Acceleration of cure polyurethane adhesive composition

Abstract

To provide: an adhesive that cures sufficiently to allow driving away in a short amount of time while also providing consistent uniform adhesive beads and sufficient workability under varying ambient conditions; and an application method.SOLUTION: An adhesive composition comprises a moisture-curable adhesive comprising an isocyanate-terminated prepolymer and a cure accelerator having two curative components having different cure kinetics. The cure accelerator comprises an isocyanate reactive compound comprising a primary, secondary or tertiary amino group or a primary thiol group having faster curing kinetics resulting in an increase in bead stability within the first minutes, and a polyol selected from a diol and / or triol with slower curing kinetics allowing sufficient open time and yet a fast strength build up. A preferred method of application of the adhesive system is via a 1K application gun.SELECTED DRAWING: Figure 1

Description

Technical Field

[0001] The present invention relates to a moisture-curing adhesive composition useful for bonding glass to vehicles and buildings. In particular, the present invention provides one component that improves the stability of the bead within the first few minutes due to its fast curing speed, and another component that enables sufficient open time while exhibiting rapid strength development due to its slow curing speed. The present invention relates to a moisture-curing isocyanate-terminated prepolymer adhesive composition containing two curing agent components having different curing speeds, combined with a separate curing accelerator. In particular, the present invention provides one component that improves the stability of the bead within the first few minutes due to its fast curing speed, and another component that enables sufficient open time while exhibiting rapid strength development due to its slow curing speed. The present invention relates to a moisture-curing isocyanate-terminated prepolymer adhesive composition containing two curing agent components having different curing speeds, combined with a separate curing accelerator. In particular, the present invention provides one component that improves the stability of the bead within the first few minutes due to its fast curing speed, and another component that enables sufficient open time while exhibiting rapid strength development due to its slow curing speed. The present invention relates to a moisture-curing isocyanate-terminated prepolymer adhesive composition containing two curing agent components having different curing speeds, combined with a separate curing accelerator. In particular, the present invention provides one component that improves the stability of the bead within the first few minutes due to its fast curing speed, and another component that enables sufficient open time while exhibiting rapid strength development due to its slow curing speed. The present invention relates to a moisture-curing isocyanate-terminated prepolymer adhesive composition containing two curing agent components having different curing speeds, combined with a separate curing accelerator.

Background Art

[0002] One-component moisture-curing adhesive compositions have been used to bond windows to buildings and vehicles. Examples of adhesives useful for these applications are described in U.S. Patent Nos. 4,374,237; 4,687,533; 4,780,520; 5,063,269; 5,623,044; 5,603,798; 5,922,809; 6,015,475; 6,512,033; 6,657,035; 6,709,539; 7,101,950; 7,226,523; 7,361,292; 8,236,891; Canadian Patent No. 2,564,992; and International Publication No. 2015 / 171307 Pamphlet. ,687,533; 4,780,520; 5,063,269 ; 5,623,044; 5,603,798; 5 ,922,809; 6,015,475; 6,512,033 ; 6,657,035; 6,709,539; 7 ,101,950; 7,226,523; 7,361,292 ; 8,236,891; Canadian Patent No. 2,564,992 : and International Publication No. 2015 / 171307 Pamphlet. In automobile factories, windows are installed using robotic and computer-controlled processes that facilitate the use of various high-performance adhesives, such as non-conductive adhesives and high modulus adhesives. New vehicles are ​Since you won't be driving very far for a few days after installing the windows, the speed of cure is not a major issue. do not have.

[0003] In contrast, if a vehicle needs a window replaced, it is likely to be driven immediately after. Replacement is often done remotely or under the control of an installer working from the vehicle. As a result, vehicle owners should The speed of cure is important because you want to be able to drive your vehicle quickly. A one-part moisture-curable adhesive useful for vehicle window replacement that makes it easy to apply is disclosed in U.S. Pat. No. 5,976,305. No. 6,709,539 and No. 7,226,523 These adhesives developed sufficient integrity to make the vehicle drivable within a short period of time. However, it still requires a much longer time to fully cure and is sensitive to temperature and relative humidity. It showed inconsistent cure depending on ambient conditions such as humidity.

[0004] Isocyanate functional compounds or prepolymers in one part and isocyanate reaction Two-part compositions containing a compound and / or a prepolymer having a reactive component have also been used. Generally, it is understood that the two parts, referred to as Part A and Part B, have essentially the same volume. One part contains an isocyanate-functional compound or prepolymer, and the other part contains an isocyanate Examples of two-part compositions containing compounds and / or prepolymers having heat-reactive components are listed in the European Patent No. 1,524,282 and U.S. Patent No. 5,852,103; Nos. 6,709,539; 7,101,950; and 7,361, However, these are not suitable for keeping the two liquids separate. tend to have problems with complex delivery systems and require sufficient mixing during dispensing to achieve a uniform product. Similarly, two-component adhesive compositions tend to react rapidly and form a skin, which may result in insufficient working time to properly position replacement windows under certain conditions (higher temperature and higher relative humidity). Therefore, even if two-component compositions can enable replacement of automotive windows such that the vehicle is driven within 30 minutes after the window is bonded, these typically do not allow for a more rapid drivable time and care must be taken to ensure a consistently uniform adhesive bead.

[0005] More recently, a two-component dual-cure adhesive composition composed of an isocyanate- terminated prepolymer in one liquid and an acrylate monomer in the other liquid is described in International Publication No. WO 2012 / 151085. In this composition, one liquid contains an isocyanate-terminated polyether prepolymer and the other liquid contains a hydroperoxidized compound and an acrylic or acrylate monomer. The hydroperoxide compound is reduced to form free radicals when mixed with the other liquid, and by achieving sufficient integrity through the development of an initial polyacrylic or polyacrylate matrix, enables a relatively rapid drivable time. However, the working time, bead consistency, workability, and final cure properties have not been desirable.

[0006] Therefore, while curing sufficiently to be drivable in a short time such as 15 minutes, providing a consistent and uniform adhesive bead, and sufficient workability (placing and It is possible, and still sufficient adhesion time) can be obtained, to obtain an adhesive that can run in a short time for joining a glass to a structure. It would be desirable to obtain an adhesive that can run in a short time for joining a glass to a structure. Summary of the Invention Means for Solving the Problems

