Rapid development of curing polyurethane adhesive compositions

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 joining glass to vehicles and buildings. In particular, the present invention relates to a separate curing accelerator comprising two curing agent components having different curing rates: one component that improves the stability of the bead within the first few minutes due to its fast curing rate, and another component that exhibits strength rapidly while allowing for a sufficient open time due to its slow curing rate, in combination with a moisture-curing isocyanate-terminated prepolymer adhesive composition.

Background Art

[0002] One-component moisture-curing adhesive compositions have been used to join 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. 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 ​​​​​Since the car won't be driven very far for the first few days after the windows are installed, the curing speed isn't a major issue. do not have.

[0003] In contrast, if a vehicle requires window replacement, it is often driven immediately afterward. The replacement is often done remotely by an installer working from the vehicle, or controlled It is done under conditions where it has not been done. As a result, the vehicle owner can do as much as possible after the windows have been installed. Since the desire is to drive the vehicle as soon as possible, the curing speed is important. A one-component moisture-curing adhesive useful for easily replacing vehicle windows, U.S. price 5,976,305 Specification No.; as described in Specification Nos. 6,709,539 and Nos. 7,226,523. These adhesives exhibited sufficient integrity to allow for driving in a short time. However, it still takes a much longer time to fully harden, and temperature and relative temperature also play a role. Depending on ambient conditions such as humidity, it exhibited inconsistent curing.

[0004] An isocyanate-functional compound or prepolymer in one liquid, and an isocyanate reaction Two-component compositions containing compounds and / or prepolymers having a property component have also been used. Generally, two liquids, referred to as Agent A and Agent B, are understood to have essentially the same volume. One liquid contains an isocyanate-functional compound or prepolymer, and the other liquid contains an isocyanate Examples of two-component compositions containing compounds and / or prepolymers having reactive components are found in Europe. Japanese Patent No. 1,524,282 and U.S. Patent No. 5,852,103; the same Specification No. 6,709,539; Specification No. 7,101,950; and Specification No. 7,361, This is disclosed in Specification No. 292. However, these hold the two liquids separately. Therefore, they tend to have problems with complex delivery systems and distribution in order to achieve uniform products. Thorough mixing is also required during this process. Similarly, two-part adhesive compositions tend to react quickly. Yes, it forms a skin that can be replaced under specific conditions (higher temperature and higher relative humidity). This may result in insufficient working time to properly position the windows. Therefore The two-component composition is applied to the car window so that the car can be driven within 30 minutes of the window being attached to the car. Even if replacement is possible, these usually do not enable faster running time. Care must be taken to ensure that a uniform adhesive bead is obtained.

[0005] More recently, an isocyanate-terminated prepolymer in one liquid and an action in the other liquid A two-component dual-curing adhesive composition composed of lyl acrylate monomer has been internationally disclosed. It is described in pamphlet No. 2012 / 151085. In this composition, one of the liquids The solution contains an isocyanate-terminated polyether prepolymer, and the other solution undergoes hydroperoxide formation. The compound comprises an acrylic or acrylate monomer, and the hydroperoxide compound is the other. When mixed with liquid, it is reduced to form free radicals, which are the initial polyacrylic or polyacrylic compounds. The development of the relative matrix allows for sufficient integrity, enabling relatively fast travel. Time is made possible. However, working time, bead consistency, workability, and final curing characteristics. Sex was not desirable.

[0006] Therefore, it hardens sufficiently to allow driving in a short time, such as 15 minutes, while maintaining consistent uniformity. A smooth adhesive bead and excellent workability under various ambient conditions (when placing or manipulating glass). to be able to obtain a time (while still obtaining sufficient adhesive strength) to make it possible to join the glass to the structure in a short running time It would be desirable to obtain an adhesive that can run in a short time for joining the glass to the structure. SUMMARY OF THE INVENTION MEANS FOR SOLVING THE PROBLEM

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

[0008] In a preferred embodiment of the present invention, the isocyanate-reactive compound (i) has 2 to 4.5<00G0090>OH, NH, and / or SH functional groups and is present in an amount of less than 5% by weight of the curing accelerator (B). 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,<COOOOG6>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, Alternatively, a polyol that does not have a tertiary amino group or a primary thiol group, and a diol and A polyol selected from bi and / or triols, wherein component B) is essential A process in which the isocyanate-terminated prepolymer and the curing accelerator are prepared separately, without the presence of water. b) Mix the curing accelerator and the isocyanate-terminated prepolymer to form an adhesive mixture. Steps: a) Applying the adhesive mixture to at least a portion of the first substrate; d) Applying the adhesive mixture A substrate having the compound on it is brought into contact with a second substrate, and the adhesive mixture is between them. A step to make it so; and a step to cure the adhesive mixture and join the substrates together. A method for promoting the curing of an adhesive composition consisting of these, which includes, essentially, these. Preferably, the first substrate is a substrate in which at least a portion of the substrate is optically transparent. Yes, the second substrate is a vehicle or building, and more preferably the first substrate is an adhesive mixture. A coating is applied, and it has an opaque portion that comes into contact with a second substrate, preferably the first substrate being glass. Alternatively, it is a method using polycarbonate. [Brief explanation of the drawing]

[0010] [Figure 1] This is a plot of deck height versus time for Comparative Example A and Example 8. [Figure 2] This is a plot of deck height versus time for Examples 9-11. [Modes for carrying out the invention]

[0011] The present invention relates to a formulation of accelerated polyurethane adhesive that cures regardless of humidity, and This method uses the aforementioned accelerated polyurethane adhesive. The adhesive of the present invention is a 2K adhesive. The curing performance of the adhesive is determined from a 1K polyurethane adhesive cartridge, sausage, or drum. Application of 1K adhesive using a standard 1K application gun, which is typically used in automated application equipment. It will be shown in conjunction with performance.

[0012] In one embodiment, the adhesive of the present invention is used in peeler cartridges or sausage solutions. Applied using 2K packaging solutions for sausages and other products in the market. These are used together with a standard 1K coating gun in combination with a static mixer. This is possible. For example, U.S. Patent No. 9,821,512 (this is by reference to the present invention). See (included in the details). To use the static mixer, both The viscosity of the adhesive component needs to be lowered to allow for a sufficiently fast application speed.

