhesion promoter compositions are labeled Z1 to Z14 and are specified in table 5 and in the tables relating to the adhesion results.

(25) TABLE-US-00006 TABLE 5 Ready-mixed inventive and noninventive (reference) adhesion promoter compositions Z1 to Z14, consisting of the respective components KA and KB or KAB. Adhesion promoter composition KA KB KAB Z1 KA1 KB1 — Z2 KA2 KB1 — Z3 KA2 KB2 — Z4 KA2 KB3 — Z5 KA2 KB4 — Z6 KA2 KB5 — Z7 (Ref.) KA2 KB6 — Z8 KA3 KB3 — Z9 (Ref.) KA4 KB1 — Z10 (Ref.) KA4 KB6 — Z11 (Ref.) KA5 KB3 — Z12 (Ref.) KA5 KB6 — Z13 — — KAB1 Z14 (Ref.) — — KAB2

(26) Adhesion Tests for Adhesion Promotion and Storage Stability

(27) The individual completed aqueous adhesion promoter compositions Z1 to Z14 of table 5 were tested, with regard to their promotion of adhesion to various substrates, as adhesion promoters in combination with various adhesives. To verify the storage stability, individual components KA, KB or KAB were stored for different times (up to 13 months) at 23° C. In some cases, in order to simulate accelerated aging, storage was carried out at an elevated temperature.

(28) Adhesives used for the test bonds were SikaTack® MOVE.sup.IT (“Move”), Sikaflex®-205 HMA-3 (“HMA3”), Sikaflex®-250 HMV-2+(“HMV2”), and Sikaflex®-265 (“S256”), which are one-component moisture-curing polyurethane adhesives that comprise polyurethane prepolymers having isocyanate groups and are available commercially from Sika Schweiz AG.

(29) Substrates used were float glass (tin-side “F—Sn” or air-side “F-air”), Ferro Frit 14251 (“14251”), Ferro Frit 3402 (“3402”), and Ferro Frit 14279 (“14279”). The aforementioned glass substrates are sold by Rocholl AG, Germany. They are laboratory substrates corresponding to the usual commercial glass ceramics for VSG and ESG glasses. Ferro is the manufacturer of the glass ceramic paste; the numbers are the type designation of the ceramics used.

(30) The aqueous compositions were applied to the respective substrate using a melamine sponge soaked with the compositions, and were flashed off for 60 minutes. A triangular bead of the adhesive was applied by extrusion cartridge and nozzle under standard conditions (23±1° C., 50±5% relative humidity).

(31) The bond was tested after a cure time of normally 7 days of conditioned storage under standard conditions at 23° C. (“RT”) and 50% relative humidity, and also after subsequent heat-and-humidity storage (“CP”) at 70° C. and 100% relative humidity for up to 21 days. The precise conditions of storage and the respective storage times are reported in the corresponding tables.

(32) The adhesion of the adhesive was tested by means of a ‘bead test’. In this test, the bead is incised at the end just above the bond area. The incised end of the bead is held with rounded-end tweezers and pulled from the substrate. This is done by cautiously rolling the bead up onto the tip of the tweezers, and by applying a cut at right angles to the direction of bead pulling, down to the bare substrate. The bead pulling rate should be selected such that a cut has to be made approximately every 3 seconds. The test distance must be at least 8 cm. After the bead has been pulled off, an assessment is made of the adhesive remaining on the substrate (cohesive fracture). The adhesion properties are evaluated by visual determination of the cohesive component of the adhesion area.

(33) The higher the cohesive fracture component, the better the estimation of the bond. Test results with cohesive fractures of less than 70% are typically considered to be inadequate. A cohesive fracture of 0% corresponds to a 100% adhesive fracture with complete failure of the bond and thus of the adhesion promoter. The results (numbers in % cohesive fracture) are summarized in tables 6a to 14b.

(34) TABLE-US-00007 TABLE 6a Comparison of inventive adhesion promoter compositions Z4 and Z8 with nonadhesive composition Z7 through bonds of different substrates using different adhesives after 7 d (days) RT and 7 d RT + 7 d CP. 7 d RT 7 d CP Storage Adhesive Adhesive Ex. Substrate Move HMA3 HMV2 S265 Move HMA3 HMV2 S265 Z4 F—Sn 100 100 100 100 100 100 100 100 F-air 100 100 100 100 100 100 100 100  3402 100 100 100 100 100 100 100 100 14251 100 100 100 100 100 100 100 100 14279 100 100 100 100 100 100 100 100 Z8 F—Sn 100 100 100 100 100 100 100 100 F-air 100 100 100 100 100 100 100 0  3402 100 100 100 100 100 99 100 100 14251 100 100 100 100 100 100 100 10 14279 100 100 100 100 100 90 100 100 Z7 F—Sn 10 10 50 100 0 0 0 0 (Ref) F-air 10 10 30 100 0 0 0 0  3402 10 70 30 100 100 100 100 100 14251 10 70 50 100 0 0 0 0 14279 10 30 10 100 0 0 95 80