[0007] In one embodiment, the present invention includes a moisture-curing adhesive comprising A) an isocyanate-terminated prepolymer and B) a curing accelerator, consisting essentially of these, consisting of these, wherein the curing accelerator is i) 1) a primary, secondary, or tertiary amino group, or a primary thiol group, and 2) an isocyanate-reactive compound containing 2 to 7 OH, NH, and / or SH functional groups, and ii) a polyol having no primary, secondary, or tertiary amino group or primary thiol group, the polyol being selected from diols and / or triols, and containing, consisting essentially of these, or consisting of these, preferably component B) is an adhesive system essentially free of water. In one embodiment, the present invention includes a moisture-curing adhesive comprising A) an isocyanate-terminated prepolymer and B) a curing accelerator, consisting essentially of these, consisting of these, wherein the curing accelerator is i) 1) a primary, secondary, or tertiary amino group, or a primary thiol group, and 2) an isocyanate-reactive compound containing 2 to 7 OH, NH, and / or SH functional groups, and ii) a polyol having no primary, secondary, or tertiary amino group or primary thiol group, the polyol being selected from diols and / or triols, and containing, consisting essentially of these, or consisting of these, preferably component B) is an adhesive system essentially free of water. In one embodiment, the present invention includes a moisture-curing adhesive comprising A) an isocyanate-terminated prepolymer and B) a curing accelerator, consisting essentially of these, consisting of these, wherein the curing accelerator is i) 1) a primary, secondary, or tertiary amino group, or a primary thiol group, and 2) an isocyanate-reactive compound containing 2 to 7 OH, NH, and / or SH functional groups, and ii) a polyol having no primary, secondary, or tertiary amino group or primary thiol group, the polyol being selected from diols and / or triols, and containing, consisting essentially of these, or consisting of these, preferably component B) is an adhesive system essentially free of water. In one embodiment, the present invention includes a moisture-curing adhesive comprising A) an isocyanate-terminated prepolymer and B) a curing accelerator, consisting essentially of these, consisting of these, wherein the curing accelerator is i) 1) a primary, secondary, or tertiary amino group, or a primary thiol group, and 2) an isocyanate-reactive compound containing 2 to 7 OH, NH, and / or SH functional groups, and ii) a polyol having no primary, secondary, or tertiary amino group or primary thiol group, the polyol being selected from diols and / or triols, and containing, consisting essentially of these, or consisting of these, preferably component B) is an adhesive system essentially free of water. In one embodiment, the present invention includes a moisture-curing adhesive comprising A) an isocyanate-terminated prepolymer and B) a curing accelerator, consisting essentially of these, consisting of these, wherein the curing accelerator is i) 1) a primary, secondary, or tertiary amino group, or a primary thiol group, and 2) an isocyanate-reactive compound containing 2 to 7 OH, NH, and / or SH functional groups, and ii) a polyol having no primary, secondary, or tertiary amino group or primary thiol group, the polyol being selected from diols and / or triols, and containing, consisting essentially of these, or consisting of these, preferably component B) is an adhesive system essentially free of water. In one embodiment, the present invention includes a moisture-curing adhesive comprising A) an isocyanate-terminated prepolymer and B) a curing accelerator, consisting essentially of these, consisting of these, wherein the curing accelerator is i) 1) a primary, secondary, or tertiary amino group, or a primary thiol group, and 2) an isocyanate-reactive compound containing 2 to 7 OH, NH, and / or SH functional groups, and ii) a polyol having no primary, secondary, or tertiary amino group or primary thiol group, the polyol being selected from diols and / or triols, and containing, consisting essentially of these, or consisting of these, preferably component B) is an adhesive system essentially free of water. In one embodiment, the present invention includes a moisture-curing adhesive comprising A) an isocyanate-terminated prepolymer and B) a curing accelerator, consisting essentially of these, consisting of these, wherein the curing accelerator is i) 1) a primary, secondary, or tertiary amino group, or a primary thiol group, and 2) an isocyanate-reactive compound containing 2 to 7 OH, NH, and / or SH functional groups, and ii) a polyol having no primary, secondary, or tertiary amino group or primary thiol group, the polyol being selected from diols and / or triols, and containing, consisting essentially of these, or consisting of these, preferably component B) is an adhesive system essentially free of water. In one embodiment, the present invention includes a moisture-curing adhesive comprising A) an isocyanate-terminated prepolymer and B) a curing accelerator, consisting essentially of these, consisting of these, wherein the curing accelerator is i) 1) a primary, secondary, or tertiary amino group, or a primary thiol group, and 2) an isocyanate-reactive compound containing 2 to 7 OH, NH, and / or SH functional groups, and ii) a polyol having no primary, secondary, or tertiary amino group or primary thiol group, the polyol being selected from diols and / or triols, and containing, consisting essentially of these, or consisting of these, preferably component B) is an adhesive system essentially free of water.

[0008] In a preferred embodiment of the present invention, the isocyanate-reactive compound (i) has 2 to 4.5 OH, NH, and / or SH functional groups and is present in an amount of less than 5% by weight of the curing accelerator (B). In a preferred embodiment of the present invention, the isocyanate-reactive compound (i) has 2 to 4.5 OH, NH, and / or SH functional groups and is present in an amount of less than 5% by weight of the curing accelerator (B). In a preferred embodiment of the present invention, the isocyanate-reactive compound (i) has 2 to 4.5 OH, NH, and / or SH functional groups and is present in an amount of less than 5% by weight of the curing accelerator (B).

[0009] Another embodiment of the present invention is a process of preparing a moisture-curing adhesive composition comprising a) A) an isocyanate-terminated prepolymer and B) a curing accelerator, wherein the curing accelerator is i) 1) a primary, secondary, or tertiary amino group, or a primary thiol group, and 2) an isocyanate-reactive compound containing 2 to 7 OH, NH, and / or SH functional groups, and ii) a polyol having no primary, secondary, or tertiary amino group or primary thiol group, the polyol being selected from diols and / or triols, and containing, consisting essentially of these, or consisting of these, preferably component B) is an adhesive system essentially free of water. Another embodiment of the present invention is a process of preparing a moisture-curing adhesive composition comprising a) A) an isocyanate-terminated prepolymer and B) a curing accelerator, wherein the curing accelerator is i) 1) a primary, secondary, or tertiary amino group, or a primary thiol group, and 2) an isocyanate-reactive compound containing 2 to 7 OH, NH, and / or SH functional groups, and ii) a polyol having no primary, secondary, or tertiary amino group or primary thiol group, the polyol being selected from diols and / or triols, and containing, consisting essentially of these, or consisting of these, preferably component B) is an adhesive system essentially free of water. Another embodiment of the present invention is a process of preparing a moisture-curing adhesive composition comprising a) A) an isocyanate-terminated prepolymer and B) a curing accelerator, wherein the curing accelerator is i) 1) a primary, secondary, or tertiary amino group, or a primary thiol group, and 2) an isocyanate-reactive compound containing 2 to 7 OH, NH, and / or SH functional groups, and ii) a polyol having no primary, secondary, or tertiary amino group or primary thiol group, the polyol being selected from diols and / or triols, and containing, consisting essentially of these, or consisting of these, preferably component B) is an adhesive system essentially free of water. Another embodiment of the present invention is a process of preparing a moisture-curing adhesive composition comprising a) A) an isocyanate-terminated prepolymer and B) a curing accelerator, wherein the curing accelerator is i) 1) a primary, secondary, or tertiary amino group, or a primary thiol group, and 2) an isocyanate-reactive compound containing 2 to 7 OH, NH, and / or SH functional groups, and ii) a polyol having no primary, secondary, or tertiary amino group or primary thiol group, the polyol being selected from diols and / or triols, and containing, consisting essentially of these, or consisting of these, preferably component B) is an adhesive system essentially free of water. Or a polyol having no tertiary amino group or primary thiol group, which is a polyol selected from diols and / or triols, and preferably component B) essentially contains no water, and the step of separately preparing an isocyanate-terminated prepolymer and a curing accelerator ; b) a step of mixing a curing accelerator and an isocyanate-terminated prepolymer to form an adhesive mixture; c) a step of applying the adhesive mixture to at least a part of a first substrate; d) a step of bringing the substrate having the adhesive mixture thereon into contact with a second substrate so that the adhesive mixture is therebetween ; and e) a step of curing the adhesive mixture to integrally bond the substrates; A method for accelerating the curing of an adhesive composition consisting essentially of or consisting of these wherein preferably the first substrate is a substrate at least a part of which is optically transparent, the second substrate is a vehicle or a building, and more preferably the first substrate has an opaque portion to which the adhesive mixture is applied and which comes into contact with the second substrate, and preferably the first substrate is glass or polycarbonate. or a method of using the accelerated polyurethane adhesive. The adhesive of the present invention is a 2K adhesive

Brief Description of Drawings

[0010]

Figure 1

Figure 2

Embodiments for Carrying Out the Invention

[0011] The present invention relates to a formulation of a polyurethane adhesive that cures rapidly regardless of humidity, and a method of using the accelerated polyurethane adhesive. The adhesive of the present invention is a 2K adhesive The curing performance of the sizing agent is from a 1K polyurethane adhesive cartridge or sausage or drum The application of the 1K adhesive is shown in combination with the performance using a standard 1K application gun typically used in an automatic coating apparatus for this.

[0012] In one embodiment, the adhesive of the present invention is applied using a 2K packaging solution such as a sausage in a peeler cartridge or sausage solution These can both be used with a standard 1K application gun combined with a static mixer. See, for example, U.S. Patent No. 9,821,512, which is incorporated herein by reference For use with a static mixer, it is necessary to lower the viscosities of both adhesive components to enable a sufficiently fast application rate. For conventional adhesives, the low viscosities of both components that enable mixing using a static mixer typically reduce the stability of the bead against the sinking of the window, which may be called deck performance. The present invention addresses the use of a low-viscosity adhesive formulation that rapidly develops strength to enable standing the window on the adhesive (deck ) immediately after application of the adhesive, while the developed strength does not adversely affect the open time of the adhesive.

