Curable Compositions Comprising At Least One Silane-Modified Polymer

Abstract

The invention relates to adhesive, sealant, and/or coating materials comprising a curable composition and the use thereof, the curable composition comprising I. at least one silane-modified polymer obtainable by reacting (A) at least one polymer terminated with amine groups at both ends, which polymer is selected from polyester, polyether polyols, poly(meth)acrylates, polyolefins, and/or copolymers of the aforementioned and has a molecular weight M.sub.w between 250 and 10,000 Dalton, (B) at least one cycloaliphatic diisocyanate compound, and (C) at least one secondary aminosilane with two hydrolysable groups; II. surface treated silica; III. surface treated calcium carbonate; IV. at least one additional aminosilane; V. optionally, at least one adhesion promoter; VI. optionally, at least one pigment; VII. optionally, at least one catalyst; VIII. optionally, at least one plasticizer.

Claims

1. A curable composition comprising I. at least one silane-modified polymer obtainable by reacting (A) at least one polymer terminated with amine groups at both ends, wherein the at least one polymer is selected from polyester, polyether polyols, poly(meth)acrylates, polyolefins, and/or copolymers of the aforementioned and has a molecular weight M.sub.w between 250 and 10,000 Dalton, (B) at least one cycloaliphatic diisocyanate compound, and (C) at least one secondary aminosilane with two hydrolysable groups; II. surface treated silica; III. surface treated calcium carbonate; IV. at least one additional aminosilane; V. optionally, at least one adhesion promoter; VI. optionally, at least one pigment; VII. optionally, at least one catalyst; VIII. optionally, at least one plasticizer.

2. The curable composition according to claim 1, wherein the at least one polymer terminated with amine groups at both ends has formula (E I): ##STR00008## wherein at least one of xx, yy and zz is within a range from 1 to 250.

3. The curable composition according to claim 2, wherein xx, yy and zz are, independently of one another, within the range of from 1 to 250.

4. The curable composition according to claim 1, wherein one or more of the at least one polymer terminated with amine groups at both ends has a weight average molecular weight M.sub.w within a range of from 500 to 10,000 Dalton.

5. The curable composition according to claim 1, wherein one or more of the at least one polymer terminated with amine groups at both ends has an average amine hydrogen equivalent weight (AHEW) within a range of from 200 g/eq to 800 g/eq.

6. The curable composition according to claim 1, wherein (B) the at least one cycloaliphatic diisocyanate is selected from the group consisting of cyclobutane-1,3-diisocyanate, cyclohexane-1,3-diisocyanate, cyclohexane-1,4-diisocyanate, 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethylcyclohexane (isophorone diisocyanate, IPDI), 2,4-hexahydrotoluylene diisocyanate, 2,6-hexahydrotoluylene diisocyanate, hexahydro-1,3-phenylene diisocyanate or hexahydro-1,4-phenylene diisocyanate; partially or completely hydrogenated cycloalkyl derivatives of benzidine diisocyanate, naphthalene-1,5-diisocyanate, xylylene diisocyanate (XDI), tetramethylxylylene diisocyanate (TMXDI), 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, 2,4-toluylene diisocyanate (2,4-TDI), 2,6-toluylene diisocyanate (2,6-TDI), especially completely hydrogenated 2,4-TDI and 2,6-TDI (H6-2,4- and 2,6-TDI), 2,4-diphenylmethane diisocyanate, 2,2-diphenylmethane diisocyanate, 4,4-diphenylmethane diisocyanate (MDI), especially completely hydrogenated MDI (H12-MDI), alkyl-substituted diphenylmethane diisocyanates, especially mono-, di-, tri-, or tetraalkyldiphenylmethane diisocyanate, 4,4-diisocyanatophenylperfluorethane, phthalic acid-bis-isocyanatoethyl ester, 1 chloromethylphenyl-2,4- or -2,6-diisocyanate, 1-bromomethylphenyl-2,4-diisocyanate, 1-bromomethylphenyl-2,6-diisocyanate, 3,3-bis-chloromethyl ether-4,4-diphenyl diisocyanate; and mixtures of two or more of said diisocyanates.

