One-component polyurethane adhesive

Abstract

Provided herein are one-component polyurethane adhesive compositions that exhibit excellent adhesive strength on both press-bent glass frit surfaces and painted metal surfaces.

Description

Technical Field

[0001] The present invention relates to a one-component polyurethane adhesive, particularly to the field of polyurethane adhesives for adhesion to glass and acid-resistant coating substrates without the need for a primer.

Background Art

[0002] One-component polyurethane adhesives are widely used in the automotive industry, particularly for adhering the front glass to the window flange of the vehicle body. Commercially available adhesives are designed to provide both strong adhesion performance and good physical properties. Many adhesives require a primer on the glass frit of the front glass and the coated window flange to provide good adhesion strength (lap shear value > 362 psi) and a good failure mode. The use of primers in automotive OEM plants increases volatile organic compounds, production steps, quality problems, and manufacturing costs.

[0003] Adhesives that provide primerless adhesion to either glass frit or coated metal panels have been reported, but these adhesives lack primerless adhesion performance to both glass frit and coated panels, especially to press-bent glass frit and acid-resistant coated panels.

Summary of the Invention

Problems to be Solved by the Invention

[0004] There is a strong need for a one-component polyurethane adhesive that can provide good primerless adhesion to glass frit and coated panels.

Means for Solving the Problems

[0005] In a first aspect, the present invention is a one-component polyurethane adhesive composition comprising (A) at least one polyether prepolymer in a total content of 30 to 75% by weight of polyether prepolymers; (B) At least one polyester prepolymer in the total content of polyester prepolymers at 0.5 to 2.0% by weight; (C) At least one aliphatic polyisocyanate in a total aliphatic polyisocyanate content of 0.5 to 3.0% by weight; (D) At least one aromatic polyisocyanate in the total aromatic polyisocyanate content of 0.2 to 2.0% by weight; (E) At least one isocyanate-functionalized silane in a total isocyanate-functionalized silane content of 0.2 to 3.0% by weight; (F) 0.1-0.6% by weight of amine catalyst; (G) At least one mercaptosilane in a total mercaptosilane content of 0 to 1.5% by weight, wherein the combination of amino and / or mercaptosilane is at least 0.5% by weight; and / or (G') At least one aminosilane in a total aminosilane content of 0 to 1.5% by weight; (H) 10-35% by weight of carbon black; (I) Optionally, 0 to 20% by weight of calcium carbonate; (J) Optionally, 0 to 20% by weight of fillers other than carbon black and calcium carbonate; At least one organometallic catalyst capable of catalyzing the reaction between (K) isocyanate and a functional group having at least one reactive hydrogen, and silane condensation. The present invention provides an adhesive composition comprising a total polyisocyanate content of 1 to 5% by weight, a total calcium carbonate + filler content of 0 to 20% by weight, and weight percentages based on the total weight of the polyurethane adhesive.

[0006] In a second aspect, the present invention is Glass substrate; Second substrate; A layer of the adhesive composition of the present invention that is in adhesive contact with both substrates. The provided product is a bonded assembly that includes the above.

[0007] In a third aspect, the present invention relates to a method for bonding a glass substrate to a second substrate, (1) A step of providing a glass substrate and a second substrate; (2) The step of applying the adhesive composition of the present invention to a glass substrate, a second substrate, or both without a primer; (3) Step of assembling the glass substrate and the second substrate so that the adhesive composition is in adhesive contact with both substrates. This provides a method that includes this.

[0008] The composition of the present invention is useful for bonding glass and a painted substrate together without the need for a primer. The composition provides lap shear strength that meets industry standards and offers durable adhesion. In preferred embodiments, after curing for 7 days at 23°C ± 2°C, the composition exhibits a tensile strength of 6 MPa (870 psi) or higher, a Young's modulus of 3 MPa (435 psi) or higher, a lap shear adhesive strength of 2.5 MPa (362 psi) or higher at 100 percent cohesive failure, an elongation of 270% or higher, and quick-knife bonding at 100 percent cohesive failure after 7 days of curing at 23°C and 50% relative humidity, as well as other environmental aging conditions. The composition of the present invention is pumpable at room temperature and does not require heating. [Modes for carrying out the invention]

[0009] The inventors unexpectedly discovered that the adhesive composition described in claim 1 provides good primerless adhesion to both glass and painted substrates, even after environmental aging conditions.

[0010] Definitions and Abbreviations MDI 4,4'-Methylenebis(phenylisocyanate) HDI Hexamethylene Diisocyanate PU (Polyurethane) SEC size exclusion chromatography.

[0011] The molecular weights of polymers reported herein are reported in Datons (Da) as number or weight-average molecular weights determined by size exclusion chromatography (SEC).

[0012] The one-component polyurethane adhesive composition of the present invention is (A) At least one polyether prepolymer in the total content of 30-75% by weight of polyether prepolymers; (B) At least one polyester prepolymer in the total content of polyester prepolymers at 0.5 to 2.0% by weight; (C) At least one aliphatic polyisocyanate in a total aliphatic polyisocyanate content of 0.5 to 3.0% by weight; (D) At least one aromatic polyisocyanate in the total aromatic polyisocyanate content of 0.2 to 2.0% by weight; (E) At least one isocyanate-functionalized silane in a total isocyanate-functionalized silane content of 0.2 to 3.0% by weight; (F) 0.1-0.6% by weight of amine catalyst; (G) At least one mercaptosilane in a total mercaptosilane content of 0 to 1.5% by weight, wherein the combination of amino and / or mercaptosilane is at least 0.5% by weight; and / or (G') At least one aminosilane in a total aminosilane content of 0 to 1.5% by weight; (H) 10-35% by weight of carbon black; (I) Optionally, 0 to 20% by weight of calcium carbonate; (J) Optionally, 0 to 20% by weight of fillers other than carbon black and calcium carbonate; At least one organometallic catalyst capable of catalyzing the reaction between (K) isocyanate and a functional group having at least one reactive hydrogen, and silane condensation. The total polyisocyanate content is 1-5% by weight, the total calcium carbonate + filler content is 0-20% by weight, and the weight percentages are based on the total weight of the polyurethane adhesive.

[0013] Polyether prepolymer (A) The composition of the present invention contains a polyether prepolymer in an amount of 30 to 75% by weight, based on the total weight of the composition.

[0014] Polyether prepolymers include polymers produced by polymerizing one or more polyether polyols in the presence of a polyisocyanate, preferably a diisocyanate. Useful polyether polyols 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 etherdiols and triols prepared by reacting unsubstituted or halogen- or aromatically substituted ethylene oxide or propylene oxide with an initiator compound containing two or more active hydrogen groups, such as water, ammonia, polyalcohol, or amine. Generally, polyether polyols can be prepared by polymerizing alkylene oxides in the presence of an activated water-containing initiator compound. Preferred polyether polyols contain one or more alkylene oxide units in the main chain of the polyol. Preferred alkylene oxide units are ethylene oxide, propylene oxide, butylene oxide, and mixtures thereof. Preferably, the polyol contains propylene oxide units, ethylene oxide units, or mixtures thereof. In embodiments in which a mixture of alkylene oxide units is contained in the polyol, the different units may be arranged randomly or in blocks of each alkylene oxide. In one preferred embodiment, the polyol contains propylene oxide chains such that the ethylene oxide chains cap the polyol. In a preferred embodiment, the polyether polyol is a mixture of polyetherdiol and polyethertriol. Preferably, the polyether polyol or mixture has a functional value of at least about 1.5, more preferably at least about 1.8, most preferably at least about 2.0; 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 about 5,000 or less, more preferably about 3,000 or less, and most preferably about 2,500 or less.

[0015] A more specific example would be: 1. The alkylene group is C2-C4, and the poly(alkylene oxide) diol is a bifunctional polyol (diol) such as poly(ethylene oxide) diol, poly(propylene oxide) diol, and poly(tetramethylene oxide) diol, with poly(propylene oxide) diol being particularly preferred. In a particularly preferred embodiment, the polyether prepolymer contains nominally bifunctional poly(propylene oxide) (1000 equivalents) having a hydroxyl value of 56. 2. Trifunctional polyols (triols), particularly ethylene oxide, propylene oxide, tetramethylene oxide, and butylene oxide, such as those based on alkylene oxides initiated with trifunctional polyols such as trimethylolpropane, in which the alkylene group is C2-C4, with propylene oxide being particularly preferred. In a particularly preferred embodiment, the polyether prepolymer comprises nominally trifunctional poly(propylene oxide) (equivalent 1558) having a hydroxyl value of 36; the polymer may or may not be capped with ethylene oxide to modify its reactivity. 3. A mixture of 1 and 2. A mixture of 1 and 2 is particularly preferred, and more particularly preferred is a mixture of a) a nominally bifunctional poly(propylene oxide) having a hydroxyl value of 56 (equivalent 1000) and b) a nominally trifunctional poly(propylene oxide) having a hydroxyl value of 36 (equivalent 1558) in a weight ratio of 1:2 to 2:1 b) / a).

[0016] The diisocyanates that can be used to produce polyether prepolymers are not particularly limited. Aliphatic and aromatic diisocyanates can be used. Examples of preferred 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.

[0017] In a particularly preferred embodiment, the polyether prepolymer comprises a nominally trifunctional poly(propylene oxide) (equivalent 1000) having a hydroxyl value of 56 and a nominally trivalent poly(propylene oxide) (equivalent 1558) having a hydroxyl value of 36, which are reacted with MDI.

[0018] 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 described in column 12, rows 38-49 of U.S. Patent No. 5,922,809.

[0019] The polyether prepolymer is present in an amount of 30-75% by weight, more preferably 45-65% by weight, and even more preferably 55-64% by weight, based on the total weight of the adhesive composition.

[0020] In a particularly preferred embodiment, the adhesive composition of the present invention comprises a nominally trifunctional poly(propylene oxide) (equivalent 1558) having a hydroxyl value of 36 and a nominally trifunctional poly(propylene oxide) (equivalent 1000) having a hydroxyl value of 56, reacted with MDI, and contains 58 to 64% by weight of a polyether prepolymer based on the total weight of the adhesive composition, having an isocyanate content of 1.25% by weight and a viscosity of 16,000 cps at 23°C as measured according to the procedure described in columns 12, rows 38-49 of U.S. Patent No. 5,922,809.

