One-component polyurethane adhesive composition

Abstract

Provided herein are two-part polyurethane adhesive compositions.

Description

[Technical field]

[0001] The present invention relates to the field of one-part moisture-curable polyurethane adhesive compositions. [Background technology]

[0002] One-part moisture-cure polyurethane adhesives ("1K PU") are widely used in the automotive industry. Commercially available adhesives are designed to provide both strong adhesive performance and good physical properties.

[0003] A typical paste-like 1K PU adhesive is based on an isocyanate-functional prepolymer with terminal isocyanate (NCO) groups. This prepolymer is produced by reacting an excess of a diisocyanate with a polyol to form an NCO-terminated prepolymer. As a result of this synthesis method, excess monomeric diisocyanates remain as contaminants.

[0004] During use, 1K PU adhesives are applied and react with atmospheric moisture to form carbamic acids, which decompose into amines and carbon dioxide. The resulting amines react with remaining isocyanate groups to crosslink and form urea bonds, hardening the adhesive (Equation 1). The advantage of 1K PU adhesives is based on the fact that they are based on only one component, so no mixing is required and they are very easy to apply. [ka] Summary of the Invention [Problem to be solved by the invention]

[0005] A disadvantage of 1K PU adhesives is that they contain residual diisocyanate monomers, which are considered toxic. New regulations require that the residual diisocyanate content be less than 0.1%, and if this is not the case, users must undergo special training (https: / / echa.europa.eu / registry-of-restriction-intentions / - / dislist / details / 0b0236e180876053). [Means for solving the problem]

[0006] One way to reduce the monomeric diisocyanate content is to remove the excess monomer by distillation, but this process is expensive, time- and energy-consuming and therefore undesirable.To eliminate potential hazard risks, it is preferable to formulate 1K PU adhesives without the use of isocyanates.

[0007] In a first aspect, the present invention provides a method for producing a composition comprising the steps of: (A) reacting at least one polyisocyanate with at least one polyol (to yield intermediate I), and then reacting the resulting mixture with a polyisocyanate having the formula I: [ka] (In the formula, R 1 and R 2 are independently hydrogen and C 1 ~C 6 alkyl, n is an integer from 1 to 2, and R 3 is C 1 ~C 6 a polyurethane prepolymer prepared by reacting a molecule of (B) Polyamines, in which the amine groups are blocked by groups that are cleaved upon exposure to humidity; (C) optionally, a catalyst capable of catalyzing the reaction of an amine with a moiety derived from a molecule of formula I The present invention provides a one-component moisture-curable polyurethane adhesive composition comprising:

[0008] In a second aspect, the present invention provides a method for producing a composition comprising the steps of: (1) applying an adhesive composition according to the present invention to a first substrate, a second substrate, or both; (2) bringing a first substrate and a second substrate into adhesive contact; (3) curing the adhesive composition by exposing it to moisture; The present invention provides a method for bonding a first substrate and a second substrate, comprising:

[0009] In a third aspect, the present invention provides a method for producing a method for treating a cancer cell comprising the steps of: (1) providing a one-component moisture-curable polyurethane adhesive composition according to the present invention; (2) applying the adhesive composition to a first substrate, a second substrate, or both; (3) placing the first and second substrates in adhesive contact, whereby the adhesive composition is sandwiched therebetween; (4) curing the adhesive composition; The present invention provides a method for bonding two substrates, comprising:

[0010] In a fourth aspect, the present invention provides a method for producing a composition comprising the steps of: (1) a first substrate; (2) a second substrate; (3) the one-component moisture-curable polyurethane adhesive composition according to the present invention; wherein first and second substrates are in adhesive contact with the adhesive composition sandwiched therebetween. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0011] The inventors have found that isocyanate-functional prepolymers can be blocked so that no residual isocyanate groups remain. These blocked prepolymers are stable and do not react with moisture. In combination with the blocked prepolymer, a second compound based on a multifunctional blocked amine (e.g., polyaldimine or polyoxazolidine) is added to the formulation. The blocked amine reacts with moisture to form an amine, which in turn can react with the blocked PU prepolymer to crosslink and form a cured polyurethane network. Thus, moisture-curing one-part polyurethane adhesive compositions can be formulated without any isocyanate. The reaction with oxazolidine is shown diagrammatically below: [ka]

[0012] Definitions and Abbreviations MDI: Methylene bis(phenyl isocyanate) HDI: Hexamethylene diisocyanate IPDI: Isophorone diisocyanate PU: Polyurethane SEC: Size Exclusion Chromatography RH: Relative humidity

[0013] Polymer molecular weights reported herein are reported in Daltons (Da) as number or weight average molecular weights as determined by size exclusion chromatography (SEC).

[0014] Polyisocyanates and polyols The compositions of the present invention comprise a polyurethane prepolymer prepared by reacting at least one polyisocyanate with at least one polyol (yielding intermediate I), and then reacting with at least one molecule of formula I in an amount to react all of the NCO groups.

[0015] The at least one polyol is preferably selected from polyether polyols, polyester polyols (e.g., polycaprolactone), polybutadiene diols, polycarbonate diols, aliphatic diols (polyols), and mixtures of any of these. Polyether polyols are particularly preferred.

[0016] The at least one polyol is preferably a diol, triol or tetraol, preferably a triol or a mixture of triols and diols, with triols being particularly preferred.

[0017] Polyether polyols useful in the present invention include, for example, polyether polyols, poly(alkylene carbonate) polyols, hydroxyl-containing polythioethers, polymer polyols, and mixtures thereof. Polyether polyols are well known in the art and include, for example, polyoxyethylene, polyoxypropylene, polyoxybutylene, and polytetramethylene ether diols and triols, which can be prepared, for example, by reacting unsubstituted or halogen- or aromatic-substituted ethylene oxide or propylene oxide with an initiator compound containing two or more active hydrogen groups, such as water, ammonia, polyhydric alcohols, or amines. In general, polyether polyols can be prepared by polymerizing alkylene oxides in the presence of active hydrogen-containing initiator compounds. Preferred polyether polyols contain one or more alkylene oxide units in the polyol backbone. Preferred alkylene oxide units are ethylene oxide, propylene oxide, butylene oxide, and mixtures thereof. Preferably, the polyol comprises propylene oxide units, ethylene oxide units or mixtures thereof. In embodiments in which a mixture of alkylene oxide units is included in the polyol, the different units can be arranged randomly or in blocks of each alkylene oxide. In a preferred embodiment, the polyol comprises propylene oxide chains. In a preferred embodiment, the polyether polyol is a mixture of polyether diols and polyether triols. Preferably, the polyether polyol or mixture has a functionality of at least about 2.0; and preferably is about 3.0 or more, e.g., 3.5, 4.0 or more. Preferably, the equivalent weight of the polyether polyol mixture is at least about 200, more preferably at least about 500, even more preferably at least about 1,000; and preferably is about 5,000 or less, more preferably is about 3,000 or less.

[0018] More specific examples of polyether polyols include the following:

[0019] 1. Bifunctional polyols (diols), e.g., polyols in which the alkylene group is C 2 ~C 4 In a particularly preferred embodiment, the polyether polyol comprises a nominally difunctional poly(propylene oxide) having an equivalent weight of 100 to 10,000, more preferably 500 to 3,000, and especially preferably 1,000 to 2,000.

[0020] 2. Trifunctional polyols (triols), e.g., polyols in which the alkylene group is C 2 ~C 4 Those based on alkylene oxide initiated with a trifunctional polyol such as trimethylolpropane, particularly ethylene oxide, propylene oxide, butylene oxide, tetramethylene oxide and butylene oxide, with propylene oxide being especially preferred. In a particularly preferred embodiment, the polyether polyol comprises a nominally trifunctional poly(propylene oxide) having an equivalent weight of 100 to 10,000, more preferably 500 to 3,000, and especially preferably 1,000 to 2,000; the polymer may or may not be capped with ethylene oxide to modify its reactivity.