[0013] This results in at least 10 minutes or more in length from the time when the adhesive starts to have sufficient strength (deck height ≤ 5.5 mm) to hold the window until the time when the strength of the bead of the adhesive becomes so large that the window cannot be pushed into the bead of the adhesive (deck height ≥ 1.7 mm). This is "rapid" in the adhesive of the present invention and increases the stability of the bead within the first few minutes. and two curing agents having different speeds, the second curing agent having a "slow" curing speed and enabling sufficient open time while still enabling the development of fast strength, by using a polyol component. The fast curing agent is an isocyanate reaction compound, preferably an amine, preferably a primary, secondary, or tertiary amino group, and / or is a polyol containing a thiol, preferably a primary thiol group, and the isocyanate-reactive compound preferably has 2 to 7 OH, NH, and / or SH functional groups. The slow curing agent is a diol or triol selected from those having no primary, secondary, or tertiary amino group, or primary thiol group, for example, a polyether diol or an alkyl diol ( for example, 1,4-butanediol). The moisture-curing adhesive composition of the present invention containing an isocyanate-terminated prepolymer is desirable for attaching repair glass when repairing chipped or cracked glass of a vehicle while still having sufficient working time and final curing characteristics, and has been found to cure in a significantly shorter time. As an example, this adhesive mixture can have a working time of about 5, 8, 10, or even 15 minutes, while basically curing in 60 minutes. Similarly, the method of the present invention

[0014] enables consistent application of these moisture-curing adhesives under widely different ambient conditions. The adhesive system of the present invention can be used to integrally bond various substrates. Examples of substrates include coated substrates such as plastics, glass, wood, ceramics, metals, and plastics coated with wear-resistant coatings such as wear-resistant coatings.

[0015] ​​​​​​The adhesive system of the present invention can be used to integrally bond similar and dissimilar substrates. It is particularly useful for bonding glass or plastic provided with a wear-resistant coating to other substrates such as vehicles (e.g., automobiles) and buildings. The composition of the present invention is also useful for integrally bonding parts of module components such as vehicle module components. Glass or plastic coated with a wear-resistant coating can be bonded to the coated and uncoated parts of the vehicle. The composition of the present invention is particularly useful for bonding replacement windows to a structure. The adhesive is pumpable, has sag resistance, and bonds parts together at temperatures from -10°C to 45°C. Preferably, the composition has sag of uncured samples less than 2 mm and a deck force of 1.5

[0016] pounds to 15 pounds under typical ambient conditions (i.e., temperatures from -10°C to 35°C and relative humidity from 25% to 75%). Preferably, the deck height from when the adhesive has sufficient strength to hold the window until the strength of the adhesive bead is high enough to push the window into the adhesive bead is from 1.0 mm to 5.5 mm. This allows the adhesive prepared from the composition of the present invention to be applied over a wide range of ambient temperatures. Heating of the material is not required for application of the adhesive. Surprisingly, this adhesive system provides a unique and excellent combination that enables rapid curing to make the vehicle drivable even after just 30 minutes, an appropriate deck force to allow placement of the windshield immediately after application, and sufficient time to allow repositioning. It has been found that it can be achieved.

[0017] Thus, the adhesive prepared from the composition of the present invention can be applied at a wide range of ambient temperatures. Heating of the material is not required for application of the adhesive. Surprisingly, this adhesive system provides a unique and excellent combination that enables rapid curing to make the vehicle drivable even after just 30 minutes, an appropriate deck force to allow placement of the windshield immediately after application, and sufficient time to allow repositioning. It has been found that it can provide a unique and excellent combination that enables rapid curing to make the vehicle drivable even after just 30 minutes, an appropriate deck force to allow placement of the windshield immediately after application, and sufficient time to allow repositioning.

[0018] The "nominal" used with respect to the functionality number means the theoretical functionality number, which usually can be calculated from the stoichiometry of the raw materials used. Generally, the actual functionality number is different due to the imperfection of the raw materials, the incomplete conversion of the reactants, and the formation of by-products. The "nominal" used with respect to the functionality number means the theoretical functionality number, which usually can be calculated from the stoichiometry of the raw materials used. Generally, the actual functionality number is different due to the imperfection of the raw materials, the incomplete conversion of the reactants, and the formation of by-products. The "nominal" used with respect to the functionality number means the theoretical functionality number, which usually can be calculated from the stoichiometry of the raw materials used. Generally, the actual functionality number is different due to the imperfection of the raw materials, the incomplete conversion of the reactants, and the formation of by-products.

[0019] Preferred polyisocyanates for use in preparing prepolymers include those disclosed in column 3, line 32 to column 4, line 24 of U.S. Patent No. 5,922,809, which is incorporated herein by reference. Preferably, the polyisocyanate is an aromatic or alicyclic polyisocyanate such as diphenylmethane-4,4'-diisocyanate, isophorone diisocyanate, tetramethylxylene diisocyanate, and most preferably diphenylmethane-4,4'-diisocyanate. Diols and triols are generally called polyols. Preferred polyisocyanates for use in preparing prepolymers include those disclosed in column 3, line 32 to column 4, line 24 of U.S. Patent No. 5,922,809, which is incorporated herein by reference. Preferably, the polyisocyanate is an aromatic or alicyclic polyisocyanate such as diphenylmethane-4,4'-diisocyanate, isophorone diisocyanate, tetramethylxylene diisocyanate, and most preferably diphenylmethane-4,4'-diisocyanate. Diols and triols are generally called polyols. Preferred polyisocyanates for use in preparing prepolymers include those disclosed in column 3, line 32 to column 4, line 24 of U.S. Patent No. 5,922,809, which is incorporated herein by reference. Preferably, the polyisocyanate is an aromatic or alicyclic polyisocyanate such as diphenylmethane-4,4'-diisocyanate, isophorone diisocyanate, tetramethylxylene diisocyanate, and most preferably diphenylmethane-4,4'-diisocyanate. Diols and triols are generally called polyols. Preferred polyisocyanates for use in preparing prepolymers include those disclosed in column 3, line 32 to column 4, line 24 of U.S. Patent No. 5,922,809, which is incorporated herein by reference. Preferably, the polyisocyanate is an aromatic or alicyclic polyisocyanate such as diphenylmethane-4,4'-diisocyanate, isophorone diisocyanate, tetramethylxylene diisocyanate, and most preferably diphenylmethane-4,4'-diisocyanate. Diols and triols are generally called polyols. Preferred polyisocyanates for use in preparing prepolymers include those disclosed in column 3, line 32 to column 4, line 24 of U.S. Patent No. 5,922,809, which is incorporated herein by reference. Preferably, the polyisocyanate is an aromatic or alicyclic polyisocyanate such as diphenylmethane-4,4'-diisocyanate, isophorone diisocyanate, tetramethylxylene diisocyanate, and most preferably diphenylmethane-4,4'-diisocyanate. Diols and triols are generally called polyols. Preferred polyisocyanates for use in preparing prepolymers include those disclosed in column 3, line 32 to column 4, line 24 of U.S. Patent No. 5,922,809, which is incorporated herein by reference. Preferably, the polyisocyanate is an aromatic or alicyclic polyisocyanate such as diphenylmethane-4,4'-diisocyanate, isophorone diisocyanate, tetramethylxylene diisocyanate, and most preferably diphenylmethane-4,4'-diisocyanate. Diols and triols are generally called polyols. Preferred polyisocyanates for use in preparing prepolymers include those disclosed in column 3, line 32 to column 4, line 24 of U.S. Patent No. 5,922,809, which is incorporated herein by reference. Preferably, the polyisocyanate is an aromatic or alicyclic polyisocyanate such as diphenylmethane-4,4'-diisocyanate, isophorone diisocyanate, tetramethylxylene diisocyanate, and most preferably diphenylmethane-4,4'-diisocyanate. Diols and triols are generally called polyols.