[0021] Preferably, the prepolymer has a Brookfield viscosity of at least 6,000 centipoise or at least about 8,000 centipoise, 30,000 centipoise, or 20,000 centipoise. If the viscosity is too high, it will be difficult to pump the final adhesive. If the viscosity is too low, the final adhesive will be too runny and / or drip.

[0022] The prepolymer has at least 840 isocyanate equivalents corresponding to a 5% by weight NCO content. The isocyanate equivalents of the prepolymer can be at least 1050 (4% NCO content), at least 1400 (3% NCO content), or at least 1680 (2.5% NCO content), for example, 10,000 (0.42% NCO content) or less, 8400 (0.5% NCO content) or less, 7000 (0.6% NCO content) or less, or 5000 (0.84% ​​NCO content) or less. The polyether prepolymer has an average isocyanate functional value of at least about 2.0 and a molecular weight (weight average) of at least about 2,000. Preferably, the average isocyanate functional value of the prepolymer is at least about 2.2, more preferably at least about 2.4. Preferably, the isocyanate functional value is about 3.5 or less, more preferably about 3.0 or less, and most preferably about 2.8 or less. Preferably, the weight-average molecular weight of the prepolymer is at least about 2,500, more preferably at least about 3,000; preferably about 40,000 or less, even more preferably about 20,000 or less, more preferably about 15,000 or less, and most preferably about 10,000 or less. The prepolymer can be prepared by any suitable method, such as by reacting an isocyanate-reactive compound containing at least two highly isocyanate-reactive active hydrogen-containing groups with a polyisocyanate in excess of stoichiometric value, under reaction conditions sufficient to form the corresponding prepolymer.

[0023] The prepolymer equivalents and molecular weight are measured according to the procedure disclosed in column 12, rows 50-64 of U.S. Patent No. 5,922,809, which is incorporated herein by reference.

[0024] Polyester prepolymer (B) The adhesive composition of the present invention contains a polyester prepolymer in an amount of 0.5 to 2.0% by weight, based on the total weight of the composition.

[0025] Polyester prepolymers include polymers produced by reacting one or more linear copolyesters having primary hydroxyl functional groups 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.

[0026] The diisocyanates that can be used to produce polyester prepolymers are not particularly limited. Aliphatic and aromatic diisocyanates can be used. Examples of preferred 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.

[0027] In a preferred embodiment, the polyester prepolymer is produced by reacting a copolyester with a molecular weight of 3,500 Da with MDI. Preferably, it has a melting point of 45 to 90°C.

[0028] The polyester prepolymer is present in an amount of 0.5 to 2.0% by weight based on the total weight of the composition, preferably 0.9 to 1.5% by weight, and more preferably 1 to 1.3% by weight based on the total weight of the adhesive composition.

[0029] In a preferred embodiment, the polyester prepolymer is produced by reacting a copolyester with a molecular weight of 3,500 Da with MDI, having a melting point of 45-90°C, and is used in an amount of 1-1.3% by weight based on the total weight of the adhesive composition.

[0030] Aliphatic polyisocyanates (C) The adhesive composition of the present invention contains at least one aliphatic polyisocyanate in a total aliphatic polyisocyanate content of 0.5 to 3.0% by weight.

[0031] Aliphatic polyisocyanates are not particularly limited. Some examples include isophorone diisocyanate, 1,6-hexamethylene diisocyanate, bis(4-isocyanatocyclohexyl)methane, and trimethylhexamethylene diisocyanate, all of which may be modified to include a biuret group, allophanate group, urea group, carbamate group, isocyanurate group, or carbodiimide group.

[0032] In a preferred embodiment, the aliphatic polyisocyanate is based on an HDI trimer having an NCO content of 21.8 ± 0.3% (according to DIN EN ISO 11 909).

[0033] Aliphatic polyisocyanates are present in the adhesive composition of the present invention in an amount of 0.5 to 3.0% by weight based on the total weight of the composition, preferably 0.8 to 2.5% by weight based on the total weight of the adhesive composition.

[0034] 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) at a concentration of 0.8 to 2.5% by weight based on the total weight of the adhesive composition.

[0035] Aromatic polyisocyanates (D) The adhesive composition of the present invention contains (D) at least one aromatic polyisocyanate in a total aromatic polyisocyanate content of 0.2 to 2.0% by weight based on the total weight of the adhesive composition.

[0036] Aromatic polyisocyanates are not particularly limited. Examples include diphenylmethane diisocyanate (MDI), polymethylene polyphenyl isocyanate, polymeric MDI (PMDI, a mixture of diphenylmethane diisocyanate and polymethylene polyphenyl isocyanate), tetramethylxylene diisocyanate, and toluene diisocyanate, all of which may be modified to include a biuret group, allophanate group, urea group, carbamate group, isocyanurate group, or carbodiimide group.

[0037] In a preferred embodiment, the aromatic polyisocyanate is a polymethylene polyphenyl isocyanate having an NCO content of 30.4% (according to DIN EN ISO 11 909).

[0038] Aromatic polyisocyanates are used in an amount of 0.2 to 2.0% by weight, preferably 0.3 to 0.65% by weight, based on the total weight of the adhesive composition.

[0039] In a particularly preferred embodiment, the aromatic polyisocyanate is a polymethylene polyphenyl isocyanate having an NCO content of 30.4% (according to DIN EN ISO 11 909) at a concentration of 0.3 to 0.65% by weight based on the total weight of the adhesive composition.

[0040] Isocyanate-functionalized silane (E) The adhesive composition of the present invention contains (E) at least one isocyanate-functionalized silane in a total isocyanate-functionalized silane content of 0.2 to 3.0% by weight based on the total weight of the adhesive composition.

[0041] The isocyanate-functionalized silane is not particularly limited. Examples include polyisocyanate compounds such as toluene diisocyanate and methylenediphenyl diisocyanate, with 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 C1~C 20 Alkyl, C6~C 20 Aryl, C1~C 20 It is an aralkyl group, and R is C1~C 20 (Selected from hydrocarbon groups, particularly the propylene (-CH2-CH2-CH2-) group, and b is 0, 1, or 2) Examples include those produced by reacting a silane compound with an active hydrogen-containing group W.

[0042] Further examples include, • Reaction products of aminosilane and polyisocyanate; • Reaction products of mercaptosilane and polyisocyanate; • Reaction products of carboxylate-functionalized silanes and polyisocyanates; • Isocyanate-functionalized silanes such as (3-isocyanatopropyl)trimethoxysilane These are some examples.

[0043] Reaction products of aminosilanes, and more particularly secondary amine-aminosilanes, with polyisocyanates are especially preferred.

[0044] In preferred embodiments, the isocyanate-functionalized silane is a reaction product of a secondary aminoalkoxysilane and a polyisocyanate, for example, a reaction product of N,N-bis[(3-trimethoxysilyl)-propyl]amine reacted with HDI-biuret.

[0045] 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, having an isocyanate content of 7%. The isocyanate-functionalized silane may contain additional inert additives such as plasticizers.

[0046] The isocyanate-functionalized silane is present in an amount of 0.2 to 3% by weight, preferably 0.5 to 2.6% by weight, and more preferably 0.5 to 2.5% by weight, based on the total weight of the adhesive composition.

[0047] 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, having an isocyanate content of 7%, and is used in an amount of 0.8 to 1.0% by weight, preferably 0.5 to 2.5% by weight, based on the total weight of the adhesive composition.

[0048] Amine catalyst (F) The adhesive composition of the present invention contains (F) an amine catalyst in an amount of 0.1 to 0.6% by weight based on the total weight of the adhesive composition.

[0049] The amine catalyst is any amine catalyst capable of catalyzing the reaction between isocyanate and water. Tertiary amines, such as aliphatic cyclic and acyclic amines including N,N-dimethylcyclohexaneamine, triethylenediamine, N,N,N,N-tetramethylalkylenediamine, N,N,N,N-pentamethyldiethylenetriamine, triethylamine, N,N-dimethylbenzylamine, N,N-dimethylhexadecylamine, N,N-dimethylbutylamine, and 2,2'-dimorpholinodiethyl ether, are preferred.

[0050] 2,2'-dimorpholinodiethyl ether is particularly preferred.

[0051] The amine catalyst is used in an amount of 0.1 to 0.6% by weight, preferably 0.1 to 0.35% by weight, more preferably 0.14 to 0.3% by weight, based on the total weight of the adhesive composition.

[0052] In a preferred embodiment, the amine catalyst is 2,2'-dimorpholinodiethyl ether in an amount of 0.14 to 0.3% by weight based on the total weight of the adhesive composition.

[0053] Mercaptosilane (G) The adhesive composition of the present invention contains at least one mercaptosilane of (G) 0 to 1.5% by weight and / or at least one aminosilane of (G') 0 to 1.5% by weight, and the combination of aminosilane and / or mercaptosilane is at least 0.5% by weight based on the total weight of the adhesive composition.

[0054] The mercaptosilane is not particularly limited. The following formula:

Chemical formula

[0055] R 1 , R 2 and R 3 are OCH3 and n is 1 to 6 of mercaptosilane is particularly preferred.

[0056] In a preferred embodiment, the mercaptosilane is γ-mercaptopropyltrimethoxysilane.

[0057] At least one mercaptosilane is preferably present in a total mercaptosilane content of 0 to 1.5% by weight, more preferably 0.75 to 1.2% by weight, and particularly preferably 0.75 to 1.0% by weight, based on the total weight of the adhesive composition.

[0058] In a particularly preferred embodiment, at least one mercaptosilane is γ-mercaptopropyltrimethoxysilane in an amount of 0.75 to 1.0% by weight based on the total weight of the adhesive composition.

[0059] Aminosilane (G') The adhesive composition of the present invention comprises (G) 0 to 1.5% by weight of at least one mercaptosilane and / or (G') 0 to 1.5% by weight of at least one aminosilane, wherein the combination of amino and / or mercaptosilane is at least 0.5% by weight based on the total weight of the adhesive composition.

