One-component polyurethane adhesive

Abstract

Provided herein are one-component polyurethane adhesive compositions that exhibit excellent adhesive strength to glass surfaces.

Description

[Technical field]

[0001] The present invention relates to the field of one-component polyurethane adhesives, in particular for bonding to glass. [Background technology]

[0002] One-part polyurethane adhesives are widely used in the automotive industry, especially to facilitate fast windshield repairs. Commercially available adhesives are designed to provide a high modulus (Young's modulus less than 4.0 MPa) to provide good vehicle stiffness and a smooth ride. To meet consumer demands, adhesives are designed to allow the customer to safely drive the vehicle within 30 minutes of applying the adhesive (MDAT, minimum drive-away time). However, such adhesives require a primer on the glass frit of the replacement windshield to obtain good bond strength (lap shear value less than 350 psi). Although adhesives that provide primerless adhesion to glass frit have been reported, these adhesives lack the desired high modulus and 30-minute MDAT. Summary of the Invention [Problem to be solved by the invention]

[0003] There is a need for a one-part polyurethane adhesive for windshield repair that provides high modulus, excellent primerless adhesion, and an MDAT of 30 minutes or less. [Means for solving the problem]

[0004] In a first aspect, the present invention provides a one-component polyurethane adhesive composition comprising: (A) at least one polyether prepolymer in a total polyether prepolymer content of 50 to 57% by weight; (B) at least one polyester prepolymer in a total content of polyester prepolymers of 1.2 to 2.0 wt. %; (C) at least one aliphatic polyisocyanate in a total aliphatic polyisocyanate content of 0.4 to 1.2 wt. %; (D) at least one aromatic polyisocyanate in a total aromatic polyisocyanate content of 0.4 to 1.2% by weight; (E) at least one isocyanate-functionalized silane in a total isocyanate-functionalized silane content of 0.4 to 1.5 wt.%; (F) 0.50 to 0.99 wt. % of an amine catalyst; (G) at least one mercaptosilane in a total mercaptosilane content of less than 1.2 wt.%, with the combination of amino and / or mercaptosilane being at least 0.6 wt.%, and / or (G') at least one aminosilane in a total aminosilane content of less than 0.5 wt.%; (H) 17-20% by weight carbon black; (I) 3 to 30% by weight of calcium carbonate; (J) optionally, 0 to 27% by weight of a filler other than calcium carbonate and / or carbon black; wherein the total polyisocyanate content is 1.2-3 wt. %, the sum of calcium carbonate plus filler is 20-30 wt. %, and the weight percentages are based on the total weight of the polyurethane adhesive.

[0005] In a second aspect, the present invention provides a method for producing a pharmaceutical composition comprising the steps of: A glass substrate; A second substrate; wherein a layer of the adhesive composition of the present invention is in adhesive contact with both substrates.

[0006] In a third aspect, the present invention provides a method for bonding a glass substrate to a second substrate, comprising the steps of: (1) providing a glass substrate and a second substrate; (2) applying the adhesive composition of the present invention to a glass substrate, a second substrate, or both; (3) assembling the glass substrate with a second substrate such that the adhesive is in adhesive contact with both substrates; The present invention provides a method comprising: DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0007] The inventors have surprisingly found that the adhesive composition according to claim 1 meets the requirement of a 30 minute drive-away time, i.e. · Impact strength after 30 minutes exceeding 3.4 J; ·Young's modulus above 4 MPa; Lap shear strength on fritted glass exceeding 350 psi and cohesive failure exceeding 80% after 3 days at 23°C and 50% RH; Preferably 1×10 8 Electrical resistivity above ohm*cm It was found that the following is satisfied.

[0008] Definitions and Abbreviations MDI: 4,4'-methylenebis(phenylisocyanate) HDI: Hexamethylene diisocyanate PU: Polyurethane.

[0009] Polymer molecular weights reported herein are reported as number average or weight average molecular weight in Daltons (Da) as determined by size exclusion chromatography (SEC).

[0010] The one-component polyurethane adhesive composition of the present invention comprises: (A) at least one polyether prepolymer in a total polyether prepolymer content of 50 to 57% by weight; (B) at least one polyester prepolymer in a total content of polyester prepolymers of 1.2 to 2.0 wt. %; (C) at least one aliphatic polyisocyanate in a total aliphatic polyisocyanate content of 0.4 to 1.2 wt. %; (D) at least one aromatic polyisocyanate in a total aromatic polyisocyanate content of 0.4 to 1.2% by weight; (E) at least one isocyanate-functionalized silane in a total isocyanate-functionalized silane content of 0.4 to 1.5 wt.%; (F) 0.50 to 0.99 wt. % of an amine catalyst; (G) at least one mercaptosilane in a total mercaptosilane content of less than 1.2 wt.%, with the combination of amino and / or mercaptosilane being at least 0.6 wt.%, and / or (G') at least one aminosilane in a total aminosilane content of less than 0.5 wt.%; (H) 17-20% by weight carbon black; (I) 3 to 30% by weight of calcium carbonate; (J) optionally, 0 to 27% by weight of a filler other than calcium carbonate and / or carbon black; wherein the total polyisocyanate content is 1.2-3 wt. %, and the sum of calcium carbonate plus filler is 20-30 wt. %, and the weight percentages are based on the total weight of the polyurethane adhesive.

[0011] Polyether prepolymer (A) The composition of the present invention comprises 50 to 57 weight percent of the polyether prepolymer, based on the total weight of the composition.

[0012] Polyether prepolymers include polymers made by polymerizing one or more polyether polyols in the presence of a polyisocyanate, preferably a diisocyanate. Polyether polyols useful in the present invention include, for example, polyether polyols, poly(alkylene carbonate) polyols, hydroxyl-containing polythioethers, polymer polyols, and mixtures thereof. Polyether polyols are well known in the art and include, for example, polyoxyethylene, polyoxypropylene, polyoxybutylene, and polytetramethylene ether diols and triols, which are prepared by reacting unsubstituted or halogen- or aromatic-substituted ethylene oxide or propylene oxide with an initiator compound containing two or more active hydrogen groups, such as water, ammonia, polyhydric alcohols, or amines. Typically, polyether polyols can be prepared by polymerizing alkylene oxides in the presence of active hydrogen-containing initiator compounds. Preferred polyether polyols contain one or more alkylene oxide units in the polyol backbone. Preferred alkylene oxide units are ethylene oxide, propylene oxide, butylene oxide and mixtures thereof. Preferably, the polyol comprises propylene oxide units, ethylene oxide units or mixtures thereof. In embodiments where a mixture of alkylene oxide units is included in the polyol, the different units may be arranged randomly or in blocks of each alkylene oxide. In a preferred embodiment, the polyol comprises propylene oxide chains with ethylene oxide chains capping the polyol. In a preferred embodiment, the polyether polyol is a mixture of polyether diols and polyether triols. Preferably, the polyether polyol or mixture has a functionality of at least about 1.5, more preferably at least about 1.8, most preferably at least about 2.0; it is preferably about 4.0 or less, more preferably about 3.5 or less, most preferably about 3.0 or less.Preferably, the equivalent weight of the polyether polyol mixture is at least about 200, more preferably at least about 500, more preferably at least about 1,000; preferably no more than about 5,000, more preferably no more than about 3,000, and most preferably no more than about 2,500.

[0013] More specific examples include: 1. Difunctional polyols (diols) such as poly(alkylene oxide) diols, in which the alkylene groups are C2-C4, particularly poly(ethylene oxide) diol, poly(propylene oxide) diol and poly(tetramethylene oxide) diol, with poly(propylene oxide) diol being especially preferred. In a particularly preferred embodiment, the polyether prepolymer comprises a nominally difunctional poly(propylene oxide) (equivalent weight 1000) having a hydroxyl number of 56. 2. Trifunctional polyols (triols), such as those based on alkylene oxides initiated with a trifunctional polyol such as trimethylolpropane, where the alkylene groups are C2-C4, especially ethylene oxide, propylene oxide and butylene oxide, with propylene oxide being especially preferred. In a particularly preferred embodiment, the polyether prepolymer comprises a nominally trifunctional poly(propylene oxide) (equivalent weight 1558) having a hydroxyl number of 36; the polymer may or may not be capped with ethylene oxide to modify reactivity. 3. Mixtures of 1 and 2. Particularly preferred are mixtures of 1 and 2, more particularly preferred are mixtures of a) a nominally difunctional poly(propylene oxide) having a hydroxyl number of 56 (equivalent weight 1000) with b) a nominally trifunctional poly(propylene oxide) having a hydroxyl number of 36 (equivalent weight 1558), especially in a weight ratio b) / a) of 1:2 to 2:1.

[0014] The diisocyanate that can be used to prepare polyether prepolymer is not particularly limited.Aliphatic and aromatic diisocyanates can be used.Examples of suitable diisocyanates include toluene diisocyanate (TDI), hexamethylene diisocyanate (HDI), naphthalene diisocyanate (NDI), methylene bis-cyclohexyl isocyanate (HMDI) (hydrogenated MDI) and isophorone diisocyanate (IPDI), with MDI being particularly preferred.

[0015] In a particularly preferred embodiment, the polyether prepolymer comprises a nominally trifunctional poly(propylene oxide) having a hydroxyl number of 36 (equivalent weight 1558) and a nominally trifunctional poly(propylene oxide) having a hydroxyl number of 56 (equivalent weight 1000) reacted with MDI.

[0016] In a preferred embodiment, the polyether prepolymer has an isocyanate content of 1.25% by weight and a viscosity of 16,000 cps at 23° C. as measured according to the procedure set forth in U.S. Pat. No. 5,922,809, column 12, lines 38-49.