[0013] Conventional adhesives require mixing of both components using a static mixer. Low degree of beading is typically referred to as deck performance, which is the beading against window sinking. This invention reduces the stability of the window. The present invention allows the window to be placed on the adhesive immediately after the adhesive is applied (deck To enable this, the strength develops rapidly, and at the same time, the developed strength does not open up the adhesive. We are working on using low-viscosity adhesive formulations that do not negatively impact lap times. From the time when the adhesive starts to have sufficient strength to hold the window (deck height ≤ 5.5 mm), The bead becomes too strong, making it impossible to press the window into the adhesive bead for a certain amount of time. A length of at least 10 minutes can be obtained up to a deck height of ≥1.7 mm. The adhesive of the invention is "rapid" and increases bead stability within the first few minutes. It has a "slow" curing speed, and while it allows for sufficient open time, it still Using two types of curing agents with different curing rates, a second curing agent that enables rapid strength development. This is achieved by incorporating polyol components. The rapid curing agent is an isocyanate reaction. A compound, preferably an amine, preferably a primary, secondary, or tertiary amino group, and / or This is a polyol containing a thiol, preferably a primary thio group, and is an isocyanate-reactive compound. The material preferably has 2 to 7 OH, NH, and / or SH functional groups. The slow curing agent is Diols or triols that do not have a primary, secondary, or tertiary amino group, or a primary thiol group. Polyols selected from all, for example, polyetherdiols or alkyldiols ( For example, 1,4-butanediol.

[0014] The moisture-curing adhesive composition of the present invention, which contains an isocyanate-terminated prepolymer, is used in vehicles. Desired for installing replacement glass when repairing chipped or broken glass. While still having sufficient working time and final curing characteristics, it can be cured in a significantly shorter time. It was found that this could be done. For example, this adhesive mixture can be used in 5, 8, 10, and even 15 minutes. While it may require some working time, it basically hardens in 60 minutes. Similarly, the method of the present invention This allows for consistent application of these moisture-curing adhesives under vastly different ambient conditions.

[0015] The adhesive system of the present invention can be used to integrally bond various substrates. Examples of materials include plastics, glass, wood, ceramics, metals, and wear-resistant coatings. Examples include coated substrates such as plastics coated with a coating. The adhesive system of the present invention can be used to integrally bond similar and dissimilar substrates. The adhesive is used to bond glass or plastic to a vehicle with an abrasion-resistant coating on top. The composition of the present invention is particularly useful for bonding to other substrates such as automobiles and buildings. The object is used to join together the parts of modular components such as vehicle module components. It is also useful for glass or plastic coated with abrasion-resistant coatings. It can be bonded to the coated and uncoated parts of the vehicle. Cut.

[0016] The composition of the present invention is particularly useful for joining replacement windows to a structure. The adhesive is It is pump-transferable, resistant to sagging, and can bond components together at temperatures from -10°C to 45°C. The composition is preferably prepared under typical ambient conditions (i.e., a temperature of -10°C to 35°C). Under relative humidity of 25% to 75%, the uncured sample should not sag more than 2 mm, and 1.5 It has a deck strength of 15 pounds. Preferably, the adhesive is sufficient to hold the window in place. From the moment it gains strength, the strength of the adhesive bead is sufficient to press the window into the adhesive bead. The deck height at its highest point is between 1.0 mm and 5.5 mm.

[0017] This allows the adhesive prepared from the composition of the present invention to be applied over a wide range of ambient temperatures. This becomes possible. Heating of the material is not required for adhesive application. Surprisingly, this adhesive The adhesive type offers rapid curing, allowing the vehicle to be driven even after just 30 minutes, and also allows for immediate application. The decking force is sufficient to allow the windshield to be positioned later, and to allow for repositioning. It was found that a unique and superior combination could be provided to realize time.

[0018] The term "nominal" as used in relation to functional cardinals refers to the theoretical functional cardinal, and this is usually the case. It can be calculated from the stoichiometry of the raw materials used. Generally, the actual number of functional groups is calculated from the raw materials. The results differ due to imperfections in the reagents, incomplete conversion of the reactants, and the formation of by-products.

[0019] Preferred polyisocyanates for use in the preparation of prepolymers are, for reference, From column 3, line 32 of U.S. Patent No. 5,922,809, which is incorporated herein by reference Examples include those disclosed in column 4, line 24. Preferably, polyisocyanates are , diphenylmethane-4,4'-diisocyanate, isophorone diisocyanate, teto Aromatic or alicyclic polyisocyanates such as methylxylene diisocyanate, Most preferably, diphenylmethane-4,4'-diisocyanate. Diols and Triols are commonly referred to as polyols.

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

[0021] Polyether polyols such as polyester polyols known in the art It is also understood that small amounts of other polyols can be used to form polymers. Typical Other polyols such as the poly used to produce the prepolymer It may be present in an amount of up to 5% by weight of all. However, the prepolymer is such It may be manufactured in the absence of polyols.

[0022] The isocyanate-terminated prepolymer can be polymerized in any preferred manner, such as bulk polymerization or solution polymerization. It can be prepared by method. The reaction to prepare the prepolymer is carried out under anhydrous conditions, preferably in nitrogen. Under an inert atmosphere such as a plain blanket, the crosslinking of isocyanate groups by moisture in the atmosphere This is done to prevent it. The reaction is determined by titration of the sample to determine the residual isocyanate content. The temperature range is 0°C to 150°C, more preferably 25°C to 9°C, until the quantity approaches the desired theoretical value. This can be done at a temperature of 0°C. "Isocyanate content" is calculated based on the total weight of the prepolymer. This refers to the weight percentage of the isocyanate moiety. Reaction for preparing prepolymers. This can be done in the presence of a urethane catalyst. An example of such is octane. Carbohydrates such as stannous acid, stannous oleate, stannous acetate, and stannous laurate Examples include stannous salts of nitrate. Also, dibutyltin dilaurate and dibutyltin dilaurate. Dialkyltin dicarboxylates such as cete, as well as tertiary amines and tin mercaptites Similarly, urethane catalysts are known in the art. Preferably, the prepolymer is The reaction for preparation is catalyzed by stannous octanoate. The amount of catalyst used is Generally, depending on the properties of the isocyanate, 0.005 to 5 parts by weight of the catalyzed mixture. Preferably, the reaction is carried out in a mixture with a plasticizer, which is described in detail below.

