Fast curing adhesive useful for bonding to glass

0001The present invention relates to a fast-hardening system that joins two substrates together, including one or more isocyanate functional components. The present invention also includes methods of using such a system to join substrates together.

0002Compositions with isocyanate-functional constituents are often utilized to bond glass-like substrates in the form of windows together into the structure. In automobile assembly plants, windows are often joined by a one-component coating composition containing isocyanate functional constituents that cure by reaction with ambient moisture and then cure over hours to days. In the assembly plant, the car is not driven for several hours, which is acceptable. The one-component moisture-curing adhesives known for this technology are U.S. Pat. Nos. 4,374,237, 4,687,533, 4,780,520, 5,063,269, 5,623,044, 5,603,798, 5,852,137, It is disclosed in No. 5,922,809, No. 5,976,305, No. 5,852,137, and No. 6,512,033, and the relevant parts are incorporated herein by reference.

0003A two-component composition containing an isocyanate-functional prepolymer in one portion and a compound having an isocyanate-reactive component in the other portion is used when curing speed is important, such as in the aftermarket glass replacement business of automobiles. Will be done. Customers want the adhesive to cure quickly so that they can drive the car as soon as possible after replacing the windows. Examples of two-component compositions are disclosed in European Patent Nos. 1,524,282, US Pat. Nos. 5,852,103, 6,709,539, 7,101,950, and 7,361,292, which are hereby incorporated by reference in their entirety. Is incorporated into. In certain applications, even two-component compositions containing isocyanate-functional prepolymers do not cure rapidly enough for certain applications or customers. One previously commercially available solution involves contacting an isocyanate-functional prepolymer with a water-containing paste, the United States of Hsieh et al., Which is incorporated herein by reference in its entirety. See Pat. No. 4,687,533. In the manufacture of counterparty trademark products, the use of two-component systems has been replaced by one-component systems containing catalysts that promote rapid curing, the entire US patent of Risk et al., Which is incorporated herein by reference. See Nos. 4,780,520. Some skilled in the art have attempted to address this problem by increasing the catalyst concentration or by other formulation adjustments, many of which result in the formation of air bubbles in the adhesive. Bubbles in the cured adhesive can result in a dramatic reduction in the strength of the cured adhesive. Since these adhesives can be used in safety-related applications, such a reduction in strength is unacceptable.

0004Curing rates for adhesive systems with fast curing catalysts are slower than desirable when the temperature is significantly below the ambient temperature (about 23 ° C) and / or when the ambient relative humidity is low (less than 50 percent RH). obtain. When the temperature and / or relative humidity is low, there is a need for a faster curing system. Therefore, what is needed is an adhesive system that exhibits a rapid curing rate at low ambient temperature and humidity and does not form bubbles in the cured adhesive.

0005The present invention a) one or more isocyanate functional constituents, b) one or more catalysts for the reaction of isocyanate groups with active hydrogen-containing groups, c) does not enhance pore formation during curing 1 One or more fillers, d) one-component adhesives containing one or more fillers with basic characteristics, and e) one or more liquid carriers, f) water, and g) one or more pastes. It is a composition containing a curing accelerator containing a forming agent. The one-component adhesive composition can be used alone if ambient temperature and humidity provide reasonably fast curing rates. The curing accelerator can be used when the temperature and / or humidity is sufficiently low that the curing rate of the adhesive alone is unacceptable for a particular use. Preferably, one or more fillers that do not enhance pore formation upon curing are selected from high surface area carbon black. In some embodiments, the paste-forming agent comprises one or more materials that form a homogeneous paste with water and a liquid carrier. In some embodiments, the liquid carrier is a glycol ether or a polyether polyol. In some embodiments, the equivalent ratio of hydroxyl groups to isocyanate groups contained in the curing accelerator in the adhesive is 0.7: 1.0 to 1.3: 1.0. Preferably, one or more fillers with basic characteristics exhibit a pH of 9.0 or higher when dissolved or dispersed in deionized water. Preferably, one or more fillers with basic characteristics include one or more talc or calcium carbonate.

0006In another embodiment, the invention i) contacts the adhesive with a curing accelerator and ii) contacts the contacted portion with one or both of the first and / or second substrate. That, iii) the first and second substrates are brought into contact with the contact area placed between the two substrates, and iv) the adhesive is cured to form the two substrates. It is a method that includes joining together. Preferably, the adhesive and curing accelerator contacted in step i) are mixed prior to contact with the substrate.

0007In one embodiment, the one-component curable composition and the curing accelerator have a viscosity at 25 ° C such that the viscosity ratio of the one-component curable composition to the curing accelerator is about 0.1 to 10.0. Each has. In some embodiments, the present invention is i) contacting the one-component curable composition with a cure accelerator, wherein the one-component curable composition and the cure accelerator are one-component curable. At 25 ° C, the viscosity ratio of the composition to the cure accelerator is about 0.1 to 10.0 and the volume ratio of the one-component curable composition to the cure accelerator is about 25: 1 or more. Ii) contact the mixture with the first substrate, and iii) place the first substrate between at least a portion of each substrate with the mixed constituents. It can be a method comprising contacting with a second substrate as described above.

0008The compositions and methods of the present invention allow the substrates to adhere quickly together, especially at temperatures below ambient and / or relative humidity. The cured composition has a lap shear strength of preferably about 100 psi or higher, more preferably about 150 psi or higher, most preferably 190 psi or higher 4 hours after the two parts come into contact at 10 ° C and 30 percent relative humidity. Shown. The composition is useful as an adhesive to bond substrates together and is used to bond similar and different substrates such as plastics, glass, wood, ceramics, metals, coated substrates, etc. together. Can be done. The composition is particularly useful for joining glass together with other substrates such as automobiles and buildings, as well as components of modular components such as modular components for automobiles. The glass can be joined to the coated and uncoated parts of the vehicle. In one embodiment, the composition is well bonded to the uncoated coating metal. Preferably, the composition exhibits an air-drying time of about 10-15 minutes or longer, more preferably about 15-20 minutes or longer. The composition is particularly useful for joining glass to automotive structures.

0009<figref num="1">It is an image of the cut surface of the cured composition of the present invention.</figref><figref num="2">An image of a cut surface of a cured composition that does not meet the requirements of the claimed invention for comparative purposes.</figref>

0010One or more means that, as used herein, at least one, or more than one, of the listed components may be used as disclosed. Durability in this context, once the composition has been cured, maintains sufficient strength to perform the designed function, and in embodiments where the cured composition is an adhesive, the adhesive Means holding the substrate together for the life or most of the life of the structure containing the cured composition. As an indicator of durability, the cured composition (eg, adhesive) preferably shows excellent results during accelerated aging. Preferably, this means that after the set of substrates joined by the compositions of the invention has been exposed to heat aging, the failure mode of the quick knife adhesion or lap shear test is agglomeration, the substrate. It means that the adhesive breaks before the bond to the adhesive breaks. Isocyanate content means the weight percent of isocyanate groups in the specified constituents, which can be measured by analytical techniques known to those skilled in the art, such as potentiometric titration with active hydrogen-containing compounds such as dibutylamine. Hydrocarbyl refers to a group containing one or more carbon atom backbones and hydrogen atoms, which can optionally contain one or more heteroatoms. If the hydrocarbyl group contains a heteroatom, the heteroatom may form one or more functional groups well known to those of skill in the art. The term isocyanate-reactive compound, as used herein, includes any organic compound that nominally has at least two isocyanate-reactive groups. For the purposes of the present invention, isocyanate-reactive groups, active hydrogen-containing groups, are located in the molecule according to the Zerewitinoff test described by Wohler in the Journal of the American Chemical Society, Vol.49, p.3181 (1927). Refers to a hydrogen atom-containing group that exhibits significant activity for. Examples of isocyanate-reactive groups are -COOH, -OH, -NH.₂, -NH-, -CONH₂, -SH, and -CONH-. Preferred compounds containing isocyanate-reactive groups include polyols, polyamines, polymercaptans, and polyacids.