[0017] The polyether prepolymer is present in an amount of 50 to 57% by weight, more preferably 51 to 54% by weight, and more particularly preferably 52 to 54% by weight, based on the total weight of the adhesive composition.

[0018] In a particularly preferred embodiment, the adhesive composition of the present invention comprises 52-54 wt. % polyether prepolymer, based on the total weight of the adhesive composition, comprising a nominally trifunctional poly(propylene oxide) having a hydroxyl number of 36 (equivalent weight 1558) and a nominally trifunctional poly(propylene oxide) having a hydroxyl number of 56 (equivalent weight 1000), reacted with MDI, and has an isocyanate content of 1.25 wt. % and a viscosity of 16,000 cps at 23° C., as measured according to the procedure described in U.S. Pat. No. 5,922,809, column 12, lines 38-49.

[0019] Polyester prepolymer (B) The adhesive composition of the present invention contains 1.2 to 2.0% by weight of the polyester prepolymer, based on the total weight of the composition.

[0020] Polyester polyols include polymers made by reacting one or more linear copolyesters having primary hydroxyl functionality with a polyisocyanate, preferably a diisocyanate. Copolyesters having a molecular weight of 3,000 to 4,000 Da, preferably 3,500 Da, are particularly preferred.

[0021] The diisocyanate that can be used in the preparation of polyester prepolymer is not particularly limited.Aliphatic and aromatic diisocyanates can be used.Examples of suitable diisocyanates include toluene diisocyanate (TDI), hexamethylene diisocyanate (HDI), naphthalene diisocyanate (NDI), methylene bis-cyclohexyl isocyanate (HMDI) (hydrogenated MDI) and isophorone diisocyanate (IPDI), with MDI being particularly preferred.

[0022] In a preferred embodiment, the polyester prepolymer is made by reacting a 3,500 Da molecular weight copolyester with MDI, preferably having a melting point of 45-90°C.

[0023] The polyester prepolymer is present at 1.2 to 2.0 weight percent based on the total weight of the composition, preferably 1.25 to 1.55 weight percent, and more preferably 1.3 to 1.5 weight percent based on the total weight of the adhesive composition.

[0024] Aliphatic polyisocyanate (C) The adhesive composition of the present invention contains at least one aliphatic polyisocyanate in a total aliphatic polyisocyanate content of 0.4 to 1.2% by weight.

[0025] Aliphatic polyisocyanates are not particularly limited. Some examples include isophorone diisocyanate, 1,6-hexamethylene diisocyanate, bis(4-isocyanatocyclohexyl)methane, and trimethylhexamethylene diisocyanate, any of which may be modified to include biuret, allophanate, urea, carbamate, isocyanurate, or carbodiimide groups.

[0026] In a preferred embodiment, the aliphatic polyisocyanate is based on an HDI trimer with an NCO content of 21.8±0.3% (according to DIN EN ISO 11 909).

[0027] The aliphatic polyisocyanate is present in the adhesive composition of the present invention at 0.4 to 1.2 wt %, preferably 0.45 to 1 wt %, and more preferably 0.5 to 1 wt %, based on the total weight of the composition.

[0028] In a particularly preferred embodiment, the aliphatic polyisocyanate is an HDI trimer having an NCO content of 21.8±0.3% (according to DIN EN ISO 11 909), which is 0.5 to 1% by weight, based on the total weight of the adhesive composition.

[0029] Aromatic polyisocyanates (D) The adhesive composition of the present invention contains (D) at least one aromatic polyisocyanate, with the total content of the aromatic polyisocyanate being 0.4 to 1.2 wt % based on the total weight of the adhesive composition.

[0030] Examples of aromatic polyisocyanates include, but are not limited to, diphenylmethane diisocyanate (MDI), polymethylene polyphenylisocyanate, polymeric MDI (PMDI, a mixture of diphenylmethane diisocyanate and polymethylene polyphenylisocyanate), tetramethylxylene diisocyanate, and toluene diisocyanate, any of which may be modified to include biuret, allophanate, urea, carbamate, isocyanurate, or carbodiimide groups.

[0031] In a preferred embodiment, the aromatic polyisocyanate is an MDI-containing polymethylene polyphenylisocyanate with an NCO content (according to DIN EN ISO 11 909) of 30.4%.

[0032] The aromatic polyisocyanate is used in an amount of 0.4 to 1.2% by weight, preferably 0.5 to 1% by weight, and more preferably 0.75% by weight, based on the total weight of the adhesive composition.

[0033] In a particularly preferred embodiment, the aromatic polyisocyanate is a polymethylene polyphenylisocyanate containing 0.5 to 1 wt.-%, more preferably 0.75 wt.-%, MDI, based on the total weight of the adhesive composition, having an NCO content of 30.4% (according to DIN EN ISO 11 909).

[0034] Isocyanate-functionalized silanes (E) The adhesive composition of the present invention comprises (E) at least one isocyanate-functionalized silane, with a total isocyanate-functionalized silane content of 0.4 to 1.5 weight percent, based on the total weight of the adhesive composition.

[0035] The isocyanate-functionalized silane is not particularly limited. For example, a polyisocyanate compound such as toluene diisocyanate, methylene diphenyl diisocyanate, etc. is reacted with a polyalkylene oxide having a terminal hydroxyl group to produce a polyalkylene oxide having a terminal isocyanate group, and then the polyalkylene oxide having the formula: [ka] (Wherein, W is an active hydrogen-containing group selected from the group consisting of a hydroxyl group, a carboxyl group, a mercapto group, a primary amino group, and a secondary amino group; X is a hydrolyzable alkoxy group; R 4 is C1~C 20 Alkyl, C6-C 20 Aryl, C1-C20 An aralkyl group, R is C1-C 20 and b is 0, 1 or 2. with the active hydrogen-containing group W of the silicone compound.

[0036] For more examples, · reaction products of aminosilanes with polyisocyanates; · reaction products of mercaptosilanes with polyisocyanates; · reaction products of carboxylate-functionalized silanes with polyisocyanates; · Isocyanate-functionalized silanes such as (3-isocyanatopropyl)trimethoxysilane Examples include:

[0037] Particularly preferred are the reaction products of aminosilanes with polyisocyanates, more particularly aminosilanes that are secondary amines.

[0038] In a preferred embodiment, the isocyanate-functionalized silane is the reaction product of a secondary aminoalkoxysilane and a polyisocyanate, such as the reaction product of N,N-bis[(3-trimethoxysilyl)-propyl]amine reacted with HDI-biuret.

[0039] In a particularly preferred embodiment, the isocyanate-functionalized silane is a reaction product of N,N-bis[(3-trimethoxysilyl)-propyl]amine) reacted with HDI-biuret and has an isocyanate content of 7%. The isocyanate-functionalized silane may include additional inert additives such as plasticizers.

[0040] The isocyanate functionalized silane is present at 0.4 to 1.5 weight percent, preferably 0.6 to 1.2 weight percent, and more preferably 0.85 to 0.97 weight percent, based on the total weight of the adhesive composition.

[0041] In a particularly preferred embodiment, the isocyanate-functionalized silane is a reaction product of N,N-bis[(3-trimethoxysilyl)-propyl]amine) reacted with HDI-biuret at 0.8-1.0 wt. %, preferably 0.85-0.97 wt. %, based on the total weight of the adhesive composition, having an isocyanate content of 7%.

[0042] Amine Catalyst (F) The adhesive composition of the present invention contains (F) 0.50 to 0.99% by weight of an amine catalyst, based on the total weight of the adhesive composition.

[0043] The amine catalyst is any amine catalyst capable of catalyzing the reaction of isocyanates with moisture.Preferred are tertiary amines, such as aliphatic cyclic and non-cyclic tertiary amines, such as N,N-dimethylcyclohexane, triethylenediamine, N,N,N,N-tetramethylalkylenediamine, N,N,N,N-pentamethyldiethylenetriamine, triethylamine, N,N-dimethylbenzylamine, N,N-dimethylhexadecylamine, N,N-dimethylbutylamine, 2,2'-dimorpholinodiethyl ether.

[0044] 2,2'-Dimorpholinodiethyl ether is particularly preferred.

[0045] The amine catalyst is used in an amount of 0.5 to 0.99 wt %, preferably 0.6 to 0.8 wt %, and more preferably 0.75 wt %, based on the total weight of the adhesive composition.

[0046] In a preferred embodiment, the amine catalyst is 0.75 wt % 2,2'-dimorpholinodiethyl ether, based on the total weight of the adhesive composition.

[0047] The adhesive composition of the present invention may additionally include tin catalysts, zinc catalysts (eg, zinc carboxylates), bismuth catalysts, and mixtures thereof.

[0048] Mercaptosilane (G) The adhesive composition of the present invention comprises (G) less than 1.2 wt. % of at least one mercaptosilane, and / or (G') less than 0.5 wt. % of at least one aminosilane, the combination of amino and / or mercaptosilane being at least 0.6 wt. % based on the total weight of the adhesive composition.

[0049] The mercaptosilane is not particularly limited. [ka] (In the formula, R 1 , R 2 and R 3 are independently selected from OCH3 and OC2H5; and R 4 is C n H 2n and n is an integer from 1 to 12. Mercaptosilanes of the formula: are particularly preferred.

[0050] Particularly preferred is R 1 , R 2 and R 3 is OCH3, and n is 1 to 6.

[0051] In a preferred embodiment, the mercaptosilane is gamma-mercaptopropyltrimethoxysilane.