[0023] Moisture-curing adhesives generally also contain fillers such as carbon black. Depending on its structure and the molecular weight of the prepolymer, the oil absorption capacity (ASTM D-2) of the buck is determined. As shown in 414-09), it can extend to a wide range of structures. For example, carbon black Typically, it has an oil absorption capacity (OAN) of 80-200 cc per 100 grams. It is desirable to do so. Preferably, the carbon oil absorption is at least 90, more preferably is at least 100, most preferably at least 110 to preferably up to 180, more Preferably, the maximum is 165 ccs / 100 grams, most preferably a maximum of 150 ccs / 100 grams.

[0024] The appropriate amount of carbon black can be determined for a given amount of carbon black. Typically, the amount of carbon black in the adhesive composition is in the order of increasing preference. At least 10% by weight, 15% by weight, up to a maximum of 38% by weight, in order of increasing preference. The weight is 35%, 32%, 30%, or 28%.

[0025] The carbon black used is standard carbon black that has not been specially treated to be non-conductive. It may be carbon black. Standard carbon black is specially surface-treated or oxidized. It is a carbon black that is not conductive. Or, one or more types of non-conductive carbon black are used. These can be used alone or in combination with standard carbon black. As for the shoes, the RAVEN (trademark) 790 and RAVE are available from Colombian. N (trademark) 450, RAVEN (trademark) 500, RAVEN (trademark) 430, RAVEN (Trademark) 420 and RAVEN (Trademark) 410 Carbon Black, and from Cabot Available ELFTEX S5100, S7100, and MONARCH 120, 57 CSX Carbon Black, such as 0 and 590, and Evonik Industri PRINTEX® 30 Carbon Black, available from es, Mobile, AL. Examples include Colombian Che RAVEN (commercial) available from micals Company, Marietta, GA Examples include (Trademark) 1040 and RAVEN (Trademark) 1060 carbon black.

[0026] Moisture-curing adhesives may also contain reactive silicon. Reactive silicon is a silane. It can exist as any separate molecule. This may be located within the skeleton, or as described above. Reactive silicon may be present as terminal groups in the repolymer. Reactive silicon is typically rated at a strength of 6. Hydration, such as what is described in the fourth column, lines 25-55 of the specifications for Nos. 613 and 816. It is capable of receiving a solution. Other exemplary reactive silicon is described in U.S. Patent Application Publication No. Paragraphs 0055 to 0065 of Specification No. 2002 / 0100550, and Hsie h is described in column 5, line 27 to column 6, line 41 of U.S. Patent No. 6,015,475. It is being done.

[0027] The amount of reactive silicon present in moisture-curing adhesives is usually the total amount of the adhesive composition. This is 0.001% to 2% by weight. (Note: This is the amount of reactive silicon, measured by the weight of silicon itself.) (For example, it does not contain any organic groups attached to it) at least of the adhesive composition 0.005%, 0.01%, 0.02%, 0.04%, 0.06%, 0.08%, or 0 From 0.1%, up to a maximum of 1.8%, 1.6%, 1.4%, 1.2%, 1%, 0.8%, and 0.5%. That's fine.

[0028] Moisture-curing adhesives may also contain one or more organic polymers dispersed within them. Preferably, the organic polymer is dispersed in a dispersion tray in which particles of the organic polymer are dispersed. By including ols, they are included in the prepolymer. Dispersed triols are typically It is understood that at least a portion of the particles are grafted with polyol. Preferred dispersion Triol is incorporated herein by reference by Zhou's U.S. 6,709,5 This is disclosed in column 4, line 13 to column 6, line 18 of specification No. 39. Preferably, organic particles The triol used to disperse the offspring is a polyethertriol, which is preferable. Preferably, it is a polyoxyalkylene-based triol. Preferably, such a poly Polyoxyalkylene oxide triol is a polyoxyethylene end cap. Contains a rioxypropylene chain. Preferably, the triol is 3,000 or more, more preferably It has a molecular weight of 4,000 or more, most preferably 5,000 or more. Preferably, Triols like the one described have a molecular weight of 8,000 or less, more preferably 7,000 or less. To produce the prepolymer compositions described herein, a dispersed polyol polyol A polyol (e.g., a triol) is contained in the polyol, and the copolymer particles of the dispersed polyol are composed of It is understood that it is a filler in a substance.

[0029] Moisture-curing adhesives typically further contain plasticizers. Plasticizers are used to enhance rheological properties. It can be used to change the consistency. Such materials do not contain water and It must be inert to isocyanate groups. Plasticizers are used in polyurethane adhesives. It may be a general plasticizer that is useful in the process and is well known to those skilled in the art, and this will be discussed later. These are called polar plasticizers. Plasticizers are effective in dispersing isocyanate-terminated prepolymers. It is present in a small amount. The plasticizer is also present during the preparation of the prepolymer before being placed in the first part. It can be added to the prepolymer in any of the prepolymer formulations. Preferably The plasticizer is approximately 1% by weight of the prepolymer formulation (prepolymer plus plasticizer). More preferably about 20% by weight or more, most preferably about 30% by weight The above is present. Preferably, the plasticizer is present in about 45% by weight of the prepolymer formulation. They are present, more preferably, at a weight of about 35 percent or less.

[0030] Preferably, two plasticizers are used, one being a highly polar plasticizer and the other a low polar plasticizer. It is a polar plasticizer. High-polarity plasticizers are polar more polar than aromatic diesters such as phthalates. These are plasticizers with high polarity. Low-polarity plasticizers have the same or lower polarity as aromatic diesters. It is a plasticizer with the following polarity.