(35) TABLE-US-00008 TABLE 6b Comparison of inventive adhesion promoter compositions Z4 and Z8 with nonadhesive composition Z7 through bonds of different substrates using different adhesives after 7 d RT + 14 d CP and 7 d RT + 21 d CP. 14 d CP 21 d CP Storage Adhesive Adhesive Ex. Substrate Move HMA3 HMV2 S265 Move HMA3 HMV2 S265 Z4 F—Sn 100 100 100 100 100 100 100 100 F-air 100 100 100 100 100 100 100 100  3402 100 100 100 100 100 100 100 100 14251 100 100 100 100 100 100 100 100 14279 100 100 100 100 100 100 100 100 Z8 F—Sn 100 99 100 0 100 90 100 0 F-air 100 99 100 0 99 90 100 0  3402 100 30 100 10 100 0 100 10 14251 100 80 100 0 99 90 95 0 14279 100 20 100 10 100 0 100 0 Z7 F—Sn 0 0 0 0 0 0 0 0 (Ref) F-air 0 0 0 0 0 0 0 0  3402 100 100 100 100 100 100 100 100 14251 0 0 0 0 0 0 0 0 14279 0 0 95 80 0 0 90 50

(36) Tables 6a and 6b show that the inventive adhesion promoter compositions Z4 and Z8 are significantly superior to the noninventive composition Z7, especially after heat-and-humidity storage.

(37) TABLE-US-00009 TABLE 7a Comparison of inventive adhesion promoter composition Z1 with nonadhesive composition Z10 through bonds of different substrates using different adhesives after 7 d (days) RT and 7 d RT + 7 d CP. Volume mixing ratio of KA to KB in both cases Z1 and Z10 was 4:1. 7 d RT 7 d CP Storage Adhesive Adhesive Ex. Substrate Move HMA3 HMV2 S265 Move HMA3 HMV2 S265 Z1 F—Sn 100 99 100 100 100 100 100 100 14279 90 99 100 100 100 100 100 100 14251 100 100 100 100 100 100 100 100  3402 99 100 100 100 90 95 100 100 Z10 F—Sn 0 0 30 10 0 0 0 100 (Ref.) 14279 100 20 100 100 0 0 0 50 14251 100 100 100 100 0 0 0 20  3402 100 100 100 100 0 0 0 0

(38) TABLE-US-00010 TABLE 7b Comparison of inventive adhesion promoter composition Z1 with nonadhesive composition Z10 through bonds of different substrates using different adhesives after 7 d RT + 14 d CP and 7 d RT + 21 d CP. Volume mixing ratio of KA to KB in both cases Z1 and Z10 was 4:1. 14 d CP 21 d CP Storage Adhesive Adhesive Ex. Substrate Move HMA3 HMV2 S265 Move HMA3 HMV2 S265 Z1 F—Sn 95 100 100 99 70 60 90 95 14279 99 99 99 100 95 95 99 99 14251 95 100 100 100 50 99 100 100  3402 20 70 100 100 10 20 100 100 Z10 F—Sn 0 0 0 80 0 0 0 50 (Ref.) 14279 0 0 0 20 0 0 0 30 14251 0 0 0 0 0 0 0 0  3402 0 0 0 0 0 0 0 0

(39) The comparison of the inventive Z1 with the noninventive Z10 (without aminosilane AS and without inorganic base BA) in tables 7a and 7b shows clearly the superiority of the inventive adhesion promoter composition.

(40) TABLE-US-00011 TABLE 8a Comparison of inventive adhesion promoter compositions Z2 and Z3 on bonds of different substrates using different adhesives after 7 d (days) RT and 7 d RT + 7 d CP. Volume mixing ratio of KA to KB in the case of Z2 was 4:1. 7 d RT 7 d CP Storage Adhesive Adhesive Ex. Substrate Move HMA3 HMV2 S265 Move HMA3 HMV2 S265 Z2 F—Sn 100 100 100 100 100 100 100 100 14279 100 100 100 100 100 100 100 100 14251 100 100 100 100 100 100 100 100  3402 100 100 100 100 100 100 100 100 Z3 F—Sn 100 100 100 100 100 100 100 100 14279 100 100 100 100 100 100 100 100 14251 100 100 100 100 100 100 100 100  3402 100 100 100 100 100 100 100 100