0011The present invention includes a one-component adhesive composition containing an isocyanate functional component adapted for use with a curing accelerator as a reactive component. The present invention further includes a curing accelerator useful for accelerating the curing of a one-component adhesive containing an isocyanate functional component as a reactive component. The present invention further includes a one-component adhesive composition and a curing accelerator. The adhesive and the curing accelerator are mixed in a volume ratio such that the equivalent ratios discussed herein are achieved. Preferably, the volume ratio of the adhesive to the curing accelerator is about 25: 1 or higher, most preferably about 30: 1 or higher. Preferably, the volume ratio of the adhesive to the curing accelerator is about 200: 1 or less, more preferably about 100: 1 or less, and most preferably about 50: 1 or less.

0012Isocyanate-based (polyurethane or polyurea forming) curing systems contain isocyanate functional constituents. The isocyanate functional constituents contain one or more compounds having an average of more than one isocyanate group per molecule. The isocyanate functional component can be any component containing more than one isocyanate group (part) on average. Isocyanate-functional constituents include isocyanate-functional prepolymers, monomers or oligomers having isocyanate groups or additions of one or more monomers or oligomers, and, on average, more than one isocyanate-reactive group, preferably two or more. Can be in the form of a compound containing an isocyanate group of. The isocyanate prepolymer can be any prepolymer prepared by reacting an isocyanate functional compound with one or more compounds having an average of more than one isocyanate functional group.

0013One or more isocyanate-functional constituents, preferably prepolymers, are present in sufficient amounts to provide cohesive strength and, in adhesive applications, adhesive properties to the composition. Such isocyanate-functional components, such as prepolymers, have an average isocyanate functionality that is sufficient to allow the preparation of crosslinked polyurethanes upon curing and is not high enough to make the polymer unstable. Prepolymers useful as isocyanate functional constituents are prepared by reacting one or more polyisocyanates with one or more compounds containing an average of more than one isocyanate-reactive group per molecule. To. The prepolymer, which is an isocyanate functional component, preferably has a free isocyanate content that promotes the strength allowed in the prepared composition, as described above herein. The isocyanate content in the isocyanate-functional constituents is preferably about 0.4% by weight or more, more preferably about 0.7% by weight or more, even more preferably about 1.0% or more, even more preferably, based on the weight of the isocyanate-functional component. Is about 8 weight percent or more, most preferably about 1.2 weight percent or more. The isocyanate content in the isocyanate functional constituents is preferably about 15 weight percent or less, more preferably about 10 weight percent or less, even more preferably about 5.0 weight percent or less, most preferably about 5.0 weight percent or less, based on the weight of the isocyanate functional component. Is less than about 3.0 weight percent.

0014Preferably, the polyisocyanate used in the preparation of the isocyanate functional constituents of the present invention includes any aliphatic, alicyclic, aromatic aliphatic (araliphatic), heterocyclic, or aromatic polyisocyanate or aromatic polyisocyanate thereof. Contains a mixture. Preferably, the polyisocyanate used has an isocyanate functional value of about 2.0 or higher and an equivalent of about 80 or higher on average. Preferably, the isocyanate functional value of the polyisocyanate is 2.2 or more, most preferably about 2.4 or more, preferably about 4.0 or less, more preferably about 3.5 or less, and most preferably about 3.0 or less. Higher functional values can be used, but can cause excessive cross-linking, resulting in a composition that is too viscous to handle easily and cannot be applied, making the cured composition brittle. It may be too much. Preferably, the equivalent of the polyisocyanate is about 110 or more, most preferably about 120 or more, preferably about 300 or less, more preferably about 250 or less, and most preferably about 200 or less. Examples of preferred polyisocyanates include those disclosed in Wu US Pat. No. 6,512,033, column 3, lines 3 to 49, which are incorporated herein by reference. More preferred isocyanates are aromatic isocyanates, alicyclic isocyanates, and derivatives thereof. Preferably, the aromatic isocyanate has an isocyanate group directly attached to the aromatic ring. Even more preferable polyisocyanates include diphenylmethane diisocyanate and its polymer derivatives, isophorone diisocyanate, tetramethylxylene diisocyanate, 1, Includes 6-hexamethylene diisocyanate and its polymer derivatives, bis (4-isocyanatosyl ohexyl) methane, and trimethylhexamethylene diisocyanate. The most preferred isocyanate is diphenylmethane diisocyanate. The amount of isocyanate-containing compound used in the preparation of the prepolymer is an amount that gives the desired properties, i.e. the appropriate free isocyanate content and viscosity discussed herein. Preferably, the isocyanate is prepared in a prepolymer by an amount of about 1.3 equivalents or more of isocyanate (NCO) per equivalent of active hydrogen, more preferably about 1.4 equivalents or more, and most preferably about 1.5 equivalents or more. used. Preferably, the polyisocyanate used to prepare the prepolymer is an amount of about 3.0 equivalents or less, more preferably about 2.5 equivalents or less, and most preferably about 2.0 equivalents or less, per equivalent of active hydrogen. Used in.

0015Preferably, the isocyanate functional component is a reaction product of one or more polyisocyanates and one or more compounds having more than one, preferably two or more isocyanate-reactive groups, in excess. Isocyanate groups are present on an equivalent basis. Preferably, such isocyanate-reactive groups are hydroxyl and amino groups. Preferred categories of such compounds include polyols, preferably mixtures of one or more polyether diols and / or one or more polyether triols. Preferably, polyols useful in the preparation of prepolymers include Wu's US Pat. No. 6,512, which is incorporated herein by reference. 033, column 4, lines 10-64, including, for example, polyether polyols, polyester polyols, poly (alkylene carbonate) polyols, hydroxyl-containing polythioethers, and mixtures thereof. Is done. Preferred polyols are polyether polyols containing one or more alkylene oxide units in the backbone of the polyol. Preferred alkylene oxide units are ethylene oxide, propylene oxide, butylene oxide, and mixtures thereof. The alkylene oxide can contain straight chain or branched chain alkylene units. Preferably, the polyol contains propylene oxide units, ethylene oxide units, or a mixture thereof. In embodiments where a mixture of alkylene oxides is contained in the polyol, different units can be randomly arranged or arranged as blocks of alkylene oxide. In one embodiment, the polyol comprises a propylene oxide chain having an ethylene oxide chain capping the polyol. Preferably, the ethylene oxide capped polypropylene oxide is hydrophobic and preferably contains less than about 20 mole percent ethylene oxide, more preferably less than 10 mole percent ethylene oxide in the main chain. In a preferred embodiment, the polyol is a mixture of diol and triol. Preferably, the isocyanate-reactive compound has a functional value of about 1.8 or more, more preferably about 1.9 or more, most preferably about 1.95 or more, preferably about 4.0 or less, more preferably about 3.5 or less, and Most preferably, it is about 3.0 or less. Preferably, the equivalent of the isocyanate-reactive compound is about 200 or more, more preferably about 500 or more, more preferably about 1,000 or more, preferably about 5,000 or less, more preferably about 3,000 or less, most preferably. Is about 2, It is less than 500. The isocyanate-reactive constituents are present in an amount sufficient to react with most of the isocyanate groups of the isocyanate to leave sufficient isocyanate groups to correspond to the desired free isocyanate content of the prepolymer. Preferably, the isocyanate-reactive component is present in an amount of about 50 parts by weight or more, more preferably about 65 parts by weight or more, and most preferably about 80 parts by weight or more based on the weight of the isocyanate functional component. Preferably, the isocyanate component is present in an amount of about 95 parts by weight or less, most preferably about 90 parts by weight or less, based on the weight of the isocyanate functional component.

