Two-component compositions based on silane-functional polymers

Abstract

The invention relates to a two-component composition, including a component A, which includes at least one silane-functional polymer and at least one hardener or accelerator for epoxy resins, and a component B, which includes at least one aqueous emulsion of at least one epoxy resin. Two-component compositions according to the invention are suitable as adhesives, sealants or coatings.

Claims

1. A method of adhesive bonding, sealing, or coating a substrate, comprising: mixing a component A and a component B of a two-component composition together to obtain a hardenable composition; applying the hardenable composition to the substrate; and hardening the hardenable composition applied to the substrate, wherein: component A, at the time of mixing, comprises at least one silane-functional polymer, and at least one hardener or accelerator for epoxy resins; component B, at the time of mixing, comprises at least one aqueous emulsion including epoxy resin particles and an emulsifier formed by emulsifying at least one liquid epoxy resin in the presence of the emulsifier and water; the silane-functional polymer includes (i) a silane-functional polyurethane polymer obtainable by reacting a silane that includes at least one group reactive toward isocyanate groups and a polyurethane polymer that includes isocyanate groups, or (ii) a silane-functional polyurethane polymer obtainable by reacting an isocyanatosilane and a polymer that includes functional end groups reactive toward isocyanate groups; and the epoxy resin particles have a mean particle size in the range of 0.05 to 10 μm.

2. The method according to claim 1, wherein the aqueous emulsion contains 10 to 40% by weight of water.

3. The method according to claim 1, wherein the emulsion has a particle size distribution, in which the size ratio of the largest to the smallest particles has a value in the range of ≦25.

4. The method according to claim 1, wherein 90% of the particles in the emulsion are smaller than 6 μm.

5. The method according to claim 1, wherein the hardener or accelerator for epoxy resins is selected from the group consisting of tertiary polyamines, Mannich bases, polymercaptans and imidazoles.

6. The method according to claim 1, wherein the hardener or accelerator for epoxy resins is selected from the group consisting of pentamethyl-diethylenetriamine, N,N-dimethyl-N′-(dimethylamino-propyl)-1,3-propanediamine, bis(2-dimethylaminoethyl)ether, bis-(-dimethyl-aminoethyl)-piperazine, N,N′-dimethylpiperazine, dimethylaminomethyl-phenol, 2,4,6-tris(dimethyl-aminomethyl)-phenol, 2,4,6-tris((3-(dimethylamino)propyl)-aminomethyl)phenol, 1-methylimidazole, 1-ethylimidazole, 1-vinylimidazole, 2-methylimidazole, 2-ethylimidazole, 2-isopropylimidazole, 2-heptadecylimidazole, 2-ethyl-4-methylimidazole and 1-benzyl-2-methylimidazole.

7. The method according to claim 1, wherein the two-component composition further comprises at least one catalyst for cross-linking the silane-functional polymer with the aid of moisture.

8. The method according to claim 7, wherein the catalyst for cross-linking the silane-functional polymer using moisture is selected from the group consisting of organotin compounds, titanates, zirconates, tertiary amines, amidines and guanidines.

9. The method according to claim 1, wherein the two-component composition further comprises at least one aminosilane, an epoxysilane or a mercaptosilane.

10. The method according to claim 1, wherein the two-component composition further comprises at least one filler.

11. The method according to claim 1, wherein the fraction of the hardener or accelerator for epoxy resins is 0.5 to 15% by weight based on component A.

12. The method according to claim 1, wherein the weight ratio of component A to component B is 1:1 to 100:1.

13. The method according to claim 1, wherein hardening the hardenable composition results in a partially hardened composition.

14. The method according to claim 1, wherein hardening the hardenable composition results in a completely hardened composition.

15. The method according to claim 1, wherein the silane-functional polymer is the polymer of (i), in which the silane is a mercaptosilane or an aminosilane.

16. The method according to claim 1, wherein the weight ratio of component A to component B is 2.5:1 to 100:1.

17. The method according to claim 1, wherein component A is in a non-aqueous system at the time of coming into contact with component B.