[0020] The prepolymer is produced from polyols such as diols and triols as described in column 4, line 60 to column 5, line 50 of U.S. Patent No. 5,922,809. The polyols (diols and triols) are preferably polyether polyols, more preferably polyoxyalkylene oxide polyols. The most preferred triol is a polyol capped with ethylene oxide, which is prepared by reacting glycerin with propylene oxide and then reacting the product with ethylene oxide. The prepolymer is produced from polyols such as diols and triols as described in column 4, line 60 to column 5, line 50 of U.S. Patent No. 5,922,809. The polyols (diols and triols) are preferably polyether polyols, more preferably polyoxyalkylene oxide polyols. The most preferred triol is a polyol capped with ethylene oxide, which is prepared by reacting glycerin with propylene oxide and then reacting the product with ethylene oxide. The prepolymer is produced from polyols such as diols and triols as described in column 4, line 60 to column 5, line 50 of U.S. Patent No. 5,922,809. The polyols (diols and triols) are preferably polyether polyols, more preferably polyoxyalkylene oxide polyols. The most preferred triol is a polyol capped with ethylene oxide, which is prepared by reacting glycerin with propylene oxide and then reacting the product with ethylene oxide. The prepolymer is produced from polyols such as diols and triols as described in column 4, line 60 to column 5, line 50 of U.S. Patent No. 5,922,809. The polyols (diols and triols) are preferably polyether polyols, more preferably polyoxyalkylene oxide polyols. The most preferred triol is a polyol capped with ethylene oxide, which is prepared by reacting glycerin with propylene oxide and then reacting the product with ethylene oxide. The prepolymer is produced from polyols such as diols and triols as described in column 4, line 60 to column 5, line 50 of U.S. Patent No. 5,922,809. The polyols (diols and triols) are preferably polyether polyols, more preferably polyoxyalkylene oxide polyols. The most preferred triol is a polyol capped with ethylene oxide, which is prepared by reacting glycerin with propylene oxide and then reacting the product with ethylene oxide. The prepolymer is produced from polyols such as diols and triols as described in column 4, line 60 to column 5, line 50 of U.S. Patent No. 5,922,809. The polyols (diols and triols) are preferably polyether polyols, more preferably polyoxyalkylene oxide polyols. The most preferred triol is a polyol capped with ethylene oxide, which is prepared by reacting glycerin with propylene oxide and then reacting the product with ethylene oxide. The prepolymer is produced from polyols such as diols and triols as described in column 4, line 60 to column 5, line 50 of U.S. Patent No. 5,922,809. The polyols (diols and triols) are preferably polyether polyols, more preferably polyoxyalkylene oxide polyols. The most preferred triol is a polyol capped with ethylene oxide, which is prepared by reacting glycerin with propylene oxide and then reacting the product with ethylene oxide.

[0021] Polyether prepolymers such as polyester polyols as known in the art It is also understood that small amounts of other polyols can be used to form the polymer. Typically such other polyols can be present in an amount of up to 5% by weight of the polyol used to produce the prepolymer. However, the prepolymer may be produced in the absence of such polyols.

[0022] The isocyanate-terminated prepolymer can be prepared by any suitable method, such as bulk polymerization and solution polymerization. The reaction to prepare the prepolymer is carried out under anhydrous conditions, preferably under an inert atmosphere such as a nitrogen blanket, to prevent cross-linking of the isocyanate groups by moisture in the air. The reaction is carried out at a temperature of 0°C to 150°C, more preferably 25°C to 90°C, until the residual isocyanate content, determined by titration of the sample, is very close to the desired theoretical value. "Isocyanate content" means the weight percentage of isocyanate moieties relative to the total weight of the prepolymer. The reaction to prepare the prepolymer can be carried out in the presence of a urethane catalyst. Examples of such include stannous carboxylates such as stannous octoate, stannous oleate, stannous acetate, and stannous laurate. Also, dialkyltin dicarboxylates such as dibutyltin dilaurate and dibutyltin diacetate, as well as tertiary amines and tin mercaptides, are known in the art as urethane catalysts. Preferably, the reaction to prepare the prepolymer is catalyzed by stannous octoate. The amount of catalyst used is generally 0.005 to 5 parts by weight of the mixture being catalyzed, depending on the nature of the isocyanate. Preferably, the reaction is carried out in a mixture with a plasticizer as described in detail below. ​​​​​​​​​​​​​​​​

[0023] Moisture-curing adhesives generally also contain fillers such as carbon black. Carbon bla ck can have a wide range of structures, depending on its structure and the molecular weight of the prepolymer, as indicated by the oil absorption (ASTM D-2 414-09). For example, carbon black typically has an oil absorption (OAN) of 80 to 200 ccs per 100 grams. Desirably, the oil absorption of carbon is at least 90, more preferably at least 100, most preferably at least 110, preferably up to 180, more preferably up to 165, most preferably up to 150 ccs / 100 grams.

[0024] The appropriate amount of carbon black can be determined for a given carbon black. Typically, the amount of carbon black is, in order of desirability, at least 10 wt%, 15 wt% of the adhesive composition, and at most, in order of desirability, 38 wt%, 35 wt%, 32 wt%, 30 wt%, or 28 wt%.

[0025] The carbon black used may be standard carbon black that has not been specially treated to be non-conductive. Standard carbon black is carbon black that has not been specially surface-treated or oxidized. Alternatively, one or more non-conductive carbon blacks can be used alone or in combination with standard carbon black. Suitable standard carbon bla cks include RAVEN™ 790, RAVE N™ 450, RAVEN™ 500, RAVEN™ 430, RAVEN available from Colombian, etc. N(™) 450, RAVEN(™) 500, RAVEN(™) 430, RAVEN N(™) 450, RAVEN(™) 500, RAVEN(™) 430, RAVEN (TM) 420 and RAVEN (TM) 410 carbon blacks, and from Cabot Available ELFTEX S5100 and S7100 and MONARCH 120, 57 0, and CSX carbon black such as 590, and Evonik Industrial PRINTEX™ 30 Carbon Black available from es, Mobile, AL Suitable non-conductive carbon blacks include Colombian Che RAVEN (trade name) available from Michaels Company, Marietta, GA Examples of carbon black include RAVEN™ 1040 and RAVEN™ 1060 carbon black.

[0026] The moisture curable adhesive may also include reactive silicones. Reactive silicones include silanes. It may be present within the framework or may be present as a separate molecule. The reactive silicon may be present as an end group in the copolymer. ,613,816, Column 4, Lines 25 to 55 of the specification Other exemplary reactive silicons are disclosed in U.S. Pat. Paragraphs 0055 to 0065 of 2002 / 0100550 and Hsie h, U.S. Patent No. 6,015,475, column 5, line 27 to column 6, line 41 It has been done.

[0027] The amount of reactive silicon, if present in a moisture curable adhesive, is typically about 100% of the total adhesive composition. The amount of reactive silicon (note, the weight of silicon itself) is 0.001% to 2% by weight. (e.g., does not include an organic group attached thereto) is at least one of the adhesive composition. 0.005%, 0.01%, 0.02%, 0.04%, 0.06%, 0.08%, or 0 .1% to a maximum of 1.8%, 1.6%, 1.4%, 1.2%, 1%, 0.8%, 0.5% may be.

[0028] The moisture-curing adhesive may also contain one or more organic polymers dispersed therein . Preferably, the organic polymer is included in the prepolymer by including a dispersion trio ol in which particles of the organic polymer are dispersed therein. The dispersion triol is typically understood to have at least a portion of the particles grafted with a polyol. Preferred dispersion triols are disclosed in columns 4, line 13 to column 6, line 18 of Zhou's U.S. Patent No. 6,709,5 39, which is incorporated herein by reference. Preferably, the triol used to disperse the organic particles is a polyether triol, more preferably a polyoxyalkylene-based triol. Preferably, such a po lyoxyalkylene oxide triol contains a polyoxypropylene chain capped with polyoxyethylene . Preferably, the triol has a molecular weight of 3,000 or more, more preferably 4,000 or more, and most preferably 5,000 or more. Preferably, such a tri ol has a molecular weight of 8,000 or less, more preferably 7,000 or less . To produce the prepolymer composition described herein, the polyol of the dispersed polyol (e.g., triol) is included in the polyol, and the copolymer particles of the dispersed polyol are understood to be fillers in the composition .

[0029] The moisture-curing adhesive typically further contains a plasticizer. The plasticizer is used to obtain desired rheological properties​ It can be used to change to a rare consistency. Such materials do not contain water and must be inert to isocyanate groups. Plasticizers are useful for polyurethane adhesives and can be common plasticizers well-known to those skilled in the art, which will be hereinafter referred to as low polar plasticizers. Plasticizers are present in sufficient amounts to disperse the isocyanate-terminated prepolymer. Plasticizers can be added to the prepolymer either during the preparation of the prepolymer or during the compounding of the prepolymer before being placed in the first part. Preferably, the plasticizer is present in an amount of about 1 weight percent or more, more preferably about 20 weight percent or more, and most preferably about 30 weight percent or more of the prepolymer formulation (prepolymer plus plasticizer). Preferably, the plasticizer is present in an amount of about 45 weight percent or less, more preferably about 35 weight percent or less of the prepolymer formulation. Preferably, two plasticizers are used, one is a high-polarity plasticizer and the other is a low-polar plasticizer. The high-polarity plasticizer is a plasticizer having a polarity greater than that of aromatic diesters such as phthalic acid esters. The low-polarity plasticizer is a plasticizer having a polarity equal to or lower than that of aromatic diesters.