[0021] 3. Mixtures of 1 and 2. Particularly preferred are mixtures of 1 and 2, more particularly preferred are mixtures of a) a nominally difunctional poly(propylene oxide) having an equivalent weight of 100 to 10,000, more preferably 500 to 3,000, particularly preferably 1,000 to 2,000, and b) a nominally trifunctional poly(propylene oxide) having an equivalent weight of 1,000 to 2,000, especially in a weight ratio b) / a) of 0:1 to 2:1.

[0022] In a particularly preferred embodiment, the at least one polyol comprises a propylene oxide-based triol. Preferably, the polypropylene oxide-based triol has a molecular weight of 1,000 to 5,000 Da, more preferably 1,000 to 3,000 Da.

[0023] Polyester polyols include hydroxyl-terminated polyesters. Particularly preferred are hydroxyl-terminated aliphatic polyesters and polycaprolactones. Polyester diols and triols are preferred, particularly polyester triols. Particularly preferred are copolyesters having a molecular weight of 2,000 to 4,000 Da, preferably 3,500 Da.

[0024] There is no particular limitation on the polyisocyanate that can be used in the production of intermediate I. Diisocyanates are preferred.

[0025] Aliphatic and aromatic diisocyanates may be used, with aliphatic being preferred. Examples of suitable diisocyanates include toluene diisocyanate (TDI), hexamethylene diisocyanate (HDI), naphthalene diisocyanate (NDI), methylene biscyclohexyl isocyanate (HMDI) (hydrogenated MDI), methylene diphenyl diisocyanate (MDI, particularly 4,4'- and 4,2-MDI) and isophorone diisocyanate (IPDI), with HDI being particularly preferred.

[0026] In a preferred embodiment, intermediate I is prepared by reacting a polyether triol with HDI. In a particularly preferred embodiment, it is prepared by reacting a polypropylene oxide-based triol with HDI. In a more particularly preferred embodiment, it is prepared by reacting a 4,800 molecular weight polypropylene oxide-based triol with HDI.

[0027] In a preferred embodiment, intermediate I is prepared by reacting an aliphatic polyester having a molecular weight of 3,500 with MDI. In a particularly preferred embodiment, the polyester prepolymer is prepared by reacting 65-80% by weight of a polyester diol with 5-15% by weight of MDI.

[0028] Intermediate I may comprise a mixture of a polyether polyol-based prepolymer and a polyester-based prepolymer.

[0029] In a particularly preferred embodiment, intermediate I is based on polyether diols and polyether triols.

[0030] The diisocyanate that can be used in the preparation of intermediate I is not particularly limited. Aliphatic diisocyanates and aromatic diisocyanates can be used. Examples of suitable diisocyanates include toluene diisocyanate (TDI), hexamethylene diisocyanate (HDI), naphthalene diisocyanate (NDI), methylene biscyclohexyl isocyanate (HMDI) (hydrogenated MDI), MDI (especially 4,4'- and 4,2-MDI) and isophorone diisocyanate (IPDI), with HDI being particularly preferred.

[0031] In particularly preferred embodiments, intermediate I comprises nominally trifunctional poly(propylene oxide) and nominally trifunctional poly(propylene oxide) reacted with MDI or HDI.

[0032] In a particularly preferred embodiment, intermediate I comprises a nominally trifunctional poly(propylene oxide) having a hydroxyl number of 56 (equivalent weight 1000), and a nominally trifunctional poly(propylene oxide) having a hydroxyl number of 36 (equivalent weight 1558) reacted with MDI or HDI.

[0033] Intermediate I is prepared by reacting at least one polyol with a polyisocyanate using a catalyst capable of catalyzing the reaction of NCO groups with hydroxyl groups. Preferred catalysts are listed below.

[0034] The polymerization can be carried out in the presence of a plasticizer, such as a high-boiling ester or diester, such as diisononyl phthalate, with diisononyl phthalate being particularly preferred.

[0035] In a preferred embodiment, intermediate I comprises 18 to 30% by weight, more preferably 19 to 25% by weight, more particularly preferably 22 to 23% by weight of polyol diol, based on the total weight of intermediate I.

[0036] In a preferred embodiment, intermediate I comprises 40 to 90% by weight, 50 to 90% by weight, more particularly preferably 75 to 85% by weight of polyol triol, based on the total weight of intermediate I.

[0037] In a preferred embodiment, intermediate I comprises 5 to 15% by weight, more preferably 8 to 12% by weight, and more particularly preferably 8 to 10% by weight of diisocyanate, based on the total weight of intermediate I.

[0038] In a particularly preferred embodiment, intermediate I comprises, based on the total weight of intermediate I, 22 to 23 weight percent polyol diol, 32 to 33 weight percent polyol triol, and 9 to 11 weight percent diisocyanate.

[0039] In a preferred embodiment, intermediate I comprises 18 to 30 wt. %, more preferably 19 to 25 wt. %, and more particularly preferably 22 to 23 wt. %, based on the total weight of intermediate I, of a nominally difunctional poly(propylene oxide) having a hydroxyl number of 56 (1000 equivalent weight).

[0040] In a preferred embodiment, intermediate I comprises 25 to 40 wt. %, 28 to 35 wt. %, and more particularly preferably 32 to 33 wt. %, based on the total weight of intermediate I, of a nominally trifunctional poly(propylene oxide) having a hydroxyl number of 36 (equivalent weight 1558).

[0041] In a preferred embodiment, intermediate I contains 5 to 15% by weight, more preferably 8 to 12% by weight, more particularly preferably 9 to 11% by weight, of MDI or HDI, based on the total weight of intermediate I.

[0042] In a particularly preferred embodiment, intermediate I comprises 22-23 wt. % of a nominally difunctional poly(propylene oxide) having a hydroxyl number of 56 (equivalent weight 1000), 32-33 wt. % of a nominally trifunctional poly(propylene oxide) having a hydroxyl number of 36 (equivalent weight 1558), and 9-11 wt. % MDI, based on the total weight of intermediate I.

[0043] In a particularly preferred embodiment, intermediate I comprises 22-23 weight percent of a nominally difunctional poly(propylene oxide) having a hydroxyl number of 56 (equivalent weight 1000), 32-33 weight percent of a nominally trifunctional poly(propylene oxide) having a hydroxyl number of 36 (equivalent weight 1558), and 9-11 weight percent MDI, based on the total weight of intermediate I, and has an isocyanate content of 1.25 weight percent, a viscosity of 16,000 cps at 23° C., as measured according to the procedure described in U.S. Pat. No. 5,922,809, column 12, lines 38-49.

[0044] End Groups (Molecules of Formula I) The prepolymer can be prepared by reacting at least one polyisocyanate with at least one polyol (to yield intermediate I) and then reacting the polyisocyanate with a polyol of formula I: [ka] (In the formula, R 1 and R 2 are independently hydrogen and C 1 ~C6 alkyl, n is an integer from 1 to 2, and R 3 is C 1 ~C 6 It is prepared by reacting a cyclic alkyl group with a cyclic alkyl group.

[0045] Preferably, R 1 and R 2 are independently H and C 1 ~C 4 Alkyl, more preferably H and C 1 ~C 2 alkyl, particularly preferably R 1 and R 2 is H.

[0046] Preferably, n is 1.

[0047] Preferably, R 3 is C 1 ~C 4 is preferably alkyl, more preferably R 3 is C 1 ~C 2 alkyl, particularly preferably R 3 is ethyl.