(41) TABLE-US-00012 TABLE 8b Comparison of inventive adhesion promoter compositions Z2 and Z3 on bonds of different substrates using different adhesives after 7 d RT + 14 d CP and 7 d RT + 21 d CP. Volume mixing ratio of KA to KB in the case of Z2 was 4:1. 14 d CP 21 d CP Storage Adhesive Adhesive Ex. Substrate Move HMA3 HMV2 S265 Move HMA3 HMV2 S265 Z2 F—Sn 100 100 100 100 100 100 100 100 14279 99 99 100 100 99 100 100 100 14251 100 100 100 100 100 100 100 50  3402 100 100 100 100 100 100 100 100 Z3 F—Sn 100 100 100 100 100 100 100 100 14279 100 100 100 100 100 100 100 100 14251 100 100 100 100 100 100 100 90  3402 100 100 100 100 100 100 100 100

(42) Tables 8a and 8b show that inventive compositions with a KA:KB mixing ratio of 1:1 (Z3) and those with a ratio of 4:1 (Z2) permit outstanding adhesion results.

(43) TABLE-US-00013 TABLE 9a Comparison of inventive adhesion promoter compositions Z5 and Z6 and noninventive composition Z7 on bonds of different substrates using different adhesives after 7 d (days) RT and 7 d RT + 7 d CP. 7 d RT 7 d CP Storage Adhesive Adhesive Ex. Substrate Move HMA3 HMV2 S265 Move HMA3 HMV2 S265 Z5 F—Sn 99 100 100 100 0 0 80 100 F-air 100 100 100 100 0 0 95 100 Z6 F—Sn 100 100 100 100 20 70 30 100 F-air 99 100 100 100 100 100 100 100 Z7 F—Sn 10 10 50 100 0 0 0 0 (Ref.) F-air 10 10 30 100 0 0 0 0

(44) TABLE-US-00014 TABLE 9b Comparison of inventive adhesion promoter compositions Z5 and Z6 and noninventive composition Z7 on bonds of different substrates using different adhesives after 7 d RT + 14 d CP and 7 d RT + 21 d CP. 14 d CP 21 d CP Storage Adhesive Adhesive Ex. Substrate Move HMA3 HMV2 S265 Move HMA3 HMV2 S265 Z5 F—Sn 0 0 70 100 0 0 70 100 F-air 0 0 70 100 0 0 50 100 Z6 F—Sn 70 30 20 100 30 10 80 100 F-air 100 100 100 100 100 100 100 100 Z7 F—Sn 0 0 0 0 0 0 0 0 (Ref.) F-air 0 0 0 0 0 0 0 0

(45) Tables 9a and 9b show that inventive compositions with barium hydroxide (Z5) and magnesium hydroxide (Z6) as inorganic base BA also exhibit good adhesion results. The noninventive Z7 yields significantly poorer results.

(46) TABLE-US-00015 TABLE 10a Comparison of the inventive Z8 with the noninventive adhesion promoter compositions Z11 and Z12 on bonds of different substrates using different adhesives after 3 d (days) RT and 3 d RT + 7 d CP. Volume mixing ratio of KA to KB in the case of Z12 was 2:1. 7 d RT 7 d CP Storage Adhesive Adhesive Ex. Substrate Move HMA3 HMV2 S265 Move HMA3 HMV2 S265 Z8 F—Sn 100 100 100 100 100 100 100 100  3402 100 100 100 100 100 99 100 100 14251 100 100 100 100 100 100 100 10 14279 100 100 100 100 100 90 100 100 Z11 F—Sn 100 100 100 100 0 10 70 10 (Ref.)  3402 100 100 100 100 0 0 0 90 14251 100 100 100 100 0 0 0 10 14279 100 100 100 100 0 0 0 50 Z12 F—Sn 100 100 100 100 0 0 50 10 (Ref.)  3402 100 100 100 100 0 0 0 0 14251 100 100 100 100 0 0 0 0 14279 100 100 100 100 0 0 0 0