[0031] Suitable high-polarity plasticizers include alkyl esters of sulfonic acids and alkylalkyl esters. Polyester diester, polyester resin, polyglycol diester, high polymer polyester Tricarboxylic acid esters, dialkyl ether diesters, dialkyl ether aromatics One or more of the following are esters, aromatic phosphate esters, and aromatic sulfonamides Examples include aromatic sulfonamides and aromatic phosphoric acid. More preferred highly polar plasticizers include aromatic sulfonamides and aromatic phosphoric acid. Examples include esters, dialkyl ether aromatic esters, and alkyl esters of sulfonic acids. The most preferred highly polar plasticizers are alkyl esters of sulfonic acid and tol Examples include sulfonates. Alkyl esters of sulfonic acids include Lanxess It contains alkyl sulfonate phenyl ester, available under the trademark MESAMOLL. Aromatic phosphate esters include PHOSFLEX (trademark) 31 L isopropylated Diphenyl phosphate ester, DISFLAMOLL (trademark) DPO diphenyl-2-ethyl Luhexyl phosphate and DISFLAMOL® TKP tricresyl phosphate It contains dialkyl ether aromatic esters, including BENZOFLE(trademark)2. -45 contains diethylene glycol dibenzoate. Aromatic sulfonamides include K ETJENFLE(trademark)8 contains o and p,N-ethyltoluenesulfonamide. .

[0032] Suitable low-polarity plasticizers include one or more aromatic diesters, aromatic triesters, Aliphatic diesters, epoxidized esters, epoxidized oils, chlorinated hydrocarbons, aromatic oils, A Lukyl ether monoester, naphthenic oil, alkyl monoester, glyceride oil, parabens Examples include fin-based oils and silicone oils. Preferred low-polarity plasticizers include phthalic acid. Alkyl phthalates such as diisononyl, dioctyl phthalate, and dibutyl phthalate, Partially hydrogenated terpene, epoxy plasticizer, chloroparaffin, which is sold commercially as "HB-40" Examples include phosphates, adipic acid esters, castor oil, toluene, and alkylnaphthalenes. The most preferred low-polarity plasticizer is alkyl phthalate.

[0033] The amount of low-polarity plasticizer in the adhesive composition is such that it imparts the desired rheological properties and maintains the system This is a sufficient amount to disperse the catalyst. The amounts disclosed herein are used during the preparation of the prepolymer. and the amount added to the adhesive formulation. Preferably, the low-polarity plasticizer is used in moisture-curing adhesives. Based on the weight of the adhesive, approximately 5 parts by weight or more, more preferably approximately 10 parts by weight or more, It is used in an amount of approximately 18 parts by weight or more. Low polarity plasticizers are preferably moisture-curing adhesives. Based on the total amount of the agent, approximately 40 parts by weight or less, more preferably approximately 35 parts by weight or less, most preferably It is used in quantities of approximately 30 parts by weight or less.

[0034] The amount of highly polar plasticizer in a moisture-curing adhesive depends on the desired rheological properties and distribution. This is the amount that gives the moisture-curing adhesive acceptable sagging and stringing properties. Preferably When used, the high-polarity plasticizer should be 0.2 parts by weight based on the weight of the moisture-curing adhesive. More preferably 0.5 parts by weight or more, and most preferably 1 part by weight or more, of a moisture-curing type. Used in adhesives. The high-polarity plasticizer is preferably added based on the total amount of the moisture-curing adhesive. and 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. It is used.

[0035] Moisture-curing adhesives are used, for example, to improve the elastic modulus of a cured composition, or to coat To improve the adhesion of adhesive compositions to specific substrates such as coated substrates, a multifunctional I It may contain more isocyanates. The term "polyfunctionality" used in relation to isocyanates is 2 This refers to isocyanates having the above number of functional groups. Polyisocyanates nominally have approximately 2 or more. Any monomeric, oligomeric, or polymeric isocyanate having the number of functional groups It may also be the case that the polyfunctional isocyanate has 2.7 or more nominal functional groups. It has a number. Preferably, the polyfunctional isocyanate is about 5 or less, more preferably about It has a nominal number of functional groups of 4.5 or less, most preferably about 3.5 or less.

[0036] Polyisocyanates are monomers; trimers of monomeric isocyanates Rate or biuret; oligomeric or polymeric monomeric isocya The reaction product may be several units of a nate. Examples of preferred polyfunctional isocyanates. As for trademarks and names, DESMODUR N3300 and N100 are used by Bayer. Hexamethylene diisocyanate trimers, as well as PAPI, which are available from various sources. PAPI trademarks, including 580N polymer isocyanate, are used by The Dow Chemistry. Polymeric MDI (methylenedioxide) such as those sold by Al Company. Examples include polymeric isocyanates such as phenyl diisocyanate. If present, socianates typically affect the elastic modulus of the cured composition of the present invention. It is present in an amount sufficient to provide or improve adhesion to the specific substrates mentioned above.

[0037] If present, the polyfunctional isocyanate preferably adds to the weight of the moisture-curing adhesive. As a guideline, 0.5 parts by weight or more, more preferably 1.0 part by weight or more, and most preferably 2 parts by weight or more. It is present in amounts greater than or equal to 1 part. The polyfunctional isocyanate is based on the weight of the moisture-curing adhesive. Preferably 12 parts by weight or less, more preferably 8 parts by weight or less, and most preferably 4 parts by weight. It exists in the following quantities.