[0048] In a particularly preferred embodiment, in the molecule of formula I, R 1 and R 2 is H, n is 1, and R 3 is ethyl [2-(ethoxycarbonyl)cyclopentanone, CPEE]. [ka]

[0049] The molecule of formula I reacts with the NCO groups of intermediate I. It is preferably used in an amount which reacts with all the NCO groups of intermediate I, i.e. at least a stoichiometric equivalent to the free NCO groups of intermediate I, or in an excess, for example 1, 1.1 or 1.2 equivalents.

[0050] To reduce or eliminate monomeric diisocyanates in intermediate I, the amount or molecule of Formula I added may be calculated to react not only with the NCO groups of intermediate I, but also with residual monomeric diisocyanates, thereby eliminating substantially all of the NCO groups of both the prepolymer and the free monomeric diisocyanates.

[0051] Catalyst for polyurethane prepolymer Intermediate I is prepared by reacting at least one polyisocyanate with at least one polyol in the presence of a catalyst capable of catalyzing the reaction of NCO and OH functional groups.

[0052] Examples of such catalysts include tertiary amine catalysts, bismuth catalysts, alkyltin carboxylates, oxides and mercaptides.Specific examples include triethylenediamine, 1,4-diazabicyclo[2.2.2]octane, dimethylcyclohexylamine, dimethylethanolamine and bis-(2-dimethylaminoethyl)ether, bismuth catalysts, dibutyltin dilaurate, stannas octoate, with bismuth catalysts being particularly preferred.

[0053] Zinc catalysts, especially zinc carboxylate catalysts, are preferred for the reaction with molecules of formula I. In a preferred embodiment, a mixture of zinc and bismuth carboxylates is used.

[0054] When an organometallic catalyst is used, it is any organometallic catalyst that can catalyze the reaction between an isocyanate and a functional group having at least one reactive hydrogen. For example, metal carboxylates such as bismuth catalysts, tin carboxylates, zinc carboxylates, etc. Metal alkanoates include stannas octoate, bismuth octoate, or bismuth neodecanoate. Preferably, at least one organometallic catalyst is a bismuth catalyst or an organotin catalyst, for example, dibutyltin dilaurate, dimethyltin dineodecanoate, dimethyltin mercaptide, dimethyltin carboxylate, dimethyltin dioleate, dimethyltin dithioglycolate, dibutyltin mercaptide, dibutyltin bis(2-ethylhexylthioglycolate), dibutyltin sulfide, dioctyltin dithioglycolate, dioctyltin mercaptide, dioctyltin dioctoate, dioctyltin dineodecanoate, dioctyltin dilaurate. In a particularly preferred embodiment, it is a bismuth catalyst.

[0055] The catalyst is preferably used in an amount of 0.05 to 2% by weight, more preferably 0.1 to 1% by weight, based on the total weight of the adhesive composition.

[0056] In a preferred embodiment, the catalyst is a zinc and bismuth catalyst and is used at 0.05 to 0.3 wt %, based on the total weight of the adhesive composition.

[0057] Polyurethane Prepolymer The polyurethane prepolymers resulting from the reaction of intermediate I above with molecules of formula I, and any combination of polyols, polyisocyanates and molecules of formula I are contemplated herein.

[0058] In a particularly preferred embodiment, the polyurethane prepolymer comprises 75-90 wt. % of a polypropylene oxide based triol having a MW of 4800 g / mol, 5-10 wt. % of 1,6-HDI, and 5-10 wt. % of CPEE.

[0059] In a particularly preferred embodiment, the polyurethane prepolymer comprises 82.68 wt. % of a polypropylene oxide-based triol having a MW of 4800 g / mol, 8.68 wt. % of 1,6-HDI, and 8.54 wt. % of CPEE.

[0060] The polyurethane prepolymer is preferably present in the one-component polyurethane adhesive at 20 to 70% by weight, more preferably 30 to 55% by weight, and more particularly preferably 35 to 40% by weight, based on the total weight of the adhesive.

[0061] In a particularly preferred embodiment, the adhesive composition of the present invention comprises 20 to 70 wt. %, more preferably 35 to 40 wt. %, based on the total weight of the adhesive composition, of a polyurethane prepolymer comprising a nominally trifunctional poly(propylene oxide) having a hydroxyl number of 36 (equivalent weight 1558) and a nominally difunctional poly(propylene oxide) having a hydroxyl number of 56 (equivalent weight 1000) reacted with MDI and having an isocyanate content of 1.25 wt. %.

[0062] Preferably, the prepolymer or prepolymer mixture has a Brookfield viscosity of at least 6,000 centipoise or at least about 8,000 centipoise, and up to 30,000 centipoise or up to 20,000 centipoise. If the viscosity is too high, the final adhesive composition will be difficult to pump. If the viscosity is too low, the final adhesive composition will be very watery and will drip.

[0063] Prepolymer equivalent weight and molecular weight are measured according to the procedures disclosed in US Pat. No. 5,922,809 at column 12, lines 50-64, which is incorporated herein by reference.

[0064] In a preferred embodiment, the polyurethane prepolymer has a viscosity of 16,000 cps at 23° C., measured according to the procedure described in US Pat. No. 5,922,809, column 12, lines 38-49.

[0065] In a particularly preferred embodiment, the polyurethane prepolymer has an isocyanate content of less than 0.1 wt.%, more preferably 0 wt.%.

[0066] In another preferred embodiment, the polyurethane prepolymer has an isocyanate content of less than 0.1 wt%, more preferably 0 wt%, and a viscosity of 16,000 cps at 23° C., measured according to the procedure described in U.S. Pat. No. 5,922,809, column 12, lines 38-49.

[0067] The adhesive composition of the present invention preferably contains at least one polyurethane prepolymer in an amount of 1 to 90% by weight, more preferably 35 to 85% by weight, and particularly preferably 40 to 50% by weight, based on the total weight of the adhesive composition.

[0068] In a particularly preferred embodiment, the adhesive composition comprises 40-50 wt.%, especially 44 wt.%, of a polyurethane prepolymer prepared by reacting a polypropylene oxide-based triol with HDI and then reacting with a molecule of formula I.

[0069] In a particularly preferred embodiment, the adhesive composition comprises 40-50 wt.%, especially 44 wt.%, of a polyurethane prepolymer prepared by reacting a polypropylene oxide-based triol with HDI and then with CPEE.

[0070] Blocked Amines The adhesive composition of the present invention comprises a polyamine, preferably a diamine or triamine, which has its amine groups blocked or masked by groups that are cleaved upon exposure to moisture.

[0071] Examples include:

[0072] 1. Polyoxazolidines, molecules with two or more oxazolidine groups of formula II or III: [ka] (In formula II, R 10 is a branched or unbranched divalent organic group, R 11 and R 12 independently represents H and branched or unbranched C 1 ~C 8 -alkyl, In formula III, R 13 is a branched or unbranched trivalent organic group, R 14 , R 15 and R 16 independently represents H and branched or unbranched C 1 ~C 8 -alkyl).

[0073] 2. Aldimino, ketimino and enamino groups of formula (IVa) or (IVb) [ka] (In formula IVa, R 1 and R 2 are independently selected from H and a monovalent hydrocarbon radical having 1 to 12 carbon atoms, or together are part of a divalent hydrocarbon radical having 4 to 20 carbon atoms and an optionally substituted carbocyclic ring having 5 to 8, preferably 6, carbon atoms; R 3 is H, branched or unbranched alkyl, cycloalkyl, alkenyl or cycloalkenyl, substituted or unsubstituted aryl, arylalkyl, and the formula: [ka] R 5 is a substituted or unsubstituted aryl, arylalkyl, alkyl, and [ka] R6 is selected from H, alkyl and arylalkyl, preferably having 1 to 12 carbon atoms, preferably R 6 is H and R 7 is a hydrocarbon group having 1 to 30 carbon atoms and optionally an ether oxygen atom, or R 7 is expressed by the following formula: [ka] is a group of R 8 is selected from H and a hydrocarbon group having 1 to 5 carbon atoms; And in formula IVb, R 4 is a substituted or unsubstituted aryl or heteroaryl having a ring size of 5 to 8, preferably 6 atoms, or is of the formula: [ka] R 9 is H or an alkoxy group, or is a substituted or unsubstituted alkenyl or arylalkenyl having at least 6 carbon atoms.