[0030] Preferably, two plasticizers are used, one is a high-polarity plasticizer and the other is a low-polar plasticizer. The high-polarity plasticizer is a plasticizer having a polarity greater than that of aromatic diesters such as phthalic acid esters. The low-polarity plasticizer is a plasticizer having a polarity equal to or lower than that of aromatic diesters. plasticizer. The high-polarity plasticizer is a plasticizer having a polarity greater than that of aromatic diesters such as phthalic acid esters. The low-polarity plasticizer is a plasticizer having a polarity equal to or lower than that of aromatic diesters. plasticizer.

[0031] Suitable high-polarity plasticizers include one or more of alkyl esters of sulfonic acids, alkyl alkyl ethers diesters, polyester resins, polyglycol diesters, high molecular weight polyesters, tricarboxylic acid esters, dialkyl ether diesters, dialkyl ether aromatic esters, aromatic phosphate esters, and aromatic sulfonamides. tricarboxylic acid esters, dialkyl ether diesters, dialkyl ether aromatic esters, aromatic phosphate esters, and aromatic sulfonamides. tricarboxylic acid esters, dialkyl ether diesters, dialkyl ether aromatic esters, aromatic phosphate esters, and aromatic sulfonamides. can be mentioned. More preferable high-polarity plasticizers include aromatic sulfonamides, aromatic phosphates esters, dialkyl ether aromatic esters, and alkyl esters of sulfonic acids. Most preferable high-polarity plasticizers include alkyl esters of sulfonic acids and tol uenesulfonamide. The alkyl esters of sulfonic acids include phenyl esters of alkyl sulfonic acids available from Lanxess under the trademark MESAMOLL. The aromatic phosphate esters include PHOSFLEX (trademark) 31 L isopropyl ated triphenyl phosphate, DISFLAMOLL (trademark) DPO diphenyl-2-ethyl hexyl phosphate, and DISFLAMOL (trademark) TKP tricresyl phosphate. The dialkyl ether aromatic esters include BENZOFLE (trademark) 2 -45 diethylene glycol dibenzoate. The aromatic sulfonamides include K ETJENFLE (trademark) 8 o and p,N-ethyltoluene sulfonamide. .

[0032] Suitable low-polarity plasticizers include one or more aromatic diesters, aromatic triesters, aliphatic diesters, epoxidized esters, epoxidized oils, chlorinated hydrocarbons, aromatic oils, a lkyl ether monoesters, naphthenic oils, alkyl monoesters, glyceride oils, para ffin oils, and silicone oils. Preferable low-polarity plasticizers include alkyl phthalates such as diisononyl phthalate, dioctyl phthalate, and dibutyl phthalate, partially hydrogenated terpene commercially available as " HB-40", epoxy plasticizers, chloroparaff ins, adipic acid esters, castor oil, toluene, and alkyl naphthalenes. ​. The most preferred low-polarity plasticizer is an alkyl phthalate.

[0033] The amount of the low-polarity plasticizer in the adhesive composition imparts the desired rheological properties and is sufficient to disperse the catalyst in the system. The amounts disclosed herein include the amounts added during the preparation of the prepolymer and during the formulation of the adhesive. Preferably, the low-polarity plasticizer is about 5 parts by weight or more, more preferably about 10 parts by weight or more, and most preferably about 18 parts by weight or more, based on the weight of the moisture-curing adhesive. The low-polarity plasticizer is preferably used in an amount of about 40 parts by weight or less, more preferably about 35 parts by weight or less, and most preferably about 30 parts by weight or less, based on the total amount of the moisture-curing adhesive. about 5 parts by weight or more, more preferably The amount of the high-polarity plasticizer in the moisture-curing adhesive is an amount that gives the desired rheological properties and the acceptable sagging and stringing properties of the dispensed moisture-curing adhesive. Preferably, when used, the high-polarity plasticizer is 0.2 parts by weight or more, more preferably 0.5 parts by weight or more, and most preferably 1 part by weight or more, based on the weight of the moisture-curing adhesive. The high-polarity plasticizer is preferably used in an amount of 20 parts by weight or less, more preferably 12 parts by weight or less, and most preferably 8 parts by weight or less, based on the total amount of the moisture-curing adhesive.

[0034] The moisture-curing adhesive may further contain a polyfunctional isocyanate, for example, to improve the elastic modulus of the cured form of the composition or to improve the adhesiveness of the adhesive composition to a specific substrate such as a coated substrate. The "polyfunctional" used in relation to the isocyanate refers to an isocyanate having 2 or more functional groups. The polyisocyanate nominally has about 2 or more

[0035] The moisture-curing adhesive may further contain a polyfunctional isocyanate, for example, to improve the elastic modulus of the cured form of the composition or to improve the adhesiveness of the adhesive composition to a specific substrate such as a coated substrate. The "polyfunctional" used in relation to the isocyanate refers to an isocyanate having 2 or more functional groups. The polyisocyanate nominally has about 2 or more functional groups.​​​​​​​ Any monomeric, oligomeric or polymeric isocyanate having a functionality number of may be used. More preferably, the polyfunctional isocyanate has a nominal functionality number of 2.7 or more. Preferably, the polyfunctional isocyanate has a nominal functionality number of about 5 or less, even more preferably about

[0036] The polyisocyanate may be monomeric; trimers of monomeric isocyanates such as isocyanurates or biurets; oligomeric or polymeric reaction products of one or more units of monomeric isocyanates. Examples of preferred polyfunctional isocyanates include trimers of hexamethylene diisocyanate such as those available from Bayer under the trademarks and designations DESMODUR N3300 and N100, and polymeric isocyanates such as PAPI 580N high molecular weight isocyanate, a polymeric MDI (methylene diphenyl diisocyanate) commercially available from The Dow Chemical Company under the trademark PAPI. The polyfunctional isocyanate, if present, typically affects the modulus of elasticity of the cured composition of the present invention or is present in an amount sufficient to improve the adhesion to the

[0037] The polyfunctional isocyanate, if present, is preferably present in an amount of 0.5 part by weight or more, more preferably 1.0 part by weight or more, and most preferably 2 parts by weight or more based on the weight of the moisture-curing adhesive. The polyfunctional isocyanate is preferably 12 parts by weight or less, They are present in the following amounts.

[0038] The moisture-curing adhesive may also contain a catalyst that catalyzes the reaction between the isocyanate moiety and water or an active hydrogen-containing compound. Such compounds are well known in the art. The catalyst may be any catalyst known to those skilled in the art in the reaction between the isocyanate moiety and water or an active hydrogen-containing compound. Among the preferred catalysts are organotin compounds, metal alkanoates, and tertiary amines. A mixture of catalyst classifications may be used. A mixture of a tertiary amine and a metal salt is preferred. Tertiary amines such as dimorpholinodiethyl ether or triethylenediamine, and metal alkanoates such as bismuth octanoate or dimethyltin dineodecanoate are more preferred. Useful catalysts include organotin compounds such as alkyltin oxides, stannous alkanoates, dialkyltin carboxylates, and tin mercaptides. Stannous alkanoates include stannous octanoate. Alkyl tin oxides include dialkyltin oxides such as dibutyltin oxide and its derivatives. Organotin catalysts are preferably dialkyltin dicarboxylates or dialkyltin dimercaptides. Dialkyltin dicarboxylates with fewer total carbon atoms are more active catalysts in the compositions of the present invention and are therefore preferred. Preferred dialkyldicarboxylates include 1,1-dimethyltin dilaurate, 1,1 -dibutyltin diacetate, and 1,1-dimethyldimaleate. Preferred metal alkanoates include bismuth octoate or bismuth neodecanoate. are included. Dialkyltin oxides include dibutyltin oxide and its derivatives such as dibutyltin oxide. Organotin catalysts are preferably dialkyltin dicarboxylates or dialkyltin dimercaptides. Dialkyltin dicarboxylates with fewer total carbon atoms are more active catalysts in the compositions of the present invention and are therefore preferred. Preferred dialkyldicarboxylates include 1,1-dimethyltin dilaurate, 1,1 -dibutyltin diacetate, and 1,1-dimethyldimaleate. Preferred metal alkanoates include bismuth octoate or bismuth neodecanoate. are included. -dibutyltin diacetate, and 1,1-dimethyldimaleate. Preferred metal alkanoates include bismuth octoate or bismuth neodecanoate. are included.