[0038] Moisture-curing adhesives react with water or an active hydrogen-containing compound. This may also include catalysts. Such compounds are well known in the art. The catalyst is isopropyl alcohol. Any reaction between the annealing moiety and water or an active hydrogen-containing compound known to those skilled in the art It may be a catalyst. Preferred catalysts include organotin compounds, metal alkanoates, and Examples include tertiary amines. A mixture of catalyst classifications may be used. Tertiary amines and metal salts A mixture with dimorpholinodiethyl ether or triethylenediamine is preferred. Tertiary amines, and metals such as bismuth octanoate or dimethyltin dineodecanoate. Alkanoates are even more preferred. Useful catalysts include alkyltin oxides and stannous alkanoates. Noates, dialkyltin carboxylates, and organotin compounds such as tin mercaptides It contains substances. Stannous alkanoates include stannous octanoate. Alkyl Tin oxides include dialkyltin oxides such as dibutyltin oxide and its derivatives. It contains . The organotin catalyst is preferably dialkyltin dicarboxylate or dia It is a dialkyltin dicarboxy with fewer total carbon atoms. Since the rates are more active catalysts in the compositions of the present invention, they are preferred. The dialkyldicarboxylates include 1,1-dimethyltin dilaurate, 1,1 -Includes dibutyltin diacetate and 1,1-dimethyl dimaleate. Preferred Metallic alkanoates include bismuth octoate or bismuth neodecanoate. ru.

[0039] The organotin or metal alkanoate catalyst is present in a percentage of the total weight of the moisture-curing adhesive. As a general rule, typically 60 parts per million or more, preferably 120 parts per million or more. From the top, up to 1.0 weight percent, preferably 0.5 weight, more preferably 0.1 weight It exists in a percentage amount.

[0040] Useful tertiary amine catalysts include dimorpholino dialkyl ethers and di((dialkyl (Mormorpholino)alkyl) ether, bis-(2-dimethylaminoethyl) ether, Diethylenediamine, pentamethyldiethylenetriamine, N,N-dimethylcyclohex Silamine, N,N-dimethylpiperazine 4-methoxyethylmorpholine, N-methyl methyl Examples include dimorpholine, N-ethylmorpholine, and mixtures thereof. Preferred dimorpholine The linodialkyl ether is dimorpholinodiethyl ether. Preferred di((di (di-(2-(3,5-dimethylmorpholino)alkyl) ether is (di-(2-(3,5-dimethylmorpholino) It is an ethyl ether. When used, tertiary amines are preferably moisture-curable. Based on the weight of the adhesive composition, approximately 0.01 parts by weight or more, more preferably approximately 0.05 parts by weight. At least 0.1 parts by weight, more preferably about 0.1 parts by weight or more, and 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 It is used in an amount of approximately 1.0 part by weight or less, most preferably approximately 0.4 parts by weight or less.

[0041] Regarding the use of moisture-curing adhesives other than carbon black and in adhesive compositions: It can be compounded with fillers other than additives known in the prior art. Addition of such materials This allows for the modification of physical properties such as viscosity-flow rate. However, To prevent premature hydrolysis of the moisture-sensitive groups of the socio-cyanate-terminated prepolymer, the filler is used. It needs to be thoroughly dried before mixing. Other exemplary fillers include clay, two Titanium dioxide, calcium carbonate, surface-treated silica, titanium dioxide, fumed silica, talc Examples include wollastonite. In one embodiment, two or more reinforcing fillers are used. It is possible.

[0042] Moisture-curing adhesives suppress and prevent premature crosslinking of isocyanates in the adhesive. It may also contain stabilizers. Stabilizers known to those skilled in the art can be used for moisture-curing adhesives. Examples of stabilizers include diethyl malonate, alkylphenol alkylate, and Latoluenesulfonate isocyanate, benzoyl chloride, and alkyl orthoformate It can be listed as follows: The stabilizer is typically about 0.1 times the total weight of the moisture-curing adhesive. Use in an amount of 0.5 parts by weight or more, preferably about 0.5 parts by weight or more, more preferably about 0.8 parts by weight or more. Such stabilizers are used. Preferably, the amount of stabilizer is about 5.0 parts by weight or less, based on the weight of the adhesive. It is used in an amount of approximately 2.0 parts by weight or less, most preferably approximately 1.4 parts by weight or less.

[0043] Other components commonly used in adhesive compositions are used in moisture-curing adhesives. Such materials can be used. Such materials are well known to those skilled in the art, and they include ultraviolet light. Examples include stabilizers, antioxidants, and heat stabilizers.

[0044] Moisture-curing adhesives are made by blending the components together using methods known in the art. It can be blended by mixing. Generally, the components are blended in a suitable mixer. Such blending is preferably done using oxygen to prevent premature reactions. The process is carried out in an inert atmosphere in the absence of atmospheric moisture. A considerable amount of polyester-based isopropyl alcohol is used. In embodiments in which an annealing functional prepolymer is used, the adhesive composition is polyester Temperatures above the melting point of the isocyanate-functionalized prepolymer and temperatures at which significant side reactions occur. Blending can be done at temperatures below a certain degree. In this embodiment, the temperature used is The temperature is between 40°C and less than 90°C, more preferably 50°C to 70°C. The adhesive composition is blended. Afterward, it is packaged in a suitable container to protect it from moisture and oxygen in the air. When it comes into contact with moisture in the air, the polyurethane prepolymer containing isocyanate groups undergoes rapid reaction. This could lead to excessive bridge construction.

[0045] The adhesive system is a polyether or polyol having an amino group in the main chain of the polyol. The rapid curing accelerator includes any isocyanate-reactive compound. A compound may have a terminal OH group and at least one amino group in its main chain. Isocyanate-reactive compounds having an average number of OH functional groups is usually between 2 and 5. The number of OH groups is (total number of moles of OH / total number of moles of polyol). The average number of OH functional groups is preferably, 2.2, 2.5, 3.0, 3.5, or 3.8 or higher, and 4.8, 4.5, or 4.2 or lower. It is below.

[0046] An isocyanate-reactive compound having an amino group has at least one amino group in its skeleton. It has a mino group. The skeleton is used to produce isocyanate-terminated prepolymers. The above applies to polyols (e.g., aliphatic, polyether, or polyester skeletons). It may be the same as the above. Isocyanate-reactive compounds having an amino group are polyfunctional amino It can be formed by initiating the formation of a polyol using a compound. Generally, all amino groups present in a skeleton are essentially tertiary amines.