[0060] The aminosilane is not particularly limited. Primary and secondary aminosilanes may be used. Specifically, secondary aminosilanes, such as those of the following formula: [ka] (In the formula, R 1 , R 2 , R 3 , R 4 , R 5 and R 6 It is selected independently from OCH3 and OC2H5; and R 7 and R 8 C n H 2n (Independently selected, where n is an integer between 1 and 6, preferably n is 3) The aminosilane is particularly preferred.

[0061] In a preferred embodiment, at least one aminosilane is a bis(γ-trimethoxysilylpropyl)amine.

[0062] At least one aminosilane is preferably present in a total aminosilane content of 0 to 1.5% by weight, more preferably 0.01 to 0.5% by weight, more preferably 0.05 to 0.2% by weight, and most preferably 0.1 to 0.15% by weight, based on the total weight of the adhesive composition.

[0063] In a particularly preferred embodiment, at least one aminosilane is a bis(γ-trimethoxysilylpropyl)amine in an amount of 0.09 to 0.2% by weight based on the total weight of the adhesive composition.

[0064] Carbon Black (H) The adhesive composition of the present invention contains (H) carbon black in an amount of 10 to 35% by weight based on the total weight of the adhesive composition.

[0065] The carbon black is not particularly limited. Preferred carbon black is at least 80 cm³ per 100 g of carbon black, as measured according to ASTM D-2414-09. 3 Preferably at least 90 cm 3 , more preferably at least 95 cm 3 The refueling value of dibutyl phthalate is shown. In addition, carbon black preferably has an iodine value of at least 80 as measured according to ASTM D1510-11.

[0066] Carbon black is present in an amount of 10 to 35% by weight, preferably 17.6 to 25% by weight, and more preferably 20 to 23% by weight, based on the total weight of the adhesive composition.

[0067] Calcium(I) carbonate The adhesive composition of the present invention optionally contains (I) calcium carbonate in an amount of 0 to 20% by weight based on the total weight of the adhesive composition. The calcium carbonate particles may be untreated or surface-modified by treatment with chemicals such as organic acids or esters of organic acids.

[0068] Preferably, calcium carbonate is present in an amount of 5 to 10% by weight, more preferably 6 to 9% by weight, based on the total weight of the adhesive composition.

[0069] The total content of calcium carbonate + carbon black and fillers other than calcium carbonate is 3 to 15% by weight, more preferably 5 to 12% by weight, based on the total weight of the composition.

[0070] Filler (J) The adhesive composition of the present invention optionally contains 0 to 15% by weight of additional fillers other than calcium carbonate and / or carbon black, based on the total weight of the composition.

[0071] Suitable fillers include fumed silica, clay, calcium oxide, organic clay, talc, ceramics such as glass powder and boron nitride, metals, crosslinked organic polymers, and lignocellulose powder.

[0072] When fumed silica is used, the particles may be untreated or surface-modified by treatment with chemicals such as chlorosilane, dichlorosilane, alkyltrialkoxysilane, or polydimethylsiloxane.

[0073] The filler may be fumed silica and / or clay present in 0-20% by weight.

[0074] The total content of calcium carbonate + filler, such as fumed silica and / or clay, is 0 to 20% by weight based on the total weight of the composition.

[0075] In preferred embodiments, the adhesive composition of the present invention contains 0.1 to 1% by weight, more preferably 0.2 to 0.75% by weight, and particularly preferably 0.3 to 0.6% by weight of filler, based on the total weight of the adhesive composition.

[0076] In a preferred embodiment, the filler is fumed silica, present in an amount of 0.1 to 1% by weight, more preferably 0.2 to 0.75% by weight, and particularly more preferably 0.3 to 0.6% by weight, based on the total weight of the adhesive composition.

[0077] Organometallic catalyst (K) The adhesive comprises at least one organometallic catalyst capable of catalyzing the reaction between an isocyanate and a functional group having at least one reactive hydrogen, as well as silane condensation. The metal carboxylate includes tin carboxylate and zinc carboxylate. The metal alkanoate includes tin(II) octanoate, bismuth octanoate, or bismuth neodecanoate. Preferably, the at least one organometallic catalyst is an organotin catalyst. Examples include dibutyltin dilaurate, dimethyltin dineodecanoate, dimethyltin mercaptide, dimethyltin carboxylate, dimethyltin dioleate, dimethyltin dithioglycolate, dibutyltin mercaptide, dibutyltin bis(2-ethylhexylthioglycolate), dibutyltin sulfide, dioctyltin dithioglycolate, dioctyltin mercaptide, dioctyltin dioctoate, dioctyltin dineodecanoate, and dioctyltin dilaurate. In a particularly preferred embodiment, it is dimethyltin dineodecanoate.

[0078] The organometallic catalyst is present in an amount of preferably 0.001 to 2% by weight, more preferably 0.005 to 1% by weight, and particularly preferably 0.01 to 0.5% by weight, based on the total weight of the adhesive.

[0079] In a particularly preferred embodiment, the organometallic catalyst is an organotin catalyst, particularly selected from those listed above, used in an amount of 0.01 to 0.5% by weight based on the total weight of the adhesive.

[0080] In another preferred embodiment, the organometallic catalyst is dimethyltin dineodecanoate, used in an amount of 0.01 to 0.5% by weight based on the total weight of the adhesive.

[0081] Other ingredients The adhesive composition of the present invention may further contain, for example, one or more plasticizers (such as diisononyl phthalate), one or more stabilizers, and other components such as heat, visible light, and UV stabilizers.

[0082] Examples of heat stabilizers include alkyl-substituted phenols, phosphites, sebacates, and cinnamates. If present, preferred heat stabilizers are organic phosphites, more specifically trisnonylphenyl phosphite, as disclosed in U.S. Patent No. 6,512,033, incorporated herein by reference. The heat stabilizer may constitute at least 0.01 weight percent or at least 0.3 weight percent, and at most 5 weight percent, 2 weight percent or less, or 1.0 weight percent or less, based on the total weight of the adhesive composition. The adhesive composition may lack such stabilizers.

[0083] Regarding UV light stabilizers, these include benzophenones and benzotriazoles. Specific UV light absorbers include those manufactured by BASF, such as TINUVIN® P, TINUVIN® 326, TINUVIN® 213, TINUVIN® 327, TINUVIN® 571, and TINUVIN® 328, as well as those manufactured by 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. One or more UV light absorbers may constitute at least 0.1 weight percent, at least 0.2 weight percent, or at least 0.3 parts by weight of the adhesive composition, and may constitute 3 weight percent or less, 2 weight percent or less, or 1 weight percent.

[0084] The adhesive composition of the present invention may further contain one or more visible light stabilizers. Preferred visible light stabilizers include hindered amine visible light stabilizers such as TINUVIN® 144, TINUVIN® 622, TINUVIN® 77, TINUVIN® 123, TINUVIN® 765, and CHIMASSORB® 944, all available from Cytec; and CYASORB® UV-500, CYASORB® UV-3581, and CYASORB® UV-3346, all available from Ciba-Geigy. Of these, TINUVIN® 765 is a preferred choice. The visible light stabilizer may constitute at least 0.1 weight percent, at least 0.2 weight percent, or at least 0.3 weight percent of the adhesive composition, and may constitute 3 weight percent or less, 2 weight percent or less, or 1.5 weight percent or less.

[0085] In preferred embodiments, the stabilizer includes trisnonylphenyl phosphite, bis(1,2,2,6,6-pentamethyl-4-piperidyl) sebacate and methyl 1,2,2,6,6-pentamethyl-4-piperidyl sebacate, 2-(2H-benzotriazol-2-yl)-6-dodecyl-4-methylphenol, and mixtures thereof, and it is particularly preferred to use mixtures thereof.

[0086] viscosity The viscosity of the adhesive composition is expressed as press-flow viscosity, which is the time (in seconds) it takes for 20 g of the adhesive composition to pass through a 4.0 mm orifice at 23°C under an applied pressure of 552 kPa. The press-flow viscosity may be, for example, at least 5 seconds, at least 10 seconds, at least 15 seconds, and may be, for example, 150 seconds or less, 120 seconds or less, 80 seconds or less, or 70 seconds or less.

[0087] Adhesive assembled product In one aspect, the present invention is Glass substrate; Second substrate; A layer of the adhesive composition of the present invention that is in adhesive contact with both substrates. We provide adhesive assemblies that include the following:

[0088] The second substrate is not particularly limited and may be, for example, glass, metal (especially primerd metal), electrodeposited surface, painted surface, wood, and cured polyurethane. In preferred embodiments, the second substrate is selected from automotive topcoat coated surfaces (metal coated with automotive topcoat), electrodeposited surfaces, cured polyurethane, and cured silane polyurethane.

[0089] In a particularly preferred embodiment, the assembly of the present invention is Glass substrate; Substrates coated with automotive paint (such as silane-based automotive paint); A layer of the adhesive composition of the present invention that is in adhesive contact with both substrates. Includes.

[0090] Manufacturing method The adhesive composition of the present invention is manufactured by mixing the components under inert and dry conditions and / or under vacuum until a homogeneous mixture is obtained. In one preferred method of manufacture, a polyether prepolymer, aminosilane (if used), isocyanatosilane, diisononylphthalate plasticizer (if used), aliphatic isocyanate, aromatic isocyanate, and mercaptosilane (if used) are charged into a mixer vessel (such as a Ross mixer) and heated to 60°C or about 60°C with stirring under vacuum (for example, for 5 minutes or about 5 minutes). Amine catalysts and organometallic catalysts are added, and the mixture is stirred under vacuum (for example, for 5 minutes or about 5 minutes). The vacuum is broken, and under an inert atmosphere (e.g., N2 or Ar), fillers (if used, e.g., fumed silica), carbon black, and calcium carbonate (if used) are added to the reactor and stirred (for example, for 2-5 minutes). Fillers (if used, e.g., fumed silica) can also be added to the mixer before the carbon and calcium carbonate. The mixture is placed under vacuum and stirred for a longer period (e.g., 15 minutes). The polyester prepolymer (preheated to 80°C or approximately 80°C) and stabilizers (if used) are added, vacuum is re-established, and the mixture is stirred for a further 5 minutes. The resulting adhesive composition is placed in a container, for example, it may be placed in an airtight tube, which is then stored in a nitrogen-filled sealed aluminum bag.