(47) TABLE-US-00016 TABLE 10b Comparison of the inventive Z8 with the noninventive adhesion promoter compositions Z11 and Z12 on bonds of different substrates using different adhesives after 7 d RT + 14 d CP and 7 d RT + 21 d CP. Volume mixing ratio of KA to KB in the case of Z12 was 2:1. 14 d CP 21 d CP Storage Adhesive Adhesive Ex. Substrate Move HMA3 HMV2 S265 Move HMA3 HMV2 S265 Z8 F—Sn 100 99 100 0 100 90 100 0  3402 100 30 100 10 100 0 100 10 14251 100 80 100 0 99 90 95 0 14279 100 20 100 10 100 0 100 0 Z11 F—Sn 0 10 70 0 0 0 70 0 (Ref.)  3402 0 0 10 10 0 0 0 0 14251 0 0 0 0 0 0 0 0 14279 0 0 0 10 0 0 0 0 Z12 F—Sn 0 0 30 0 0 0 30 0 (Ref.) 3402 0 0 0 0 0 0 0 0 14251 0 0 0 0 0 0 0 0 14279 0 0 0 0 0 0 0 0

(48) From tables 10a and 10b it can be seen that noninventive compositions without acid HS (Z11) and without acid HS and also without inorganic base BA (Z12), particularly after heat-and-humidity storage, yield significantly poorer results than a comparable inventive composition (Z8). Moreover, the acid-free compositions undergo gelling usually within a few weeks.

(49) TABLE-US-00017 TABLE 11a Comparison of the noninventive Z9 with the inventive adhesion promoter composition Z1 on bonds of different substrates using different adhesives after 3 d RT + 14 d CP and 3 d RT + 21 d CP and using components having undergone different heat aging. The volume mixing ratio of KA to KB for all compositions was 4:1. The temperature figures relate to storage of the component for 7 days at the stated temperature. The substrate in all cases was the tin side of float glass. 3 d RT 7 d CP Storage Adhesive Adhesive Ex. KA KB Move HMA3 HMV2 S265 Move HMA3 HMV2 S265 Z9 RT RT 95 95 100 100 0 0 0 5 (Ref.) RT 40° C. 99 99 100 100 0 0 0 20 RT 60° C. 40 95 95 95 0 0 0 60 40° C. RT 20 95 95 100 0 0 0 40 40° C. 40° C. 95 95 99 99 0 0 0 40 40° C. 60° C. 95 90 95 100 0 0 0 50 Z1 RT RT 99 99 99 100 100 100 100 100 RT 40° C. 70 80 80 99 100 100 100 100 RT 60° C. 30 95 100 100 90 80 80 100 40° C. RT 95 100 100 100 100 90 100 100 40° C. 40° C. 95 95 95 100 95 99 99 100 40° C. 60° C. 95 99 99 100 95 80 100 100

(50) TABLE-US-00018 TABLE 11b Comparison of the noninventive Z9 with the inventive adhesion promoter composition Z1 on bonds of different substrates using different adhesives after 7 d (days) RT and 7 d RT + 7 d CP and using components having undergone different heat aging. The volume mixing ratio of KA to KB for all compositions was 4:1. The temperature figures relate to storage of the component for 7 days at the stated temperature. The substrate in all cases was the tin side of float glass. 14 d CP 21 d CP Storage Adhesive Adhesive Ex. KA KB Move HMA3 HMV2 S265 Move HMA3 HMV2 S265 Z9 RT RT 0 0 0 5 0 0 0 0 (Ref.) RT 40° C. 0 0 0 10 0 0 0 5 RT 60° C. 0 0 0 30 0 0 0 20 40° C. RT 0 0 0 10 0 0 0 0 40° C. 40° C. 0 0 0 20 0 0 0 5 40° C. 60° C. 0 0 0 20 0 0 0 5 Z1 RT RT 100 100 100 100 95 95 99 99 RT 40° C. 100 100 100 100 90 95 95 95 RT 60° C. 90 90 90 100 70 50 70 99 40° C. RT 99 95 99 100 80 70 95 99 40° C. 40° C. 95 99 99 100 80 90 99 99 40° C. 60° C. 95 99 99 100 80 90 99 99

(51) Tables 11a and 11b show adhesion results after heat aging (simulated accelerated aging) of components KA and KB of an inventive (Z1) against a noninventive (Z9) composition. The inventive Z1 exhibits very good adhesion promotion in all combinations of fresh and aged components.

(52) TABLE-US-00019 TABLE 12a Differently aged KA2 of the inventive adhesion promoter composition Z4, tested on bonds of different substrates using different adhesives after 7 d (days) RT and 7 d RT + 7 d CP. The details in the first column describe the aging of the KA2 (13 months RT or 7 d 40° C. plus 13 months RT). KB3 was fresh in each case. 7 d RT 7 d CP Storage Adhesive Adhesive KA2 Substrate Move HMA3 HMV2 S265 Move HMA3 HMV2 S265 13 m RT F—Sn 100 100 100 100 100 100 100 100 F-air 100 100 100 100 100 100 100 100  3402 100 100 100 100 100 100 100 100 14251 100 100 100 100 100 100 100 100 14279 100 100 100 100 100 100 100 100 7 d 40° C. + F—Sn 100 100 100 100 100 100 100 100 13 m RT F-air 100 100 100 100 100 100 100 100  3402 100 100 100 100 100 100 100 100 14251 100 100 100 100 100 100 100 100 14279 100 100 100 100 100 90 100 100