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

[0048] Similarly, the OH value (OH#) of an isocyanate-reactive compound having an amino group is desired. To achieve a suitable curing speed and workability, any useful material can be used. The OH# is at least 25 to 2000. Preferably, the OH value is at least 100, 2 The values ​​are 50, 500, and even 550. The OH value is the wet formula of the hydroxyl content of the polyol. It is obtained by analytical methods. This is obtained from 1 gram of polyol or other hydroxyl compound. This is the amount of potassium hydroxide in milligrams corresponding to the droxyl content, and is given by the following formula:

number

[0049] Isocyanate-reactive compounds containing an amino group may also have any useful molecular weight. Typically, the molecular weight of the polyol is at least 200 to 10,000. Preferably, Molecular weights can range from a maximum of 5000, 3000, 1500, 1000, 500, or even 400. Yes, preferably the molecular weight is at least 100, at least 200, or 250. In preferred embodiments, the isocyanate-reactive compound having an amino group is 3.5 to 4 It has an average number of OH functional groups of 0.2 and an OH value of at least 500.

[0050] A curing accelerator affects the curing speed of the adhesive mixture, for example, by causing foaming. It may contain a small amount of water as long as it does not adversely affect workability and curing properties. The amount is usually less than 1% of the total weight of the curing accelerator and moisture-curing adhesive. In terms of type, the amount of water is 500 parts per milliliter of the total weight of the moisture-curing adhesive and curing accelerator. It is desirable that the amount be as small as possible for practical use, such as a trace amount like ON. Preferably, The amount of water can be determined using known methods for determining water content, ranging from a maximum of 100 ppm. It does not contain water or is essentially water-free.

[0051] The curing accelerator is a filler, a polyol that does not have an amino group in its skeleton, a catalyst, a plasticizer, or a rheo. One of the useful ingredients used in rosé modifiers, UV stabilizers, or moisture-curing adhesives. It may contain more than two other components. Fillers, polyols, plasticizers, and catalysts are as described above. Or any of those known in the relevant art. The quantities of each of these are: The desired amount of socianate-reactive groups (e.g., OH), and the uniform mixing and application of the adhesive system. Other physical characteristics, such as rheological properties, can be useful in determining certainty. It is possible.

[0052] The curing accelerator contains fillers, amino group-free polyols, catalysts, and plasticizers. If present, they typically exist in the following amounts: isocyanates containing an amino group. Reactive compounds are typically present in amounts of 5% to 50% by weight of the curing accelerator. Polyols that do not contain the 20% to 80% by weight of the curing accelerator are typically used in this form. Yes, they exist. Fillers or combinations of fillers typically make up 10% to 35% of the curing accelerator. It is present in an amount of 0.01% or more of the curing accelerator. The catalyst or combination of catalysts is typically present in an amount of 0.01% or more of the curing accelerator. It exists in a quantity of 2%.

[0053] Curing accelerators are used to accelerate the curing of moisture-curing adhesives. In addition, the curing accelerator and moisture-curing adhesive are supplied separately, otherwise they are mixed together. The reaction will occur before the fabric is exposed. This is publicly known in the relevant technical field, and was reported by Zhu on April 10, 2014. Page 1, paragraph 10 of the concurrently pending U.S. Patent Application No. 61 / 977668 filed by them. Items listed from the first line to the eighth line on page 2, etc., which have different volumes and will be mixed later. Any suitable method can be used to provide the two reactive materials. Preferably, The moisture-curing adhesive and curing accelerator are supplied in the two-component reaction partition system described in the aforementioned U.S. patent application. To be given.

[0054] Moisture-curing adhesives contain isocyanate-terminated prepolymers and are moisture-curing. Therefore, the isocyanate index of the adhesive system (i.e., the isocyanate / reactive group in the curing accelerator) The amount obtained by multiplying the quantity by 100 is usually 85-200, but preferably 100-170. Similarly, since moisture-curing adhesives are used, typically, for moisture-curing adhesives... 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 moisture-curing adhesives and curing accelerators are as described above in the United States. By any appropriate means, including those described in the application and those known in the relevant art. This can be done. Preferably, mixing, coating, and contact are performed using the method of the above-mentioned U.S. application. It will be carried out.

[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 particular embodiment, the surface to which the adhesive is applied is cleaned before application and a primer is used. Treatment is possible, but a primer is not essential. For example, for a typical application: , U.S. Patent No. 4,525,511; U.S. Patent No. 3,707,521, and U.S. See Statement No. 3,779,794.

[0057] Typically, adhesive systems are used in the presence of moisture in the atmosphere (typically 20% to 99% relative humidity). Typical ambient conditions (23°C) ± It is applied at 10°C. To test the curing behavior, 2 A temperature of 3°C ± 2°C and an RH of 50% ± 5% are suitable. Curing occurs by adding additional water to the atmosphere. Or, by applying heat during the curing of the adhesive through convection or microwave heating. It can be accelerated.

[0058] The adhesive system is preferably made of plastic coated with glass or an abrasion-resistant coating. It is used to bond the material to other substrates such as metal or plastic. Preferred implementation In this configuration, the first substrate is made of glass or plastic coated with an abrasion-resistant coating. The first substrate is a window, and the second substrate is a window frame. In another preferred embodiment, the first substrate The second is glass, or plastic coated with an abrasion-resistant coating, a window, and the second is The base material is an automobile window frame. Preferably, the glass window is cleaned before joining. Abrasion resistance Plastics coated with a coating include polycarbonate, acrylic resin, and hydrogenated plastics. Polystyrene or styrene-conjugated dienes with a styrene content of more than 50 percent It can be any clean plastic, such as block copolymers. The coating includes any coating that is wear-resistant, such as a polysiloxane coating. This is possible. Preferably, the coating has a light-shielding additive containing an ultraviolet pigment. Preferably, the glass or plastic window blocks UV light from reaching the adhesive. Therefore, an opaque coating is placed in the area that will come into contact with the adhesive.