18. The method according to claim 1, wherein the aqueous emulsion has a solids content of 70 to 90% by weight.

19. A method of adhesive bonding, sealing, or coating a substrate, comprising: mixing a component A and a component B of a two-component composition together to obtain a hardenable composition; applying the hardenable composition to the substrate; and hardening the hardenable composition applied to the substrate, wherein: component A, at the time of mixing, comprises at least one silane-functional polymer, and at least one hardener or accelerator for epoxy resins; component B, at the time of mixing, comprises at least one aqueous emulsion including epoxy resin particles and an emulsifier formed by emulsifying at least one liquid epoxy resin in the presence of the emulsifier and water; component A is in a non-aqueous system prior to coming into contact with component B; and the epoxy resin particles have a mean particle size in the range of 0.05 to 10 μm.

20. The method according to claim 19, wherein the silane-functional polymer includes (i) a silane-functional polyurethane polymer obtainable by reacting a silane that includes at least one group reactive toward isocyanate groups and a polyurethane polymer that includes isocyanate groups, (ii) a silane-functional polyurethane polymer obtainable by reacting an isocyanatosilane and a polymer that includes functional end groups reactive toward isocyanate groups, or (iii) a silane-functional polymer obtainable by a hydroxysilylation reaction of polymers with terminal double bonds.

21. The method according to claim 19, wherein the aqueous emulsion has a solids content of 70 to 90% by weight.

Description

EXAMPLES

(1) In the following, illustrative embodiments are presented, which are intended to explain the invention described in greater detail. Naturally, the invention is not limited to these illustrative embodiments described.

(2) Description of Measurement Methods

(3) The viscosity was measured on a thermostatically controlled ball-plate viscometer, Physica UM (ball diameter 20 mm, ball angle 1°, ball tip-plate distance 0.05 mm, shear speed 10 to 1000 s.sup.−1).

(4) The mean particle size was measured by laser diffraction on a Sympatec device with the HELOS laser diffraction sensor.

(5) The odor was evaluated qualitatively by smelling the mixed composition with the nose, grading an unpleasant, penetrating amine odor as “strong” and a weak or undetectable odor as “mild.”

(6) To determine the creep resistance, the composition was applied to an upright piece of cardboard using a wooden spatula, and the flow behavior was observed. The creep resistance was graded “good” if the composition had drifted slightly downward within one minute without flowing down and as “very good” if it did not move at all.

(7) To measure the tack-free time (skin formation time), a small piece of the composition at room temperature was applied to a piece of cardboard in a layer thickness of about 3 mm and under standard climate conditions (23±1° C., 50±5% relative humidity) the time required until gently touching the surface of the composition with a LDPE pipette first failed to leave any residue on the pipette.

(8) The tensile strength, the elongation at break and the modulus of elasticity were determined according to DIN EN 53504 (pulling speed: 200 mm/min) on dumbbells with a length of 75 mm, at a bar length of 30 mm and a bar width of 4 mm, produced by punching out from film with a thickness of about 3 mm of the composition hardened under the respectively reported conditions.

(9) The Shore A hardness was determined according to DIN 53505 on test pieces hardened in a standard climate.

(10) Production of N-(3-trimethoxysilyl-propyl)-amino succinic acid diethyl ester

(11) To 179 g (1 mol) 3-aminopropyl-trimethoxysilane (Silquest® A-1110 from Momentive Performance Materials) under exclusion of moisture, 172 g (1 mol) of maleic acid diethyl ester are slowly dropped in under good agitation and then agitated for an additional 2 hours. A colorless liquid with a viscosity at 20° C. of 60 mPa.Math.s was obtained.

(12) Production of Silane-Functional Polymer P1

(13) Under exclusion of moisture, 1000 g of the polyol Acclaim® 12200 (from Bayer; low mono) polyoxypropylenediol, OH number 11.0 mg KOH/g, water content approx. 0.02% by weight), 43.6 g Isophorone diisocyanate (Vestanat® IPDI from Degussa), 126.4 g diisodecyl phthalate (DIDP; Palatinol® Z, from BASF) and 0.12 g dibutyltin dilaurate were heated to 90° C. under continuous agitation and left at this temperature until the titrimetrically determined content of free Isocyanate groups had reached a value of 0.63% by weight. Then 62.3 g N-(3-trimethoxysilylpropyl)-amino succinic acid diethyl ester was mixed in and the mixture agitated at 90° C. until free isocyanate could no longer be detected by FT-IR spectroscopy The silane-functional polyurethane polymer was cooled to room temperature and stored under exclusion of moisture.