0016The isocyanate functional component may contain an alkoxysilane moiety. All isocyanate functional components used in the adhesive may contain alkoxysilane moieties, or such isocyanate functional components may be blended with one or more isocyanate functional components that do not contain an alkoxysilane moiety. Can be done. The isocyanate functional component may contain sufficient alkoxysilane moieties to improve adhesion to substrates such as glass and coated substrates. The alkoxysilane content in the isocyanate functional constituents is preferably about 0.1% by weight or more, more preferably about 0.4% by weight or more, and most preferably about 0.8% by weight or more. The alkoxysilane content in the isocyanate functional constituents is preferably about 3.0 weight percent or less, more preferably about 2.0 weight percent or less, and most preferably about 1.0 weight percent or less. "Alkoxysilane content" means the weight percentage of the alkoxysilane moiety to the total weight of the prepolymer.

0017The isocyanate functional constituents may include one or more prepolymers containing one or more organic-based polymer particles dispersed therein or grafted onto the main chain. Preferably, the organic-based polymer particles are included in the prepolymer by including a dispersed triol having the organic-based polymer particles dispersed or grafted onto the main chain. Preferred polyols are disclosed in Zhou U.S. Pat. No. 6,709,539, columns 4, lines 13-6, 18, and are incorporated herein by reference. Preferably, the polyol comprises one or more polyether triols, more preferably triols based on one or more polyoxyalkylenes. Preferably, such a polyoxyalkylene oxide triol comprises a polyoxypropylene chain having a polyoxyethylene terminal cap. In one embodiment, the prepolymer also comprises a polyol containing organic-based polymer particles. Preferably, the particles dispersed in the dispersed triol include one or more thermoplastic polymers, rubber modified thermoplastic polymers, or polyureas. Preferably, such prepolymers are contained in the adhesive in an amount of about 0.5 weight percent or more. Preferably, such prepolymers are contained in the adhesive in an amount of about 5 weight percent or less.

0018The one-component composition useful as an adhesive may further comprise one or more isocyanate-functional prepolymers containing one or more polyester-based polyols that are solid at an ambient temperature of about 23 ° C. Polyester-based polyols have a melting point such that the prepolymer provides sufficient untreated strength and prevents the substrates from moving to each other due to attraction at ambient temperature. For the installation of windows in automobiles or buildings, polyester-based prepolymers prevent the windows from slipping after installation. Preferably, the polyester polyol has a melting point of about 40 ° C. or higher, even more preferably about 45 ° C. or higher, most preferably about 50 ° C. or higher. Preferably, the polyester polyol has a melting point of about 85 ° C or less, even more preferably about 70 ° C or less, most preferably about 60 ° C or less. Polyester-based isocyanate prepolymers can be prepared using one or more polyester polyols, preferably aromatic polyisocyanates. It can be diluted with a plasticizer to facilitate pumping. Preferably, the isocyanate prepolymer based on the polyester polyol is present in the composition in an amount sufficient to enhance the untreated strength, rheology, and pump pumping required for the composition. If the amount is too large, the composition will not be applicable by hand gun at ambient temperature. Preferably, the isocyanate prepolymer based on the polyester polyol is added to the composition in an amount of about 0 weight percent or more, more preferably about 1 weight percent or more, most preferably about 2 weight percent or more, based on the weight of the composition. Exists. Preferably, the isocyanate prepolymer based on the polyester polyol is present in the composition in an amount of about 10 weight percent or less, even more preferably about 5 weight percent or less, and most preferably about 3 weight percent or less.

0019The isocyanate functional constituents can be prepared by any suitable method such as bulk polymerization and solution polymerization. The reaction to prepare the isocyanate functional constituents is carried out under anhydrous conditions, preferably in an inert atmosphere such as a nitrogen blanket, to prevent cross-linking of isocyanate groups by atmospheric moisture. The reaction is preferably at a temperature of about 0 ° C to about 150 ° C, more preferably about 25 ° C to about 90 ° C, until the residual isocyanate content determined by sample titration approaches the desired theoretical value. Will be implemented. The reaction to prepare the isocyanate functional constituents is a urethane catalyst, such as stannous octanoate, stannous oleate, stannous acetate, and stannous salts of carboxylic acids such as stannous laurate, dibutyltin. It can be performed in the presence of dialkyl tin dicarboxylates such as dilaurate and dibutyltin diacetate, tertiary amines, and tin mercaptide. The amount of catalyst used is generally about 0.005 to about 5 parts by weight of the catalyst mixture. Preferably, the reaction is carried out with a mixture with a plasticizer.

0020The isocyanate-functional constituents make the cured composition strong enough for design purposes such that the adhesive can bond the substrates together and provide the desired aggregation and adhesion strength. It is present in the composition in an amount sufficient to have. Preferably, the isocyanate functional constituents are present in an amount of about 10 weight percent or more, more preferably about 40 weight percent or more, most preferably about 45 weight percent or more, based on the weight of the composition. Preferably, the isocyanate functional constituents are present in an amount of about 70 weight percent or less, more preferably about 65 weight percent or less, and most preferably about 55 weight percent or less, based on the weight of the composition.

0021The one-component composition useful as an adhesive can further include one or more polyfunctional isocyanates for the purpose of improving the adhesion of the composition to the surface of the substrate. "Polyfunctional" refers to an isocyanate having a functionality of 2 or higher when used in the context of isocyanates. The polyisocyanate can be any monomer, oligomer, or polymeric isocyanate having a nominal functional value of about 3 or more, more preferably about 3.2 or more. Preferably, the polyfunctional isocyanate has a nominal functional value of about 5 or less, even more preferably about 4.5 or less, most preferably about 4.2 or less. The polyfunctional isocyanate can be any isocyanate that is reactive with the polyisocyanate prepolymer and / or isocyanate-reactive constituents used in the composition and that improves the elastic modulus of the cured composition. Polyisocyanates can be monomeric, trimer isocyanurates or biurets of monomeric isocyanates, oligomers, or polymers, reaction products of several units of one or more monomeric isocyanates. Examples of preferred polyfunctional isocyanates include the trademark and trade name DESMODUR. N3300, hexamethylene diisocyanate trimmers such as those available from Bayer by DESMODUR N-100, and polymer MDI (methylene diphenyl) such as those marketed by The Dow Chemical Company under the PAPI trademark including PAPI20 and PAPI27 polymer isocyanates. Diisocyanates) include polymeric isocyanates. The polyfunctional isocyanate is present in an amount sufficient to affect the elastic modulus of the cured composition of the present invention. If too much is used, the curing rate of the composition will be unacceptably slow. If too small an amount is used, the desired level of elasticity may not be achieved. The polyfunctional isocyanate is present in an amount of preferably about 0.5 weight percent or more, more preferably about 1.0 weight percent or more, and most preferably about 1.4 weight percent or more, based on the weight of the composition. The polyfunctional isocyanate is present in an amount of preferably about 8 weight percent or less, more preferably about 5 weight percent or less, and most preferably about 3 weight percent or less, based on the weight of the composition.