[0052] The at least one mercaptosilane is preferably present in a total mercaptosilane content of less than 1.2 wt.-%, more preferably 0.9-1 wt.-%, especially preferred 0.91-0.95 wt.-%, based on the total weight of the adhesive composition.

[0053] In particularly preferred embodiments, the at least one mercaptosilane is 0.93, 0.94, or 0.95 wt. % gamma-mercaptopropyltrimethoxysilane, based on the total weight of the adhesive composition.

[0054] Aminosilane (G') The adhesive composition of the present invention comprises (G) less than 1.2 wt. % of at least one mercaptosilane, and / or (G') less than 0.5 wt. % of at least one aminosilane, the combination of amino and / or mercaptosilane being at least 0.6 wt. % based on the total weight of the adhesive composition.

[0055] The aminosilane is not particularly limited. Primary and secondary aminosilanes can be used. Silanes containing secondary amines, particularly those having the following formula: [ka] (In the formula, R 1 , R 2 , R 3 , R 4 , R 5 and R 6 is independently selected from OCH3 and OC2H5; and R 7 and R 8 is C n H 2n where n is an integer from 1 to 6, and preferably n is 3. The aminosilanes of the formula are particularly preferred.

[0056] In a preferred embodiment, the at least one aminosilane is bis(γ-trimethoxysilylpropyl)amine.

[0057] The at least one aminosilane is preferably present at a total aminosilane content of less than 0.5 wt%, more preferably less than 0.15 wt%, for example 0.05 or 0.11 wt%, based on the total weight of the adhesive composition.

[0058] In a particularly preferred embodiment, the at least one aminosilane is bis(γ-trimethoxysilylpropyl)amine at 0.11 wt %, based on the total weight of the adhesive composition.

[0059] Carbon Black (H) The adhesive composition of the present invention contains (H) carbon black in an amount of 17 to 20% by weight based on the total weight of the adhesive composition.

[0060] The carbon black is not particularly limited. Preferred carbon black has a molecular weight of at least 80, preferably at least 90, more preferably at least 95 cm3 of dibutyl phthalate per 100 g of carbon black as measured in accordance with ASTM D-2414-09. 3 Additionally, the carbon black desirably has an iodine number of at least 80 as determined in accordance with ASTM D1510-11.

[0061] The carbon black is present at 17 to 20 weight percent, preferably 17.6 to 18 weight percent, based on the total weight of the adhesive composition.

[0062] Calcium carbonate(I) The adhesive composition of the present invention contains (I) 3 to 30% by weight of calcium carbonate, based on the total weight of the adhesive composition.

[0063] Preferably, the calcium carbonate is present at 6 to 10 wt %, more preferably 7 to 8 wt %, based on the total weight of the adhesive composition.

[0064] The total content of calcium carbonate plus filler is 20-30% by weight based on the total weight of the composition.

[0065] Filler(J) The adhesive composition of the present invention optionally contains an additional filler other than calcium carbonate and / or carbon black, in an amount of 0 to 27% by weight, based on the total weight of the composition.

[0066] Examples of suitable fillers include clays, zeolites and silicates.

[0067] The filler may be a clay, which may be present at 0-27% by weight. The clay is not particularly limited. Preferably, the clay is in the form of a crushed powder, spray-dried beads or finely ground particles. Surface-treated aluminum silicate is an example. Calcined aluminum silicate clay (kaolin) is preferred.

[0068] The total content of calcium carbonate plus filler, e.g. clay, is 20-30% by weight, based on the total weight of the composition.

[0069] In a preferred embodiment, the adhesive composition of the present invention contains 20 to 25 wt %, more preferably 21 to 24 wt %, particularly preferably 22 to 23 wt %, of clay, based on the total weight of the adhesive composition.

[0070] Other Ingredients The adhesive composition of the present invention may additionally contain other ingredients such as, for example, one or more plasticizers (such as diisononyl phthalate), one or more stabilizers such as heat stabilizers, light stabilizers, and UV stabilizers.

[0071] Examples of heat stabilizers include alkyl-substituted phenols, phosphites, sebacates and cinnamates. When present, the preferred heat stabilizer is an organic phosphite, more specifically trisnonylphenyl phosphite, as disclosed in U.S. Pat. No. 6,512,033 (hereby incorporated by reference). The heat stabilizer may comprise at least 0.01 or at least 0.3 wt.%, up to 5 wt.%, up to 2 wt.%, or up to 1.0 wt.%, based on the total weight of the adhesive composition. The adhesive composition may be free of such heat stabilizers.

[0072] As for the UV light stabilizer, benzophenone and benzotriazole are included.Specific UV light absorbers include those from BASF such as TINUVIN® P, TINUVIN® 326, TINUVIN® 213, TINUVIN® 327, TINUVIN® 571, TINUVIN® 328, and those from Cytec such as CYASORB® UV-9, CYASORB® UV-24, CYASORB® UV-1164, CYASORB® UV-2337, CYASORB® UV-2908, CYASORB® UV-5337, CYASORB® UV-531 and CYASORB® UV-3638.Among these, TINUVIN® 571 is preferred. The one or more UV light absorbers may comprise at least 0.1 wt%, at least 0.2 wt%, or at least 0.3 wt% of the adhesive composition's weight, and may comprise up to 3 wt%, up to 2 wt%, or up to 1 wt% thereof.

[0073] The adhesive composition of the present invention may further comprise one or more light stabilizers. Preferred light stabilizers included hindered amine light stabilizers such as TINUVIN® 144, TINUVIN® 622, TINUVIN® 77, TINUVIN® 123, TINUVIN® 765, CHIMASSORB® 944 available from Cytec; CYASORB® UV-500, CYASORB® UV-3581, CYASORB® UV-3346, all available from Ciba-Geigy. Among these, TINUVIN® 765 is a preferred choice. The light stabilizer may comprise at least 0.1%, at least 0.2%, or at least 0.3% by weight of the adhesive composition, and may comprise up to 3%, up to 2%, or up to 1.5% by weight thereof.

[0074] Glued Assembly In one aspect, the present invention provides a method for producing a method for treating a cancer cell comprising: A glass substrate; A second substrate; wherein a layer of the adhesive composition of the present invention is in adhesive contact with both substrates.

[0075] The second substrate is not particularly limited and may be, for example, glass, metal (especially primed metal), e-coated surfaces, painted surfaces, wood, and cured polyurethane. In a preferred embodiment, the second substrate is selected from metal (especially primed metal), e-coated surfaces, cured polyurethane, and cured silane-treated polyurethane.

[0076] The adhesive of the present invention is particularly suitable for use in the aftermarket, particularly for bonding windshields to automobile chassis. Typically, damaged windshields are removed from the chassis, leaving the original cured adhesive, which is cut or trimmed to remove excess. The adhesive of the present invention is applied to the cut cured adhesive (usually a PU-based adhesive, but could be a silanated PU). The adhesive of the present invention achieves an impact strength (and other requirements) of over 3.4 J after 30 minutes, allowing for a 30 minute drive away time.

[0077] In a particularly preferred embodiment, the assembly of the invention comprises: A glass substrate; A cured adhesive substrate (such as cured polyurethane or cured silanized polyurethane) and a layer of the adhesive composition of the present invention is in adhesive contact with both substrates.

[0078] Manufacturing method The adhesive compositions of the present invention are prepared by mixing the ingredients under inert and dry conditions and / or under vacuum until a homogeneous mixture is obtained.

[0079] In one preferred method of manufacture, calcium carbonate, filler (if used), and carbon black are mixed and dried at high temperature (e.g., at or about 204° C.) for an extended period of time (e.g., at or about 20 hours), then cooled in a closed container to form a filler mixture. The polyester prepolymer may be heated to 80° C. for about 15 hours before use. The polyether prepolymer, amine catalyst, aliphatic polyisocyanate, optional plasticizer (e.g., diisononyl phthalate), and isocyanate-functionalized silane are placed in a mixer. The mixture may be degassed and mixed under vacuum. The vacuum is broken with nitrogen, and the mercaptosilane and aminosilane are added, followed by further degassing and mixing under vacuum. The vacuum is broken again with nitrogen, and the filler mixture is added to the mixer. Mixing is performed to wet the filler. The vacuum is applied and mixing is continued. After the vacuum is broken with nitrogen, the mixture is scraped down and the polyester prepolymer is added along with any stabilizers. Mixing under vacuum is continued. The resulting adhesive composition can be packaged, for example, in an airtight tube, which is stored in a sealed aluminum bag filled with nitrogen.

[0080] use The adhesive compositions of the present invention are particularly suitable for bonding glass to a second substrate. In particular, they meet the 30 minute drive-away time requirement, i.e. · Impact strength after 30 minutes exceeding 3.4 J; ·Young's modulus above 4 MPa; Lap shear strength on AD3402 greater than 350 psi and cohesive failure greater than 80% after 3 days at 23°C and 50% RH; Preferably 1×10 8 Electrical resistivity above ohm*cm It is designed to satisfy.

[0081] In use, the adhesive is applied to a glass substrate and / or a second substrate. Optionally, for example if the second substrate is metal, the second substrate may be cleaned and primed before the adhesive is applied. Typically in an after-sales windshield replacement, the second substrate is essentially the cured adhesive (usually PU or silanized PU) that previously held the windshield in place. The glass substrate and the second substrate are then brought into adhesive contact with each other with the adhesive of the present invention sandwiched between them. The adhesive of the present invention gives excellent results without the use of a primer. This is desirable since application of a primer involves an additional step as well as drying time.

[0082] Curing is effected by atmospheric moisture.

[0083] Particularly preferred embodiments The following are particularly preferred embodiments of the adhesive composition of the present invention.