(14) Preparation of Epoxy Resin Emulsions

(15) Emulsion E1: 68.5 parts by weight bisphenol A liquid resin (Araldite® GY-250 von Huntsman) were mixed at 50° C. with 10 parts by weight reactive diluent (Araldite® DY-E from Huntsman) and 1.5 parts by weight emulsifier (Disponil® 23 from Cognis) and then continuously emulsified with 20 parts by weight of water over a stator-rotor mixer at a rotation speed of 22 m/s. The white emulsion obtained had a creamy consistency, a viscosity at 20° C. of about 1100 mPa.Math.s, an epoxy group content of 4.08 mEq/g and a mean particle size of about 1.6 μm, with 90% of the particles smaller than 2.7 μm, and remained unchanged for more than one year at room temperature.

(16) Emulsion E2: 68.5 parts by weight bisphenol A liquid resin (Araldite® GY-250 from Huntsman) and 10 parts by weight bisphenol F liquid resin (D.E.R.™ 354 from Dow Chemical) were mixed at 50° C. with 1.5 parts by weight emulsifier (Disponil® 23 from Cognis) and then emulsified continuously with 20 parts by weight water on a stator-rotor mixer at a rotation speed of 22 m/s. The white emulsion obtained was of a creamy consistency, had a viscosity at 20° C. of about 1500 mPa.Math.s, an epoxy group content of 4.28 mEq/g, [and] a mean particle size of about 1.5 μm, with 90% of the particles smaller than 2.6 μm, and remained unchanged at room temperature for more than one year.

(17) Preparation of Compositions

Examples 1 to 6 and Ref1

(18) For each example according to Table 1, under standard climate conditions, the silane-functional polymer P1 was mixed with a hardener or accelerator for epoxy resins in the form of a Mannich base (Ancamine® K54=2,4,6-tris(dimethyl-aminomethyl)phenol, from Air Products), a catalyst (10% by weight dibutyltin dilaurate in diisodecyl phthalate) and an aminosilane (N-(2-aminoethyl)-3-aminopropyl-trimethoxysilane; Silquest® A-1120 from Momentive Performance Materials) and this composition as component A was mixed with emulsion E1 as component B in the indicated weight ratio using a dynamic mixer, applied immediately thereafter and hardened under standard climate conditions.

(19) TABLE-US-00001 TABLE 1 Two-component compositions. (Quantities in parts by weight) Example Ref1 1 2 3 4 5 6 component A: Polymer P1 92 92 92 92 92 92 92 Ancamine ® K54 6 6 6 6 6 6 6 Catalyst 1 1 1 1 1 1 1 Aminosilane 1 1 1 1 1 1 1 component B: Emulsion E1 — 10 20 40 60 80 100

(20) After hardening, the compositions obtained in this way were tested for odor, stability, tack-free time and mechanical properties.

(21) The results of these tests are presented in Table 2.

(22) TABLE-US-00002 TABLE 2 Properties of the compositions. Example Ref1 1 2 3 4 5 6 Odor strong slight slight slight slight slight slight Stability none none none good good good good Tack-free time.sup.a 65 55 50 42 47 52 50 (min.) Mechanical properties (21 days, standard climate): Tensile strength 0.4 1.2 3.4 2.9 3.0 2.3 2.1 (MPa) Elongation at 50 180 290 260 260 250 230 break (%) Modulus of 0.9 1.4 1.8 1.6 3.5 4.0 4.9 elasticity (MPa).sup.b Mechanical properties (21 days standard climate + 2 days 80° C.): Tensile strength 0.3 0.8 2.3 4.5 6.1 6.7 6.6 (MPa) Elongation at 40 140 220 230 220 210 150 break (%) Modulus of 0.8 1.0 1.6 2.2 7.2 11.5 19.6 elasticity (MPa).sup.b .sup.aTime to disappearance of tackiness. .sup.bat 0.5 to 50% elongation.