0022The composition may also contain one or more catalysts that catalyze the reaction of the isocyanate moiety with water or an active hydrogen-containing compound. The catalyst is any catalyst known to those skilled in the art for the reaction of the isocyanate moiety with the isocyanate-reactive compound and may include tertiary amines, metal catalysts such as organotin compounds and metal alcantates. Mixtures of metal catalysts such as tertiary amines and organotin compounds are preferred. Exemplary organotin compounds include alkyl tin oxide, stannous alkanoate, dialkyl tin carboxylate, and tin mercaptide. Stannous alkanoate includes stannous octanoate. Alkyl tin oxides include dialkyl tin oxides such as dibutyl tin oxide and its derivatives. The organotin catalyst is preferably dialkyltin dicarboxylate or dialkyltin dimercaptide. Dialkyltin dicarboxylates with fewer total carbon atoms are preferred as they are more active catalysts. Preferably, the dialkyldicarboxylate is 1,1-dimethylin dilaurate (1,1-dimethyl-in). Dilaurate), 1,1-dibutyltin diacetate, and 1,1-dimethyldimaleate are included. Preferred metal alkane salts include bismuth octate or bismuth neodecanoate. The metal catalyst is present in an amount of about 60 million or more, more preferably 120 million or more, based on the weight of the composition. The metal catalyst is present in an amount of about 1.0 percent or less, more preferably about 0.5 percent or less, most preferably about 0.3 percent or less, based on the weight of the composition.

0023The tertiary amine catalyst may comprise one or more compounds having one or more tertiary amine groups capable of facilitating the reaction of the isocyanate moiety with the active hydrogen containing compound. Exemplary tertiary amine catalysts include dimorpholino dialkyl ethers, di ((dialkylmorpholino) alkyl) ethers, bis- (2-dimethylaminoethyl) ethers, triethylenediamine, pentamethyldiethylenetriamine, N, N-dimethylcyclohexyl. Includes amines, N, N-dimethylpiperazin 4-methoxyethyl morpholine, N-methyl morpholine, N-ethyl morpholine, and mixtures thereof. A preferred dimorpholino dialkyl ether is dimorpholino diethyl ether. The preferred di-((dialkylmorpholino) alkyl) ether is (di-(2- (3,5-dimethylmorpholino) ethyl) -ether). Other classes of tertiary amines include diazabicyclo compounds, which are compounds with a diazobicyclo structure. Of these, preferred diazabicyclohydrocarbons include diazabicycloalkanes and diazabicycloalkene salts. In some embodiments, the catalyst preferably comprises one or more diazabicycloalkanes and one or more diazabicycloalkene salts. Preferred diazabicycloalkanes include diazabiclooctanes available from Air Products under the trademark and trade names DABCO, DABCO WT, DABCO DC1, DABCO DC2, and DABCO DC21. Preferred diazabicycloalkene salts include those of the phenolates, ethylcaproates, oleates, and formates available from Air Products under the trade names POLYCAT SA1, POLYCAT SA1 / 10, POLYCAT SA102, and POLYCAT SA610. Includes the form of iazabicycloundecene. One or more compounds containing one or more tertiary amines are about 0. It is present in an amount of 05 weight percent or more, more preferably about 0.1 weight percent or more, most preferably about 0.15 weight percent or more. One or more compounds containing one or more tertiary amine groups are about 5.0 weight percent or less, more preferably about 2.0 weight percent or less, most preferably about 1.0 weight percent or less, based on the weight of the composition. Exists in quantity.

0024One-component compositions useful as adhesives are included in Mahdi's US Patent Publication No. 2002/0100550, paragraphs 0055-0065 and Hsieh's US Pat. Nos. 6,015,475, column 5, line 27, which are incorporated herein by reference. It may further include an adhesion-enhancing agent or an adhesion-enhancing component, such as that disclosed in column 6, line 41 from the eye. Preferably, the adhesion-enhancing agent is Wu et al., US Pat. No. 6,512,033, 5th, 38th-7th, 27th, US Pat. No. 5,623,044, the relevant part of which is incorporated herein by reference. It contains silanes that are present in several forms as disclosed in Nos. 4,374,237, 4,345,053, and 4,625,012. Silanes can be blended with isocyanate functional constituents. In some embodiments, the silane has one or more active hydrogen atoms that are reactive with isocyanate. In some embodiments, a silane having an active hydrogen atom that is reactive with the isocyanate moiety can be reacted with the terminal isocyanate moiety of the prepolymer. Such reaction products are disclosed in US Pat. Nos. 4,374,237 and 4,345,053, the relevant parts of which are incorporated herein by reference. In another embodiment, a silane having an active hydrogen atom that is reactive with the isocyanate moiety is reacted in the preparation of the prepolymer by reaction of such a silane with a starting material to form the main chain of the prepolymer. You can put it inside. The process for preparing prepolymers containing silane in the main chain is described in US Pat. No. 4,625, It is disclosed in 012 and the relevant parts are incorporated herein by reference. Such silanes with active hydrogen moieties can be reacted with polyisocyanates to form adducts, which have been reacted with polyurethane prepolymers or averaged reactive with polyisocyanates and isocyanate moieties. It is blended with a prepolymer that has been reacted with a compound having more than one moiety. Preferably, the adduct is a reaction product of a secondary amine or mercaptoalkoxysilane and polyisocyanate, and the adduct has, on average, at least one silane group and at least one isocyanate group per molecule ( From this specification onward, "additives"). Exemplary polyisocyanates used in the preparation of adducts include those described above as suitable for use in the preparation of prepolymers, in particular isophorone diisocyanate, polymethylene polyphenyl isocyanate, and hexa. Includes aliphatic polyisocyanates such as methylene diisocyanate. Exemplary organic functional silanes useful as adhesion enhancers or for preparing adducts include amino or mercaptoalkoxysilanes, isocyanatealkoxysilanes, methacryloxysilanes, epoxyalkoxysilanes, alkenylalkoxysilanes and the like. Is done. Examples of such compounds include N, N-bis [(3-triethoxysilyl) propyl] amine, N, N-bis [(3-tripropoxy-silyl) propyl] amine, N- (3-trimethoxysilyl) propyl-3- [N- (3-trimethoxysilyl) -propylamino] propion-amide, N-( 3-Triethoxysilyl) Propyl-3- [N-3-triethoxysilyl) -propyl-amino] propionamide, N- (3-trimethoxysilyl) propyl-3- [N-3-triethoxysilyl)- Propylamino] propionamide, 3-trimethoxysilyl-propyl 3- [N- (3-trimethoxysilyl) -propylamino] -2-methylpropionate, 3-triethoxysilylpropyl 3- [N- (3) -Triethoxysilyl) -propylamino] -2-methylpropionate, 3-trimethoxysilylpropyl 3- [N- (3-triethoxy-silyl) -propylamino] -2-methylpropionate, etc. are included. .. Aminoalkoxysilanes are not used to prepare alkoxysilane-modified prepolymers or adducts, but are not commonly used as additives because they can react with the isocyanate groups of the prepolymer during storage. The amount of adhesion facilitator present is an amount that enhances the adhesion of the adhesive to the surface of the substrate. The amount of adhesion facilitator present is preferably about 0.1 weight percent or more, most preferably about 0.5 weight percent or more, based on the weight of the adhesive. The amount of adhesion enhancer used is preferably no more than about 10 weight percent, most preferably no more than about 2.0 weight percent.

0025The one-component composition useful as an adhesive can further include one or more and one or more fillers that do not enhance the formation of pores upon curing. The reaction of isocyanates with active hydrogen-containing compounds can produce carbon dioxide during curing and which can form pores in the cured composition. It has been discovered that certain fillers can affect the formation of such pores. Therefore, fillers that do not enhance or reduce the formation of pores are desirable for use in compositions. Preferred fillers that do not enhance or reduce the formation of pores include one or more high surface area carbon blacks. In some embodiments, more than one filler can be used, one of which is an amount of carbon black sufficient to color the composition black. Other fillers that may be present that increase the strength of the composition and provide the composition with thixotropy properties include titanium dioxide, surface treated silica, titanium oxide, and fumed silica. Fillers that do not enhance the formation of pores upon curing are used in sufficient amounts to increase the strength of the composition and to provide the composition with thixotropy properties. Preferably, such fillers are present in an amount of about 1 weight percent or more, more preferably about 10 weight percent or more, and most preferably about 15 weight percent or more of the composition. Preferably, such fillers are present in an amount of about 35 weight percent or less, more preferably about 30 weight percent or less, and most preferably about 25 weight percent or less of the composition. High surface area is determined by the method of ASTM D1510. A preferred high surface area filler exhibits an iodine adsorption amount of about 100 g / kg or more, most preferably about 130 g / kg or more.