[0084] 1. An adhesive composition comprising: (A) at least one polyether prepolymer in a total polyether prepolymer content of 52 to 54% by weight; (B) at least one polyester prepolymer in a total content of polyester prepolymers of 1.3 to 1.5 wt. %; (C) at least one aliphatic polyisocyanate in a total aliphatic polyisocyanate content of 0.5 to 1% by weight; (D) at least one aromatic polyisocyanate in a total aromatic polyisocyanate content of 0.5 to 1% by weight; (E) at least one isocyanate-functionalized silane in a total isocyanate-functionalized silane content of 0.6 to 1.2 wt.%; (F) 0.6-0.8 wt. % amine catalyst; (G) at least one mercaptosilane in a total mercaptosilane content of 0.9 to 1 wt.%, with the combination of amino and / or mercaptosilane being at least 0.6 wt.%, and / or (G') at least one aminosilane in a total aminosilane content of 0.03 to 0.15 wt.%; (H) 17.6 to 18% by weight carbon black; (I) 7-8% by weight of calcium carbonate; (J) 21-24% clay by weight wherein the total polyisocyanate content is 1.2-3 wt.%, and the sum of calcium carbonate + clay is 20-30 wt.%, and the weight percentages are based on the total weight of the polyurethane adhesive.

[0085] 1. An adhesive composition comprising: (A) at least one polyether prepolymer prepared by polymerizing one or more polyols in the presence of a polyisocyanate, preferably a diisocyanate, where the polyether polyol may be selected from polyether polyols, hydroxyl-containing polythioethers, polymeric polyols, and mixtures thereof (polyether polyols are well known in the art and include, for example, polyoxyethylene, polyoxypropylene, polyoxybutylene, and polytetramethylene ether diols and triols, which are prepared by reacting unsubstituted or halogen- or aromatic-substituted ethylene oxide or propylene oxide with an initiator compound containing two or more active hydrogen groups, such as water, ammonia, polyhydric alcohols, or amines. Typically, polyether polyols can be prepared by polymerizing alkylene oxides in the presence of an active hydrogen-containing initiator compound); (B) at least one polyester prepolymer, in a total content of polyester prepolymer of 1.2 to 2.0 wt. %, prepared by reacting one or more linear copolyesters having primary hydroxyl functionality with a polyisocyanate, preferably a diisocyanate; (C) at least one aliphatic polyisocyanate selected from isophorone diisocyanate, 1,6-hexamethylene diisocyanate, bis(4-isocyanatocyclohexyl)methane, and trimethylhexamethylene diisocyanate, any of which may be modified to contain a biuret group, an allophanate group, a urea group, a carbamate group, an isocyanurate group, or a carbodiimide group, in a total aliphatic polyisocyanate content of 0.4 to 1.2 weight percent; (D) at least one aromatic polyisocyanate selected from diphenylmethane diisocyanate (MDI), polymethylene polyphenylisocyanate, polymeric MDI (PMDI, a mixture of diphenylmethane diisocyanate and polymethylene polyphenylisocyanate), tetramethylxylene diisocyanate, toluene diisocyanate, any of which may be modified to contain a biuret group, an allophanate group, a urea group, a carbamate group, an isocyanurate group, or a carbodiimide group, in a total aromatic polyisocyanate content of 0.4 to 1.2 weight %; (E) A polyisocyanate compound such as toluene diisocyanate, methylene diphenyl diisocyanate, etc. is reacted with a polyalkylene oxide having a terminal hydroxyl group to produce a polyalkylene oxide having a terminal isocyanate group, and then a reaction product of the formula: [ka] (Wherein, W is an active hydrogen-containing group selected from the group consisting of a hydroxyl group, a carboxyl group, a mercapto group, a primary amino group, and a secondary amino group; X is a hydrolyzable alkoxy group; R 4 is C1~C 20 Alkyl, C6-C 20 Aryl, C1-C 20 An aralkyl group, R is C1-C 20 and b is 0, 1 or 2. with an active hydrogen-containing group W of a silicone compound of formula (I); (F) 0.50 to 0.99 wt. % of a tertiary amine catalyst; (G) a combination of amino and / or mercaptosilanes of at least 0.6% by weight, at a total mercaptosilane content of less than 1.2% by weight, of the formula: [ka] (In the formula, R 1 , R 2 and R 3 are independently selected from OCH3 and OC2H5; and R 4 is C n H 2n and n is an integer from 1 to 12. and / or (G') at least one mercaptosilane of the following formula, in a total aminosilane content of less than 0.5 wt. %: [ka] (In the formula, R 1 , R 2 , R 3 , R 4 , R 5 and R 6 are independently selected from OCH3 and OC2H5; and R 7 and R 8 is C n H 2n where n is an integer from 1 to 6, and preferably n is 3. at least one aminosilane; (H) 17-20% by weight carbon black; (I) 3 to 30% by weight of calcium carbonate; (J) optionally, 0 to 27% by weight clay; wherein the total polyisocyanate content is 1.2-3 wt.%, and the sum of calcium carbonate + clay is 20-30 wt.%, and the weight percentages are based on the total weight of the polyurethane adhesive.

[0086] 1. An adhesive composition comprising: (A) at least one polyether prepolymer, in a total polyether prepolymer content of 50 to 57 wt. %, prepared by polymerizing one or more polyether polyols in the presence of a polyisocyanate, preferably a diisocyanate, wherein the polyol is selected from polyether polyols, polyester polyols, poly(alkylene carbonate) polyols, hydroxyl-containing polythioethers, polymeric polyols, and mixtures thereof; (B) at least one polyester prepolymer, in a total content of polyester prepolymer of 1.2 to 2.0 wt. %, prepared by reacting one or more linear copolyesters having primary hydroxyl functionality with a polyisocyanate, preferably a diisocyanate; (C) at least one aliphatic polyisocyanate selected from isophorone diisocyanate, 1,6-hexamethylene diisocyanate, bis(4-isocyanatocyclohexyl)methane, and trimethylhexamethylene diisocyanate, any of which may be modified to contain a biuret group, an allophanate group, a urea group, a carbamate group, an isocyanurate group, or a carbodiimide group, in a total aliphatic polyisocyanate content of 0.4 to 1.2 weight percent; (D) at least one aromatic polyisocyanate selected from diphenylmethane diisocyanate (MDI), polymethylene polyphenylisocyanate, polymeric MDI (PMDI, a mixture of diphenylmethane diisocyanate and polymethylene polyphenylisocyanate), tetramethylxylene diisocyanate, toluene diisocyanate, any of which may be modified to contain a biuret group, an allophanate group, a urea group, a carbamate group, an isocyanurate group, or a carbodiimide group, in a total aromatic polyisocyanate content of 0.4 to 1.2 weight %; (E) A polyisocyanate compound such as toluene diisocyanate, methylene diphenyl diisocyanate, etc. is reacted with a polyalkylene oxide having a terminal hydroxyl group to produce a polyalkylene oxide having a terminal isocyanate group, and then a reaction product of the formula: [ka] (Wherein, W is an active hydrogen-containing group selected from the group consisting of a hydroxyl group, a carboxyl group, a mercapto group, a primary amino group, and a secondary amino group; X is a hydrolyzable alkoxy group; R 4 is C1~C 20 Alkyl, C6-C 20 Aryl, C1-C 20 An aralkyl group, R is C1-C 20 and b is 0, 1 or 2. with an active hydrogen-containing group W of a silicone compound of formula (I); (F) 0.50 to 0.99 wt. % of a tertiary amine catalyst; (G) a combination of amino and / or mercaptosilanes of at least 0.6% by weight, at a total mercaptosilane content of less than 1.2% by weight, of the formula: [ka] (In the formula, R 1 , R 2 and R 3 are independently selected from OCH3 and OC2H5; and R 4 is C n H 2n and n is an integer from 1 to 12. and / or (G') at least one mercaptosilane of the following formula, in a total aminosilane content of less than 0.5 wt. %: [ka] (In the formula, R 1 , R 2 , R 3 , R 4 , R 5 and R 6 are independently selected from OCH3 and OC2H5; and R 7 and R 8 is C n H 2n where n is an integer from 1 to 6, and preferably n is 3. at least one aminosilane; (H) 17-20% by weight carbon black; (I) 3 to 30% by weight of calcium carbonate; (J) optionally, 0 to 27% by weight clay; wherein the total polyisocyanate content is 1.2-3 wt.%, and the sum of calcium carbonate + clay is 20-30 wt.%, and the weight percentages are based on the total weight of the polyurethane adhesive.