[0091] use The adhesive composition of the present invention is particularly suitable for bonding glass to a painted or coated substrate without the need for a primer.

[0092] In use, the adhesive is applied to the glass substrate and / or the second coating substrate. If necessary, both substrates may be cleaned before applying the adhesive. The glass substrate and the second coating substrate are then brought into adhesive contact with each other, with the adhesive of the present invention sandwiched between them.

[0093] Hardening is achieved by atmospheric moisture.

[0094] Particularly Preferred Embodiment The following are particularly preferred embodiments of the adhesive composition of the present invention: 1. A one-component polyurethane adhesive composition, (A) At least one polyether prepolymer in the total content of 30-75% by weight of polyether prepolymers; (B) At least one polyester prepolymer in the total content of polyester prepolymers at 0.5 to 2.0% by weight; (C) At least one aliphatic polyisocyanate in a total aliphatic polyisocyanate content of 0.5 to 3.0% by weight; (D) At least one aromatic polyisocyanate in the total aromatic polyisocyanate content of 0.2 to 2.0% by weight; (E) At least one isocyanate-functionalized silane in a total isocyanate-functionalized silane content of 0.2 to 3.0% by weight; (F) 0.1-0.6% by weight of amine catalyst; (G) At least one mercaptosilane in a total mercaptosilane content of 0 to 1.5% by weight, wherein the combination of amino and / or mercaptosilane is at least 0.5% by weight; and / or (G') At least one aminosilane in a total aminosilane content of 0 to 1.5% by weight; (H) 10-35% by weight of carbon black; (I) Optionally, 0 to 20% by weight of calcium carbonate; (J) Optionally, 0 to 20% by weight of fillers other than carbon black and calcium carbonate; At least one organometallic catalyst capable of catalyzing the reaction between (K) isocyanate and a functional group having at least one reactive hydrogen, and silane condensation. An adhesive composition comprising, with a total polyisocyanate content of 1-5% by weight, a total calcium carbonate + filler content of 0-20% by weight, and weight percentages based on the total weight of the polyurethane adhesive. 2. The adhesive composition according to Embodiment 1, wherein at least one polyether prepolymer (A) is produced by reacting one or more polyols in the presence of a polyisocyanate, preferably a diisocyanate, and the polyether polyol can be selected from polyether polyols, hydroxyl-containing polythioethers, polymer polyols, and mixtures thereof. 3. The adhesive composition according to Embodiment 1 or 2, wherein at least one polyether prepolymer is produced by reacting a polyisocyanate with a polyether polyol. 4. The adhesive composition according to Embodiment 1, 2, or 3, wherein the polyether prepolymer is produced by reacting a polyisocyanate with a polyol selected from poly(oxyethylene oxide)diol, poly(oxypropylene oxide)diol, poly(oxybutylene oxide)diol, and poly(tetramethylene oxide)diol. 5. The adhesive composition according to any one of Embodiments 1 to 4, wherein the polyether prepolymer is produced by reacting a polyisocyanate selected from toluene diisocyanate (TDI), hexamethylene diisocyanate (HDI), naphthalene diisocyanate (NDI), methylene bis-cyclohexyl isocyanate (HMDI) (hydrogenated MDI), isophorone diisocyanate (IPDI) and mixtures thereof with a bifunctional polyether polyol selected from poly(alkylene oxide)diols having C2 to C4 alkylene groups, a trifunctional polyol based on a poly(alkylene oxide)diol initiated with a trifunctional polyol having C2 to C4 alkylene groups, and mixtures thereof. 6. The adhesive composition according to any one of Embodiments 1 to 5, wherein the polyether prepolymer comprises a nominally trifunctional poly(propylene oxide) (equivalent 1558) having a hydroxyl value of 36 and a nominally bifunctional poly(propylene oxide) (equivalent 1000) having a hydroxyl value of 56, which have been reacted with MDI. 7. The adhesive composition according to any one of Embodiments 1 to 6, wherein at least one polyester prepolymer (B) is produced by reacting one or more linear copolyesters having primary hydroxyl functional groups with a polyisocyanate, preferably a diisocyanate. 8. The adhesive composition according to any one of Embodiments 1 to 7, wherein at least one polyester prepolymer (B) is produced by reacting one or more linear copolyesters having primary hydroxyl functional groups with a polyisocyanate selected from toluene diisocyanate (TDI), hexamethylene diisocyanate (HDI), naphthalene diisocyanate (NDI), methylene bis-cyclohexyl isocyanate (HMDI) (hydrogenated MDI), isophorone diisocyanate (IPDI), and mixtures thereof. 9. The adhesive composition according to any one of Embodiments 1 to 8, wherein at least one polyester prepolymer (B) is produced by reacting a copolyester with a molecular weight of 3,500 Da with MDI. 10. An adhesive composition according to any one of Embodiments 1 to 9, wherein at least one aliphatic polyisocyanate (C) is selected from isophorone diisocyanate, 1,6-hexamethylene diisocyanate, bis(4-isocyanatocyclohexyl)methane, and trimethylhexamethylene diisocyanate, all of which can be modified to include a biuret group, an allophanate group, a urea group, a carbamate group, an isocyanurate group, or a carbodiimide group. 11. An adhesive composition according to any one of Embodiments 1 to 10, wherein at least one aliphatic polyisocyanate (C) is based on an HDI trimer. 12. An adhesive composition according to any one of Embodiments 1 to 11, wherein at least one aromatic polyisocyanate (D) is selected from diphenylmethane diisocyanate (MDI), polymethylene polyphenyl isocyanate, polymeric MDI (PMDI, a mixture of diphenylmethane diisocyanate and polymethylene polyphenyl isocyanate), tetramethylxylene diisocyanate, and toluene diisocyanate, and each of these can be modified to include a biuret group, an allophanate group, a urea group, a carbamate group, an isocyanurate group, or a carbodiimide group. 13. The adhesive composition according to any one of Embodiments 1 to 12, wherein at least one aromatic polyisocyanate (D) is polymethylene polyphenyl isocyanate. 14. At least one isocyanate-functionalized silane (E) contains a polyisocyanate compound such as toluene diisocyanate or methylenediphenyl diisocyanate, with 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 C1~C 20 Alkyl, C6~C 20 Aryl, C1~C 20 It is an aralkyl group, and R is C1~C 20 Selected from hydrocarbon groups, particularly the propylene (-CH2CH2CH2-) group, and b is 0, 1, or 2. An adhesive composition according to any one of Embodiments 1 to 13, selected from silanes produced by reacting a silane compound with an active hydrogen-containing group W. 15. The adhesive composition according to any one of Embodiments 1 to 14, wherein at least one isocyanate-functionalized silane (E) is a reaction product of N,N-bis[(3-trimethoxysilyl)-propyl]amine reacted with HDI-biuret. 16. The adhesive composition according to any one of Embodiments 1 to 15, wherein the amine catalyst (F) is a tertiary amine catalyst. 17. The adhesive composition according to any one of Embodiments 1 to 16, 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'-dimorpholinodiethyl ether and mixtures thereof. 18. The adhesive composition according to any one of Embodiments 1 to 17, wherein the amine catalyst (F) is 2,2'-dimorpholinodiethyl ether. 19. At least one mercaptosilane (G) is given by the following formula: [ka] (In the formula, R 1 , R 2 and R 3 This is selected from OCH3 and OC2H5; and R 4 is -C n H 2n - where n is an integer between 1 and 12) The adhesive composition according to any one of Embodiments 1 to 18. 20.R 1 , R 2 and R 3 The adhesive composition according to Embodiment 19, wherein is OCH3 and n is 1 to 6. 21. The adhesive composition according to any one of Embodiments 1 to 20, wherein at least one mercaptosilane (G) is γ-mercaptopropyltrimethoxysilane. 22. At least one aminosilane (G') is given by the following formula: [ka] (In the formula, R 1 , R2 , R 3 , R 4 , R 5 and R 6 It is selected independently from OCH3 and OC2H5; and R 7 and R 8 is -C n H 2n (Selected independently from -, where n is an integer between 1 and 6) The adhesive composition according to any one of Embodiments 1 to 21. 23.n is 3, the adhesive composition according to Embodiment 22. 24. The adhesive composition according to any one of Embodiments 1 to 23, wherein at least one polyether prepolymer is present in an amount of 45 to 65% by weight based on the total weight of the adhesive composition. 25. The adhesive composition according to any one of Embodiments 1 to 24, wherein at least one polyether prepolymer is present in an amount of 58 to 64% by weight based on the total weight of the adhesive composition. 26. The adhesive composition according to any one of Embodiments 1 to 25, wherein at least one polyester prepolymer is present in an amount of 0.9 to 1.5% by weight based on the total weight of the adhesive composition. 27. The adhesive composition according to any one of Embodiments 1 to 26, wherein at least one polyester prepolymer is present in an amount of 1 to 1.3% by weight based on the total weight of the adhesive composition. 28. The adhesive composition according to any one of Embodiments 1 to 27, wherein at least one aliphatic polyisocyanate is present in an amount of 0.5 to 3.0% by weight based on the total weight of the adhesive composition. 29. The adhesive composition according to any one of Embodiments 1 to 28, wherein at least one aliphatic polyisocyanate is present in an amount of 0.8 to 2.5% by weight based on the total weight of the adhesive composition. 30. The adhesive composition according to any one of Embodiments 1 to 29, wherein at least one aromatic polyisocyanate is present in an amount of 0.3 to 0.65% by weight based on the total weight of the adhesive composition. 31. The adhesive composition according to any one of Embodiments 1 to 30, wherein at least one isocyanate-functionalized silane is present in an amount of 0.5 to 2.8% by weight based on the total weight of the adhesive composition. 32. The adhesive composition according to any one of Embodiments 1 to 31, wherein at least one isocyanate-functionalized silane is present in an amount of 0.5 to 2.5% by weight based on the total weight of the adhesive composition. 33. The adhesive composition according to any one of Embodiments 1 to 32, wherein the amine catalyst is present in an amount of 0.1 to 0.6% by weight based on the total weight of the adhesive composition. 34. The adhesive composition according to any one of Embodiments 1 to 33, wherein the amine catalyst is present in an amount of 0.14 to 0.3% by weight based on the total weight of the adhesive composition. 35. The adhesive composition according to any one of Embodiments 1 to 34, wherein mercaptosilane is present in an amount of 0.75 to 1.2% by weight based on the total weight of the adhesive composition. 36. The adhesive composition according to any one of Embodiments 1 to 35, wherein mercaptosilane is present in an amount of 0.75 to 1.0% by weight based on the total weight of the adhesive composition. 37. The adhesive composition according to any one of Embodiments 1 to 36, wherein aminosilane is present in an amount of 0.05 to 0.5% by weight based on the total weight of the adhesive composition. 38. The adhesive composition according to any one of Embodiments 1 to 37, wherein aminosilane is present in an amount of 0.09 to 0.2% by weight based on the total weight of the adhesive composition. 39. The adhesive composition according to any one of Embodiments 1 to 38, wherein aminosilane is present in an amount of 0.1 to 0.15% by weight based on the total weight of the adhesive composition. 40. The adhesive composition according to any one of Embodiments 1 to 39, wherein carbon black is present in an amount of 17.6 to 25% by weight based on the total weight of the adhesive composition. 41. The adhesive composition according to any one of Embodiments 1 to 40, wherein carbon black is present in an amount of 20 to 23% by weight based on the total weight of the adhesive composition. 42. The adhesive composition according to any one of Embodiments 1 to 41, wherein calcium carbonate is present in an amount of 6 to 9% by weight based on the total weight of the adhesive composition. 43. The adhesive composition according to any one of Embodiments 1 to 42, wherein at least one organometallic catalyst is an organotin catalyst. 44. An adhesive composition according to any one of Embodiments 1 to 43, wherein at least one organometallic catalyst is selected from dibutyltin dilaurate, dimethyltin dineodecanoate, dimethyltin mercaptide, dimethyltin carboxylate, dimethyltin dioleate, dimethyltin dithioglycolate, dibutyltin mercaptide, dibutyltin bis(2-ethylhexylthioglycolate), dibutyltin sulfide, dioctyltin dithioglycolate, dioctyltin mercaptide, dioctyltin dioctoate, dioctyltin dineodecanoate, dioctyltin dilaurate, and mixtures thereof. 45. The adhesive composition according to any one of Embodiments 1 to 44, wherein at least one organometallic catalyst is dimethyltin dineodecanoate. 46. ​​The adhesive composition according to any one of Embodiments 1 to 45, wherein at least one organometallic catalyst is used in an amount of 0.01 to 0.05% by weight based on the total weight of the adhesive composition. 47. An adhesive composition according to any one of Embodiments 1 to 46, further comprising a heat, visible light, and UV light stabilizer. 48. An adhesive composition according to any one of Embodiments 1 to 47, further comprising trisnonylphenyl phosphite, bis(1,2,2,6,6-pentamethyl-4-piperidyl) sebacate and methyl 1,2,2,6,6-pentamethyl-4-piperidyl sebacate, 2-(2H-benzotriazol-2-yl)-6-dodecyl-4-methylphenol and a stabilizer selected from mixtures thereof. 49. An adhesive composition according to any one of Embodiments 1 to 48, further comprising at least one plasticizer. 50. An adhesive composition according to any one of Embodiments 1 to 49, further comprising at least one plasticizer which is diisononyl phthalate. 51. An adhesive composition, (A) At least one polyether prepolymer containing, in a total content of 45-65% by weight, nominally trifunctional poly(propylene oxide) (equivalent 1558) having a hydroxyl value of 36 and nominally bifunctional poly(propylene oxide) (equivalent 1000) having a hydroxyl value of 56, reacted with MDI; (B) At least one polyester prepolymer produced by reacting a copolyester with a molecular weight of 3,500 Da with MDI in a total content of 0.5 to 2.0% by weight of the polyester prepolymer; (C) At least one aliphatic polyisocyanate based on an HDI trimer in the total aliphatic polyisocyanate content of 0.75 to 2.5% by weight; (D) At least one aromatic polyisocyanate, which is polymethylene polyphenyl isocyanate, in a total aromatic polyisocyanate content of 0.2 to 2.0% by weight; (E) At least one isocyanate-functionalized silane that is a reaction product of N,N-bis[(3-trimethoxysilyl)-propyl]amine reacted with HDI-biuret, in a total isocyanate-functionalized silane content of 0.5-2.6% by weight; (F) 0.1 to 0.35% by weight of an amine catalyst, which is 2,2'-dimorpholinodiethyl ether; (G) At least one mercaptosilane, which is γ-mercaptopropyltrimethoxysilane, in a total mercaptosilane content of 0 to 1.5% by weight, wherein the combination of amino and / or mercaptosilane is at least 0.5% by weight; and / or (G') At least one aminosilane, which is bis(γ-trimethoxysilylpropyl)amine, in a total aminosilane content of 0 to 1.5% by weight; (H) 10-35% by weight of carbon black; (I) Optionally, 0 to 20% by weight of calcium carbonate; (J) Optionally, 0 to 20% by weight of fillers other than carbon black and calcium carbonate; (K) Dimethyltindineodecanoate, or at least one organometallic catalyst. An adhesive composition comprising, with a total polyisocyanate content of 1-5% by weight, a total calcium carbonate + filler content of 0-20% by weight, and weight percentages based on the total weight of the polyurethane adhesive. 52. Adhesive composition, (A) At least one polyether prepolymer containing, in a total content of 58-64% by weight, nominally trifunctional poly(propylene oxide) (equivalent 1558) having a hydroxyl value of 36 and nominally bifunctional poly(propylene oxide) (equivalent 1000) having a hydroxyl value of 56, reacted with MDI; (B) At least one polyester prepolymer produced by reacting a copolyester with a molecular weight of 3,500 Da with MDI in a total content of 1 to 1.3% by weight of the polyester prepolymer; (C) At least one aliphatic polyisocyanate based on an HDI trimer in the total aliphatic polyisocyanate content of 0.8 to 2.5% by weight; (D) At least one aromatic polyisocyanate, which is polymethylene polyphenyl isocyanate, in a total aromatic polyisocyanate content of 0.3 to 0.65% by weight; (E) At least one isocyanate-functionalized silane that is a reaction product of N,N-bis[(3-trimethoxysilyl)-propyl]amine reacted with HDI-biuret, in a total isocyanate-functionalized silane content of 0.5 to 2.5% by weight; (F) 0.14-0.3% by weight of an amine catalyst, which is 2,2'-dimorpholinodiethyl ether; (G) At least 0.7% by weight of a combination of amino and / or mercaptosilanes, in a total mercaptosilane content of 0.75 to 1.0% by weight, including at least one mercaptosilane that is γ-mercaptopropyltrimethoxysilane, and / or (G') At least one aminosilane that is bis(γ-trimethoxysilylpropyl)amine in a total aminosilane content of 0.1 to 0.15% by weight; (H) 20-23% by weight of carbon black; (I) 6-12% by weight of calcium carbonate; (J) 0.3-0.6% by weight of fumed silica; (K) 0.01-0.05 wt% by weight of at least one organometallic catalyst, which is dimethyltin dineodecanoate. An adhesive composition comprising, wherein the total polyisocyanate content is 1.0 to 4.0% by weight, the total calcium carbonate + filler content is 3 to 15% by weight, and the weight percentage is based on the total weight of the polyurethane adhesive. 53. Glass substrate; Second substrate; A layer of the adhesive composition according to any one of embodiments 1 to 52, which is in adhesive contact with both substrates. A glued assembly including the glued parts. 54. A method for adhering a glass substrate to a second coated substrate, (1) A step of providing a glass substrate and a second coating substrate; (2) The step of applying the adhesive composition described in any one of Embodiments 1 to 52 to a glass substrate, a second coating substrate, or both; (3) Step of assembling the glass substrate and the second coated substrate so that the adhesive makes adhesive contact with both substrates. A method that includes this. [Examples]