[0074] If a polyoxazolidine is used, it is preferably a bis-oxazolidine.

[0075] In the preferred polyoxazolidines of formula II, R 10 is selected from alkylene, arylalkylene, arylene, heteroarylene, divalent polyether, divalent polyester and divalent polyurethane, with polyurethane being particularly preferred.

[0076] Particularly preferred polyoxazolidines are those of formula V, VI or XII. [ka] In formula V, R 17 and R 18is independently a branched or unbranched C 1 ~C 8 -alkyl, preferably C 7 -Alkyl or C 3 Particularly preferably, R 17 and R 18 is expressed by the following formula: [ka] It is.

[0077] In formula VI, R 19 and R 20 is independently a branched or unbranched C 1 ~C 8 -alkyl, preferably C 7 -alkyl, particularly preferably 1-ethylpentyl.

[0078] In formula XII, R 21 and R 22 is independently a branched or unbranched C 1 ~C 8 -alkyl, preferably C 3 ~ 7 -alkyl, preferably C 3 -alkyl, particularly preferably R 21 and R 22 is expressed by the following formula: [ka] It is.

[0079] Very particularly preferred polyoxazolidines have the formula: [ka]

[0080] Particularly preferably, the polyoxazolidine has formula VIII or XI, more particularly preferably formula VIII.

[0081] The blocked amine is preferably used in a 1:1 ratio of amino groups to end groups of the polyurethane prepolymer.

[0082] Method for producing polyurethane prepolymer An example of a method for producing a polyurethane prepolymer is 1. Stirring at least one polyol under an inert atmosphere (e.g., nitrogen or argon), optionally in the presence of a plasticizer (e.g., diisononyl phthalate); 2. Adding at least one polyisocyanate; 3. adding a catalyst to obtain intermediate I; 4. Once the desired NCO content is reached, adding a molecule of formula I, preferably in an amount sufficient to react with all of the NCO groups of intermediate I; Includes.

[0083] A preferred embodiment of the method comprises: 1. Stirring at least one polyol under an inert atmosphere (e.g., nitrogen or argon), optionally in the presence of a plasticizer (e.g., diisononyl phthalate); 2. adding at least one polyisocyanate in an NCO:OH ratio of 1.5:1, 2:1, 4:1, 5:1 or greater; 3. adding a catalyst to obtain intermediate I; 4. Once the desired NCO content is reached, adding a molecule of formula I in an NCO:formula I ratio of 1 to 1.5, preferably 1 to 1.1. Includes.

[0084] In a preferred embodiment, the method for producing a polyurethane prepolymer comprises the steps of: 1. Stirring at least one polyol in an inert atmosphere (e.g., nitrogen or argon), optionally in the presence of a plasticizer (e.g., diisononyl phthalate), heating to 65-150°C, and then cooling to 60-80°C; 2. Adding at least one polyisocyanate; 3. Adding a catalyst and reacting the mixture at 60-100°C; 4. Once the desired NCO content is reached, cool the mixture of step 3 to 50-70° C. and add a molecule of formula I in an NCO:formula I ratio of 1-1.5, preferably 1-1.1. Includes.

[0085] Method for producing adhesive composition The adhesive composition of the invention comprises at least one polyurethane prepolymer, at least one blocked amine, and optionally a catalyst. The adhesive composition is prepared by mixing the components homogeneously, preferably under dry conditions. After mixing, the adhesive composition is preferably stored under dry conditions, for example under vacuum or dry nitrogen.

[0086] Optional Ingredients The adhesive composition of the present invention may optionally include a catalyst capable of catalyzing the reaction of an amine with a moiety derived from a molecule of formula I. An example includes bismuth neodecanoate. If used, the catalyst is typically present at 0.1 to 0.5 weight percent, based on the total weight of the adhesive composition.

[0087] The adhesive composition of the present invention may optionally contain an antioxidant, particularly a phenolic antioxidant. A typical example is 4,6-bis(octylthiomethyl)-o-cresol. When used, the antioxidant is typically present at 0.2 to 1.5 wt%, preferably 0.3 to 0.6 wt%, based on the total weight of the adhesive composition. In a particularly preferred embodiment, 4,6-bis(octylthiomethyl)-o-cresol is used at 0.3 to 0.6 wt%, more preferably 0.5 to 0.6 wt%, based on the total weight of the adhesive composition.

[0088] The adhesive composition of the present invention may optionally contain a plasticizer. Examples of plasticizers are esters, especially diesters and triesters, especially those with a viscosity of <10 at 23° C. -4Examples of suitable plasticizers include dialkyl phthalates, alkyl esters of fatty acids, and phosphate esters (such as trioctyl phosphate). Diisononyl phthalate is particularly preferred. When used, the plasticizer is typically present at 10-20% by weight, preferably 12-18% by weight, based on the total weight of the adhesive composition. In a particularly preferred embodiment, diisononyl phthalate is used at 12-18% by weight, more preferably 16-17% by weight, based on the total weight of the adhesive composition.

[0089] The adhesive composition of the present invention may optionally contain a filler, such as carbon black, clay, carbonates (e.g., calcium carbonate), metal hydrates, and fumed silica. The filler is preferably used in an amount of 0 to 80% by weight, more preferably 10 to 70% by weight, and even more preferably 20 to 60% by weight.

[0090] In a preferred embodiment, the adhesive of the present invention comprises clay as filler, preferably kaolin, in particular calcined kaolin. If used, the clay is used in an amount of 5 to 15% by weight, more preferably 8 to 12% by weight, based on the total weight of the adhesive composition. In a particularly preferred embodiment, the kaolin is used in an amount of 8 to 12% by weight, more preferably 9% by weight, based on the total weight of the adhesive composition.

[0091] In a preferred embodiment, the adhesive of the present invention includes carbon black as a filler. The carbon black is not particularly limited. The preferred carbon black has a viscosity of at least 80, preferably at least 90, more preferably at least 95 cm3 per 100 g of carbon black, as measured according to ASTM D-2414-09. 3 Additionally, it is preferred that the carbon black have an iodine number of at least 80, as measured in accordance with ASTM D1510-11.

[0092] When used, carbon black is used in an amount of 5 to 30% by weight, more preferably 15 to 25% by weight, based on the total weight of the adhesive composition. In a particularly preferred embodiment, carbon black is used in an amount of 15 to 25% by weight, preferably 22 to 23% by weight, based on the total weight of the adhesive composition.

[0093] The adhesive composition of the present invention may optionally contain 0 to 20% by weight, more preferably 5 to 15% by weight, and particularly preferably 9 to 10% by weight, of calcium carbonate, based on the total weight of the adhesive composition. The calcium carbonate particles may be untreated or surface modified by treatment with chemicals such as organic acids or esters of organic acids.

[0094] The adhesive composition of the present invention may optionally contain 0 to 1.5 wt %, more preferably 0.5 to 1 wt %, of fumed silica, based on the total weight of the adhesive.

[0095] When fumed silica is used, the particles may be untreated or may be surface modified with chemicals such as chlorosilanes, dichlorosilanes, alkyltrialkoxysilanes, or polydimethylsiloxanes.