[0087] 1. An adhesive composition comprising: (A) at least one polyether prepolymer, in a total content of polyether prepolymer of 50 to 57% by weight, prepared by polymerizing one or more polyether polyols in the presence of a polyisocyanate, preferably a diisocyanate; (B) at least one polyester prepolymer, in a total content of polyester prepolymer of 1.2 to 2.0 wt. %, prepared by reacting one or more linear copolyesters having primary hydroxyl functionality with a polyisocyanate, preferably a diisocyanate; (C) at least one aliphatic polyisocyanate selected from isophorone diisocyanate, 1,6-hexamethylene diisocyanate, bis(4-isocyanatocyclohexyl)methane, and trimethylhexamethylene diisocyanate, any of which may be modified to contain a biuret group, an allophanate group, a urea group, a carbamate group, an isocyanurate group, or a carbodiimide group, in a total aliphatic polyisocyanate content of 0.4 to 1.2 weight percent; (D) at least one aromatic polyisocyanate selected from diphenylmethane diisocyanate (MDI), polymethylene polyphenylisocyanate, polymeric MDI (PMDI, a mixture of diphenylmethane diisocyanate and polymethylene polyphenylisocyanate), tetramethylxylene diisocyanate, toluene diisocyanate, any of which may be modified to contain a biuret group, an allophanate group, a urea group, a carbamate group, an isocyanurate group, or a carbodiimide group, in a total aromatic polyisocyanate content of 0.4 to 1.2 weight %; (E) at least one isocyanate-functionalized silane, which is a reaction product of an aminosilane with a polyisocyanate or a reaction product of a mercaptosilane with a polyisocyanate, in a total isocyanate-functionalized silane content of 0.4 to 1.5 wt. %; (F) 0.50 to 0.99 wt. % of a tertiary amine catalyst; (G) a combination of amino and / or mercaptosilanes of at least 0.6% by weight, at a total mercaptosilane content of less than 1.2% by weight, of the formula: [ka] (In the formula, R 1 , R 2 and R 3is independently selected from OCH3 and OC2H5; and R 4 is C n H 2n and n is an integer from 1 to 12. and / or (G') at least one mercaptosilane of the following formula, in a total aminosilane content of less than 0.5 wt. %: [ka] (In the formula, R 1 , R 2 , R 3 , R 4 , R 5 and R 6 is independently selected from OCH3 and OC2H5; and R 7 and R 8 is C n H 2n where n is an integer from 1 to 6, and preferably n is 3. at least one aminosilane; (H) 17-20% by weight carbon black; (I) 3 to 30% by weight of calcium carbonate; (J) optionally, 0 to 27% by weight clay; wherein the total polyisocyanate content is 1.2-3 wt.%, and the sum of calcium carbonate + clay is 20-30 wt.%, and the weight percentages are based on the total weight of the polyurethane adhesive.

[0088] 1. An adhesive composition comprising: (A) 50-57 wt. % of a polyether prepolymer, based on the total weight of the adhesive composition, comprising a mixture of polyalkylene oxide diols and triols reacted with MDI, the polyether prepolymer having an isocyanate content of 1.25 wt. % and a viscosity of 16,000 cps at 23° C., as measured according to the procedure described in U.S. Pat. No. 5,922,809, column 12, lines 38-49; (B) 1.2-2.0 wt. % polyester prepolymer prepared by reacting a 3,500 Da molecular weight copolyester with MDI, preferably having a melting point of 40-90°C; (C) 0.4 to 1.2% by weight of an aliphatic polyisocyanate, which is an HDI trimer having an NCO content of 21.8 ± 0.3% (according to DIN EN ISO 11 909); (D) 0.4 to 1.2% by weight of an aromatic polyisocyanate, which is a polymethylene polyphenylisocyanate containing MDI, having an NCO content (according to DIN EN ISO 11 909) of 30.4%; (E) 0.4-1.5 wt. % of a functionalized silane, which is a reaction product of N,N-bis[(3-trimethoxysilyl)-propyl]amine reacted with HDI-biuret, having an isocyanate content of 7%; (F) 0.5 to 0.99 wt. % of an amine catalyst which is 2,2'-dimorpholinodiethyl ether; (G) less than 1.2 wt. % γ-mercaptopropyltrimethoxysilane, with at least 0.6 wt. % of a combination of amino and / or mercaptosilane, and / or (G') less than 0.5 wt. % bis(γ-trimethoxysilylpropyl)amine; (H) 17-20% by weight carbon black; (I) 3 to 30% by weight of calcium carbonate; (J) optionally, 0 to 27% by weight clay; wherein the total polyisocyanate content is 1.2-3 wt.%, and the sum of calcium carbonate + clay is 20-30 wt.%, and the weight percentages are based on the total weight of the polyurethane adhesive.

[0089] 1. An adhesive composition comprising: (A) 50-57 weight percent, based on the total weight of the adhesive composition, of a polyether prepolymer comprising a nominally trifunctional poly(propylene oxide) having a hydroxyl number of 36 (equivalent weight 1558) and a nominally trifunctional poly(propylene oxide) having a hydroxyl number of 56 (equivalent weight 1000), the polyether prepolymer having an isocyanate content of 1.25 weight percent and a viscosity of 16,000 cps at 23° C. as measured according to the procedure set forth in U.S. Pat. No. 5,922,809, column 12, lines 38-49; (B) 1.2-2.0 wt. % polyester prepolymer prepared by reacting a 3,500 Da molecular weight copolyester with MDI, preferably having a melting point of 40-90°C; (C) 0.4 to 1.2% by weight of an aliphatic polyisocyanate, which is an HDI trimer having an NCO content of 21.8 ± 0.3% (according to DIN EN ISO 11 909); (D) 0.4 to 1.2% by weight of an aromatic polyisocyanate, which is a polymethylene polyphenylisocyanate containing MDI, having an NCO content (according to DIN EN ISO 11 909) of 30.4%; (E) 0.4-1.5 wt. % of a functionalized silane, which is a reaction product of N,N-bis[(3-trimethoxysilyl)-propyl]amine reacted with HDI-biuret, having an isocyanate content of 7%; (F) 0.5 to 0.99 wt. % of an amine catalyst which is 2,2'-dimorpholinodiethyl ether; (G) less than 1.2 wt. % γ-mercaptopropyltrimethoxysilane, with at least 0.6 wt. % of a combination of amino and / or mercaptosilane, and / or (G') less than 0.5 wt. % bis(γ-trimethoxysilylpropyl)amine; (H) 17-20% by weight carbon black; (I) 3 to 30% by weight of calcium carbonate; (J) optionally, 0 to 27% by weight clay; wherein the total polyisocyanate content is 1.2-3 wt.%, and the sum of calcium carbonate + clay is 20-30 wt.%, and the weight percentages are based on the total weight of the polyurethane adhesive.

[0090] 1. An adhesive composition comprising: (A) 52-54 weight percent, based on the total weight of the adhesive composition, of a polyether prepolymer comprising a nominally trifunctional poly(propylene oxide) partially endcapped with ethylene oxide, a nominally difunctional poly(propylene oxide) reacted with MDI, having an isocyanate content of 1.25 weight percent and a viscosity of 16,000 cps at 23° C. as measured according to the procedure set forth in U.S. Pat. No. 5,922,809, column 12, lines 38-49; (B) 1.2-2.0 wt. % polyester prepolymer prepared by reacting a 3,500 Da molecular weight copolyester with MDI, the polyester prepolymer preferably having a melting point of 60-70°C; (C) 0.5 to 1% by weight of an aliphatic polyisocyanate, which is an HDI trimer having an NCO content of 21.8 ± 0.3% (according to DIN EN ISO 11 909); (D) 0.5 to 1% by weight of an aromatic polyisocyanate, which is a polymethylene polyphenylisocyanate containing MDI, having an NCO content (according to DIN EN ISO 11 909) of 30.4%; (E) 0.8-1.0 wt. % of a functionalized silane, which is a reaction product of N,N-bis[(3-trimethoxysilyl)-propyl]amine) reacted with HDI-biuret, having an isocyanate content of 7%; (F) 0.75% by weight or about 0.75% by weight of an amine catalyst which is 2,2'-dimorpholinodiethyl ether; (G) 0.93, 0.94, or 0.95 weight percent of a mercaptosilane which is gamma-mercaptopropyltrimethoxysilane; (G') 0.11% by weight or about 0.11% by weight of an aminosilane which is bis(γ-trimethoxysilylpropyl)amine; (H) 17.6 to 18% by weight carbon black; (I) 7-8% by weight of calcium carbonate; (J) 22-23% by weight clay wherein the total polyisocyanate content is 1.2-3 wt.%, and the sum of calcium carbonate + clay is 20-30 wt.%, and the weight percentages are based on the total weight of the polyurethane adhesive.