[0095] [Table 1]

[0096] 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 charged into a 4 liter reaction kettle under nitrogen, mixed, and heated to 54°C. All subsequent steps were carried out under nitrogen. 160.64 g of molten MDI was added and mixed, and 0.08 g of tin(II) octanoate catalyst was added dropwise. The temperature in the reaction kettle rose due to the exothermic reaction; the reaction mixture was maintained at 80°C-90°C for 30 minutes. The reaction mixture was then cooled to 60°C, 501.20 g of diisononyl phthalate and 15.36 g of diethyl malonate were added, mixed for 30 minutes, and then cooled to room temperature. The resulting polyether-based polyurethane prepolymer 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 column 12, rows 38-49 of U.S. Patent No. 5,922,809.

[0097] Polyester prepolymer (B): 280 g of diisononyl phthalate was placed in a container under nitrogen and heated to 50°C. 172.80 g of MDI was added, followed by slow addition of molten Dynacoll 7381. The mixture was stirred and reacted at 80-90°C for 40 minutes. The resulting prepolymer was allowed to cool and stored under an inert atmosphere. The polyester prepolymer had an NCO content of 2% by weight based on the total weight of the prepolymer.

[0098] Isocyanate-functionalized silane (E): The reaction product of a secondary aminoalkoxysilane and a polyisocyanate was prepared by charging 333.3 g of diisononyl phthalate into a reactor under nitrogen. 729.75 g of Desmodur N-100 (a solvent-free aliphatic polyisocyanate resin based on hexamethylene diisocyanate-biuret) was added, the mixture was thoroughly mixed, and purged under an N2 atmosphere. 436.95 g of N,N-bis[(3-trimethoxysilyl)-propyl]amine) was slowly added to the mixture, and the mixture was reacted under nitrogen for 30 minutes. The adduct had an isocyanate content of 7.1% by weight based on the total weight of the adduct.

[0099] Stabilizer mixture 140 g of Tinuvin 765, 140 g of Tinuvin 571, and 120 g of Doverphos 4 were added to a reaction kettle while being mixed under nitrogen. The mixture was stirred under nitrogen for 60 minutes and then stored under an inert atmosphere.