[0096] The adhesive composition of the present invention may optionally include flame retardants and synergists. Examples of suitable flame retardants and synergists include: 1. Aluminum diethylphosphinate, zinc and titanium salts, in particular aluminum diethylphosphinate; 2. Nitrogen- and / or phosphorus-containing molecules, such as melamine polyphosphate, melamine pyrophosphate, melamine cyanurate; 3. Aluminum phosphite and / or zinc phosphite Examples include:

[0097] A preferred flame retardant / synergist combination is aluminum diethylphosphinate plus melamine polyphosphate.

[0098] The adhesive composition of the present invention has high thermal conductivity (>2Wm-1 K -1 If it is desired to have a thermally conductive filler such as aluminum oxide or aluminum hydroxide, a thermally conductive filler may be added.

[0099] The adhesive compositions of the present invention may optionally include one or more additional stabilizers, such as heat, visible light, and UV stabilizers.

[0100] Examples of heat stabilizers include alkyl-substituted phenols, phosphites, sebacates and cinnamates. When present, the preferred heat stabilizer is an organic phosphite, more specifically trisnonylphenyl phosphite, as disclosed in U.S. Pat. No. 6,512,033, which is incorporated herein by reference. The heat stabilizer may comprise at least 0.01% by weight, or at least 0.3% by weight, up to 5% by weight, up to 2% by weight or up to 1.0% by weight, based on the total weight of the adhesive composition. The adhesive composition may not include such a heat stabilizer.

[0101] UV stabilizers include benzophenones and benzotriazoles.Specific UV absorbers include, for example, TINUVIN P, TINUVIN 326, TINUVIN 213, TINUVIN 327, TINUVIN 571, TINUVIN 328 from BASF, and for example, CYASORB UV-9, CYASORB UV-24, CYASORB UV-1164, CYASORB UV-2337, CYASORB UV-2908, CYASORB UV-5337, CYASORB UV-531 and CYASORB UV-3638 from Cytec.Among these, TINUVIN 571 is preferred. The one or more UV absorbers may comprise at least 0.1 wt%, at least 0.2 wt%, or at least 0.3 wt%, and may comprise up to 3 wt%, up to 2 wt%, or up to 1 wt%, of the weight of the pressure sensitive adhesive composition.

[0102] The adhesive composition of the present invention may further comprise one or more visible light stabilizers. Preferred visible light stabilizers include hindered amine-based visible light stabilizers such as TINUVIN™ 144, TINUVIN™ 622, TINUVIN™ 77, TINUVIN™ 123, TINUVIN™ 765, CHIMASSORB™ 944 available from Cytec; CYASORB™ UV-500, CYASORB™ UV-3581, CYASORB™ UV-3346 available from Ciba-Geigy. Of these, TINUVIN™ 765 is a preferred choice. The visible light stabilizer may comprise at least 0.1%, at least 0.2%, or at least 0.3% by weight of the adhesive composition, and may comprise up to 3%, up to 2%, or up to 1.5% by weight.

[0103] Manufacturing method The adhesive composition of the present invention is prepared by mixing the ingredients under inert and dry conditions and / or under vacuum until a homogeneous mixture is obtained.

[0104] The resulting adhesive composition can be packaged, for example, in an airtight container, such as an airtight tube, which is stored in a nitrogen-filled, sealed aluminum bag.

[0105] How to use In a second aspect, the present invention provides a method for producing a composition comprising the steps of: (1) providing a one-component moisture-curable polyurethane adhesive composition according to the present invention; (2) applying the adhesive composition to a first substrate, a second substrate, or both; (3) placing the first and second substrates in adhesive contact, whereby the adhesive composition is sandwiched therebetween; (4) curing the adhesive composition; The present invention provides a method for bonding two substrates, comprising:

[0106] As mentioned above, a preferred method of providing the adhesive of the present invention is in an airtight container, such as a hermetically sealed container, which is opened immediately prior to use.

[0107] The adhesive composition of the present invention may be applied by any application method including, for example, spreading, application through a nozzle, manually or using a robotic device.

[0108] In a preferred embodiment, one or both of the first and second substrates are selected from metal, glass, glass with primer, glass with enamel coating, plastic (e.g. polypropylene with talc or glass fiber), polycarbonate, sheet molding compound, composite material (e.g. carbon fiber reinforced epoxy, glass fiber reinforced polyamide). In a preferred embodiment, at least one of the first and second substrates is metal, particularly steel or aluminum, particularly preferably e-coated steel, e-coated aluminum. In a particularly preferred embodiment, both substrates are steel.

[0109] Curing is accomplished by exposing the adhesive to atmospheric moisture. Curing may be accomplished at room temperature or at elevated temperatures, for example, above 50° C. or above 70° C. Typical curing conditions include 23° C. and 50% RH for 3 to 7 days.

[0110] Effect of the Invention The adhesive composition of the present invention preferably exhibits less than 0.1 wt. %, more preferably 0 wt. %, both monomeric contaminants and NCO content in the adhesive molecule.

[0111] The adhesive composition of the present invention exhibits good adhesive properties. Using the lap shear adhesion test described in the examples, the adhesive composition of the present invention preferably exhibits a lap shear strength of at least 1.5 MPa, more preferably greater than 2 MPa, after curing for 7 days at 23° C. and 50% RH.

[0112] Using the Lap Shear Strength Test described in the Examples, the adhesive compositions of the present invention preferably exhibit a lap shear strength of 360 psi or greater, more preferably 370 psi or greater, after curing for 7 days at 23° C. and 50% RH.

[0113] Using the tensile strength test described in the Examples, the adhesive composition of the present invention, after curing for 7 days at 23° C. and 50% RH,

[0114] Using the Lap Shear Strength Test described in the Examples, the adhesive compositions of the present invention preferably exhibit a tensile strength of 1.5 MPa or greater, more preferably 2 MPa or greater, after curing for 7 days at 23° C. and 50% RH.

[0115] Using the E Modulus test described in the Examples, the adhesive compositions of the present invention preferably exhibit an E Modulus of 1 MPa or greater after curing for 7 days at 23° C. and 50% RH.

[0116] Using the Elongation at Break Test described in the Examples, the adhesive compositions of the present invention preferably exhibit an elongation at break of at least 200%, more preferably at least 300%, and especially preferably at least 400%, after curing for 7 days at 23° C. and 50% RH.

[0117] Particularly preferred embodiments The following are particularly preferred embodiments of the adhesive composition of the present invention.

[0118] 1. (A) reacting at least one polyisocyanate with at least one polyol (to yield intermediate I), and then reacting the resulting mixture with a polyisocyanate having formula I: [ka] (In the formula, R 1 and R 2 are independently hydrogen and C 1 ~C 6 alkyl, n is an integer from 1 to 2, and R 3 is C 1 ~C6 a polyurethane prepolymer prepared by reacting a molecule of (B) Polyamines, in which the amine groups are blocked by groups that are cleaved upon exposure to humidity; (C) optionally, a catalyst capable of catalyzing the reaction of an amine with a moiety derived from a molecule of formula I A one-component moisture-curable polyurethane adhesive composition comprising:

[0119] 2. The adhesive composition of embodiment 1, wherein the at least one polyol is a polyether polyol or a polyester polyol.

[0120] 3. The adhesive composition of embodiment 1 or 2, wherein the at least one polyol is a polyether polyol.

[0121] 4. The adhesive composition of embodiment 1, 2 or 3, wherein the at least one polyol is a diol, triol or tetraol, or a mixture thereof, in particular a mixture of diols and triols.

[0122] 5. The adhesive composition of any one of the previous embodiments, wherein the at least one polyol is selected from polyoxyethylene, polyoxypropylene, polyoxybutylene, and polytetramethylene ether diols and triols.

[0123] 6. The adhesive composition of any one of the previous embodiments, wherein the polyol is a polypropylene oxide-based diol or triol, or a mixture thereof.

[0124] 7. The adhesive composition of any one of the previous embodiments, wherein the polyol is a polypropylene oxide-based triol.