Examples 7 to 13

(23) For each example, the silane-functional polymer P1 was mixed with a hardener or accelerator for epoxy resins in the form of a Mannich base (Ancamine® K54=2,4,6-tris(dimethylaminomethyl)phenol, from Air Products) or a polyamine (IPDA=Isophorone diamine), a catalyst (10% by weight dibutyltin dilaurate in diisodecyl phthalate) and an aminosilane (N-(2-aminoethyl)-3-aminopropyl-trimethoxysilane; Silquest® A-1120 from Momentive Performance Materials) according to Table 3 under standard climate conditions and this composition, as component A, was mixed with emulsion E2 as component B in the indicated weight ratio using a dynamic mixer, applied immediately thereafter and hardened under standard climate conditions.

(24) TABLE-US-00003 TABLE 3 Two-component compositions. (Quantities in parts by weight) Example 7 8 9 10 11 12 13 component A: Polymer P1 92  92  92 92  92  92  92 Ancamine ® K54 6 6 0.5 6 6 6 6 IPDA — — 5.5 — — — — Catalyst 1 1 1 1 1 1 1 Aminosilane 1 1 1 1 1 1 1 component B: Emulsion E2 10  20  30 40  60  80  100

(25) After hardening, the compositions thus obtained were tested for odor, tack-free time and mechanical properties. In addition, the stability of the hardened composition was investigated under thermal and hydrolytic stress in that some of the dumbbells produced as described above were additionally held for one week in a kiln at 100° C. or at 70° C. and 100% relative humidity (cataplasm conditions) and then tested for tensile strength, elongation at break and modulus of elasticity.

(26) The results of these tests are presented in Table 4.

(27) TABLE-US-00004 TABLE 4 Properties of the compositions. Example 7 8 9 10 11 12 13 Odor slight slight slight slight slight slight slight Tack-free time.sup.a 32 40 20 41 41 48 49 (min.) Stability none none none none good good good Mechanical properties (21 days standard climate): Tensile strength 1.0 3.1 1.3 2.3 2.9 2.4 2.7 (MPa) Elongation at 147 281 152 218 246 233 251 break (%) Modulus of 1.3 1.8 1.50 1.7 4.3 5.0 6.9 elasticity (MPa).sup.b Mechanical properties (21 days standard climate + 2 days 80° C.): Tensile strength 0.8 1.9 1.4 2.0 4.0 4.9 5.5 (MPa) Elongation at 124 203 140 152 130 109 72 break (%) Modulus of 1.1 1.4 1.82 2.0 8.1 13.2 20.4 elasticity (MPa).sup.b Mechan. properties (21 days standard climate + 2 days 80° C. + 7 days 100° C.): Tensile strength 0.5 2.0 n.d. 1.8 4.2 5.3 5.8 (MPa) Elongation at 86 201 n.d. 135 133 112 76 break (%) Modulus of 1.0 1.5 n.d. 2.0 7.4 12.8 20.5 elasticity (MPa).sup.b Mechan. properties (21 days standard climate + 2 days 80° C. + 7 days cataplasm): Tensile strength 0.6 1.8 n.d. 2.9 5.0 6.7 7.1 (MPa) Elongation at 126 200 n.d. 176 182 152 98 break (%) Modulus of 0.8 1.4 n.d. 2.2 8.3 20.5 34.9 elasticity (MPa).sup.b .sup.aTack-free time. .sup.bat 0.5 to 50% elongation. n.d. = not determined

Examples 14 to 19 and Ref2

(28) For each example according to Table 5 under standard climate a commercial STP-polymer (MS Polymer™ S 203 H from Kaneka) was mixed with a hardener or accelerator for epoxy resins in the form of a Mannich base (Ancamine® K54=2,4,6-Tris(dimethylaminomethyl)phenol from Air Products) or a polyamine (IPDA=Isophorone diamine), a catalyst (10% by weight dibutyltin dilaurate in diisodecyl phthalate) and an aminosilane (N-(2-aminoethyl)-3-aminopropyltrimethoxysilane; Silquest® A-1120 from Momentive Performance Materials) and this composition was mixed as component A with emulsion E1 as component B in the indicated weight ratio using a dynamic mixer, applied immediately thereafter and hardened under standard climate conditions.