7. The curable composition according to claim 6, wherein the at least one cycloaliphatic diisocyanate is selected from 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethylcyclohexane (isophorone diisocyanate, IPDI); completely hydrogenated 2,4-toluylene diisocyanate (H6-2,4-TDI); completely hydrogenated 2,6-toluylene diisocyanate (H6-2,6-TDI); and completely hydrogenated 4,4-diphenylmethane diisocyanate (H12-MDI).

8. The curable composition according to claim 1, wherein (C) the at least one secondary aminosilane has the formula (E II) ##STR00009## wherein a is 0 or 1; R.sup.1 is a divalent hydrocarbon residue having 1 to 12 carbon atoms and linking the N and Si atom; X, Y, Z are, independently of one another, selected from the group consisting of a hydroxyl group, a C.sub.1 to C.sub.12 alkyl, or a C.sub.1 to C.sub.12 alkoxy group with the proviso that if a is 0 one of X, Y or Z is a hydrolysable group.

9. The curable composition according to claim 1, wherein the at least one secondary aminosilane is selected from the group consisting of N-(n-butyl)-3-aminopropylmethyldimethoxysilane; (N-2-aminoethyl)-3-aminopropylmethyldimethoxysilane; 3-aminopropylmethyldiethoxysilane; N-(n-butyl)-3-aminopropylmethyldimethoxysilane; 1-butanamino-4-(dimethoxymethylsilyl)-2,2-dimethyl; (N-cyclohexylaminomethyl)-methyldiethoxysilane; (N-phenylaminomethyl)-methyldimethoxysilane; 3-(N,N-dimethylaminopropyl) aminopropylmethyldimethoxysilane and mixtures thereof.

10. The curable composition according to claim 1, wherein the at least one silane-modified polymer is obtainable by reacting at least one amine terminated polyether polyol having a molecular weight M.sub.w between 250 and 10,000 Dalton (A), at least one cycloaliphatic diisocyanate compound (B), and at least one secondary aminosilane with two a hydrolysable groups (C), in the presence of one plasticizer, and/or at least one catalyst.

11. The curable composition according to claim 1, wherein the surface treated silica has a BET surface area of 10 to 250 m.sup.2/g.

12. The curable composition according to claim 1, wherein the surface treated calcium carbonate comprises particles comprising a treatment layer on the surface of the calcium carbonate particles comprising i. a phosphoric acid ester blend of one or more phosphoric acid mono-ester and salty reaction products thereof and/or one or more phosphoric acid di-ester and salty reaction products thereof, and/or ii. at least one saturated aliphatic linear or branched carboxylic acid and salty reaction products thereof, and/or iii. at least one aliphatic aldehyde and/or salty reaction products thereof, and/or iv. at least one mono-substituted succinic anhydride consisting of succinic anhydride mono-substituted with a group selected from a linear, branched, aliphatic and cyclic group having a total amount of carbon atoms from at least C.sub.2 to C.sub.30 in the substituent and/or salty reaction products thereof, and/or v. at least one polydialkylsiloxane, and/or vi. mixtures of i. to v.

13. The curable composition according to claim 1, wherein (i) the amount of said at least one silane-modified polymer is from 5% by weight to 70% by weight; and/or (ii) the amount of said surface treated silica is from 0.01% by weight to 10% by weight; and/or (iii) the amount of said surface treated calcium carbonate is to 1% by weight to 80% by weight by weight; and/or (iv) the amount of said at least one additional aminosilane is 0.01% by weight to 15% by weight; and/or (v) the amount of said at least one catalyst is 0% by weight to 5% by weight.