[0091] Additional preferred embodiments are as follows: 1. A one-component polyurethane adhesive composition comprising: (A) at least one polyether prepolymer in a total polyether prepolymer content of 50 to 57% by weight; (B) at least one polyester prepolymer in a total content of polyester prepolymers of 1.2 to 2.0 wt. %; (C) at least one aliphatic polyisocyanate in a total aliphatic polyisocyanate content of 0.4 to 1.2 wt. %; (D) at least one aromatic polyisocyanate in a total aromatic polyisocyanate content of 0.4 to 1.2% by weight; (E) at least one isocyanate-functionalized silane in a total isocyanate-functionalized silane content of 0.4 to 1.5 wt.%; (F) 0.50 to 0.99 wt. % of an amine catalyst; (G) at least one mercaptosilane in a total mercaptosilane content of less than 1.2 wt.%, with the combination of amino and / or mercaptosilane being at least 0.6 wt.%, and / or (G') at least one aminosilane in a total aminosilane content of less than 0.5 wt.%; (H) 17-20% by weight carbon black; (I) 3 to 30% by weight of calcium carbonate; (J) optionally, 0 to 27% by weight of a filler other than calcium carbonate and / or carbon black; wherein the total polyisocyanate content is 1.2-3 wt.%, the sum of calcium carbonate + clay is 20-30 wt.%, and the weight percentages are based on the total weight of the polyurethane adhesive. 2. The adhesive composition according to embodiment 1, wherein the at least one polyether prepolymer (A) is selected from polymers prepared by polymerizing one or more polyether polyols in the presence of a polyisocyanate, preferably a diisocyanate, and mixtures of such polyether prepolymers. 3. The adhesive composition according to embodiment 1 or 2, wherein the polyether prepolymer (A) is a mixture of polyalkylene oxide diols and / or triols reacted with MDI. 4. At least one polyether prepolymer (A) is reacted with at least one polyisocyanate, (i) poly(alkylene oxide) diols having an alkylene group of C2 to C4; (ii) trifunctional polyols obtained from poly(alkylene oxide) diols reacted with trifunctional polyols, the alkylene groups being C2 to C4; (iii) (i), (ii) and mixtures of (i) and (ii) 4. The adhesive of embodiment 1, 2 or 3, wherein the adhesive is selected from a polyether prepolymer made by polymerizing at least one polyol selected from: 5. The adhesive of any one of the preceding embodiments, wherein the at least one polyether prepolymer (A) comprises a nominally trifunctional poly(propylene oxide) having a hydroxyl number of 36 (equivalent weight 1558) and a nominally trifunctional poly(propylene oxide) having a hydroxyl number of 56 (equivalent weight 1000), reacted with MDI. 6. The adhesive composition according to any one of the preceding embodiments, wherein the at least one polyester prepolymer (B) is selected from polymers prepared by reacting one or more linear copolyesters having primary hydroxyl functionality with polyisocyanates, preferably diisocyanates, and mixtures of such polyester prepolymers. 7. The adhesive composition according to any one of the preceding embodiments, wherein the at least one polyester prepolymer (B) is a reaction product of a copolyester having a molecular weight of 3,500 Da and MDI and has a melting point of 40 to 90° C. 8. The adhesive composition according to any one of the preceding embodiments, wherein the at least one aliphatic polyisocyanate (C) is selected from isophorone diisocyanate, 1,6-hexamethylene diisocyanate, bis(4-isocyanatocyclohexyl)methane and trimethylhexamethylene diisocyanate, any of which may be modified to contain biuret, allophanate, urea, carbamate, isocyanurate or carbodiimide groups, and mixtures of these aliphatic polyisocyanates. 9. The adhesive composition according to any one of the preceding embodiments, wherein the at least one aliphatic polyisocyanate (C) is an HDI trimer having an NCO content (according to DIN EN ISO 11 909) of 21.8±0.3%. 10. The adhesive composition according to any one of embodiments 1 to 9, wherein the aromatic polyisocyanate (D) is selected from diphenylmethane diisocyanate (MDI), polymethylene polyphenylisocyanate, polymeric MDI (PMDI, a mixture of diphenylmethane diisocyanate and polymethylene polyphenylisocyanate), tetramethylxylene diisocyanate, toluene diisocyanate, and mixtures of these aliphatic polyisocyanates, any of which may be modified to contain biuret groups, allophanate groups, urea groups, carbamate groups, isocyanurate groups, or carbodiimide groups. 11. The adhesive composition according to any one of the preceding embodiments, wherein the aromatic polyisocyanate (D) is an MDI-containing polymethylene polyphenylisocyanate having an NCO content (according to DIN EN ISO 11 909) of 30.4%. 12. The adhesive composition according to any one of the preceding embodiments, wherein the isocyanate-functionalized silane (E) is selected from the reaction products of aminosilanes and polyisocyanates, the reaction products of mercaptosilanes and polyisocyanates, and the like, and mixtures thereof. 13. The adhesive composition according to any one of the preceding embodiments, wherein the isocyanate-functionalized silane (E) is a reaction product of a secondary aminoalkoxysilane and a polyisocyanate. 14. The adhesive composition according to any one of the preceding embodiments, wherein the isocyanate-functionalized silane (E) is a reaction product of N,N-bis[(3-trimethoxysilyl)-propyl]amine) reacted with HDI-biuret. 15. The adhesive composition according to any one of the preceding embodiments, wherein the amine catalyst (F) is selected from a tertiary amine. 16. The adhesive composition of any one of embodiments 1 to 15, wherein the amine catalyst (F) is selected from N,N-dimethylcyclohexane, triethylenediamine, N,N,N,N-tetramethylalkylenediamine, N,N,N,N-pentamethyldiethylenetriamine, triethylamine, N,N-dimethylbenzylamine, N,N-dimethylhexadecylamine, N,N-dimethylbutylamine, 2,2'- and dimorpholinodiethyl ether. 17. The adhesive composition of any one of the preceding embodiments, wherein the amine catalyst (F) is 2,2′- and dimorpholinodiethyl ether. 18. At least one mercaptosilane (G) has the following formula: [ka] (In the formula, R 1 , R 2 and R 3is independently selected from OCH3 and OC2H5; and R 4 is C n H 2n and n is an integer from 1 to 12. and mixtures of such mercaptosilanes. 19.R 1 , R 2 and R 3 is OCH3 and n is 1 to 6. 20. The adhesive composition of any one of embodiments 1 to 19, wherein the at least one mercaptosilane (G) is γ-mercaptopropyltrimethoxysilane. 21. Aminosilane (G') has the following formula: [ka] (In the formula, R 1 , R 2 , R 3 , R 4 , R 5 and R 6 is independently selected from OCH3 and OC2H5; and R 7 and R 8 is C n H 2n where n is an integer from 1 to 6, and preferably n is 3. 21. The adhesive composition according to any one of the preceding embodiments, wherein the aminosilane is selected from the group consisting of phenyl, ... 22. The adhesive composition according to any one of the preceding embodiments, wherein the aminosilane (G') is bis(γ-trimethoxysilylpropyl)amine. 23. The adhesive composition according to any one of the preceding embodiments, wherein the filler (J) is kaolin clay. 24. The adhesive composition of any one of the preceding embodiments, wherein the at least one polyether prepolymer (A) is present in an amount of 52 to 54% by weight, based on the total weight of the adhesive composition. 25. The adhesive composition of any one of the preceding embodiments, wherein the at least one polyester prepolymer (B) is present in an amount of 1.3 to 1.5 wt.%, based on the total weight of the adhesive composition. 26. The adhesive composition of any one of the preceding embodiments, wherein the at least one aliphatic polyisocyanate (C) is present in an amount of 0.5 to 1% by weight, based on the total weight of the adhesive composition. 27. The adhesive composition of any one of embodiments 1 to 26, wherein the at least one aromatic polyisocyanate (D) is present in an amount of 0.5 to 1% by weight, based on the total weight of the adhesive composition. 28. The adhesive composition of any one of the preceding embodiments, wherein the at least one isocyanate-functionalized silane (E) is present at 0.8 to 1 wt.%, based on the total weight of the adhesive composition. 29. The adhesive composition of any one of embodiments 1-28, wherein the amine catalyst (F) is present at 0.6 to 0.8 wt %, based on the total weight of the adhesive composition. 30. The adhesive composition of any one of embodiments 1-29, wherein the mercaptosilane (G) is present at 0.91 to 0.95 wt.%, based on the total weight of the adhesive composition. 31. The adhesive composition of any one of embodiments 1 to 30, wherein the aminosilane (G') is present in an amount of 0.05 to 0.22 wt.%, based on the total weight of the adhesive composition. 32. The adhesive composition of any one of the preceding embodiments, wherein the carbon black (H) is present in an amount of 17.6 to 18% by weight, based on the total weight of the adhesive composition. 33. The adhesive composition according to any one of the preceding embodiments, wherein calcium carbonate (I) is present in an amount of 6 to 10% by weight, based on the total weight of the adhesive composition. 34. The adhesive composition according to any one of the preceding embodiments, wherein the clay (J) is present in an amount of 21 to 24% by weight, based on the total weight of the adhesive composition. 35. The adhesive composition according to any one of the preceding embodiments, having the following characteristics after 30 minutes of curing: Impact strength of over 3.4 J; ·Young's modulus above 4 MPa; Lap shear strength on fritted glass exceeding 350 psi and cohesive failure exceeding 80% after 3 days at 23°C and 50% RH; Preferably 1×10 8 Electrical resistivity greater than ohm*cm. EXAMPLES

[0092] [Table 1]

[0093] Polyether Prepolymer (A): 363.68 g of Voranol 220-056 polyol, 527.04 g of Voranol 232-036 polyol, and 32 g of diisononyl phthalate were placed in a 4 liter kettle, mixed, and heated to 54°C under nitrogen. All subsequent steps were carried out under nitrogen. 160.64 g of molten MDI was added and mixed. 0.08 g of stannous octoate catalyst was added dropwise. The temperature in the kettle increased due to the exotherm of the reaction; the reaction mixture was maintained at 80°C-90°C for 30 minutes. The reaction mixture was then cooled to 60°C, and 501.20 g of diisononyl phthalate, 15.36 g of diethyl malonate were added and mixed for 30 minutes, then cooled to room temperature. The resulting polyalkylene prepolymer solution had an isocyanate content of 1.25% by weight and a viscosity of 16,000 cps at 23° C. as measured according to the procedure disclosed in U.S. Pat. No. 5,922,809, column 12, lines 38-49.

[0094] Polyester prepolymer (B): Prepared as described in Example 5 of WO2017189057.

[0095] Isocyanate-functionalized silane (E): A reaction product of a secondary aminoalkoxysilane and a polyisocyanate was prepared by placing 485 g of Desmodur N-100 (2.59 equivalents) (a solvent-free aliphatic polyisocyanate resin based on hexamethylene diisocyanate-biuret) and 225 g of alkyl phthalate in a resin kettle equipped with a mechanical stirrer, a thermometer, a N2 inlet adapter, and an addition funnel. The mixture was mixed thoroughly and purged under a N2 blanket. Approximately 300 g of N,N-bis[(3-trimethoxysilyl)-propyl]amine) (0.88 equivalents) was slowly added to the mixture. The adduct had an isocyanate content of 7.0%.