0026One-component compositions useful as adhesives include fillers with basic characteristics. A basic feature is that when used herein, the filler exhibits a pH of 8.0 or higher, more preferably 9.0 or higher, and most preferably about 9.4 or higher when dissolved or dispersed in deionized water. means. It is measured at a temperature of about 25 ° C with a concentration of about 25 weight percent of the basic filler in deionized water. Any filler that exhibits basic characteristics and has a positive effect on the properties of the adhesive, such as cure rate, can be utilized. Examples of fillers with basic characteristics include untreated alkali metal or alkaline earth metal carbonates (eg, calcium carbonate, sodium carbonate, and potassium carbonate), talc, and the like. Fillers with basic characteristics are present in sufficient amounts to have a positive effect on the properties and cure rate of the adhesive. Preferably, the filler having basic characteristics is present in an amount of about 5 weight percent or more, more preferably about 9 weight percent or more, and most preferably about 15 weight percent or more, based on the weight of the one-component curable composition. To do. Preferably, the filler having basic characteristics is present in an amount of about 50 weight percent or less, more preferably about 35 weight percent or less, and most preferably about 25 weight percent or less, based on the weight of the one-component curable composition. To do.

0027The one-component curable composition contains one or more plasticizers to modify the rheological properties to the desired consistency. Such materials should be water-free, inert to isocyanate groups, and compatible with prepolymers. Such materials may be added to the reaction mixture to prepare an isocyanate functional component such as a prepolymer, or to prepare a final composition, but preferably to prepare an isocyanate functional component. , The reaction mixture is added so that such a mixture can be mixed and handled more easily. Examples of plasticizers are well known in the art and are linear and branched alkyl phthalates such as diisononyl phthalate, dioctyl phthalate, and dibutyl phthalate, partially hydride terpene, trioctyl phosphate, epoxy plasticizer, toluene- Includes sulfamide, chloroparaffin, adipates, castor oil, xylene, 1-methyl-2-pyrrolidinone, and toluene. The amount of plasticizer used is sufficient to give the composition the desired rheological properties and disperse the constituents. Preferably, the plasticizer is one-component cured in an amount of about 0.5 parts by weight or more, more preferably about 1.0 weight percent or more, most preferably about 5.0 weight percent or more, based on the weight of the one-component curable composition. Present in the sex composition. The plasticizer is present in an amount of preferably no more than about 35 weight percent, most preferably no more than about 30 weight percent, based on the weight of the one-component curable composition.

0028Other constituents commonly used in one-component curable compositions can be used. Such materials are well known to those of skill in the art and may include UV stabilizers, antioxidants and the like. The one-component curable composition is a Dual Cure Adhesive Useful For Bond-ing To, the relevant part of which is incorporated herein by reference, with the title Dual Cure Adhesive Useful For Bond-ing To. Glass), Jialanella's U.S. Patent Application No. 13 / 455,294, known in the art such as alkyl-substituted phenols, phosphite, sebacate, and synnametes disclosed in the co-owned patent application filed April 25, 2012. It can also contain a durability stabilizer of. Preferably, the durability stabilizer is present in the composition in an amount of about 0.1 weight percent or more, more preferably about 0.2 weight percent or more, based on the weight of the composition. Preferably, the durability stabilizer is present in the composition in an amount of about 1.0 weight percent or less, more preferably about 0.5 weight percent or less, based on the weight of the composition. The one-component curable composition can further include a light stabilizer that promotes the maintenance of a permanent bond to the substrate for a significant period of life in which the system-bonded structure can be used. A preferred light stabilizer is a hindered amine light stabilizer. An exemplary hindered amine light stabilizer is disclosed in US Pat. No. 7,416,599, column 11, lines 31-63 of Hsieh et al., Which is incorporated herein by reference. Sufficient amounts are used to enhance bonding durability to the substrate. Preferably, the light stabilizer is used in an amount of about 0.1 weight percent or more, more preferably about 0.2 weight percent or more, most preferably about 0.3 weight percent based on the weight of the one-component curable composition. Preferably, the light stabilizer is present in an amount of about 3 weight percent or less, more preferably about 2 weight percent or less, and most preferably about 1 weight percent or less, based on the weight of the one-component curable composition. The one-component curable composition can further contain ultraviolet rays that enhance the durability of bonding the composition to the substrate. Preferred UV light absorbers include benzophenone and benzotriazole. An exemplary UV absorber is described in US Pat. No. 7,416, Hsieh et al. 599, column 11, columns 64 to 12, lines 29, including those disclosed are incorporated herein by reference. Preferably, the UV absorber is used in an amount of about 0.1 weight percent or more, more preferably about 0.2 weight percent or more, and most preferably about 0.3 weight percent or more, based on the weight of the one-component curable composition. Preferably, the UV ray suppressor is used in an amount of about 3 weight percent or less, more preferably about 2 weight percent or less, most preferably about 1 weight percent or less, based on the weight of the one-component curable composition. ..

0029The curing accelerator is a paste containing water. Water-containing pastes are present to accelerate the curing of one-component curable compositions useful as adhesives, especially at low temperatures and / or low relative humidity. That is, the ambient is less than 25 ° C and / or 50 percent relative humidity, more preferably less than 15 ° C and / or 35 percent relative humidity. The curing accelerator contains water, a liquid carrier, and a paste forming agent. Preferably, the curing accelerator is a homogeneous paste. The liquid carrier is any liquid that can form a stable paste with water and paste-forming agents and does not negatively affect the properties of the one-component curable composition with respect to application and final properties. .. Preferably, the liquid carrier contains an isocyanate-reactive group and is involved in the curing of the isocyanate-functional constituents. Preferably, the liquid carrier promotes the formation of a homogeneous paste. Preferably, the liquid carrier comprises one or more glycol ethers, polyether polyols, polyamines, and polyetheramines. More preferably, the liquid carrier is one or more glycol ethers and polyether polyols, most preferably one or more polyether polyols. Preferred polyether polyols are described herein in relation to isocyanate-reactive compounds. The liquid carrier is present in an amount sufficient to form a paste, preferably a homogeneous paste. Preferably, the liquid carrier is present in an amount of about 40 weight percent or more, more preferably about 45 weight percent or more, and most preferably about 50 weight percent or more, based on the weight of the curing accelerator. Preferably, the liquid carrier is present in an amount of about 70 weight percent or less, more preferably about 65 weight percent or less, and most preferably about 62 weight percent or less, based on the weight of the curing accelerator. Preferably, the liquid carrier is about 1 weight percent or more, more preferably about 2.0 weight percent or more, most preferably about 2. by weight, based on the weight of the one-component curable composition. It is present in an amount of 25 weight percent or more. Preferably, the liquid carrier is present in an amount of about 5 weight percent or less, more preferably about 4 weight percent or less, most preferably about 3.5 weight percent or less, based on the weight of the one-component curable composition and the cure accelerator. To do.