[0039] ​Organotin or metal alkanoate catalysts are present in an amount, as a percentage of the total weight of the moisture-curing adhesive, usually 60 parts per million or more, preferably 120 parts per million or more, up to a maximum of 1.0 weight percent, preferably 0.5 weight, more preferably 0.1 weight percent. Useful tertiary amine catalysts include dimorpholinodialkyl ethers, di((dialkylmorpholino)alkyl)ethers, bis-(2-dimethylaminoethyl)ether, triethylenediamine, pentamethyldiethylenetriamine, N,N-dimethylcyclohexylamine, N,N-dimethylpiperazine, 4-methoxyethylmorpholine, N-methylmorpholine, N-ethylmorpholine, and mixtures thereof. Preferred dimorpholinodialkyl ethers are dimorpholinodiethyl ether. Preferred di((dialkylmorpholino)alkyl)ethers are (di-(2-(3,5-dimethylmorpholino)ethyl)ether). Tertiary amines, when used, are preferably in an amount of about 0.01 parts by weight or more, more preferably about 0.05 parts by weight or more, even more preferably about 0.1 parts by weight or more, most preferably about 0.2 parts by weight or more, and about 2.0 parts by weight or less, more preferably about 1.75 parts by weight or less, even more preferably about 1.0 parts by weight or less, most preferably about 0.4 parts by weight or less, based on the weight of the moisture-curing adhesive composition. The moisture-curing adhesive can be formulated with fillers other than carbon black and other than additives known in the prior art for use in adhesive compositions. The addition of such materials can provide various beneficial properties to the adhesive.

[0040]

[0041] ​​​​​​​​​​​​​​By changing the viscosity, flow rate, etc., physical properties can be changed. To prevent premature hydrolysis of the moisture-sensitive groups in the socyanate-terminated prepolymer, the filler It must be thoroughly dried before mixing with the other fillers. Other exemplary fillers include clay, Titanium oxide, calcium carbonate, surface-treated silica, titanium oxide, fumed silica, talc In one embodiment, two or more reinforcing fillers are used. It is possible.

[0042] Moisture curing adhesives inhibit and prevent premature crosslinking of isocyanates in the adhesive Stabilizers may also be included. Stabilizers known to those skilled in the art for moisture curing adhesives may be used. Examples of stabilizers include diethyl malonate, alkylphenol alkylate, and Toluenesulfonic acid isocyanate, benzoyl chloride, and alkyl orthoformate The stabilizer is typically present in an amount of about 0.1 weight percent based on the total weight of the moisture-curable adhesive. At least about 0.5 parts by weight, more preferably at least about 0.8 parts by weight. Such stabilizers are used in amounts up to about 5.0 parts by weight based on the weight of the adhesive, more preferably Preferably, it is used in an amount of about 2.0 parts by weight or less, and most preferably, about 1.4 parts by weight or less.

[0043] Other ingredients commonly used in adhesive compositions are used in moisture-curing adhesives. Such materials are well known to those skilled in the art and include, for example, ultraviolet Examples of the additives include stabilizers, antioxidants, and heat stabilizers.

[0044] Moisture curable adhesives are prepared by blending the components together using means well known in the art. It can be compounded by doing. Generally, the components are blended in a suitable mixer. Such blending is preferably carried out in an inert atmosphere in the absence of oxygen and atmospheric moisture to prevent premature reactions. In embodiments where a significant amount of polyester - based isocyanate - functional prepolymer is used, the adhesive composition can be blended at a temperature above the melting point of the polyester - based isocyanate - functional prepolymer and below the temperature at which significant side reactions occur. In this embodiment, the temperature utilized is from 40 °C to less than 90 °C, more preferably 50 °C to 70 °C. After the adhesive composition is compounded, it is packaged in a suitable container so as to be protected from atmospheric moisture and oxygen. Contact with atmospheric moisture can cause premature cross - linking of the polyurethane prepolymer containing isocyanate groups. The adhesive system includes a rapid - curing accelerator that includes any isocyanate - reactive compound having an amino group in the main chain of a polyether or polyol. The isocyanate - reactive compound can have a terminal OH group and at least one amino group in its main chain. The isocyanate - reactive compound having an amino group usually has an average OH functionality number (total moles of OH / total moles of polyol) of more than 2 and up to 5. The average OH functionality number is preferably 2.2, 2.5, 3.0, 3.5, or 3.8 or more, and 4.8, 4.5, or 4.2 or less.

[0045] The isocyanate - reactive compound having an amino group has at least one amino group within its backbone. The backbone is used to produce the isocyanate - terminated prepolymer.

[0046] ​​​​​​​The same may apply to the polyol (e.g., aliphatic, polyether, or polyester backbone) described above. The isocyanate-reactive compound having an amino group can be formed by initiating the formation of the polyol using a polyfunctional amine compound. Usually, essentially all of the amino groups present in the backbone are tertiary amines.

[0047] The average amount of amino groups in the isocyanate-reactive compound having an amino group is usually 1 to 6 . Preferably, the average amount of amino groups present in the polyol having an amino group is at least 1.5, 2, 3.0, 3.5, or 3.8, up to a maximum of 4.8, 4.5, or 4 .2.

[0048] Similarly, the OH value (OH#) of the isocyanate-reactive compound having an amino group can be any useful one to achieve the desired curing rate and workability. Usually, the OH# is at least 25 to 2000. Preferably, the OH value is at least 100, 2 50, 500, and more preferably 550. The OH value is obtained from the wet analytical method of the hydroxyl content of the polyol. This is the milligram of potassium hydroxide corresponding to the hydroxyl content in 1 gram of the polyol or other hydroxyl compound and is given by the following formula:

Equation

[0049] The isocyanate-reactive compound having an amino group can also have any useful molecular weight. Usually, the molecular weight of the polyol is at least 200 to 10,000. Preferably, The molecular weight is at most 5000, 3000, 1500, 1000, 500, or even 400. Preferably, the molecular weight is at least 100, at least 200, or 250. In a preferred embodiment, the isocyanate-reactive compound having an amino group has an average OH functionality of 3.5 to 4 .2 and an OH value of at least 500.

[0050] The curing accelerator may contain a small amount of water, provided that it does not have an adverse effect on the curing rate, workability, and curing properties of the adhesive mixture, such as by causing foaming. The amount of water in the curing accelerator is usually less than 1% based on the total weight of the curing accelerator and the moisture-curing adhesive. Typically, the amount of water is desirably as small as practicable, such as only a trace amount like 500 parts per million of the total weight of the moisture-curing adhesive and the curing accelerator. Preferably, the amount of water is from a maximum of 100 ppm to water-free or essentially water-free, using known methods for determining the water content.

[0051] The curing accelerator may contain one or more other components such as fillers, polyols having no amino groups in the backbone, catalysts, plasticizers, rheology modifiers, UV stabilizers, or other useful components used in moisture-curing adhesives. The fillers, polyols, plasticizers, and catalysts may be any of those described above or known in the art. The respective amounts of these can be determined by the desired amount of isocyanate-reactive groups (e.g., OH), and other physical characteristics such as rheological properties that may be useful to ensure uniform mixing and application of the adhesive system. of the adhesive system.

[0052] A filler, a polyol without amino groups, a catalyst, and a plasticizer are included in the curing accelerator. When they are included, they are typically present in the following amounts. The isocyanate reactive compound having an amino group is typically present in an amount of 5% to 50% by weight of the curing accelerator. The polyol without amino groups is typically present in an amount of 20% to 80% by weight of the curing accelerator. The filler or combination of fillers is typically present in an amount of 10% to 35% by weight of the curing accelerator. The catalyst or combination of catalysts is typically present in an amount of 0.01% to 2% by weight of the curing accelerator.

[0053] The curing accelerator is used to promote the curing of the moisture-curing adhesive. In such a case, the curing accelerator and the moisture-curing adhesive are supplied separately, and otherwise, they will react before coating. Any suitable method can be used to provide two reactive materials having different volumes that are mixed later, such as that described in the co-pending U.S. Patent Application No. 61 / 977,668, filed on April 10, 2014, from line 10 of page 1 to line 8 of page 2. Preferably, the moisture-curing adhesive and the curing accelerator are supplied in a two-component reaction dispensing system as described in the aforementioned U.S. patent application. The moisture-curing adhesive contains an isocyanate-terminated prepolymer and is moisture-curing. Therefore, the isocyanate index of the adhesive system (i.e., 100 times the amount of isocyanate / reactive groups in the curing accelerator) is usually 85 to 200, preferably 100 to 170.