[0100] Preparation of adhesive compositions Using the proportions listed in Table 2, calcium carbonate filler, silica, and carbon black were mixed, dried at 204°C for approximately 20 hours, and then cooled in a sealed container to form a mixture. Polyether prepolymer, aminosilane, isocyanate-functionalized silane, diisononyl phthalate, aliphatic polyisocyanate, aromatic polyisocyanate, and mercaptosilane were charged into a 2-gallon mixer and preheated to approximately 60°C. The mixture was degassed and mixed under vacuum for 5 minutes. The vacuum was broken with nitrogen, and then DMDEE and tin catalyst were added along with any stabilizer, followed by additional degassing and mixing under vacuum for 10 minutes. The vacuum was broken again with nitrogen, and then the filler mixture, including silica if used, was added to the mixer. Mixing was started to wet out the filler for 2 minutes. Vacuum was applied and mixing continued for 15 minutes. After breaking the vacuum with nitrogen, the mixture was scraped off and the polyester prepolymer was added along with any stabilizer. Mixing under vacuum was performed for 10 minutes. The resulting adhesive composition was placed in an airtight tube, and the airtight tube was stored in a nitrogen-filled, sealed aluminum bag.

[0101] Quick knife bonding The test was conducted using the following test specimens: One surface of 1-inch x 6-inch or 1-inch x 4-inch glass covered with bismuth-based press-painted frit 2L-5350, available from Johnson Matthey Inc.; 1 inch x 4 inch metal coated with Axalta RK8032 2k polyurethane paint; 1 inch x 4 inch metal coated with BASF 2K4 2k polyurethane paint; 1 inch x 4 inch metal coated with Axalta GenIV silane paint; Press-bent ceramic frit windshield We did the following.

[0102] The quick knife adhesion test is performed by distributing beads measuring 6 mm (width) x 6 mm (height) x 100 mm (length) onto a test substrate. The quick knife test is performed after initial curing of the beads under 23°C and 50 percent RH (relative humidity) for a specific period and any further environmental exposure. When testing, a slit (20-40 mm) is cut between the adhesive end and the substrate. The cured bead is then cut with a razor blade at a 60° angle to the test substrate, while pulling the end of the bead back at an angle of >90°. V-shaped notches are cut on the substrate approximately every 3-5 mm. The degree of adhesion is evaluated as adhesive failure (AF), thin film failure (TF), and / or cohesive failure (CF). In the case of AF, the cured bead can be separated from the surface of the test substrate, while in CF, separation occurs within the sealant adhesive as a result of cutting and tensile stress, and TF is a special case of CF where there is a thin film of cured adhesive remaining on the substrate after cutting and testing.

[0103] Unless otherwise specified, the press flow viscosity of an adhesive sample is measured by determining the time (in seconds) it takes for 20 g of the adhesive composition to pass through a 4.0 mm orifice under the conditions of 23°C and an applied pressure of 552 kPa.

[0104] The overlap shear test is performed according to the SAE J1529 test procedure described below. Triangular beads of adhesive composition, with a base of approximately 10 mm and a height of 10 mm, are applied along the width of a specified test specimen, such as a bismuth-based press-bent glass frit specimen, measuring 25 mm × 100 mm, and approximately 6 mm away from the end of the specimen. A second substrate, which may be a painted metal specimen, is pressed directly onto the adhesive beads to give a final height of 6 mm relative to the intermediate composition. The sample is cured for 7 days under conditions of 23°C and 50 percent relative humidity (RH) unless otherwise specified. The sample is then pulled at a speed of 50 mm / min using an Instron Tester, either immediately or after further environmental exposure. Sample area (in 2The sample breaking load (pounds) divided by ) gives the overlap shear bond strength (psi). Bonding is evaluated as adhesive failure (AF), thin film failure (TF), and / or cohesive failure (CF). In the case of AF, the cured beads can separate from the surface of the test substrate, while in CF, the separation occurs within the sealant adhesive, and TF is a special case of CF where a thin film of cured adhesive remains on the substrate after the test.

[0105] The adhesive samples were cured in round putty form at 23°C and 50% relative humidity (RH) for 7 days. Test specimens were cut from these cured sample putties and all were tested for tensile strength, elongation, and Young's modulus (1–10% strain) using an Instron Tester according to ASTM D412 (Die C).

[0106] The sagging performance is evaluated by the following method: A metal panel 10 cm high and 30 cm long is placed vertically according to its length. The adhesive composition, either before or after thermal aging conditions, is distributed as right-angled triangular beads along the top edge of the panel, which is 1.8 cm high and has a base of 0.6 cm. After 30 minutes, the amount of dripping or sagging from the tip of the adhesive beads is measured in millimeters. If there is no sagging from the tip of the beads, the sagging test result is zero millimeters.

[0107] [Table 2]

[0108] [Table 3]

[0109] [Table 4]

[0110] The results show that the adhesive of the present invention exhibits 100% cohesive failure in all substrates even after 14 days of humidity treatment and 10 days of heat aging at 90°C.

[0111] Table 4 shows the initial viscosity, thermal aging viscosity, thermal aging sag, tensile strength, elongation, and Young's modulus for Examples 1-4.

[0112] [Table 5]

[0113] All samples in Examples 1-4 exhibited zero sagging, tensile strength exceeding 900 psi, elongation exceeding 300%, and Young's modulus exceeding 3 MPa after 3 days under 54°C thermal aging conditions.

[0114] Table 5 shows the overlapping shear bonding data for Examples 2 and 3.

[0115] [Table 6]