0030Water is present in sufficient amount with the liquid carrier and the isocyanate-reactive groups cure at a moderately rapid rate when the isocyanate groups of the one-component curable composition come into contact with the two moieties. Provide a sufficient amount to react to do so. The equivalent ratio of isocyanate reactive groups in the curing accelerator to isocyanate groups in the one-component curable composition is selected to provide the desired curing rate. Preferably, the equivalent ratio of the isocyanate-reactive groups in the curing accelerator to the isocyanate groups in the one-component curable composition is about 0.3: 1 or more, more preferably about 0.5: 1 or more, most preferably. Is 0.7: 1 or higher. Preferably, the equivalent ratio of the isocyanate-reactive groups in the curing accelerator to the isocyanate groups in the one-component curable composition is about 2: 1 or less, more preferably about 1.5: 1 or less, most preferably. Is 1.3: 1 or less. Preferably, the water is present in an amount of about 1.0 weight percent or more, more preferably about 2.0 weight percent or more, most preferably about 4 weight percent or more, based on the weight of the curing accelerator. Preferably, the water is present in an amount of about 20 weight percent or less, more preferably about 10 weight percent or less, and most preferably about 8 weight percent or less, based on the weight of the curing accelerator. Preferably, the water is present in an amount of about 0.01 weight percent or more, more preferably about 0.05 weight percent or more, most preferably about 0.1 weight percent or more, based on the weight of the one-component curable composition and the cure accelerator. .. It is preferably present in an amount of about 0.5 weight percent or less, more preferably about 0.4 weight percent or less, and most preferably about 0.3 weight percent or less, based on the weight of the one-component curable composition and the cure accelerator.

0031Curing accelerators include paste-forming agents, which are materials that form a paste, preferably a homogeneous paste, when mixed with water and a liquid carrier. Paste, as used herein, means a mixture of a liquid carrier and any material that can reversibly bind to water with consistency and without separation (eg, solid powder material). To do. The paste-forming agent preferably absorbs water when in contact with water and releases water when in contact with an isocyanate functional material. An exemplary paste-forming agent is an inorganic compound that forms a hydrate with water, a porous material that can contain water in its pores, contains water in a non-stoichiometric amount, and has a paste-like consistency. Or it contains a material that forms a gel. The paste-forming agent can be organic or inorganic. Exemplary hydrates or aqua complexes include inorganic compounds having water bound in a coordinated manner or as crystallized water. An example of such a hydrate is Na₂SO₄.10H₂O, CaSO₄.2H₂O, CaSO₄.1 / 2H₂O, Na₂B₄O₇.10H₂O, DDL₄.7H₂It is O. Exemplary paste-forming materials include porous materials that seal water in cavities, such as silicates and zeolites. Diatomaceous earth and molecular sieves are particularly suitable. The size of the cavity should be chosen to be optimal for accommodating water. Therefore, a molecular sieve with a pore size of 4 Å is found to be particularly suitable. Exemplary paste-forming materials that contain water in non-chemical quantities and have a paste-like consistency or form a gel include clays such as silica gel, montmorillonite, bentonite, hectorite, or cellulose, cellulose. Includes ether (methylcellulose), polysaccharides such as starch, or polyacrylic acid. Materials that carry ionic groups are also suitable. Polyurethane polymers containing carboxyl groups or sulfonic acid groups as side chains, and salts thereof, particularly ammonium salts thereof, are useful as paste-forming materials. Preferred paste-forming materials include clay. Useful preferred clays include kaolin, surface-treated kaolin, calcined kaolin, aluminum silicate, and surface-treated anhydrous aluminum silicate. Clay can be used in any form that facilitates the formation of pumped compositions. Preferably, the clay is in the form of ground powder, spray-dried beads, or fine particles. These paste-forming materials can contain and bind to water until their water uptake capacity is exhausted. Two or more paste-forming agents can be utilized in the compositions of the present invention. In some embodiments, one of the paste-forming agents can be a thickener capable of thickening the paste. Exemplary thickening paste-forming agents include ultrafine attapulsite, bentonite, silica and the like. The paste-forming agent is used in an amount sufficient to form the paste and to bind to water until required for reaction with the isocyanate-functional constituents. Preferably, the paste-forming agent is about 1 weight percent or more, more preferably about 5 weight par, based on the weight of the curing accelerator. It is present in an amount of cents or more, most preferably about 15 weight percent or more. Preferably, the paste-forming agent is present in an amount of about 50 weight percent or less, more preferably about 45 weight percent or less, and most preferably about 40 weight percent or less, based on the weight of the curing accelerator. Preferably, the paste-forming agent is in an amount of about 0.2 weight percent or more, more preferably about 0.3 weight percent or more, most preferably about 0.4 weight percent or more, based on the weight of the one-component curable composition and the cure accelerator. Exists. Preferably, the paste-forming agent is in an amount of about 1.5 weight percent or less, more preferably about 1.0 weight percent or less, most preferably about 0.9 weight percent or less, based on the weight of the one-component curable composition and the cure accelerator. Exists. If present, the paste-forming agent in the form of a thixotropy thickener is in an amount of about 0.1 weight percent or more, more preferably about 0.5 weight percent or more, most preferably about 1.0 weight percent or more, based on the weight of the cure accelerator. Exists. Preferably, the paste-forming agent in the form of a thickener is present in an amount of about 10 weight percent or less, more preferably about 7 weight percent or less, most preferably about 5 weight percent or less, based on the weight of the curing accelerator. .. Preferably, the paste-forming agent in the form of a thickener is about 0.01 weight percent or more, more preferably about 0.02 weight percent or more, most preferably about 0.04, based on the weight of the one-component curable composition and the cure accelerator. It is present in an amount of weight percent or more. Preferably, the paste-forming agent in the form of a thixotropy thickener is one liquid in an amount of about 0.3 weight percent or less, more preferably about 0.15 weight percent or less, most preferably about 0.1 weight percent or less, based on the weight of the composition. Present in mold curable compositions and cure accelerators. It is present in an amount of 9 weight percent or less. If present, the paste-forming agent in the form of a thixotropy thickener is in an amount of about 0.1 weight percent or more, more preferably about 0.5 weight percent or more, most preferably about 1.0 weight percent or more, based on the weight of the cure accelerator. Exists. Preferably, the paste-forming agent in the form of a thickener is present in an amount of about 10 weight percent or less, more preferably about 7 weight percent or less, most preferably about 5 weight percent or less, based on the weight of the curing accelerator. .. Preferably, the paste-forming agent in the form of a thickener is about 0.01 weight percent or more, more preferably about 0.02 weight percent or more, most preferably about 0.04, based on the weight of the one-component curable composition and the cure accelerator. It is present in an amount of weight percent or more. Preferably, the paste-forming agent in the form of a thixotropy thickener is one liquid in an amount of about 0.3 weight percent or less, more preferably about 0.15 weight percent or less, most preferably about 0.1 weight percent or less, based on the weight of the composition. Present in mold curable compositions and cure accelerators. It is present in an amount of 9 weight percent or less. If present, the paste-forming agent in the form of a thixotropy thickener is in an amount of about 0.1 weight percent or more, more preferably about 0.5 weight percent or more, most preferably about 1.0 weight percent or more, based on the weight of the cure accelerator. Exists. Preferably, the paste-forming agent in the form of a thickener is present in an amount of about 10 weight percent or less, more preferably about 7 weight percent or less, most preferably about 5 weight percent or less, based on the weight of the curing accelerator. .. Preferably, the paste-forming agent in the form of a thickener is about 0.01 weight percent or more, more preferably about 0.02 weight percent or more, most preferably about 0.04, based on the weight of the one-component curable composition and the cure accelerator. It is present in an amount of weight percent or more. Preferably, the paste-forming agent in the form of a thixotropy thickener is one liquid in an amount of about 0.3 weight percent or less, more preferably about 0.15 weight percent or less, most preferably about 0.1 weight percent or less, based on the weight of the composition. Present in mold curable compositions and cure accelerators.