[0125] 8. The adhesive composition of any one of the previous embodiments, wherein the at least one polyisocyanate is a diisocyanate.

[0126] 9. The adhesive composition of any one of the previous embodiments, wherein the at least one polyisocyanate is an aliphatic polyisocyanate.

[0127] 10. The adhesive composition of any one of the previous embodiments, wherein the at least one polyisocyanate is hexamethylene diisocyanate (HDI) or 4,4'- or 4,2-methylene bis(phenylisocyanate).

[0128] 11. The adhesive composition of any one of the previous embodiments, wherein intermediate I is made by reacting a polypropylene oxide-based triol with HDI.

[0129] 12. The adhesive composition of any one of the previous embodiments, wherein intermediate I is produced by reacting a 4,800 molecular weight polypropylene oxide-based triol with HDI.

[0130] 13. The adhesive composition of any one of the previous embodiments, wherein at least one polyol and at least one polyisocyanate are reacted in the presence of a catalyst selected from a bismuth catalyst, a metal carboxylate such as a tin carboxylate, a bismuth carboxylate, a zinc carboxylate, and mixtures of any of these, particularly a mixture of a zinc carboxylate and a bismuth carboxylate.

[0131] 14. The adhesive composition of any one of the previous embodiments, wherein at least one polyol and at least one polyisocyanate are reacted in the presence of a catalyst selected from stannas octoate, bismuth octoate, or bismuth neodecanoate.

[0132] 15. The adhesive composition of any one of the previous embodiments, wherein at least one polyol and at least one polyisocyanate are reacted in the presence of a catalyst which is a bismuth catalyst.

[0133] 16. The adhesive composition of any one of the previous embodiments, wherein the prepolymer comprises at least one polyol in an amount of 40 to 95 weight percent, based on the total weight of the polyurethane prepolymer.

[0134] 17. The adhesive composition of any one of the previous embodiments, wherein the prepolymer comprises at least one polyol in an amount of 50 to 90 weight percent, based on the total weight of the polyurethane prepolymer.

[0135] 18. The adhesive composition of any one of the previous embodiments, wherein the prepolymer comprises at least one polyol in an amount of 75 to 85 weight percent, based on the total weight of the polyurethane prepolymer.

[0136] 19. The adhesive composition of any one of the previous embodiments, wherein the prepolymer comprises at least one polyisocyanate in an amount of 4 to 15 weight percent, based on the total weight of the polyurethane prepolymer.

[0137] 20. The adhesive composition of any one of the previous embodiments, wherein the prepolymer comprises at least one polyisocyanate in an amount of 5 to 10% by weight, based on the total weight of the polyurethane prepolymer.

[0138] 21. The adhesive composition of any one of the previous embodiments, wherein the prepolymer comprises at least one polyisocyanate in an amount of 7 to 9 weight percent, based on the total weight of the polyurethane prepolymer.

[0139] 22. In the molecule of formula I, R 1 and R 2 independently, H and C 1 ~C 4 The adhesive composition of any one of the previous embodiments, wherein the alkyl group is selected from the group consisting of aryl, arylalkyl, arylsulfuric acid ...

[0140] 23. In the molecule of formula I, R 1 and R 2 independently, H and C 1 ~C 2The adhesive composition of any one of the previous embodiments, wherein the alkyl group is selected from the group consisting of aryl, arylalkyl, arylsulfuric acid ...

[0141] 24. In the molecule of formula I, R 1 and R 2 The adhesive composition of any one of the previous embodiments, wherein

[0142] 25. The adhesive composition of any one of the previous embodiments, wherein in the molecule of formula I, n is 1.

[0143] 26. In the molecule of formula I, R 3 C 1 ~C 4 The adhesive composition of any one of the previous embodiments, wherein the alkyl group is alkyl.

[0144] 29. In the molecule of formula I, R 3 C 1 ~C 2 The adhesive composition of any one of the previous embodiments, wherein the alkyl group is alkyl.

[0145] 30. In the molecule of formula I, R 3 The adhesive composition of any one of the previous embodiments, wherein is ethyl.

[0146] 31. The adhesive composition of any one of the previous embodiments, wherein in the molecule of formula I, it is ethyl 2-(ethoxycarbonyl)cyclopentanone (CPEE).

[0147] 32. The adhesive composition of any one of the previous embodiments, wherein the molecule of formula I is used in an equivalent or excess amount to the NCO groups of intermediate I.

[0148] 33. The adhesive composition of any one of the previous embodiments, wherein the molecule of formula I is used in an amount of 1.1 to 1.2 relative to the NCO groups of intermediate I.

[0149] 34. The adhesive composition of any one of the previous embodiments, wherein at least one prepolymer is made by reacting a polypropylene oxide-based triol with a polyisocyanate and then reacting with a molecule of formula I.

[0150] 35. The adhesive composition of any one of the previous embodiments, wherein at least one prepolymer is made by reacting a polypropylene oxide-based triol with HDI and then reacting with a molecule of formula I.

[0151] 36. The adhesive composition of any one of the previous embodiments, wherein at least one prepolymer is made by reacting a polypropylene oxide-based triol with HDI and then reacting with a molecule of formula I, which is a CPEE.

[0152] 37. The adhesive composition of any one of the previous embodiments, wherein at least one polyurethane prepolymer is made by reacting a polypropylene oxide-based triol of molecular weight 4,800 Da with HDI and then with a molecule of formula I, which is a CPEE, and wherein the polyol is used at 82-83 wt%, the HDI is used at 8-9 wt%, and the CPEE is used at 8-9 wt%, based on the total weight of the polyurethane prepolymer.

[0153] 38. The adhesive composition of any one of the previous embodiments, wherein the amine-blocked polyamine is an aldimine or a polyoxazolidine.

[0154] 39. The adhesive composition of any one of the previous embodiments, wherein the amine-blocked polyamine is a dialdimine or a bis-oxazolidine.

[0155] 40. The adhesive composition of any one of the previous embodiments, wherein the amine-blocked polyamine is a polyoxazolidine.

[0156] 41. The adhesive composition of any one of the previous embodiments, wherein the amine-blocked polyamine is a bis-oxazolidine.

[0157] 42. The amine-blocked polyamine is represented by formula II or formula III: [ka] (In formula II, R 10 is a branched or unbranched divalent organic group, R 11 and R 12 independently represents H and branched or unbranched C 1 ~C 8 -alkyl, In formula III, R 13 is a branched or unbranched trivalent organic group, R 14 , R 15 and R 16 independently represents H and branched or unbranched C 1 ~C 8 3. The adhesive composition of any one of the previous embodiments, wherein the polyoxazolidine is selected from the group consisting of aryl, aryl-, aryl-alkyl, aryl-alkyl- ...

[0158] 43. The amine-blocked polyamine is represented by formula V, formula VI or formula XII: [ka] (In formula V, R 17 and R 18 are independently H and branched or unbranched C 1 ~C 8 -alkyl, preferably C 7 -alkyl, and In formula VI, R 19 and R 20 are independently H and branched or unbranched C 1 ~C 8 -alkyl, preferably C 7 -alkyl, and In formula XII, R 21 and R 22is independently a branched or unbranched C 1 ~C 8 -alkyl, preferably C 3 3. The adhesive composition of any one of the previous embodiments, wherein the polyoxazolidine is selected from the group consisting of aryl, aryl-, aryl-alkyl, aryl-alkyl- ...

[0159] 44.In formula V, R 17 and R 18 But the following equation [ka] The adhesive composition of embodiment 43, wherein

[0160] 45. In formula VI, R 19 and R 20 The adhesive composition of embodiment 43, wherein is 1-ethylpentyl.