[0116] The overlapping shear strength is over 400 psi at 100% cohesive failure. The present specification includes the following embodiments. Section 1: A one-component polyurethane adhesive composition, (A) At least one polyether prepolymer in the total content of 30-75% by weight of polyether prepolymers; (B) At least one polyester prepolymer in the total content of polyester prepolymers at 0.5 to 2.0% by weight; (C) At least one aliphatic polyisocyanate in a total aliphatic polyisocyanate content of 0.5 to 3.0% by weight; (D) At least one aromatic polyisocyanate in the total aromatic polyisocyanate content of 0.2 to 2.0% by weight; (E) At least one isocyanate-functionalized silane in a total isocyanate-functionalized silane content of 0.2 to 3.0% by weight; (F) 0.1-0.6% by weight of amine catalyst; (G) At least one mercaptosilane in a total mercaptosilane content of 0 to 1.5% by weight, wherein the combination of amino and / or mercaptosilane is at least 0.5% by weight; and / or (G') At least one aminosilane in a total aminosilane content of 0 to 1.5% by weight; (H) 10-35% by weight of carbon black; (I) Optionally, 0 to 20% by weight of calcium carbonate; (J) Optionally, 0 to 20% by weight of fillers other than carbon black and calcium carbonate; At least one organometallic catalyst capable of catalyzing the reaction between (K) isocyanate and a functional group having at least one reactive hydrogen, and silane condensation. A one-component polyurethane adhesive composition comprising, wherein the total polyisocyanate content is 1 to 5% by weight, the total calcium carbonate + filler content is 0 to 20% by weight, and the weight percentage is based on the total weight of the polyurethane adhesive. Section 2: The adhesive composition according to claim 1, wherein the at least one polyether prepolymer (A) is produced by polymerizing one or more polyols in the presence of a polyisocyanate, preferably a diisocyanate, and the polyether polyol can be selected from polyether polyols, hydroxyl-containing polythioethers, polymer polyols, and mixtures thereof. Section 3: The adhesive composition according to claim 1 or 2, wherein the at least one polyether prepolymer is produced by reacting a polyisocyanate with a polyether polyol. Section 4: The adhesive composition according to any one of claims 1 to 3, wherein the polyether prepolymer is produced by reacting a polyisocyanate with a polyol selected from poly(ethylene oxide)diol, poly(propylene oxide)diol, poly(butylene oxide)diol, poly(tetramethylene oxide)diol, poly(ethylene oxide)triol, poly(propylene oxide)triol, poly(butylene oxide)triol, poly(tetramethylene oxide)triol, and mixtures thereof. Section 5: The adhesive composition according to any one of claims 1 to 4, wherein the polyether prepolymer is produced by reacting a polyisocyanate selected from toluene diisocyanate (TDI), hexamethylene diisocyanate (HDI), naphthalene diisocyanate (NDI), methylene bis-cyclohexyl isocyanate (HMDI) (hydrogenated MDI), isophorone diisocyanate (IPDI) and mixtures thereof with a bifunctional polyether polyol selected from poly(alkylene oxide)diols having C2 to C4 alkylene groups, a trifunctional polyol based on a poly(alkylene oxide)triol initiated with a trifunctional polyol having C2 to C4 alkylene groups, and mixtures thereof. Item 6: The adhesive composition according to any one of claims 1 to 5, wherein the polyether prepolymer comprises a nominally trifunctional poly(propylene oxide) (equivalent 1558) having a hydroxyl value of 36 and a nominally bifunctional poly(propylene oxide) (equivalent 1000) having a hydroxyl value of 56, which are reacted with MDI. Section 7: The adhesive composition according to any one of claims 1 to 6, wherein the at least one polyester prepolymer (B) is produced by reacting one or more linear copolyesters having primary hydroxyl functional groups with a polyisocyanate, preferably a diisocyanate. Section 8: The adhesive composition according to any one of claims 1 to 7, wherein the at least one polyester prepolymer (B) is produced by reacting one or more linear copolyesters having primary hydroxyl functional groups with a polyisocyanate selected from toluene diisocyanate (TDI), hexamethylene diisocyanate (HDI), naphthalene diisocyanate (NDI), methylene bis-cyclohexyl isocyanate (HMDI) (hydrogenated MDI), isophorone diisocyanate (IPDI), and mixtures thereof. Section 9: The adhesive composition according to any one of claims 1 to 8, wherein the at least one polyester prepolymer (B) is produced by reacting a copolyester having a molecular weight of 3,500 Da with MDI. Section 10: The adhesive composition according to any one of claims 1 to 9, wherein the at least one aliphatic polyisocyanate (C) is selected from isophorone diisocyanate, 1,6-hexamethylene diisocyanate, bis(4-isocyanatocyclohexyl)methane, and trimethylhexamethylene diisocyanate, all of which can be modified to include a biuret group, an allophanate group, a urea group, a carbamate group, an isocyanurate group, or a carbodiimide group. Section 11: The adhesive composition according to any one of claims 1 to 10, wherein the at least one aliphatic polyisocyanate (C) is based on an HDI trimer. Section 12: The adhesive composition according to any one of claims 1 to 11, wherein the at least one aromatic polyisocyanate (D) is selected from diphenylmethane diisocyanate (MDI), polymethylene polyphenyl isocyanate, polymeric MDI (PMDI, a mixture of diphenylmethane diisocyanate and polymethylene polyphenyl isocyanate), tetramethylxylene diisocyanate, and toluene diisocyanate, and the at least one aromatic polyisocyanate (D) can be modified to include a biuret group, an allophanate group, a urea group, a carbamate group, an isocyanurate group, or a carbodiimide group. Section 13: The adhesive composition according to any one of claims 1 to 12, wherein the at least one aromatic polyisocyanate (D) is polymethylene polyphenyl isocyanate. Section 14: The aforementioned at least one isocyanate-functionalized silane (E) contains a polyisocyanate compound such as toluene diisocyanate or methylenediphenyl diisocyanate, with 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, and R 4 C1~C 20 Alkyl, C6~C 20 Aryl, C1~C 20 It is an aralkyl group, and R is C1~C 20 Selected from hydrocarbon groups, particularly the propylene (-CH2CH2CH2-) group, and b is 0, 1, or 2. An adhesive composition according to any one of claims 1 to 13, selected from silanes produced by reacting a silicone compound with an active hydrogen-containing group W. Section 15: The adhesive composition according to any one of claims 1 to 14, wherein the at least one isocyanate-functionalized silane (E) is a reaction product of N,N-bis[(3-trimethoxysilyl)-propyl]amine reacted with HDI-biuret. Section 16: The adhesive composition according to any one of claims 1 to 15, wherein the amine catalyst (F) is a tertiary amine catalyst. Section 17: The adhesive composition according to any one of claims 1 to 16, 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'-dimorpholinodiethyl ether and mixtures thereof. Section 18: The adhesive composition according to any one of claims 1 to 17, wherein the amine catalyst (F) is 2,2'-dimorpholinodiethyl ether. Section 19: The aforementioned at least one mercaptosilane (G) is given by the following formula: [ka] (In the formula, R 1 , R 2 and R 3 It is selected independently from OCH3 and OC2H5, and R 4 is -C n H 2n - where n is an integer between 1 and 12) An adhesive composition as described in any one of items 1 to 18. Section 20: R 1 , R 2 and R 3 The adhesive composition according to item 19, wherein is -OCH3 and n is 1 to 6. Section 21: The adhesive composition according to any one of claims 1 to 20, wherein the at least one mercaptosilane (G) is γ-mercaptopropyltrimethoxysilane. Section 22: The above-mentioned at least one aminosilane (G') is given by the following formula: [ka] (In the formula, R 1 , R 2 , R 3 , R 4, R 5 and R 6 It is selected independently from -OCH3 and -OC2H5, and R 7 and R 8 is -C n H 2n (Selected independently from -, where n is an integer between 1 and 6) An adhesive composition as described in any one of items 1 to 21. Section 23: The adhesive composition according to item 22, wherein n is 3. Section 24: The adhesive composition according to any one of claims 1 to 23, wherein the at least one polyether prepolymer is present in an amount of 45 to 65% by weight based on the total weight of the adhesive composition. Section 25: The adhesive composition according to any one of claims 1 to 24, wherein the at least one polyether prepolymer is present in an amount of 58 to 64% by weight based on the total weight of the adhesive composition. Section 26: The adhesive composition according to any one of claims 1 to 25, wherein the at least one polyester prepolymer is present in an amount of 0.9 to 1.5% by weight based on the total weight of the adhesive composition. Section 27: The adhesive composition according to any one of claims 1 to 26, wherein the at least one polyester prepolymer is present in an amount of 1 to 1.3% by weight based on the total weight of the adhesive composition. Section 28: The adhesive composition according to any one of claims 1 to 27, wherein the at least one aliphatic polyisocyanate is present in an amount of 0.75 to 2.5% by weight based on the total weight of the adhesive composition. Section 29: The adhesive composition according to any one of claims 1 to 28, wherein the at least one aliphatic polyisocyanate is present in an amount of 0.8 to 2.5% by weight based on the total weight of the adhesive composition. Section 30: The adhesive composition according to any one of claims 1 to 29, wherein the at least one aromatic polyisocyanate is present in an amount of 0.3 to 0.65% by weight based on the total weight of the adhesive composition. Section 31: The adhesive composition according to any one of claims 1 to 30, wherein the at least one isocyanate-functionalized silane is present in an amount of 0.5 to 2.8% by weight based on the total weight of the adhesive composition. Section 32: The adhesive composition according to any one of claims 1 to 31, wherein the at least one isocyanate-functionalized silane is present in an amount of 0.5 to 2.5% by weight based on the total weight of the adhesive composition. Section 33: The adhesive composition according to any one of claims 1 to 32, wherein the amine catalyst is present in an amount of 0.1 to 0.4% by weight based on the total weight of the adhesive composition. Section 34: The adhesive composition according to any one of claims 1 to 33, wherein the amine catalyst is present in an amount of 0.14 to 0.3% by weight based on the total weight of the adhesive composition. Section 35: The adhesive composition according to any one of claims 1 to 34, wherein the mercaptosilane is present in an amount of 0.5 to 1.2% by weight based on the total weight of the adhesive composition. Section 36: The adhesive composition according to any one of claims 1 to 35, wherein the mercaptosilane is present in an amount of 0.75 to 1.0% by weight based on the total weight of the adhesive composition. Section 37: The adhesive composition according to any one of claims 1 to 36, wherein the aminosilane is present in an amount of 0.05 to 0.5% by weight based on the total weight of the adhesive composition. Section 38: The adhesive composition according to any one of claims 1 to 37, wherein the aminosilane is present in an amount of 0.09 to 0.2% by weight based on the total weight of the adhesive composition. Section 39: The adhesive composition according to any one of claims 1 to 38, wherein the aminosilane is present in an amount of 0.1 to 0.15% by weight based on the total weight of the adhesive composition. Section 40: The adhesive composition according to any one of claims 1 to 39, wherein carbon black is present in an amount of 17.6 to 25% by weight based on the total weight of the adhesive composition. Section 41: The adhesive composition according to any one of claims 1 to 40, wherein carbon black is present in an amount of 20 to 23% by weight based on the total weight of the adhesive composition. Section 42: The adhesive composition according to any one of claims 1 to 41, wherein calcium carbonate is present in an amount of 6 to 9% by weight based on the total weight of the adhesive composition. Section 43: The adhesive composition according to any one of claims 1 to 42, wherein the at least one organometallic catalyst is an organotin catalyst. Section 44: The adhesive composition according to any one of claims 1 to 43, wherein the at least one organometallic catalyst is selected from dibutyltin dilaurate, dimethyltin dineodecanoate, dimethyltin mercaptide, dimethyltin carboxylate, dimethyltin dioleate, dimethyltin dithioglycolate, dibutyltin mercaptide, dibutyltin bis(2-ethylhexylthioglycolate), dibutyltin sulfide, dioctyltin dithioglycolate, dioctyltin mercaptide, dioctyltin dioctoate, dioctyltin dineodecanoate, dioctyltin dilaurate, and mixtures thereof. Section 45: The adhesive composition according to any one of claims 1 to 44, wherein the at least one organometallic catalyst is dimethyltin dineodecanoate. Section 46: The adhesive composition according to any one of claims 1 to 45, wherein the at least one organometallic catalyst is used in an amount of 0.01 to 0.05% by weight based on the total weight of the adhesive composition. Section 47: An adhesive composition according to any one of claims 1 to 46, further comprising a heat, visible light, and UV light stabilizer. Section 48: An adhesive composition according to any one of claims 1 to 47, further comprising trisnonylphenyl phosphite, bis(1,2,2,6,6-pentamethyl-4-piperidyl) sebacate and methyl 1,2,2,6,6-pentamethyl-4-piperidyl sebacate, 2-(2H-benzotriazol-2-yl)-6-dodecyl-4-methylphenol and a stabilizer selected from mixtures thereof. Section 49: An adhesive composition according to any one of claims 1 to 48, further comprising at least one plasticizer. Section 50: An adhesive composition according to any one of claims 1 to 49, further comprising at least one plasticizer which is diisononyl phthalate. Section 51: An adhesive composition, (A) At least one polyether prepolymer containing, in a total content of 30-75% by weight, nominally trifunctional poly(propylene oxide) (equivalent 1558) having a hydroxyl value of 36 and nominally bifunctional poly(propylene oxide) (equivalent 1000) having a hydroxyl value of 56, reacted with MDI; (B) At least one polyester prepolymer produced by reacting a copolyester with a molecular weight of 3,500 Da with MDI in a total content of 0.5 to 2.0% by weight of the polyester prepolymer; (C) At least one aliphatic polyisocyanate based on an HDI trimer, in a total aliphatic polyisocyanate content of 0.5 to 3.0% by weight; (D) At least one aromatic polyisocyanate, which is polymethylene polyphenyl isocyanate, in a total aromatic polyisocyanate content of 0.2 to 2.0% by weight; (E) At least one isocyanate-functionalized silane that is a reaction product of N,N-bis[(3-trimethoxysilyl)-propyl]amine reacted with HDI-biuret, in a total isocyanate-functionalized silane content of 0.2-3.0% by weight; (F) 0.1-0.6% by weight of an amine catalyst, which is 2,2'-dimorpholinodiethyl ether; (G) At least one mercaptosilane, which is γ-mercaptopropyltrimethoxysilane, in a total mercaptosilane content of 0 to 1.5% by weight, wherein the combination of amino and / or mercaptosilane is at least 0.5% by weight; and / or (G') At least one aminosilane, which is bis(γ-trimethoxysilylpropyl)amine, in a total aminosilane content of 0 to 1.5% by weight; (H) 10-35% by weight of carbon black; (I) Optionally, 0 to 20% by weight of calcium carbonate; (J) Optionally, 0 to 20% by weight of fillers other than carbon black and calcium carbonate; (K) Dimethyltindineodecanoate, or at least one organometallic catalyst. An adhesive composition comprising, wherein the total polyisocyanate content is 1 to 5% by weight, the total calcium carbonate + filler content is 3 to 20% by weight, and the weight percentage is based on the total weight of the polyurethane adhesive. Section 52: An adhesive composition, (A) At least one polyether prepolymer containing, in a total content of 58-64% by weight, nominally trifunctional poly(propylene oxide) (equivalent 1558) having a hydroxyl value of 36 and nominally bifunctional poly(propylene oxide) (equivalent 1000) having a hydroxyl value of 56, reacted with MDI; (B) At least one polyester prepolymer produced by reacting a copolyester with a molecular weight of 3,500 Da with MDI in a total content of 1 to 1.3% by weight of the polyester prepolymer; (C) At least one aliphatic polyisocyanate based on an HDI trimer in the total aliphatic polyisocyanate content of 0.8 to 2.5% by weight; (D) At least one aromatic polyisocyanate, which is polymethylene polyphenyl isocyanate, in a total aromatic polyisocyanate content of 0.3 to 0.65% by weight; (E) At least one isocyanate-functionalized silane that is a reaction product of N,N-bis[(3-trimethoxysilyl)-propyl]amine reacted with HDI-biuret, in a total isocyanate-functionalized silane content of 0.5 to 2.5% by weight; (F) 0.14-0.3% by weight of an amine catalyst, which is 2,2'-dimorpholinodiethyl ether; (G) At least 0.7% by weight of a combination of amino and / or mercaptosilanes, in a total mercaptosilane content of 0.75 to 1.0% by weight, including at least one mercaptosilane that is γ-mercaptopropyltrimethoxysilane, and / or (G') At least one aminosilane that is bis(γ-trimethoxysilylpropyl)amine in a total aminosilane content of 0.1 to 0.15% by weight; (H) 20-23% by weight of carbon black; (I) 9-12% by weight of calcium carbonate; (J) 0.3-0.6% by weight of fumed silica; (K) 0.01-0.05 wt% by weight of at least one organometallic catalyst, which is dimethyltin dineodecanoate. An adhesive composition comprising, wherein the total polyisocyanate content is 1 to 4% by weight, the total calcium carbonate + filler content is 3 to 15% by weight, and the weight percentage is based on the total weight of the polyurethane adhesive.