[0096] Preparation of Adhesive Composition Using the ratios listed in Table 2, calcium carbonate, clay and Elftex S7100 were mixed and dried at 204°C for approximately 20 hours, then cooled in a closed container to form the filler mixture. The polyester prepolymer was heated to 80°C for approximately 15 hours prior to use. The polyether prepolymer, DMDEE catalyst, aliphatic polyisocyanate, diisononyl phthalate and isocyanate functionalized silane were placed in a 2 gallon mixer. The mixture was degassed and mixed under vacuum for 5 minutes. The vacuum was broken with nitrogen, then the mercaptosilane and aminosilane were added, followed by further degassing and mixing under vacuum for 10 minutes. The vacuum was broken again with nitrogen, then the filler mixture was placed in the mixer. Mixing was started to wet the filler for 2 minutes. Vacuum was applied and mixing was continued for 15 minutes. After breaking the vacuum with nitrogen, the mixture was scraped down and the polyester prepolymer was added along with the stabilizer. Mixing under vacuum was done for 10 minutes. The resulting adhesive composition was packaged in an airtight tube and stored in a sealed aluminum bag filled with nitrogen.

[0097] Adhesive Testing Procedures The adhesive round putties were cured for 7 days at 23° C. and 50% relative humidity. Test specimens were cut from these cured sample putties and tested for Young's modulus according to ASTM D412 (Die C).

[0098] Glass specimens for primerless adhesion testing contain press bent bismuth-based frit containing a crystallizing additive to facilitate removal of the glass from the mold.

[0099] Lap shear test: All lap shear samples were made according to SAE J1529 (May 1986) with the following exceptions: metal substrate was taped to the underside of the board and glass and / or metal to the topside, urethane beads were measured after testing to provide specific areas for strength calculations, and up to three samples were made for each test. Glass was cleaned with water and solvent glass cleaner (BETACLEAN™ 3300) and a sponge. E-coats were cleaned with acetone. E-coats were primed with BETAPRIME™ 5504G or BETAPRIME™ Optimum, an all-in-one polyisocyanate surface treatment, and flashed for 15 minutes. A bead of adhesive was applied and the glass decked. Samples were placed at 23°C / 50% RH for 3 days, after which samples were immediately pulled for initial lap shear strength on an Instron tester at a speed of 1 inch / min (2.5 cm / min). Groups of at least three lap shear samples were tested and averaged. The load at break and modulus of the samples were recorded.

[0100] High Speed ​​Impact Test Impact resistance testing was performed on a TMI impact pendulum tester, model 43-01, at an impact velocity of 4 m / s. High-velocity impact resistance and ultimate strength were tested according to the following method: Samples were prepared by gluing approximately 1x1 inch pieces of fritted glass to the center of a 1x3 inch metal specimen. These were allowed to cure overnight. The glass samples were cleaned with an appropriate cleaner. An equal amount of 1x4 inch metal specimen was cleaned with acetone. The 1x4 metal specimen was primed with an appropriate body primer. The primer was flashed. The glass was inserted into a specially designed fixture that gave a 1x1x0.25 inch block of urethane. The appropriate urethane was applied to the glass and the properly primed 1x4 metal specimen was mounted perpendicular to the glass and centered. The specimen was then stored for the desired cure time and environmental conditions. The impact pendulum was then raised and latched to lock the specimen in place and the hammer was released. For each test, impact resistance is reported in kilojoules after 30 minutes at 23°C and 50% RH.

[0101] Electrical resistivity The resistivity of the adhesive samples was measured using an HP 4339B High Resistance Meter and all formulations had a resistivity of 1×10 8 It had a value of over ohm*cm.

[0102] [Table 2]

[0103] [Table 3]

[0104] [Table 4]

[0105] [Table 5]

[0106] The above table shows the results for five inventive formulations and nine comparative formulations. To meet the automobile manufacturer's requirements and obtain a safe drive-away time of 30 minutes, the adhesive must have the following characteristics: · Impact strength after 30 minutes exceeding 3.4 J; ·Young's modulus above 4 MPa; Lap shear strength on frit greater than 350 psi and cohesive failure greater than 80% after 3 days at 23°C and 50% RH; Preferably 1×10 8 Electrical resistivity greater than ohm*cm.

[0107] The performance of the comparative adhesives is lacking in at least one of the desirable performance characteristics: lap shear strength (ie, primerless adhesion), lap shear modulus, or impact strength after 30 minutes (safe drive away time). The present invention includes the following aspects. Section 1. A one-component polyurethane adhesive composition comprising: (A) at least one polyether prepolymer in a total polyether prepolymer content of 50 to 57% by weight; (B) at least one polyester prepolymer in a total content of polyester prepolymers of 1.2 to 2.0 wt. %; (C) at least one aliphatic polyisocyanate in a total aliphatic polyisocyanate content of 0.4 to 1.2 wt. %; (D) at least one aromatic polyisocyanate in a total aromatic polyisocyanate content of 0.4 to 1.2% by weight; (E) at least one isocyanate-functionalized silane in a total isocyanate-functionalized silane content of 0.4 to 1.5 wt.%; (F) 0.50 to 0.99 wt. % of an amine catalyst; (G) at least one mercaptosilane in a total mercaptosilane content of less than 1.2 wt.%, with the combination of amino and / or mercaptosilane being at least 0.6 wt.%, and / or (G') at least one aminosilane in a total aminosilane content of less than 0.5 wt.%; (H) 17-20% by weight carbon black; (I) 3 to 30% by weight of calcium carbonate; (J) optionally, 0 to 27% by weight of a filler other than calcium carbonate and / or carbon black; wherein said total polyisocyanate content is 1.2-3 wt. %, and the sum of calcium carbonate plus clay is 20-30 wt. %, said weight percentages being based on the total weight of said polyurethane adhesive. Section 2. Item 2. The adhesive composition according to item 1, wherein the at least one polyether prepolymer (A) is selected from a mixture of polyether prepolymers and polymers prepared by polymerizing one or more polyether polyols in the presence of a polyisocyanate, preferably a diisocyanate. Section 3. Item 3. The adhesive composition according to item 1 or 2, wherein the polyether prepolymer (A) is a mixture of polyalkylene oxide diols and / or triols reacted with MDI. Section 4. The at least one polyether prepolymer (A) is reacted with at least one polyisocyanate in the presence of (i) poly(alkylene oxide) diols having an alkylene group of C2 to C4; (ii) trifunctional polyols obtained from poly(alkylene oxide) diols reacted with trifunctional polyols, the alkylene groups being C2 to C4; (iii) (i), (ii) and mixtures of (i) and (ii) Item 4. The adhesive according to any one of items 1 to 3, wherein the adhesive is selected from polyether prepolymers produced by polymerizing at least one polyol selected from the following: Section 5. The at least one polyether prepolymer (A) comprises a nominally trifunctional poly(propylene oxide) having a hydroxyl number of 36 (equivalent weight 1558) and a nominally trifunctional poly(propylene oxide) having a hydroxyl number of 56 (equivalent weight 1000) reacted with MDI. The adhesive according to any one of claims 1 to 4. Section 6. The at least one polyester prepolymer (B) is selected from a polymer prepared by reacting one or more linear copolyesters having primary hydroxyl functional groups with a polyisocyanate, preferably a diisocyanate, and a mixture of the polyester prepolymers. The adhesive composition according to any one of items 1 to 5. Section 7. Item 7. The adhesive composition according to any one of items 1 to 6, wherein the at least one polyester prepolymer (B) is a reaction product of a copolyester having a molecular weight of 3,500 Da and MDI, and has a melting point of 40 to 90°C. Section 8. The at least one aliphatic polyisocyanate (C) is selected from isophorone diisocyanate, 1,6-hexamethylene diisocyanate, bis(4-isocyanatocyclohexyl)methane, and trimethylhexamethylene diisocyanate, any of which may be modified to contain a biuret group, an allophanate group, a urea group, a carbamate group, an isocyanurate group, or a carbodiimide group, and a mixture of the aliphatic polyisocyanates. The adhesive composition according to any one of items 1 to 7. Section 9. The adhesive composition according to any one of items 1 to 8, wherein the at least one aliphatic polyisocyanate (C) is an HDI trimer having an NCO content of 21.8 ± 0.3% (according to DIN EN ISO 11 909). Section 10. The aromatic polyisocyanate (D) is selected from diphenylmethane diisocyanate (MDI), polymethylene polyphenylisocyanate, polymeric MDI (PMDI, a mixture of diphenylmethane diisocyanate and polymethylene polyphenylisocyanate), tetramethylxylene diisocyanate, toluene diisocyanate, and a mixture of the aromatic polyisocyanates, all of which may be modified to include a biuret group, an allophanate group, a urea group, a carbamate group, an isocyanurate group, or a carbodiimide group. The adhesive composition according to any one of items 1 to 9. Section 11. The aromatic polyisocyanate (D) is an MDI-containing polymethylene polyphenylisocyanate having an NCO content (according to DIN EN ISO 11 909) of 30.4%. The adhesive composition according to any one of items 1 to 10. Section 12. Item 12. The adhesive composition according to any one of items 1 to 11, wherein the isocyanate-functionalized silane (E) is selected from the group consisting of reaction products of aminosilanes and polyisocyanates, reaction products of mercaptosilanes and polyisocyanates, and mixtures thereof. Section 13. Item 13. The adhesive composition according to any one of items 1 to 12, wherein the isocyanate-functionalized silane (E) is a reaction product of a secondary aminoalkoxysilane and a polyisocyanate. Section 14. Item 14. The adhesive composition according to any one of items 1 to 13, wherein the isocyanate-functionalized silane (E) is a reaction product of N,N-bis[(3-trimethoxysilyl)-propyl]amine) reacted with HDI-biuret. Section 15. Item 15. The adhesive composition according to any one of items 1 to 14, wherein the amine catalyst (F) is selected from a tertiary amine. Section 16. The adhesive composition according to any one of items 1 to 15, wherein the amine catalyst (F) is selected from N,N-dimethylcyclohexane, triethylenediamine, N,N,N,N-tetramethylalkylenediamine, N,N,N,N-pentamethyldiethylenetriamine, triethylamine, N,N-dimethylbenzylamine, N,N-dimethylhexadecylamine, N,N-dimethylbutylamine, 2,2'- and dimorpholinodiethyl ether. Section 17. Item 17. The adhesive composition according to any one of items 1 to 16, wherein the amine catalyst (F) is 2,2'- and dimorpholinodiethyl ether. Section 18. The at least one mercaptosilane (G) has the following formula: [ka] (In the formula, R 1 , R 2 and R 3 are independently selected from OCH3 and OC2H5; and R 4 is C n H 2n and n is an integer from 1 to 12. Item 18. The adhesive composition according to any one of items 1 to 17, wherein the mercaptosilane is selected from the group consisting of mercaptosilanes and mixtures of mercaptosilanes. Section 19. R 1 , R 2 and R 3 Item 19. The adhesive composition according to item 18, wherein is OCH3, and n is 1 to 6. Section 20. 20. The adhesive composition according to any one of items 1 to 19, wherein the at least one mercaptosilane (G) is γ-mercaptopropyltrimethoxysilane. Section 21. The aminosilane (G') has the following formula: [ka] (In the formula, R 1 , R 2 , R 3 , R4 , R 5 and R 6 are independently selected from OCH3 and OC2H5; and R 7 and R 8 is C n H 2n where n is an integer from 1 to 6, and preferably n is 3. 21. The adhesive composition according to any one of items 1 to 20, wherein the aminosilane is selected from the group consisting of the aminosilanes listed above and mixtures of the aminosilanes listed above. Section 22. 22. The adhesive composition according to any one of items 1 to 21, wherein the aminosilane (G') is bis(γ-trimethoxysilylpropyl)amine. Section 23. Item 23. The adhesive composition according to any one of items 1 to 22, wherein the filler (J) is kaolin clay. Section 24. 24. The adhesive composition according to any one of items 1 to 23, wherein the at least one polyether prepolymer (A) is present in an amount of 52 to 54 wt % based on the total weight of the adhesive composition. Section 25. 25. The adhesive composition according to any one of items 1 to 24, wherein the at least one polyester prepolymer (B) is present in an amount of 1.3 to 1.5 wt % based on the total weight of the adhesive composition. Section 26. 26. The adhesive composition according to any one of items 1 to 25, wherein the at least one aliphatic polyisocyanate (C) is present in an amount of 0.5 to 1 wt % based on the total weight of the adhesive composition. Section 27. 27. The adhesive composition according to any one of items 1 to 26, wherein the at least one aromatic polyisocyanate (D) is present in an amount of 0.5 to 1 wt % based on the total weight of the adhesive composition. Section 28. 28. The adhesive composition according to any one of claims 1 to 27, wherein the at least one isocyanate-functionalized silane (E) is present in an amount of 0.8 to 1 wt.%, based on the total weight of the adhesive composition. Section 29. 29. The adhesive composition according to any one of items 1 to 28, wherein the amine catalyst (F) is present in an amount of 0.6 to 0.8 wt % based on the total weight of the adhesive composition. Section 30. 30. The adhesive composition according to any one of items 1 to 29, wherein the mercaptosilane (G) is present in an amount of 0.91 to 0.95% by weight based on the total weight of the adhesive composition. Section 31. Item 31. The adhesive composition according to any one of items 1 to 30, wherein the aminosilane (G') is present in an amount of 0.05 to 0.22 wt % based on the total weight of the adhesive composition. Section 32. Item 32. The adhesive composition according to any one of items 1 to 31, wherein the carbon black (H) is present in an amount of 17.6 to 18% by weight based on the total weight of the adhesive composition. Section 33. Item 33. The adhesive composition according to any one of items 1 to 32, wherein the calcium carbonate (I) is present in an amount of 6 to 10% by weight based on the total weight of the adhesive composition. Section 34. Item 34. The adhesive composition according to any one of items 1 to 33, wherein the clay (J) is present in an amount of 21 to 24% by weight based on the total weight of the adhesive composition.