[0161] 46. ​​In formula XII, R 21 and R 22 But the following equation [ka] The adhesive composition of embodiment 43, wherein

[0162] 47. The amine-blocked polyamine is represented by the formula VII, VIII, IX, X or XI: [ka] The adhesive composition of any one of the previous embodiments,

[0163] 48. A polyamine having blocked amine groups is represented by the formula VIII: [ka] Or formula XI: [ka] and The adhesive composition of any one of the previous embodiments, preferably of Formula VIII.

[0164] 49. The adhesive composition of any one of the previous embodiments, comprising a catalyst capable of catalyzing the reaction of an amine with a moiety derived from a molecule of formula I.

[0165] 50. The adhesive composition of any one of the previous embodiments, comprising a catalyst capable of catalyzing the reaction of an amine with a moiety derived from a molecule of formula I, the catalyst being bismuth neodecanoate.

[0166] 51. The adhesive composition according to any one of the previous embodiments, wherein the polyurethane prepolymer is used in an amount of 20 to 70% by weight, more preferably 30 to 55% by weight, and more particularly preferably 35 to 40% by weight, based on the total weight of the adhesive composition.

[0167] 52. The adhesive composition of any one of the previous embodiments, wherein the ratio of amino groups in the amine-blocked polyamine to the end groups of the polyurethane prepolymer is 1:1, 0.9:1, 1.0:0.9, 0.8:1, 1:0.8, or 2:1.

[0168] 53. The adhesive composition of any one of the previous embodiments, further comprising at least one plasticizer.

[0169] 54. The adhesive composition of embodiment 53, wherein the plasticizer is an ester, in particular a diester or triester.

[0170] 55. A plasticizer is 10 -4 55. The adhesive composition of embodiment 53 or 54, having a vapor pressure of less than 1000 psi.

[0171] 56. The adhesive composition of embodiment 53 or 54, wherein the plasticizer is dinonyl phthalate.

[0172] 57. At least one prepolymer prepared by reacting a polypropylene oxide-based triol with HDI and then reacting with a molecule of formula I, which is a CPEE; 1. A blocked polyamine having the formula VIII: [ka] Or formula XI: [ka] and polyamines which are 2. The adhesive composition of any one of the preceding embodiments, comprising:

[0173] 58. Based on the total weight of the adhesive composition, 42-45 wt. % of at least one prepolymer prepared by reacting a polypropylene oxide based triol with HDI and then reacting with a molecule of formula I, which is a CPEE; 1. A blocked polyamine having the formula VIII: [ka] Or formula XI: [ka] 6 to 9% by weight of polyamine 2. The adhesive composition of any one of the preceding embodiments, comprising:

[0174] 59. Based on the total weight of the adhesive composition, 42-45 wt. % of at least one prepolymer prepared by reacting a polypropylene oxide based triol with HDI and then reacting with a molecule of formula I, which is a CPEE; 1. A blocked polyamine having the formula VIII: [ka] Or formula XI: [ka] 6 to 9% by weight of a polyamine; A catalyst, preferably 0.1 to 0.3 wt. % bismuth neodecanoate; with 12-18% by weight of a plasticizer which is dinonyl phthalate; with 8-10% by weight of clay; Carbon black 20-25% by weight 2. The adhesive composition of any one of the preceding embodiments, comprising:

[0175] 60.(1) applying an adhesive composition according to any one of the previous embodiments to a first substrate, a second substrate, or both; (2) bringing a first substrate and a second substrate into adhesive contact; (3) curing the adhesive by exposing it to moisture; A method for bonding a first substrate and a second substrate, comprising:

[0176] 61. (1) Providing a one-component moisture-curable polyurethane adhesive composition according to any one of embodiments 1 to 58; (2) applying an adhesive to a first substrate, a second substrate, or both; (3) placing the first and second substrates in adhesive contact, whereby the adhesive is sandwiched therebetween; (4) curing the adhesive; A method for bonding two substrates, comprising:

[0177] 62. The method according to embodiment 60 or 61, wherein the first and second substrates are selected from metal, glass, and polymer.

[0178] 63. The method according to embodiment 60 or 61, wherein the first and second substrates are selected from metals.

[0179] 64. The method according to embodiment 60 or 61, wherein the first and second substrates are steel.

[0180] 65. The method according to embodiment 60 or 61, wherein the first substrate is a metal and the second substrate is a polymer.

[0181] 66.(1) A first substrate; (2) a second substrate; (3) The adhesive composition according to any one of embodiments 1 to 59. A bonded assembly comprising: An assembly in which first and second substrates are in adhesive contact with an adhesive sandwiched therebetween.

[0182] 67. The bonded assembly according to embodiment 66, wherein the first and second substrates are selected from metal, glass, and polymer.

[0183] 68. The bonded assembly according to embodiment 66, wherein the first and second substrates are selected from metals.

[0184] 69. A bonded assembly according to embodiment 66, wherein the first and second substrates are steel.

[0185] 70. A bonded assembly according to embodiment 66, wherein the first substrate is metal and the second substrate is polymeric. EXAMPLES

[0186] [Table 1]

[0187] Preparation of Polyurethane Prepolymer Blocked polyurethane prepolymer 1 was prepared using the components shown in Table 2.

[0188] [Table 2]

[0189] Polyether polyol (VORANOL CP 4610) was added to a lab reactor and heated to 130°C under vacuum and stirring. Once 130°C was reached, the mixture was cooled to 70°C under stirring (material temperature). The vacuum was released and Desmodur H was added to the lab reactor. The mixture was stirred under nitrogen for 2 minutes at which point catalyst TIB KAT 718 was added. The mixture was allowed to react for 45 minutes under nitrogen with stirring at a bath temperature of 85°C. The isocyanate content was checked to be 2.37%.

[0190] The mixture was cooled to 60° C. with stirring under nitrogen. Once the material temperature reached 60° C., CPEE was added. The mixture was allowed to react for 45 minutes under stirring and nitrogen at a bath temperature of 85° C. The isocyanate content was checked to be 0%.

[0191] The mixture was stirred under vacuum with a bath temperature of 85° C. for an additional 20 min.

[0192] Blocked polyurethane prepolymer 2 was prepared using the components shown in Table 3.

[0193] [Table 3]

[0194] Cardolite NX-2026 and Desmodur E15 were mixed and heated to 60° C. Then DABCO T-12N catalyst was added. The mixture was stirred under nitrogen at 80° C. for 45 minutes and then under vacuum for 10 minutes. The mixture was cooled and stored in a closed container.

[0195] Adhesive Formulation The adhesive formulations were mixed in a planetary mixer or a double asymmetric centrifuge using the ingredients listed in Table 4. In the first stage, the liquid phase was mixed and then the solid materials were added to the formulation. The formulations were mixed under vacuum for about 30 minutes and then filled into cartridges, pails, or drums.

[0196] Test Method viscosity Viscosity was measured on a Kinexus rheometer using a plate / cone setup with a 20 mm diameter cone at an angle of 4° and a gap of 0.144 mm. Measurements were performed at 23° C. Shear rate measurements were performed from 0.1 to 10 1 / s and Newtonian viscosity is reported.

[0197] Lap Shear Test Lap shear tests were carried out on glass substrates according to DIN EN 1465 (GEX21). Float glass substrates with dimensions 100 x 25 x 5 mm were used. The substrates were primed with the glass primer BETAPRIME™ 5500. The primer was allowed to evaporate for 15 minutes before applying the adhesive composition. The adhesive composition was applied and a second substrate was joined. The overlap area of ​​the adhesive was 25 x 10 mm and the adhesive thickness was 2 mm. Lap shear tests were carried out after curing of the adhesive composition and are reported in Table 4. The tests were carried out on a Zwick tensiometer equipped with a 5 kN force measuring system with a preload of 2 N and a pulling speed of 10 mm / min. The tests were carried out at 23°C and 50% rh.