Claims

1. A one-component polyurethane adhesive composition, (A) At least one polyether prepolymer in a total content of 30 to 75% by weight; (B) At least one polyester prepolymer in a total content of 0.5 to 2.0% by weight; (C) At least one aliphatic polyisocyanate in a total content of 0.5 to 3.0% by weight; (D) At least one aromatic polyisocyanate in a total content of 0.2 to 2.0% by weight; (E) At least one isocyanate-functionalized silane in a total content of 0.2 to 3.0% by weight; (F) 0.1 to 0.6% by weight of amine catalyst; (G) a combination of aminosilane and / or mercaptosilane in which the total content is at least 0.5% by weight, (G1) at least one mercaptosilane in a total content of 0 to 1.5% by weight, and / or (G2) at least one aminosilane in a total content of 0 to 1.5% by weight; (H) 10-35% by weight of carbon black; (I) 0-20% by weight of calcium carbonate; (J) 0 to 20% by weight of fillers other than carbon black (H) and calcium carbonate (I); (K) At least one organometallic catalyst capable of catalyzing the reaction between isocyanate and a functional group having at least one reactive hydrogen, and silane condensation. A one-component polyurethane adhesive composition comprising the aliphatic polyisocyanate (C) and the aromatic polyisocyanate (D) having a total content of 1 to 5% by weight, and the total content of the calcium carbonate (I) and the filler (J) having a total content of 0 to 20% by weight, wherein the weight percentage is based on the total weight of the adhesive composition.

2. The adhesive composition according to claim 1, wherein the polyether prepolymer (A) is a reaction product of a polyisocyanate and a polyol, and the polyol can be selected from a polyether polyol, a hydroxyl-containing polythioether, a polymer polyol, and a mixture thereof.

3. The adhesive composition according to claim 1, wherein the polyether prepolymer (A) is a reaction product of polyisocyanate and polyether polyol.

4. The adhesive composition according to claim 1, wherein the polyether prepolymer (A) is a reaction product of a polyisocyanate and a polyol selected from poly(ethylene oxide)diol, poly(propylene oxide)diol, poly(butylene oxide)diol, poly(tetramethylene oxide)diol, poly(ethylene oxide)triol, poly(propylene oxide)triol, poly(butylene oxide)triol, poly(tetramethylene oxide)triol, and mixtures thereof.

5. The polyether prepolymer (A) comprises a polyisocyanate selected from toluene diisocyanate (TDI), hexamethylene diisocyanate (HDI), naphthalene diisocyanate (NDI), methylene bis-cyclohexyl isocyanate (HMDI) (hydrogenated MDI), isophorone diisocyanate (IPDI), and mixtures thereof, and an alkylene group C ２ ~C ４ A difunctional polyether polyol selected from poly(alkylene oxide)diols, wherein the alkylene group is C ２ ~C ４ The adhesive composition according to claim 1, which is a reaction product with a trifunctional polyol selected from poly(alkylene oxide)triols or a mixture thereof.

6. The adhesive composition according to claim 1, wherein the polyether prepolymer (A) comprises a reaction product of trifunctional poly(propylene oxide) (equivalent weight 1558) having a hydroxyl value of 36 and MDI, and a reaction product of bifunctional poly(propylene oxide) (equivalent weight 1000) having a hydroxyl value of 56 and MDI.

7. The adhesive composition according to claim 1, wherein the polyester prepolymer (B) is a reaction product of one or more linear copolyesters having primary hydroxyl functional groups and a polyisocyanate.

8. The adhesive composition according to claim 1, wherein the polyester prepolymer (B) is a reaction product of one or more linear copolyesters having a primary hydroxyl functional group and a polyisocyanate selected from toluene diisocyanate (TDI), hexamethylene diisocyanate (HDI), naphthalene diisocyanate (NDI), methylene bis-cyclohexyl isocyanate (HMDI) (hydrogenated MDI), isophorone diisocyanate (IPDI), and mixtures thereof.

9. The adhesive composition according to claim 1, wherein the polyester prepolymer (B) is a reaction product of a copolyester having a molecular weight of 3,500 Da and MDI.

10. The adhesive composition according to claim 1, wherein the aliphatic polyisocyanate (C) is selected from isophorone diisocyanate, 1,6-hexamethylene diisocyanate, bis(4-isocyanatocyclohexyl)methane, and trimethylhexamethylene diisocyanate, all of which can be modified to include a biuret group, an allophanate group, a urea group, a carbamate group, an isocyanurate group, or a carbodiimide group.

11. The adhesive composition according to claim 1, wherein the aliphatic polyisocyanate (C) is an isocyanate derived from an HDI trimer.

12. The adhesive composition according to claim 1, wherein the aromatic polyisocyanate (D) is selected from diphenylmethane diisocyanate (MDI), polymethylene polyphenyl isocyanate, polymeric MDI (PMDI, a mixture of diphenylmethane diisocyanate and polymethylene polyphenyl isocyanate), tetramethylxylene diisocyanate, and toluene diisocyanate, all of which can be modified to include a biuret group, an allophanate group, a urea group, a carbamate group, an isocyanurate group, or a carbodiimide group.

13. The adhesive composition according to claim 1, wherein the aromatic polyisocyanate (D) is polymethylene polyphenyl isocyanate.

14. The isocyanate-functionalized silane (E) is a polyisocyanate compound, and the formula is: 【Chemistry 1】 (In the formula, 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 C １ to C ２０ alkyl, C ６ to C ２０ aryl, C １ to C ２０ aralkyl group; R is selected from C １ to C ２０ hydrocarbon groups; and b is 0, 1, or 2). The adhesive composition according to claim 1, which is selected from silanes that are reaction products of a silicone compound with an active hydrogen-containing group W.

15. An adhesive composition, (A) At least one polyether prepolymer comprising a reaction product of MDI with a trifunctional poly(propylene oxide) having a hydroxyl value of 36 (equivalent weight 1558) in a total content of 30 to 75% by weight, and a reaction product of MDI with a bifunctional poly(propylene oxide) having a hydroxyl value of 56 (equivalent weight 1000); (B) At least one polyester prepolymer which is a reaction product of MDI with a copolyester having a molecular weight of 3,500 Da in a total content of 0.5 to 2.0% by weight; (C) At least one aliphatic polyisocyanate, which is an isocyanate derived from an HDI trimer, in a total content of 0.5 to 3.0% by weight; (D) At least one aromatic polyisocyanate, which is a polymethylene polyphenyl isocyanate, in a total content of 0.2 to 2.0% by weight; (E) At least one isocyanate-functionalized silane, which is a reaction product of HDI-biuret and N,N-bis[(3-trimethoxysilyl)-propyl]amine, in a total content of 0.2 to 3.0% by weight; (F) 0.1 to 0.6% by weight of an amine catalyst, which is 2,2'-dimorpholinodiethyl ether; (G) At least 0.5% by weight of a combination of aminosilane and / or mercaptosilane, (G1) at least one mercaptosilane which is γ-mercaptopropyltrimethoxysilane in a total content of 0 to 1.5% by weight, and / or (G2) at least one aminosilane which is bis(γ-trimethoxysilylpropyl)amine in a total content of 0 to 1.5% by weight; (H) 10-35% by weight of carbon black; (I) 0-20% by weight of calcium carbonate; (J) 0 to 20% by weight of fillers other than carbon black (H) and calcium carbonate (I); (K) Dimethyltin dineodecanoate is at least one organometallic catalyst. An adhesive composition comprising the aliphatic polyisocyanate (C) and the aromatic polyisocyanate (D) having a total content of 1 to 5% by weight, and the total content of the calcium carbonate (I) and the filler (J) having a total content of 3 to 20% by weight, wherein the weight percentage is based on the total weight of the adhesive composition.

Images