[0054] Similarly, due to the use of the moisture-curing adhesive, usually, with respect to the moisture-curing adhesive, The volume ratio of the curing accelerator is from 5 or 10 to 200, 100, 50, or 20. The iso index is essentially the same for all examples and comparative examples.

[0055] The mixing, application, contact, and curing of the moisture-curing adhesive and the curing accelerator can be carried out by any suitable method known in the art, including those described in the aforementioned US application. Preferably, the mixing, application, and contact are carried out using the method of the above US application.

[0056] The adhesive system of the present invention can be used to integrally bond various substrates. The adhesive system can be used to integrally bond porous and non-porous substrates. The adhesive system is applied to the substrate, and the adhesive on the first substrate is then brought into contact with the second substrate. In a preferred embodiment, the surface to which the adhesive is applied is cleaned and may be primer-treated before application, but the primer is not essential. For example, for typical implementations of application, refer to US Patent Nos. 4,525,511; 3,707,521, and 3,779,794. 3,779,794.

[0057] Typically, the adhesive system is applied under typical ambient conditions (23°C 10°C) in the presence of moisture in the atmosphere (typically 20% - 99% relative humidity). To test the curing behavior, 2 ± 3°C ± 2°C and 50% ± 5% RH are suitable. Curing can be accelerated by adding additional water to the atmosphere or by applying heat during curing of the adhesive, such as by convective heat or microwave heating.

[0058] ​​​​​​​​​​The adhesive system is preferably used to bond glass or plastic coated with an abrasion-resistant coating to other substrates such as metals or plastics. In a preferred embodiment, the first substrate is glass, or plastic coated with an abrasion-resistant coating, a window, and the second substrate is a window frame. In another preferred embodiment, the first substrate is glass, or plastic coated with an abrasion-resistant coating, a window, and the second substrate is an automobile window frame. Preferably, the glass window is cleaned before bonding. The plastic coated with an abrasion-resistant coating can be any clean plastic such as polycarbonate, acrylic resin, hydrogenated polystyrene, or a hydrogenated styrene conjugated diene block copolymer having a styrene content of more than 50 percent. The coating can include any abrasion-resistant coating such as a polysiloxane coating. Preferably, the coating has a light-shielding additive containing an ultraviolet pigment. Preferably, an opaque coating is disposed in the region that will come into contact with the adhesive to block UV light from reaching the adhesive for glass or plastic windows. In a preferred embodiment, the adhesive system is used to replace a window in a structure or vehicle, most preferably in a vehicle. The first step is the removal of the previous window. This can be achieved by cutting the bead of adhesive that holds the old window in place and then removing the old window. Thereafter, the new window is cleaned and, if necessary, primed. The old adhesive on the window flange can be removed, although it is not essential. In a preferred embodiment, the first substrate is glass, or plastic coated with an abrasion-resistant coating, a window, and the second substrate is a window frame. In another preferred embodiment, the first substrate is glass, or plastic coated with an abrasion-resistant coating, a window, and the second substrate is an automobile window frame. Preferably, the glass window is cleaned before bonding. The plastic coated with an abrasion-resistant coating can be any clean plastic such as polycarbonate, acrylic resin, hydrogenated polystyrene, or a hydrogenated styrene conjugated diene block copolymer having a styrene content of more than 50 percent. Preferably, the glass window is cleaned before bonding. The plastic coated with an abrasion-resistant coating can be any clean plastic such as polycarbonate, acrylic resin, hydrogenated polystyrene, or a hydrogenated styrene conjugated diene block copolymer having a styrene content of more than 50 percent. The coating can include any abrasion-resistant coating such as a polysiloxane coating. The coating can include any abrasion-resistant coating such as a polysiloxane coating. Preferably, the coating has a light-shielding additive containing an ultraviolet pigment. Preferably, an opaque coating is disposed in the region that will come into contact with the adhesive to block UV light from reaching the adhesive for glass or plastic windows. Preferably, an opaque coating is disposed in the region that will come into contact with the adhesive to block UV light from reaching the adhesive for glass or plastic windows. In a preferred embodiment, the adhesive system is used to replace a window in a structure or vehicle, most preferably in a vehicle. The first step is the removal of the previous window. This can be achieved by cutting the bead of adhesive that holds the old window in place and then removing the old window.

[0059] Thereafter, the new window is cleaned and, if necessary, primed. The old adhesive on the window flange can be removed, although it is not essential. The first step is the removal of the previous window. This can be achieved by cutting the bead of adhesive that holds the old window in place and then removing the old window. Thereafter, the new window is cleaned and, if necessary, primed. The old adhesive on the window flange can be removed, although it is not essential. , though they are most often left intact, and may be cut flat with a cutting tool. The flanges may be primed with a paint primer, but this is not required. The adhesive system is applied to the periphery of the window in a manner that will contact the window flange when the window is placed in the vehicle. The window with the adhesive on it is then applied in a tape form so that the adhesive is positioned between the window and the flange. Alternatively, the adhesive can be applied to the window flange. The adhesive bead is a continuous layer that acts to seal the joint between the window and the window flange. A continuous bead of adhesive is formed so that the bead joins at each end when they come into contact with the window and frame. The bead is positioned to form a continuous seal between the flange and the adhesive. The adhesive then hardens. be forced to do so.

[0060] The adhesive system is designed to bond large mass substrates, heavier than 20 kg and up to 120 kg, to other substrates. In one class of large mass substrates, the substrates are mass transit vehicles. and large windows such as those used in automobiles (e.g. buses or trains).

[0061] In certain applications, the adhesive system may be utilized with a primer or activating wipe. A primer or activating wipe is typically applied to the surface of the substrate. After the solvent is evaporated, the adhesive system is contacted with a substrate. The time between application of the functionalizing wipe and application of the adhesive system to the substrate should be at least 0.5 minutes. Preferably, it is 1 minute or more, and most preferably, it is 2 minutes or more. EXAMPLES

[0062] The following examples are offered to illustrate the present invention without limiting its scope. is not intended to be. Unless otherwise specified, all parts and percentages are by weight The raw materials used in the moisture-curing adhesive and the non-reactive components used in the curing accelerator are shown in Table 1

[0063] [Table 1]

[0064] Examples 1 and 2 are isocyanate components (Agent A) formulated to have the same Ballan viscosity with the following composition, and the amounts are in weight percentages. The compositions of Examples 1 and 2 are shown in Table 2. In Table 2, the Ballan viscosity is measured from the conditioned material at 23°C. The materials in the measuring cup and storage container are conditioned in a 23°C water bath for at least 1 hour. After transferring the material in the measuring cup without exposing it to air, attach the cup to a Ballan measuring device. The adhesive is extruded from a nozzle with a diameter of 2 mm and a length of 1.8 mm at a pressure of 4 ± 0.01 bar. The extrusion weight per unit time is measured. The pressure-flow viscosity is calculated in g / min

[0065] [Table 2]

[0066] Examples 3 to 6 are polyol components (Agent B) containing a curing agent. The component amounts are described as weight percentages

[0067] Example 3 contains only a "slow" curing agent (i.e., 1,4-butanediol combined with a high molecular weight polyether triol)

[0068] ​​​​​​​​​​Examples 4 to 6 react immediately after being mixed with the isocyanate groups of the isocyanate component. Both a "slow" curing agent and a "fast" curing agent are included. In Examples 4 and 5, the rapid curing agent is an increasing amount of polyether diamine.

[0069] Example 6 contains an alcohol containing a tertiary amine, which catalyzes the alcohol reaction with isocyanate faster than the respective OH groups of 1,4-butanediol within the molecule.

[0070] The compositions of Examples 3 and 6 are shown in Table 3.

[0071]

Table 3

[0072] Regarding Table 2, the isocyanate components Ex.1 and Ex.2 are produced by the following procedure: Put Components 1 and 3 into a mixer and degas under vacuum for 40 minutes. Dry Product 4 in advance and then put it into the mixer and mix at low speed under vacuum for 5 minutes until it is sufficiently wetted with the other products. Slowly increase the speed of the mixer and disperse Product 4 (carbon black) under full vacuum for 40 minutes. Then heat the mixture to 65°C while stirring. Preheat Component 2 to the same temperature of 65°C and then add it. Then turn off the heating and activate the cooling to cool to 40°C. Next, add Components 5 to 10 and mix under vacuum for another 1 hour. Then, cool the mixer to ambient temperature and take out the moisture-curing adhesive into a container under dry conditions.