14. An adhesive, sealant, or coating material comprising the curable composition according to claim 1.

Description

EXAMPLES

[0210] Unless otherwise stated, the examples which follow are carried out at a pressure of the surrounding atmosphere, in other words approximately at 1,000 hPa, and at room temperature, in other words at approximately 23 C., and/or at a temperature which comes about when the components are combined at room temperature without additional heating or cooling, and also at a relative atmospheric humidity of approximately 50%. Furthermore, all FIGURES for parts of percentages, unless otherwise stated, are by weight.

[0211] The formulations were prepared as described in the tables below, wherein the component were added to the reaction vessel in the following order: 1. polyetheramine, 2. plasticizer, 3. catalyst, 4. diisocyanate, 5. secondary aminosilane, 6. stabilizer, 7. water scavenger.

TABLE-US-00001 TABLE 1 Comparative Comparative Example 1 Example 2 Example 3 Component [wt. %] [wt. %] [wt. %] polyetherdiamine.sup.1 61.52 61.52 61.52 glutaric acid dimethylester.sup.2 10.00 10.00 10.00 dioctyltin laurate.sup.3 0.0158 0.0158 0.0158 isophorone diisocyanate 12.56 12.56 12.56 3-(dimethoxy methyl silyl) propylamine 13.22 N-(n-butyl)-3-aminopropyltrimethoxysilane.sup.4 13.22 amino silane N-(n-butyl)-3- 13.22 aminopropylmethyldimethoxysilane bis(2,2,6,6-tetramethyl-4- 1.14 1.14 1.14 piperidyl)sebaceate.sup.5 Vinyltrimethoxysilane.sup.6 1.55 1.55 1.55 .sup.1Jeffamine ED2003 available from Huntsman Corporation (USA); predominately based on a PEG backbone terminated with amine groups at both ends according to formula (E-I) with yy 39 and xx + zz 6; M.sub.w: 2,000; average Amine Hydrogen Equivalent Weight (AHEW): 575 g/eq .sup.2DBE-5 dibasic ester available from Sigma-Aldrich, an affiliate of Merck KGaA (Germany); plasticizer .sup.3TIB Kat 216 available from Nantong Haotai Products & Chemicals Co., Ltd.; catalyst .sup.4Dynasylan 1189 available from Evonik Industries AG (Germany) .sup.5Tinuvin 770 from BASF AG (Germany); stabilizer .sup.6Geniosil XL 10 from Wacker Chemie AG (Germany); water scavenger

TABLE-US-00002 TABLE 2 Comparative Comparative Comparative Example Example Component Example 4 Example 5 Example 6 7 8 Comparative Example 15.20 1 Comparative Example 19.50 14.70 2 Example 3 35.47 35.47 glutaric acid 3.00 3.00 3.00 7.00 7.00 dimethylester.sup.2 carbon black.sup.7 0.30 0.30 0.30 0.70 0.70 ultrafine surface 10.00 6.00 10.50 23.33 treated precipitated calcium carbonate.sup.8 ultrafine surface 23.33 treated precipitated calcium carbonate.sup.9 hydrophobic 0.30 / 0.30 0.70 0.70 pyrogenic silica treated with dimethyl dichlorsilane.sup.10 3-aminopropyl 0.60 0.60 0.60 1.40 1.40 trimethoxy silane.sup.11 Vinyltrimethoxysilane.sup.7 0.30 0.30 0.30 0.70 0.70 dioctyltin laurate.sup.3 0.30 0.30 0.30 0.70 0.70 .sup.7Printex 60 available from Orion Engineered Carbon S.A. (USA) .sup.8Socal U1S1 G available from Imerys S.A. (France) .sup.9Viscoexcel 30 available from Omya AG (Switzerland) .sup.10Aerosil 974 available from Evonik Industries AG (Germany) .sup.11Geniosil GF 96 available from Wacker Chemie AG (Germany)

[0212] The resulting product was subjected to curing performance tests as follows:

[0213] Tensile strength and elongation: The tensile strength and elongation at break were determined in accordance with DIN 53504. The samples were cured in a mold at room temperature over seven days. The specimen type S2 (Dog bone) was used and the speed of the pull head in the dynamometer was 200 mm/min.