0032The curing accelerator may contain a curing agent located in the second portion. Such hardeners include one or more compounds containing more than one hydroxyl group. The curing agent can be one or more hydroxyl-containing low molecular weight compounds, polymines or polyols. The polyols described above can be used as curing agents. One category of polyols can be the prepolymers described above herein, which are prepared utilizing an excess equivalent of hydroxyl groups such that the resulting prepolymer contains hydroxyl groups. The one or more low molecular weight compounds have two or more isocyanate-reactive groups and a hydrocarbon backbone, which can further contain one or more heteroatoms. Such low molecular weight compounds may be known as chain extenders in the art, such compounds may be polyfunctional or known as cross-linking agents, which average 2 per molecule. It has more than one active hydrogen group. Preferably, the molecular weight of the low molecular weight compound is about 1000 or less, more preferably about 500 or less. Preferably, the low molecular weight compound comprises one or more polyfunctional alcohols, polyfunctional amines, or one or more adducts of polyfunctional alcohols or polyfunctional amines, and alkylene oxides, or mixtures thereof. be able to. Blends of various low molecular weight compounds can be used.

0033The one-component curable composition can be formulated by blending the constituents together using methods well known in the art. The components are blended in a suitable mixer. Such blending is preferably carried out under vacuum or under an inert atmosphere such as nitrogen or argon in the absence of oxygen and atmospheric moisture to prevent premature reaction. In order to prepare the isocyanate functional constituents, it may be advantageous to add a plasticizer to the reaction mixture so that such a mixture can be easily mixed and handled. Alternatively, the plasticizer can be added while all the constituents are blended. The ingredients are blended over a period of time sufficient to prepare a well-blended mixture, preferably for about 10 to about 60 minutes. Once the composition is formulated, it is packaged in a suitable container to protect it from atmospheric moisture. Contact with atmospheric moisture can result in premature cross-linking of prepolymers containing isocyanate groups. Curing accelerators can be formulated by blending the constituents together using methods well known in the art.

0034The one-component curable composition can be used to bond glass to other substrates such as metal or plastic. The one-component curable composition can be contacted with a curing accelerator to accelerate the curing of these applications, especially when exposed to low temperatures and / or humidity. In a preferred embodiment, the first substrate is a glass or scratch resistant plastic window and the second substrate is a window frame. In another preferred embodiment, the first substrate is a window and the second substrate is an automobile window frame. Preferably, the window is clean and can have a glass wipe or primer applied to the area where the adhesive is bonded. The window flange can be primed with a paint primer. The one-component curable composition, optionally mixed with the curing accelerator, is beaded around the window, which is located in contact with the window flange when placed in an automobile. The window in which the composition is then located is placed on the flange so that the composition is located between the window and the flange. The bead of the composition is a continuous bead that functions to seal the joint between the window and the window flange. A continuous bead of a composition is a bead that is positioned so that when in contact the beads are connected at each end to form a continuous seal between the window and the flange. The composition is then cured. The one-component curable composition, optionally mixed with the curing accelerator, can be used to bond the replacement window to the structure. In this embodiment, the old window or part thereof is removed from the window flange or frame. This is typically achieved by cutting old adhesive between the glass and the flange or frame. In some embodiments, some of the old adhesive that remains on the flange or window frame remains on the frame or flange. Part of the flange or frame to which the old adhesive did not adhere can be primed. The one-component curable composition can be applied to the frame or flange over the old adhesive and is bonded to the old adhesive. Older adhesives are polyurethane, siloxane, siloxy functional polyether, or siloxy functional polyester.

0035At the time of use, the one-component curable composition is blended with a curing accelerator, as is usually done when working with two-component compositions. Application of one-component curable compositions and cure accelerators can be achieved with conventional commercial distributors, including dynamic and static mixing. Such distributors using static mixing are set forth in U.S. Pat. Nos. 4,538,920 and 5,082,147 (incorporated herein by reference) and under the trade name MIXPAC, Conprotec, Inc. (Salem, New). Available from Jersey) or by SULZER QUADRO of Sulzer Ltd., Switzerland. The blended composition is extruded from the mixing chamber onto the substrate. When using electrically driven equipment, dynamic mixing can be used. Alternatively, the two-component composition may be placed in a single tube in which the curing accelerator is located inside the bag within the one-component curable composition. In this embodiment, a single tube is used, and once the two parts are extruded from the tube, they have a mixing element that mixes the components well so that the composition can undergo curing once mixed. It passes through the contained nozzle.

0036The one-component curable composition and the curing accelerator start curing when the two parts are mixed. Curing can be accelerated by applying heat to the cured composition, such as by applying infrared, induced, convection, or microwave heating, ultrasonic vibrations, and the like. The viscosity of a portion is measured by press flow viscosity. Pressflow viscosity is measured by pushing 20 grams of material into an orifice with an opening with a diameter of 0.157 inches at 60 psi pressure and recording the time (in seconds) that the material passes through the orifice. Preferably, the press flow viscosity is about 5 seconds or longer, most preferably 8 seconds or longer. Preferably, the press flow viscosity is about 40 seconds or less, most preferably 35 seconds or less. Preferably, the portion exhibits less than 2 mm of sagging when measured as sagging from the tip of the horizontal bead.

0037In another embodiment, the compositions of the present invention can be used to join modular components to the vehicle body or to each other. Examples of modular components include automotive modules such as doors, windows, or bodies. The molecular weights described herein are number average molecular weights that can be determined by gel permeation chromatography (also called GPC). In polyurethane prepolymers, it is also possible to calculate the approximate number average molecular weight from the equivalent ratio of the isocyanate compound to which they react and the polyol compound, which is known to those skilled in the art.