(29) TABLE-US-00005 TABLE 5 Two-component compositions. (Quantities in parts by weight) Example Ref2 14 15 16 17 18 19 component A: MS polymer ™ S 92  92  92  92  92 92 92  203 H Ancamine ® K54 6 6 6 6 1 1 6 IPDA — — — — 5 5 — Catalyst 3 3 3 3 3 3 3 Aminosilane 1 1 1 1 1 1 1 component B: Emulsion E1 — 10  20  30  30 50 60 

(30) The compositions thus obtained were tested for tack-free time and mechanical properties after hardening.

(31) The results of these tests are shown in Table 6.

(32) TABLE-US-00006 TABLE 6 Properties of the compositions. Example Ref2 14 15 16 17 18 19 Curing speed: Tack-free time.sup.a >8 h 8 h 4-8 h 4-8 h 4 h 4 h 8 h Mechanical properties (11 days standard climate): Tensile strength (MPa) 0.2 0.8 1.5 1.6 1.8 1.9 1.8 Elongation at break (%) 190 360 370 390 450 470 570 Modulus of elasticity 0.13 0.19 0.22 0.20 0.19 0.26 0.12 (MPa).sup.b Mechanical properties (11 days standard climate + 2 days 80° C.): Tensile strength (MPa) 0.3 0.4 1.7 3.5 2.2 1.8 2.8 Elongation at break (%) 200 350 390 590 480 530 690 Modulus of elasticity 0.17 0.21 0.21 0.23 0.35 0.40 0.45 (MPa).sup.b .sup.aTack-free time. .sup.bat 0.5 to 50% elongation.

Examples 20 to 22 and Ref3 to Ref6

(33) For each example according to Table 7 under standard climate conditions, component A of the commercial mounting adhesive Sikaflex®-553, based on a silane-endcapped polymer (available from von Sika Schweiz AG) was mixed with a hardener or accelerator for epoxy resins in the form of a Mannich base (Ancamine® K54=2,4,6-tris(dimethylaminomethyl)phenol, from Air Products) and optionally a catalyst (DBU=1,8-diazabicyclo[5.4.0]undec-7-ene or TMG=1,1,3,3,-Tetramethylguanidine) and this composition was mixed as component A with the emulsion E2 as component B in the indicated weight ratio using a dynamic mixer, applied immediately thereafter and hardened under standard climate conditions.

(34) TABLE-US-00007 TABLE 7 Two-component compositions. (Quantities in parts by weight) Example Ref3 Ref4 Ref5 Ref6 20 21 22 component A: Sikaflex ®-553 Comp. 100 99.8 90.9 90.7  87.4  87.4  87.4  A Ancamine ® K54 — — — — 3.3 3.3 3.3 DBU —  0.2 — 0.2 — 0.2 — TMG — — — — — — 0.2 component B: Emulsion E2 — —  9.1 9.1 9.1 9.1 9.1

(35) The compositions thus obtained were tested for stability, tack-free time and mechanical properties after 7 days (tensile strength, elongation at break, modulus of elasticity) or 14 days (Shore A) of hardening under standard climate conditions.

(36) The results of these tests are presented in Table 8.

(37) TABLE-US-00008 TABLE 8 Properties of the compositions. Example Ref3 Ref4 Ref5 Ref6 20 21 22 Stability good good very very very very very good good good good good Tack-free time.sup.a (min.) 40 22 33 18 72 22 40 Tensile strength (MPa) 2.4 2.3 2.7 2.8 4.2 4.6 4.7 Elongation at break 210 240 420 440 300 240 240 (%) Modulus of elasticity.sup.b 2.8 2.8 1.6 2.2 7.0 6.6 7.0 (MPa) Shore A 51 46 41 42 70 67 67 .sup.aTack-free time. .sup.bat 0.5 to 5% elongation.