[0214] Skin-over time (SOT): Skin-over time (SOT) is defined as the time required for the material to form a non-tacky surface film. The determination of the skin over time is carried out according to DIN 50014 under standard climate conditions (23+/2 C., relative humidity 50+/5%). The temperature of the sealant must be 23+/2 C., with the sealant/adhesive stored for at least 24 h beforehand in the laboratory. The sealant/adhesive is applied to a sheet of paper and spread out with a putty knife to form a skin (thickness about 2 mm, width about 7 cm). The stopwatch is started immediately. At intervals, the surface is touched lightly with the fingertip and the finger is pulled away, with sufficient pressure on the surface that an impression remains on the surface when the skin formation time is reached. The skin-over time is reached when sealing compound no longer adheres to the fingertip. The skin-over time (SOT) is expressed in minutes.

[0215] Surface tackiness (TFT): To determine surface tackiness from an adhesive sealing material, the aforementioned compositions were homogenized and applied in a frame (50 mm130 mm2 mm) in the same way as the SOT determination. After 60 minutes, the tackiness of the surface was evaluated using a tool which has a rounded spatula at the tip (150 mm5 mm) by careful contact with the surface of the polymer film, TFT of <60 min indicates not tacky and of >60 min indicates tacky (including slightly tacky).

[0216] Shore A hardness: Shore A hardness was measured according to ISO 868.

[0217] Depth of cure (DOC): A strip of the material with a height of 10 mm (+/1 mm) and width of 20 mm (+/2 mm) was applied over a plastic foil (PP) using a Teflon spatula. After storing the sample for 24 hours at normal conditions (23+/2 C., relative humidity 50+/5%), a section of the strip was cut off and the thickness of the cured layer was measured with a caliper. The depth of cure after 24 hours is expressed in millimeters.

[0218] Peel test: If possible and needed, substrate (test panel) is cleaned prior to application using a suitable solvent (e.g., isopropanol, acetone). A bead of the material with a height of 10 mm (+/1 mm) and width of 20 mm (+/2 mm) was applied over the substrate using a Teflon spatula/cartridge and cartridge gun. The sample was stored for 7 days at normal conditions (23+/2 C., relative humidity 50+/5%). The cured material was cut back for at least 15 mm with a shape blade and the bead pulled by hand. Failure mode was recorded as.sub.ncf 60, .sub.cf 100, wherein .sub.cf XX refers to XX % of wetted surface shows cohesive break.

af (1-3): adhesion failure, additional evaluation: rating scale from 1=strong adhesion to 3=no adhesion

TABLE-US-00003 TABLE 3 Test Results Comparative Comparative Comparative Example Example Example 4 Example 5 Example 6 7 8 Skin over time 147 55 42 243 240 (SOT) [min] TFT [h] <24 <24 <24 <24 <24 Depth of cure 3.3 3.9 4.8 3.8 3.9 [mm/24 h] Shore A 70 55 69 59 59 hardness 7 d Elongation 233 290 150 642 576 Tensile strength 4.95 5.66 4.27 7.15 5.14

TABLE-US-00004 TABLE 4 Adhesion test Comparative Sample Example 5 Example 7 Example 7 Example 8 Example 8 Storage A2/1 A2/1 A2/2 A2/1 A2/2 condition.sup.12 PVC cf100 cf100 cf100 cf100 cf100 PMMA af1 cf100 cf100 af1 cf100 Glass cf100 af2 af2 af2 af2 Anodized af1 cf100 cf100 af1 af1 aluminum Brass cf100 cf100 cf100 af1 cf100 Stainless steel cf100 cf100 cf100 af1 cf100 Glass fiber cf100 cf100 cf100 af1 cf100 reinforced epoxy PA 6.6. cf60 af1 af1 af1 af1 Aluminum af2 af3 af3 af3 af3 Magnesium Silicon alloy Al-Mg-Si-1 .sup.12A2/1: 1 week at 23 C., 50% r.h.; A2/2: 2 weeks at 23 C., 50% r.h.