Claims

1. A one-component polyurethane adhesive composition comprising: (A) at least one polyether prepolymer in a total polyether prepolymer content of 50 to 57% by weight; (B) at least one polyester prepolymer in a total content of polyester prepolymers of 1.2 to 2.0 wt. %; (C) at least one aliphatic polyisocyanate in a total aliphatic polyisocyanate content of 0.4 to 1.2 wt.%; (D) at least one aromatic polyisocyanate in a total aromatic polyisocyanate content of 0.4 to 1.2 wt. %; (E) at least one isocyanate-functionalized silane in a total isocyanate-functionalized silane content of 0.4 to 1.5 wt.%; (F) 0.50 to 0.99 wt. % of an amine catalyst; (G) at least one mercaptosilane in a total mercaptosilane content of less than 1.2 wt.-% and / or (G') at least one aminosilane in a total aminosilane content of less than 0.5 wt.-%, with the combined aminosilane and / or mercaptosilane being at least 0.6 wt.-%; (H) 17 to 20% by weight of carbon black; (I) 3 to 30% by weight of calcium carbonate; (J) optionally, 0 to 27% by weight of a filler other than calcium carbonate and / or carbon black; wherein said total polyisocyanate content is 1.2-3 wt. %, and said sum of calcium carbonate plus clay is 20-30 wt. %, and said weight percentages are based on the total weight of said polyurethane adhesive.

2. 2. The adhesive composition according to claim 1, wherein the at least one polyether prepolymer (A) is selected from a mixture of said polyether prepolymers and polymers prepared by polymerizing one or more polyether polyols in the presence of a polyisocyanate.

3. 2. The adhesive composition of claim 1, wherein the polyether prepolymer (A) is a mixture of polyalkylene oxide diols and / or triols reacted with MDI.

4. The at least one polyether prepolymer (A) is, in the presence of at least one polyisocyanate, (i) the alkylene group is C ２ ~C ４ a poly(alkylene oxide) diol, (ii) a trifunctional polyol obtained from a poly(alkylene oxide) diol reacted with a trifunctional polyol, the alkylene group being ２ ~C ４ a trifunctional polyol, (iii) (i), (ii) and mixtures of (i) and (ii).

2. The adhesive composition of claim 1, wherein the polyether prepolymer is selected from polyether prepolymers prepared by polymerizing at least one polyol selected from the group consisting of:

5. 2. The adhesive composition of claim 1, wherein the at least one polyether prepolymer (A) comprises a trifunctional poly(propylene oxide) having a hydroxyl number of 36 (equivalent weight 1558) and a difunctional poly(propylene oxide) having a hydroxyl number of 56 (equivalent weight 1000) reacted with MDI.

6. 2. The adhesive composition according to claim 1, wherein the at least one polyester prepolymer (B) is selected from polymers prepared by reacting one or more linear copolyesters having primary hydroxyl functional groups with polyisocyanates and mixtures of said polyester prepolymers.

7. 2. The adhesive composition of claim 1, wherein the at least one polyester prepolymer (B) is a reaction product of a copolyester of 3,500 Da molecular weight and MDI and has a melting point of 40 to 90°C.

8. 2. The adhesive composition of claim 1, wherein the at least one aliphatic polyisocyanate (C) is selected from isophorone diisocyanate, 1,6-hexamethylene diisocyanate, bis(4-isocyanatocyclohexyl)methane and trimethylhexamethylene diisocyanate, and mixtures of said aliphatic polyisocyanates, any of which may be modified to contain biuret, allophanate, urea, carbamate, isocyanurate or carbodiimide groups.

9. 2. The adhesive composition according to claim 1, wherein the at least one aliphatic polyisocyanate (C) is a HDI trimer having an NCO content (according to DIN EN ISO 11 909) of 21.8±0.3%.

10. 2. The adhesive composition according to claim 1, wherein the aromatic polyisocyanate (D) is selected from diphenylmethane diisocyanate (MDI), polymethylene polyphenylisocyanate, polymeric MDI (PMDI, a mixture of diphenylmethane diisocyanate and polymethylene polyphenylisocyanate), tetramethylxylene diisocyanate, toluene diisocyanate and mixtures of the aromatic polyisocyanates, any of which may be modified to contain biuret, allophanate, urea, carbamate, isocyanurate or carbodiimide groups.

11. 2. The adhesive composition according to claim 1, wherein the aromatic polyisocyanate (D) is a polymethylene polyphenylisocyanate containing MDI having an NCO content (according to DIN EN ISO 11 909) of 30.4%.

12. 2. The adhesive composition of claim 1, wherein the isocyanate-functionalized silane (E) is selected from reaction products of aminosilanes and polyisocyanates, reaction products of mercaptosilanes and polyisocyanates, etc., and mixtures thereof.

13. 2. The adhesive composition of claim 1, wherein the isocyanate-functionalized silane (E) is a reaction product of a secondary aminoalkoxysilane and a polyisocyanate.

14. 2. The adhesive composition of claim 1, wherein the isocyanate-functionalized silane (E) is a reaction product of N,N-bis[(3-trimethoxysilyl)-propyl]amine) reacted with HDI-biuret.

15. The adhesive composition of claim 1 , wherein the amine catalyst (F) is selected from tertiary amines.

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