[0073] Examples and comparative examples of the curing accelerator are shown in Table 4. Each of these is produced in the same procedure in principle as follows. Regarding Table 3, put Components 1 and 4 into a mixer and under vacuum ​​​​ Degas for 30 minutes. Then, add the pre-dried components 5-8 and mix them slowly at low speed for 5 minutes under vacuum until they are sufficiently wetted by the other products. Slowly raise the speed of the mixer and disperse the added components 5-8 for 40 minutes under full vacuum. Finally, add Products 2 and 3 and mix for 20 minutes under vacuum. Then, remove the mixture to a sealed container.

[0074] Each of the curing accelerator formulations shown in Table 4 is placed into an adhesive dispensing system (two-component sausage), together with the above moisture-curing adhesive, as described in Example 1 of U.S. Patent Application No. 61 / 977668. The volume ratio of the moisture-curing adhesive to the curing accelerator is 9 to 1. For each example and comparative example, the isocyanate index is essentially the same. The moisture-curing adhesive and the curing accelerator are dispensed in the same manner as described in Example 1 of the aforementioned U.S. patent application.

[0075] The compositions of Comparative Example A and Examples 8-11 are shown in Table 4.

[0076] The following properties for Comparative Example A and Examples 8-11 are measured and reported in Table 4:

[0077] The "deck" performance is measured using a penetrometer. Apply a triangular adhesive bead with a triangular nozzle having a base of 7 mm and a height of 14 mm. Hold a 115 g weight (100 g weight + 15 g connecting rod) precisely placed at the tip of the adhesive bead. Release the grip of the weight for 5 seconds and sink it into the adhesive bead. The penetration depth is measured in millimeters. The penetration depth is measured directly 1 minute after the application of the adhesive bead and then ​​​​​​​​​​​​​​, it is measured every 2 minutes until the adhesive can no longer be easily pushed in. The deck performance immediately after mixing in the static mixer at time 0 is predicted by the time the adhesive can be pushed in or the linear approximation of the maximum penetration depth in the first 20 minutes.

[0078] "Impact strength" is determined by the GEX method 344. A metal coupon is placed in the sample holder. The adhesive is applied between the plungers and allowed to overflow onto the tape. Then, the coupon (76×25×5 mm) is placed on the plungers, and the excess adhesive is gently removed with a spatula, ensuring that the bead can withstand being in the complete shape (25×13×5 mm). The specimen is then stored at the desired cure times (e.g., 15 minutes and 30 minutes) and environmental conditions. Then, the impact pendulum is lifted and latched in place, the specimen is fixed in position, and the hammer is released (using a 10-pound hammer). The total energy that the adhesive can withstand before catastrophic failure is measured in joules;

[0079] "Lap shear strength" is measured in accordance with DIN EN527 using a shear strength device Zwick 1435 equipped with an appropriate fixture, e.g., FHM8606.00.00 or 86 06.04.00 mounting fixture. A lap shear test specimen with an adhesive bonding dimension of 10×25×1.5 mm is used. The lap shear test specimens are tested after cure times of 1 hour, 2 hours, 4 hours, and 7 days at 23°C / 50% relative humidity; "Tensile properties: strength, elongation, and modulus of elasticity E" are determined in accordance with DIN EN ISO527-1.

[0080]

Table 4

[0081] To analyze the effect of the fast curing agent on deck performance, the deck height decrease over 20 minutes or the open time of the adhesive was linearly approximated (Figure 1). Linear fitting was used to extrapolate and estimate the deck height at time t = 0. The linearly approximated deck height at 0 minutes for Comparative Example A of 7.3 mm is higher than that of Example 8 of the present invention of 6.5 mm. When 10% of Jeffamine SD-2001, which is a secondary polyether diamine, is blended in the accelerator component, the initial deck height decreases by 11%.

[0082] As shown in Figure 2, for Example 10, the addition of 20% Jeffamine SD-2001 (secondary polyether diamine) further reduces the linearly approximated deck height at 0 minutes to 5.5 mm. This improves the initial deck height by 1.8 mm or the relative height by 25%. In addition to the positive effect on the initial deck height, both formulations show improved impact peel strength at 15 and 30 minutes compared to Comparative Example A due to a higher conversion rate at that time due to the reaction of the faster curing agent.

[0083] As shown in Figure 2, for Example 10, the addition of 20% Jeffamine SD-2001 (secondary polyether diamine) further reduces the linearly approximated deck height at 0 minutes to 5.5 mm. This improves the initial deck height by 1.8 mm or the relative height by 25%. In addition to the positive effect on the initial deck height, both formulations show improved impact peel strength at 15 and 30 minutes compared to Comparative Example A due to a higher conversion rate at that time due to the reaction of the faster curing agent. higher conversion rate at that time due to the reaction of the faster curing agent, compared to Comparative Example A show improved impact peel strength at 15 and 30 minutes.

[0084] Examples 9 and 11 use the polyol component Example 6 of the present invention containing triethanolamine as the fast curing agent. The linearly approximated deck height at 0 minutes corresponds to 5.3 mm and 5.0 mm (Figure 2), which is significantly lower compared to Comparative Polyol Component Example 3 of 7.3 mm. The trifunctional triethanolamine results in faster crosslinking due to a larger number of functional groups, which usually leads to a faster development of strength over time. Open crosslinking, which usually results in a faster development of strength over time. Open​​​​​​​​​ The time is still long enough in all examples, being 10 minutes or more.

Claims

1. A) an isocyanate-terminated prepolymer; B) a curing accelerator; and an adhesive system comprising a moisture-curing adhesive, 、 i) 1) a primary, secondary, or tertiary amino group, or a primary thiol group; and 2) Isocyanate-reactive compounds containing 2 to 7 OH, NH, and / or SH functional groups and, ii) A polyol that does not have a primary, secondary, or tertiary amino group, or a primary thiol group. a polyol selected from diols and / or triols; 4. An adhesive system comprising:

2. The isocyanate-reactive compound (i) is a compound having 2 to 4.5 OH, NH, and / or S groups.

10. The adhesive system of claim 1 having H functionality.

3. The amount of the isocyanate-reactive compound (i) is less than 5% by weight of the curing accelerator (B).

2. The adhesive system of claim 1, wherein

4. 2. The adhesive system of claim 1, wherein said polyol (ii) is butanediol.

5. The adhesive system of claim 1 , wherein the accelerator is essentially free of water.

6. 2. The method of claim 1 , wherein the prepolymer comprises an isocyanate-terminated polyether prepolymer.

1. The adhesive system according to claim 1.

7. The isocyanate-terminated polyether prepolymer is 5. The method of claim 4, further comprising administering to said subject the present invention a method comprising administering to said subject the present invention, Adhesive type.

8. The moisture-curable adhesive contains no filler, no plasticizer, no polyisocyanate monomer or no olefin.

10. The adhesive system of claim 1 further comprising one or more of a ligomer or a catalyst.

9. The moisture-curable adhesive comprises a plasticizer that is linear, branched, or a combination thereof. The adhesive system of claim 11.

10. a) A) an isocyanate-terminated prepolymer; B) preparing a moisture-curable adhesive composition containing a curing accelerator, The accelerator, i) 1) a primary, secondary, or tertiary amino group, or a primary thiol group; and 2) Isocyanate-reactive compounds containing 2 to 7 OH, NH, and / or SH functional groups and, ii) A polyol that does not have a primary, secondary, or tertiary amino group, or a primary thiol group. and a polyol selected from diols and / or triols, The isocyanate-terminated prepolymer and the curing accelerator are prepared separately; b) mixing the curing accelerator with the isocyanate-terminated prepolymer to form an adhesive mixture; forming c) applying the adhesive mixture to at least a portion of a first substrate; d) contacting the substrate having the adhesive mixture thereon with a second substrate to form the adhesive. the mixture of agents being between them; and e) allowing the adhesive mixture to cure and bond the substrates together; 16. A method for accelerating the cure of an adhesive composition, comprising:

11. Step b) is carried out using an automatic application device from a 1K application gun or drum. Item 11. The method according to item 10.

12. The first substrate is a substrate having at least a portion that is optically transparent, and the second substrate is The method of claim 10, wherein the material is a vehicle or a building.

13. The adhesive mixture is applied to the opaque portion that is in contact with the second substrate. The method of claim 12 , wherein one substrate comprises:

14. The method of claim 13 , wherein the first substrate is glass or polycarbonate.

Images