[0198] Tensile Test Tensile tests were performed according to DIN EN ISO 527-2. Dogbones were cut from 2 mm thick plates cured at 23 °C and 50% rh for at least 7 days. The preload was 1.5 N, the specimen width was 4 mm and the pull-out speed was 200 mm / min. A 500 N force measuring system was used together with a MuliXtens distance measuring system. The results are reported in Table 4.

[0199] molecular weight The molecular weight data of the polyurethane prepolymer was measured by gel permeation chromatography (GPC) using a Malvern Viscothek GPC max instrument, with tetrahydrofuran (THF) as the eluent, PL GEL MIXED D (Agilent, 300*7.5mm, 5μm) as the column, and MALVERN Viscotek TDA (integrated refractive index viscometer and light scattering) as the detector.

[0200] NCO content NCO measurements were performed according to ASTM D2572-97 (Reapproved 2010) (GEX081). This test method is applicable to isocyanate-containing fluids. These include monomers (e.g., methylene diphenyl diisocyanate MDI), prepolymers, and adhesive formulations. The isocyanate (NCO) samples were reacted with an excess of dibutylamine to form the corresponding urea. The NCO content was determined from the amount of dibutylamine consumed in the reaction. Results are reported as percent NCO (wt%).

[0201] result The experimental results are shown in Tables 4 and 5. Comparative examples are designated "CE" and examples of the present invention are designated "IE".

[0202] [Table 4]

[0203] [Table 5]

[0204] CE1 shows that when CPEE-protected prepolymer 1 alone was exposed to humidity, it did not crosslink and did not show a significant increase in viscosity even after 7 days at 23° C. and 50% rh.

[0205] CE2 shows that when an isocyanate-functional prepolymer (Prepolymer 2) capped with a phenol-based common protecting group is exposed to humidity (7 days, 23°C), it also shows no reaction or increase in viscosity after 7 days at 23°C.

[0206] CE3 shows what happens when the bis-oxazolidine is exposed to moisture for 7 days at 23° C. This results in hydrolysis of the bis-oxazolidine, converting it to an amine, but no crosslinking occurs, as indicated by the very low viscosity even after 7 days at 23° C.

[0207] CE4 shows that the conventional blocked polyurethane prepolymer 2 does not crosslink even in the presence of bis-oxazolidine.

[0208] Inventive Example IE1 contains a CPEE blocked prepolymer (Prepolymer 1) in combination with a bis-oxazolidine. When this mixture is exposed to moisture, crosslinking begins and a hardened putty is formed. This crosslinking process can be assisted by the addition of a catalyst (Bicat 8108), as shown in Inventive Example IE2. This technique can be utilized to formulate a filled 1K PU adhesive composition, as shown in Inventive Example IE3. In the uncured state, the adhesive composition from IE3 is a black paste with good rheology, no sagging, and very short strings. After application, curing begins with moisture to form a crosslinked PU / polyamide polymer. The lap shear strength of a float glass substrate primed with glass primer BETAPRIME 5500 (15 min flash-off time) was 2.2 MPa in 100% cohesive failure mode. Tensile tests were performed on specimens cut from 2 mm thick plates cured for 14 days at 23°C (50% rh) showing a tensile strength of 2.7 MPa, an E modulus of 1.3 MPa and an elongation at break of 455%. Adhesion tests were performed on float glass and e-coated steel substrates. The glass substrates were primed with glass primer BETATPRIME 5500 and the e-coated steel substrates were primed with black primer BETAPRIME 5404. Peel adhesion tests were performed after 7 days of curing at 23°C and 50% relative humidity, 7 days at 23°C followed by 7 days of immersion in water at 23°C, 7 days at RT followed by 7 days of immersion in water followed by exposure at 70°C, and after 7 days at RT followed by 7 days of immersion in water followed by 7 days of exposure at 70°C followed by 7 days of cataplasma exposure (70°C, 100% rh). All peel adhesion tests showed 100% cohesive failure mode, indicating that good adhesion was observed on primed glass substrates. Cure rate tests showed that the material cured to a thickness of 3 mm within 48 hours.

Claims

1. (A) reacting at least one polyisocyanate with at least one polyol (resulting in Intermediate I), and then, Formula I: 【Chemical 1】 (wherein R １ and R ２ are independently selected from hydrogen and C １ to C ６ alkyl, n is an integer from 1 to 2, and R ３ is C １ to C ６ alkyl) by reacting with a molecule of), a polyurethane prepolymer of 20 to 70% by weight; (B) a polyamine in which the amine groups are blocked by a group that is cleaved upon exposure to humidity; (C) optionally, a catalyst capable of catalyzing the reaction of the amine with the moiety obtained from the molecule of Formula I A one-component moisture-curing polyurethane adhesive composition comprising.

2. The adhesive composition according to claim 1, wherein the at least one polyol is a polyether polyol or a polyester polyol.

3. The adhesive composition according to claim 1, wherein the at least one polyol is selected from polyoxyethylene, polyoxypropylene, polyoxybutylene, and polytetramethylene ether diol and triol.

4. The adhesive composition according to claim 1, wherein the at least one polyisocyanate is a diisocyanate.

5. The adhesive composition according to claim 1, wherein the at least one polyurethane prepolymer is produced by reacting a polypropylene oxide-based triol with HDI.

6. The adhesive composition according to claim 1, wherein the at least one polyol and the at least one polyisocyanate are reacted in the presence of a catalyst selected from metal carboxylates such as bismuth catalysts, tin carboxylates, and zinc carboxylates.

7. The adhesive composition according to claim 1, wherein the prepolymer contains at least one polyol in an amount of 40 to 95% by weight based on the total weight of the polyurethane prepolymer.

8. In the molecule of the formula I, R １ and R ２ are independently selected from H and C １ to C ４ alkyl, the adhesive composition according to claim 1.

9. The adhesive composition according to claim 1, wherein the molecule of Formula I is used in an equivalent amount or in excess of the NCO groups of Intermediate I.

10. The adhesive composition according to claim 1, wherein the polyamine with blocked amine groups is an aldimine or a polyoxazolidine.

11. The polyamine with blocked amine groups is of Formula II or Formula III: 【Chemical 2】 (In formula II, R １０ is a branched or unbranched divalent organic group, and R １１ and R １２ are independently selected from H and branched or unbranched C １ to C ８ -alkyl, In formula III, R １３ is a branched or unbranched trivalent organic group, and R １４ , R １５ and R １６ are independently H and a branched or unbranched C １ to C ８ -alkyl), and is a polyoxazolidine. The adhesive composition according to claim 1.

12. The polyamine with blocked amine groups is of Formula V, Formula VI, or Formula XII: [Chemical Formula 3] (In formula V, R １７ and R １８ are independently H and branched or unbranched C １ to C ８ -alkyl, preferably C ７ -alkyl or C ３ -alkyl, and In formula VI, R １９ and R ２０ are, independently, H, and branched or unbranched C １ to C ８ -alkyl, preferably C ７ -alkyl, and In formula XII, R ２１ and R ２２ are independently a polyoxazolidine selected from branched or unbranched C １ to C ８ -alkyl, preferably C ３ -alkyl), the adhesive composition according to claim 1.

13. The adhesive composition according to claim 1, comprising a catalyst capable of catalyzing the reaction of the amine with the moiety obtained from the molecule of Formula I.

14. Step of applying the adhesive composition according to any one of claims 1 to 13 to the first substrate, the second substrate, or both; Step of adhesively contacting the first substrate and the second substrate; Step of curing the adhesive by exposing it to moisture A method of bonding a first substrate and a second substrate, comprising:

15. (1) A first substrate; (2) A second substrate; (3) An adhesive composition according to any one of claims 1 to 13 An assembled product, comprising: An assembly in which the first and second substrates are adhesively contacted with the adhesive sandwiched therebetween.

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