[0059] In preferred embodiments, the adhesive system is used in a structure or vehicle, most preferably in a vehicle. It is used to replace windows in [location]. The first step is the removal of the old window. Cut the adhesive bead that holds the old window in place, then remove the old window. This can be achieved by [doing something]. Afterwards, the new window is cleaned and, if necessary, [do something]. The old adhesive on the window flange can be removed, although it is not mandatory. In most cases, they are left as they are, but they can also be cut flat with a cutting tool. (Window) The flange may be primed with paint primer, but this is not required. The adhesive system is positioned around the window so that it contacts the window flange when it is installed on the vehicle. It is applied in a dot shape. The adhesive is then applied to the window, and then the adhesive is applied between the window and the flange. It is placed inside the flange in that position. Alternatively, the adhesive can be applied to the window flange. The adhesive bead is a continuous seal that works to seal the joint between the window and the window flange. It is a bead. The continuous bead of the adhesive connects at each end when in contact with the window and f The bead is positioned to form a continuous seal between the lunge and the joint. The adhesive then hardens. They are made to do it.

[0060] Adhesives can transfer large substrates weighing more than 20 kg and up to 120 kg to other substrates. It is also useful for joining. One classification of large mass substrates is the substrate used in mass transport vehicles. These are large windows used in vehicles such as buses or trains.

[0061] For certain applications, adhesive systems can be used with a primer or activated wipe. The primer or activating wipe is typically applied to the surface of the substrate. After the solvent has evaporated, the adhesive system is brought into contact with the substrate. Preferably, a primer or active The time between applying the curing wipe and applying the adhesive to the substrate should be 0.5 minutes or more. Preferably, it is 1 minute or more, most preferably 2 minutes or more. [Examples]

[0062] The following examples are provided to illustrate the present invention, but do not limit its scope. This is not intended to be so. Unless otherwise specified, all parts and percentages are by weight. This is a non-reactive material used in raw materials and curing accelerators for moisture-curing adhesives. The sexual components are shown in Table 1.

[0063] [Table 1]

[0064] Examples 1 and 2 were formulated to have the same Ballan viscosity having the following composition. The isocyanate component (Agent A) is expressed in weight percent. Examples 1 and 2 The composition is shown in Table 2. In Table 2, the Ballan viscosity is given for conditioned samples at 23°C. The material is measured from the measured material. The material in the measuring cup and storage container is subjected to a minimum temperature of 23°C in a water bath. It is conditioned for 1 hour. After transferring the ingredients from the measuring cup to prevent exposure to air, Attach the cup to the balance measuring device. The adhesive is a nozzle with a diameter of 2 mm and a length of 1.8 mm. It is extruded from the barrel at a pressure of 4 ± 0.01 bar. The extrusion weight per hour is measured. The pressurized fluid viscosity is calculated in g / min.

[0065] [Table 2]

[0066] Examples 3-6 are polyol components (component B) containing a curing agent. The amount of each component is per percent by weight. It is listed as a point.

[0067] Example 3 is a “slow” curing agent (i.e., combined with a high molecular weight polyethertriol) It contains only 1,4-butanediol.

[0068] Examples 4-6 react immediately after mixing with the isocyanate group of the isocyanate component. It contains both a "slow" curing agent and a "fast" curing agent. In Examples 4 and 5, the amount of fast curing agent was increased. This is the amount of polyetherdiamine that will be used.

[0069] Example 6 contains an alcohol containing a tertiary amine, which has 1,4-bronze OH groups. The alcohol reaction with isocyanate is faster than the reaction of each OH group of the tandiol. It catalyzes within the child.

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

[0071] [Table 3]

[0072] Regarding Table 2, isocyanate components Ex.1 and Ex.2 were manufactured by the following procedure. To prepare: Put ingredients 1 and 3 into a blender and degas under vacuum for 40 minutes. Dry product 4 beforehand. Then, put it in a blender and mix under vacuum at low speed for 5 minutes until it is thoroughly wet with the other product. Slowly increase the mixer speed and blend product 4 (carbon black) under complete vacuum for 40 minutes. Disperse the mixture. Then, heat the mixture to 65°C while stirring. Add component 2 at 65°C. Add after preheating to the same temperature. Then, turn off the heating and activate the cooling to 40°C. Cool it down. Then add components 5-10 and mix under vacuum for another hour. After that, Allow the Xer to cool to ambient temperature, then remove the moisture-curing adhesive into a container under dry conditions.

[0073] Table 4 shows examples and comparative examples of curing accelerators. Each of these is, in principle, as follows. They are manufactured using the same procedure. For Table 3, ingredients 1 and 4 are placed in a mixer and then under vacuum. Degas for 30 minutes. Then add pre-dried ingredients 5-8, which are then mixed with other products. Mix slowly at low speed under vacuum for 5 minutes until thoroughly moistened. Raise the temperature and disperse the added components 5-8 under complete vacuum for 40 minutes. Finally, add product 2 and Add 3 and mix under vacuum for 20 minutes. Then transfer the mixture to a sealed container. .

[0074] Each of the curing accelerator formulations shown in Table 4 corresponds to the aforementioned U.S. Patent Application No. 61 / 97 As described in Example 1 of Specification No. 7668, the moisture-curing adhesive is used together with the adhesive. It can be placed inside a distribution system (two-part sausage). Volume ratio of moisture-curing adhesive to curing accelerator. The ratio is 9 to 1. For each example and comparative example, the isocyanate index is essentially the same. The moisture-curing adhesive and curing accelerator are described in Example 1 of the aforementioned U.S. patent application. It will be distributed in the same way as the other items.

[0075] Table 4 shows the compositions of Comparative Example A and Examples 8-11.

[0076] The following characteristics for Comparative Example A and Examples 8-11 were measured and reported in Table 4. い:

[0077] The "deck" performance is measured using a penetration meter. A triangular adhesive bead is placed at the base. Apply with a 7mm, 14mm high triangular nozzle. 115g weight (100g weight + Hold the 15g connecting rod precisely positioned at the tip of the adhesive bead. Do this. Release the weight's grip for 5 seconds and sink it into the adhesive bead. The penetration depth is in millimeters. Measured in torr units. Penetration depth is measured directly 1 minute after application of the adhesive bead, and then The adhesive is measured every two minutes until it can no longer be easily pressed into place. The deck performance immediately after mixing in a static mixer at 0 is such that the adhesive can be pressed in. It is predicted by a linear approximation of the maximum penetration depth over the available time or the first 20 minutes.