Examples 23 to 28

(38) For each example according to Table 9 under standard climate, component A of the commercial mounting adhesive Sikaflex®-553, based on silane-endcapped (available from Sika Schweiz AG) was mixed with a hardener or accelerator for epoxy resins in the form of a tertiary amine (Jeffcat® Z-130=N,N-dimethyl-N′-(dimethylaminopropyl)-1,3-propanediamine, from Huntsman; DMP=N,N′-dimethylpiperazine; Jeffcat® ZF-20=bis(2-dimethylaminoethyl)ether, from Huntsman) or an imidazole and a catalyst (DBU=1,8-diazabicyclo[5.4.0]undec-7-ene) and this composition was mixed as component A with emulsion E2 as component B in the indicated weight ratio using a dynamic mixer, applied immediately thereafter and hardened under standard climate conditions.

(39) TABLE-US-00009 TABLE 9 Two-component compositions. (Quantities in parts by weight) Example 23 24 25 26 27 28 component A: Sikaflex ®-553 Comp. A 88.4  88.6  87.7  89.2  89.0  88.7  Jeffcat ® Z-130 2.3 — — — — — DMP — 2.1 — — — — Jeffcat ® ZF-20 — — 3.0 — — — 1-Methylimidazole — — — 1.5 — — 1-Vinylimidazole — — — — 1.7 — 2-Ethyl-4- — — — — — 2.0 methylimidazole DBU 0.2 0.2 0.2 0.2 0.2 0.2 component B: Emulsion E2 9.1 9.1 9.1 9.1 9.1 9.1

(40) The compositions thus obtained were tested for stability, tack-free time and mechanical properties after 7 days (tensile strength, elongation at break, modulus of elasticity) or 14 days (Shore A) of hardening under standard climate conditions.

(41) The results of these tests are presented in Table 10.

(42) TABLE-US-00010 TABLE 10 Properties der compositions. Example 23 24 25 26 27 28 Stability very very very very very very good good good good good good Tack-free time.sup.a (min.) 8 14 13 8 7 25 Tensile strength (MPa) 3.8 3.8 3.8 3.6 3.5 3.9 Elongation at break (%) 120 240 180 290 280 230 Modulus of elasticity.sup.b 8.7 7.3 6.2 6.2 5.5 7.8 (MPa) Shore A 70 56 70 56 52 60 .sup.aTack-free time. .sup.bat 0.5 to 5% elongation.

Examples 29 and Ref7

(43) For each example according to Table 11 under standard climate conditions component A of the commercial mounting adhesive Korapop 225, based on silane-endcapped polymer (available from Kömmerling Chemische Fabrik GmbH, Germany) was mixed with a hardener or accelerator for epoxy resins in the form of a Mannich base (Ancamine® K54=2,4,6-tris(dimethylaminomethyl)phenol, from Air Products) and a (DBU=1,8-diazabicyclo[5.4.0]undec-7-ene) and this composition was mixed as component A with the emulsion E2 as component B in the indicated weight ratio using a dynamic mixer, applied immediately thereafter, and hardened under standard climate conditions.

(44) TABLE-US-00011 TABLE 11 Two-component compositions. (Quantities in parts by weight) Example Ref7 29 component A: Körapop 225 Comp. A 100 87.4 Ancamine® K54 — 3.3 DBU — 0.2 component B: emulsion E2 — 9.1

(45) The compositions thus obtained were tested for stability, tack-free time and mechanical properties after 7 days (tensile strength, elongation at break, modulus of elasticity) or 14 days (Shore A) of hardening under standard climate conditions.

(46) The results of these tests are listed in Table 12.

(47) TABLE-US-00012 TABLE 12 Properties der compositions. Example Ref7 29 Stability good very good Tack-free time.sup.a (min.) 27 23 Tensile strength (MPa) 2.6 3.0 Elongation at break (%) 420 180 Modulus of elasticity.sup.b 1.5 22.7 (MPa) Shore A 40 72 .sup.aTack-free time. .sup.bat 0.5 to 5% elongation.