(53) TABLE-US-00020 TABLE 12b Differently aged KA2 of the inventive adhesion promoter composition Z4, tested on bonds of different substrates using different adhesives after 7 d RT + 14 d CP and 7 d RT + 21 d CP. The details in the first column describe the aging of the KA2 (13 months RT or 7 d 40° C. plus 13 months RT). KB3 was fresh in each case. 14 d CP 21 d CP Storage Adhesive Adhesive KA2 Substrate Move HMA3 HMV2 S265 Move HMA3 HMV2 S265 13 M. RT F—Sn 100 100 100 100 100 100 100 100 F-air 100 100 100 100 100 100 100 100  3402 100 100 100 100 100 100 100 100 14251 100 100 100 100 100 100 100 50 14279 100 100 100 100 100 100 100 100 7 d 40° C. + F—Sn 100 100 100 100 100 100 100 100 13 M. RT F-air 100 100 100 100 100 100 100 100  3402 100 100 100 100 100 100 100 100 14251 100 100 100 100 100 100 100 50 14279 100 100 100 100 100 90 100 100

(54) Tables 12a and 12b show clearly that even storage over 13 months at room temperature, and even additional heat aging of component KA, have virtually no influence on the adhesion results of an inventive composition.

(55) TABLE-US-00021 TABLE 13 Test bonds with different flash-off times (1 min to 30 min) and after different storage of the test bond. In all cases the adhesion promoter used was Z4, the substrate used was the tin side of float glass, and the adhesive used was HMA3. Storage 1 min 2 min 5 min 10 min 15 min 30 min 7 d RT 100 100 100 100 100 100 7 d RT + 7 d CP 100 100 100 100 100 100 7 d RT + 14 d CP 100 100 100 100 100 100 7 d RT + 21 d CP 100 100 100 100 100 100

(56) Table 13 shows adhesion results after different flash-off times, using a fan. Flash-off times of no more than 1 minute, which are extremely short for aqueous compositions, can be readily employed without adversely affecting the adhesion results.

(57) TABLE-US-00022 TABLE 14a Comparison of the inventive Z13 with the noninventive adhesion promoter compositions Z14 on bonds of different substrates using different adhesives after 3 d (days) RT and 3 d RT + 7 d CP. 7 d RT 7 d CP Storage Adhesive Adhesive Ex. Substrate Move HMA3 HMV2 S265 Move HMA3 HMV2 S265 Z13 F—Sn 100 100 100 100 100 100 100 100  3402 100 100 100 100 100 100 100 100 14251 100 100 100 100 100 100 100 10 14279 100 100 100 100 100 95 100 100 Z14 F—Sn 100 100 100 100 0 10 70 10 (Ref.)  3402 100 100 100 100 0 0 0 50 14251 100 100 100 100 0 0 0 0 14279 100 100 100 100 0 0 0 10

(58) TABLE-US-00023 TABLE 14b Comparison of the inventive Z13 with the noninventive adhesion promoter composition Z14 on bonds of different substrates using different adhesives after 7 d RT + 14 d CP and 7 d RT + 21 d CP. 14 d CP 21 d CP Storage Adhesive Adhesive Ex. Substrate Move HMA3 HMV2 S265 Move HMA3 HMV2 S265 Z13 F—Sn 100 99 100 10 100 99 100 10  3402 100 50 100 20 100 20 100 20 14251 100 80 100 10 99 90 95 10 14279 100 30 100 30 100 20 100 20 Z14 F—Sn 0 10 70 0 0 0 50 0 (Ref.)  3402 0 0 10 10 0 0 0 0 14251 0 0 0 0 0 0 0 0 14279 0 0 0 10 0 0 0 0

(59) Tables 14a and 14b show that the inventive composition Z13, consisting of a single component KAB, also exhibits very good adhesion results, whereas the noninventive composition Z14 (without water-soluble carboxylic acid CHS) fails after heat-and-humidity storage. The storage stability of Z14, moreover, was just a few weeks, before it began to gel.

(60) The adhesion results show clearly that the inventive compositions are far superior to the noninventive reference examples in all cases, especially after storage under conditions of heat and humidity. The inventive compositions are storage-stable over long periods and may also be composed of components having different ages, without detriment to the promotion of adhesion.