[0078] "Impact strength" is determined by the GEX method 344. A metal coupon is placed in a sample holder. Put it in the container. Apply adhesive between the prongs and let it overflow onto the tape. Then, cool Place the pom (76 x 25 x 5 mm) on top of the prongs and use a spatula to remove any excess adhesive. Carefully remove it, ensuring the bead is in its complete shape (25 x 13 x 5 mm). Then, store the test specimens under the desired curing time (e.g., 15 minutes and 30 minutes) and environmental conditions. Then, lift the impact pendulum and latch it in place, and fix the test piece in place. Release the hammer (use a 10-pound hammer). The adhesive will withstand before destructive breakage occurs. The total energy that can be generated is measured in joules (J).

[0079] "Lap shear strength" is measured using appropriate equipment, e.g., FHM8606.00.00 or 86 06.04.00 Shear strength device with mounting device Zwick 1435 DIN Measurements are taken according to EN527. The lap shear test specimen has a 10 × 25 × 1.5 mm contact strip. Adhesive bonding dimensions are used. The lap shear test specimens are subjected to 1 hour at 23°C / 50% relative humidity. The material is tested after curing time of 2 hours, 4 hours, and 7 days; "Tensile properties: strength, elongation, and modulus E" are defined according to DIN EN ISO 527-1. It will be decided.

[0080] [Table 4]

[0081] To analyze the effect of the rapid-curing agent on deck performance, we measured the deck height over 20 minutes. The decrease in or the open time of the adhesive was linearly approximated (Figure 1). Linear fitting was used. Then, the deck height at time t=0 was estimated by extrapolation.

[0082] The linearly approximated deck height at 0 min for comparative example A of 7.3 mm is the same as the original 6.5 mm It is higher than that of Example 8 of the present invention. The accelerator component is a secondary polyetherdiamine Jeff Adding 10% amine SD-2001 reduces the initial deck height by 11%.

[0083] As shown in Figure 2, for Example 10, 20% Jeffamine was used. The addition of SD-2001 (secondary polyetherdiamine) results in a linear approximation of the deck height at 0 min. This further reduces the height to 5.5mm. This reduces the initial deck height to 1.8mm or relative to 5.5mm. It improves height by 25%. In addition to the positive effect on initial deck height, both formulations Due to the faster curing agent reaction and the resulting higher conversion rate at that point, compared to Comparative Example A The impact peel strength was improved after 15 and 30 minutes.

[0084] Examples 9 and 11 describe the polio of the present invention, which contains triethanolamine as a rapid curing agent. Example 6 of component 6 is used. The linearly approximated deck height at 0 min is 5.3 mm and This corresponds to 5.0 mm (Figure 2), compared to the comparative polyol component Example 3, which is 7.3 mm. And it is significantly lower. Trifunctional triethanolamine is faster due to a larger number of functional groups. This results in cross-linking, which usually leads to faster strength development over time. The time is still quite long in all examples, exceeding 10 minutes.

Claims

1. (A) Isocyanate-terminated prepolymer and (B) An adhesive system comprising a moisture-curing adhesive containing a curing accelerator, The curing accelerator (B) comprises (1) a tertiary amino group and (2) an isocyanate-reactive compound (i) having 3 to 7 OH functional groups, and a diol and / or triol (ii) that does not have a primary, secondary, or tertiary amino group or a primary thiol group. An adhesive system in which the isocyanate-reactive compound (i) is present in an amount of less than 5% by weight of the curing accelerator (B).

2. The adhesive system according to claim 1, wherein the isocyanate-reactive compound (i) has 3 to 4.5 OH functional groups.

3. The adhesive system according to claim 1, wherein the diol and / or triol (ii) is butanediol.

4. The adhesive system according to claim 1, wherein the curing accelerator (B) is essentially water-free.

5. The adhesive system according to claim 1, wherein the isocyanate-terminated prepolymer (A) comprises an isocyanate-terminated polyether prepolymer.

6. The adhesive system according to claim 5, wherein the isocyanate-terminated polyether prepolymer comprises a polyether skeleton containing ethylene oxide, propylene oxide, or a combination thereof.

7. The adhesive system according to claim 1, wherein the moisture-curing adhesive further comprises one or more of the following: a filler, a plasticizer, a polyisocyanate monomer or oligomer, or a catalyst.

8. Step (a): A step of preparing a moisture-curing adhesive composition comprising (A) an isocyanate-terminated prepolymer and (B) a curing accelerator, The curing accelerator (B) comprises (1) a tertiary amino group and (2) an isocyanate-reactive compound (i) having 3 to 7 OH functional groups, and a diol and / or triol (ii) that does not have a primary, secondary, or tertiary amino group or a primary thiol group, wherein the isocyanate-reactive compound (i) is present in an amount of less than 5% by weight of the curing accelerator (B). A step in which the isocyanate-terminated prepolymer (A) and the curing accelerator (B) are prepared separately; Step (b): A step of mixing the curing accelerator (B) and the isocyanate-terminated prepolymer (A) to form an adhesive mixture; Step (c): Applying the adhesive mixture to at least a portion of the first substrate; Step (d): A step of bringing the substrate having the adhesive mixture thereon into contact with a second substrate so that the adhesive mixture is between them; and Step (e): A step of curing the adhesive mixture to integrally bond the substrates; A method for accelerating the curing of an adhesive composition, including [a specific component].

9. The method according to claim 8, wherein step (b) is performed using an automatic dispensing device from a 1K dispensing gun or drum.

10. The method according to claim 8, wherein the first substrate is a substrate that is optically transparent in at least a portion, and the second substrate is a vehicle or a building.

11. The method according to claim 10, wherein the first substrate has an opaque portion to which the adhesive mixture is applied and which is in contact with the second substrate.

12. The method according to claim 11, wherein the first substrate is glass or polycarbonate.

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