<p num="0038"> The following examples are provided to illustrate the invention, but are not intended to limit its scope. All parts and percentages are by weight unless otherwise specified.</p><p num="0039"> Preparation of Isocyanate Functional Prepolymer (Prepolymer 1) Based on Polyester Polyurethane polyurethane prepolymers are prepared by mixing 364 g of polyoxypropylene diol with a weight average molecular weight of 2,000 with 527 g of polyoxypropylene triol with a weight average molecular weight of 4,500 and 32 grams of diisononyl phthalate plasticizer. To. Mixing is carried out in the reactor by heating the mixture to 54 ° C. Add 160.6 g of diphenylmethane-4,4'-diisocyanate and 0.08 g of stannous octanoate to the mixture. The whole mixture is then reacted at 80 ° C for 1 hour. Finally, 501 grams of diisononyl phthalate plasticizer and 15 grams of diethyl malonate are added to the mixture and the mixing is continued for 1 hour.</p><p num="0040"> component Prepolymer-Prepared as described above, viscosity of 11,160 centipores at 25 ° C, isocyanate content of 1.49 percent Plasticizer Diisononyl phthalate Tertiary amine catalyst-dimorpholino diethyl ether Tin catalyst DABCO DC-21 Untreated calcium carbonate with a pH of basic filler 1-9.7 (25 percent in deionized water) Basic filler 2-talc with a pH of 9.4 (25% in deionized water) Carbon Black 1 Elftex® S7100 High Surface Area Carbon Black, Iodine Absorption 189g / kg Carbon black 2 (standard) PRINTEX (registered trademark) 30 carbon black, iodine adsorption amount 90 g / kg Polyurethane polyol-PLURACOL TP440 polyether polyol Paste Formation 1 --Agent ATTAGEL 50 Ultrafine Atapargite Thickener Paste Former 2-Aluminum Silicate Clay and water</p><p num="0041"> Procedure of test. The lookfield viscosities of the liquids and low viscosity pastes described herein are disclosed in Bhat US Pat. No. 5,922,809, column 12, lines 38-49, which is incorporated herein by reference. It is determined by the procedure that has been done. The viscosity of the adhesives described herein is determined using press flow. The press flow is the time it takes for 20 grams of adhesive to pass through a 0.157 inch (4.0 mm) orifice under a pressure of 60 psi (413 kPa). The Quick Knife Adhesion (QKA) test is performed as follows. A 6.3 mm (width) x 6.3 mm (height) x 100 mm (length) adhesive bead is placed on the substrate to be tested and the construct is identified by 23 ° C and 50 percent RH (relative humidity). Cures over time. When testing, make a notch (20-40 mm) between the adhesive edge and the substrate. The cured bead is then cut with a razor blade at a 45 ° angle and at the same time the bead end is pulled back at a 180 ° angle to the substrate. The degree of adhesive strength is evaluated as adhesive breakage (AF) and / or cohesive breakage (CF). In the case of AF, the cured bead can be separated from the substrate, and in the case of CF, the separation occurs only within the adhesive bead as a result of knife cutting. The sagging test is performed using the following procedure. A triangular metal panel with a height of 10 cm and a length of 30 cm stands on a bench at 90 ° depending on its length. A right triangle bead adhesive composition with a height of 1.5 cm and a base of 0.7 cm is distributed along the top of the panel so that the bottom is in contact with the panel and the height is perpendicular to the top of the panel. To do. After 30 minutes, the slack at the tip of the adhesive composition is measured and recorded (millimeters). The cure rate is determined by a laminating shear test. The lap shear test is performed according to the SAE J1529 procedure and is described below. Almost the bottom 6. An adhesive composition of 3 mm and 8 mm high triangular beads, 25 mm x 100 mm, such as an electrically coated metal cut piece or a glass cut piece primed with Betaseal 43518 and Betaseal 43520A. It is applied along the width of the substrate of 1 and about 6 mm away from the edge of the cut piece. A second electrocoated substrate, which may or may not be primed, is immediately pressed against the adhesive bead to give the composition in between a final height of 6 mm. The sample is cured under certain conditions (eg, 10 ° C and 30 percent relative humidity) for a particular time (eg, 2 hours). The sample is then immediately withdrawn by the Instron Tester at a speed of 5 inches / min (127 mm / min). The breaking point load (lb) of the sample is the sample area (in²) To obtain the lap shear bond strength (psi). Aggregate breakage refers to separation within the adhesive beet.</p><p num="0042"> Preparation of Part I. The Part I mixture is prepared from the ingredients listed in Table 1. The prepolymer, plasticizer, dimorpholino diethyl ether, and tin catalyst are charged into the 2-gallon mixer in the amounts described. The mixture is degassed under vacuum and mixed for 15 minutes. The vacuum is interrupted and both carbon black, pre-oven-dried and cooled to room temperature, and other fillers are added to the mixer. The vacuum is applied slowly and when half of the vacuum is achieved, the mixture begins to wet the filler for 2 minutes. The vacuum valve is then fully opened and mixing is continued under full vacuum for 15 minutes. The vacuum is interrupted again and the mixture is scraped off. The complete vacuum is reapplied and the mixture is mixed under vacuum for an additional 5 minutes. The vacuum is removed with nitrogen and the Part I components are packaged in a closed tube and stored in an aluminum bag. Each sample is made on a scale of 1600 grams.</p><p num="0043"> Preparation of Part II. Using a HAUSCHILD mixer, pour all ingredients except water into the mixer cup, mix at 2100 rpm for 2 minutes, stop mixing and scrape off. Add water and mix at 2100 rpm for an additional 2 minutes. Store for later use. Each sample weighs 150 grams.</p><p num="0044"> A mixture of Part I and Part II. Using a HAUSCHILD mixer, 75 grams of Part I, 3 grams of Part II, and another 75 grams of Part I are placed in a mixer cup and mixed at 2000 rpm for 50 seconds. The composition is scraped off and then mixed at 2000 rpm for an additional 50 seconds.</p><p num="0045"><tables num="1"><img id="000003" he="125" wi="170" file="JP2016508169A_D0001.tif" img-format="tif" img-content="drawing" /></tables></p><p num="0046"> Comparative Examples 1 and 1 are mixed as disclosed and then used respectively to fill tin measuring cups 5.5 cm in diameter and 1.5 cm in depth. The material in the cup is cured at 23 ° C and 50 percent relative humidity (RH) for 7 days. Cut open the cured material for gas pocket inspection. According to the inspection of the cured material of Example 1, it is noted that there were no small number of gas pockets in the cut cross section (5.5 cm x 1.5 cm). FIG. 1 shows an example of such a sample. The inspection of the sample of Comparative Example 1 shows a large number of gas pockets (30 to 50 gas pockets) in the cut cross section. FIG. 2 is an illustrated sample of Comparative Example 1.</p><p num="0047"> Comparative Examples 2 and 3 and Examples 2-5 are tested for gas pockets as described above herein. All samples show no or few gas pockets (0-2). Curing rate tests of Comparative Examples 2 and 3 and Examples 2-5 are performed by mixing Part I with Part II, respectively, as described above herein. Over-shear samples are prepared and cured at 10 ° C and 30 percent relative humidity. Over-shear samples are tested at 2, 4, and 24 hours of application. The results are summarized in Table 2.</p><p num="0048"><tables num="2"><img id="000004" he="40" wi="170" file="JP2016508169A_D0001.tif" img-format="tif" img-content="drawing" /></tables></p><p num="0049"> A quick knife bond sample is prepared using the mixture of Example 4. Substrates are steel slabs with a carbamic acid-based finish without priming and glass slabs primed with Betaprime 5500 primer. These samples are cured at 23 ° C and 50 percent relative humidity for 3 days. These samples are then divided into two sets, each set having one primer glass slab + one painted metal slab. A first sample set of one coated metal cut piece and one undercoated glass cut piece is tested and each shows 100 percent agglutination failure. The second sample set is further exposed to 38 ° C for 14 days at 100 percent relative humidity. These samples showed 100 percent cohesive failure in a quick knife adhesion test.</p><p num="0050">The Part I formulation is measured for press flow viscosity by 60 psi pressure and 0.157 inch orifice. The results are summarized in Table 3. The results show that these samples have a low viscosity and are easily extrudable.</p><p num="0051"><tables num="3"><img id="000005" he="27" wi="170" file="JP2016508169A_D0001.tif" img-format="tif" img-content="drawing" /></tables></p><p num="0052"> Any number listed in the above application includes all values from the low to high values of one unit increment, but with a gap of at least two units between any low and any high values. It is a condition that there is. As an example, 15-85, 22-68, 43 if the amount of component or value of the process available is described as, for example, 1-90, preferably 20-80, more preferably 30-70. Values such as ~ 51, 30 ~ 32, etc. are intended to be explicitly listed in this application. For values less than 1, one unit is 0.0001, 0.001, 0.01, or 0. Considered to be 1. These are merely examples of what is specifically intended, and all possible combinations of a large number of values between the lowest and highest listed values are similarly clearly described in this application. Should be considered. Unless otherwise stated, all ranges include both endpoints and all numbers between endpoints. The use of "about" or "approximately" in relation to a range applies to both ends of the range. Therefore, "about 20 to 30" includes at least the specified end point and covers "about 20 to about 30". The term "become substantial" to describe a combination is an element, component, constituent, or step to be identified, and other elements that do not materially affect the basic and novel features of the combination. Includes ingredients, constituents, or steps. The use of the term "contains" or "included" to describe a combination of elements, components, components, or steps herein also comprises embodiments that substantially consist of elements, components, components, or steps. Consider. Multiple elements, components, components, or steps may be provided by a single integrated element, component, component, or step. Alternatively, a single integrated element, component, component, or step can be divided into separate elements, components, components, or steps. The disclosure of "a" or "one" to describe an element, component, component, or step is not intended to exclude additional element, component, component, or step.</p>