One-part moisture-curable adhesive composition

Abstract

The present invention relates to a one-component moisture-curable adhesive composition comprising 80 to 100% by weight of an isocyanate-functional prepolymer obtainable by reacting (a) a polyisocyanate mixture having an average nominal isocyanate functionality in the range of more than 2.00 and less than 2.05, the polyisocyanate mixture containing (a1) a diisocyanate including methyldiphenyldiisocyanate, and (a2) a uretonimine-modified methyldiphenyldiisocyanate having three or more isocyanate functional groups, with (b) a polyol mixture containing (b1) a linear butylene oxide-based diol having two primary hydroxyl groups, (b2) a polyether triol having three secondary hydroxyl groups, and (b3) an amine-initiated polyether polyol, the equivalent ratio of the isocyanate groups in (a) to the hydroxyl groups in (b) being in the range of 3.5 to 7.0, and the content of free isocyanate groups in the adhesive composition being in the range of 1.0 to 1.5% by weight of ASTM A1111. The present invention relates to a one-component moisture-curing adhesive composition, the polyisocyanate mixture (a) comprising an excess of diisocyanate (a1) over uretomine-modified methyldiphenyl diisocyanate (a2), the weight percent of which is in the range of 14-17%, as measured according to the D2572-19 standard. The present invention further relates to a method for bonding a first piece of material to a second piece of material using such an adhesive composition, as well as to an object, in particular a structural wood product, comprising a first piece of material and a second piece of material bonded together using such an adhesive composition.

Description

[Technical field]

[0001] The present invention relates to a one-part, moisture-curable adhesive composition comprising an isocyanate-functional prepolymer, a method for bonding a first piece of material to a second piece of material using such an adhesive composition, and an object, particularly a structural wood product, comprising a first piece of material and a second piece of material bonded with such an adhesive composition. [Background technology]

[0002] Glued laminated timber, also called laminated timber beam, glue-laminated beam or glulam, is a structural wood product made by gluing together multiple layers of sized lumber. By laminating multiple smaller pieces of wood together, large, strong single structural members can be made from the smaller pieces for use as, for example, purlins, garage lintels, floor beams, vertical supports or horizontal beams, often in curved or arched shapes. Glued laminated beams are used in a wide range of applications in building construction. Another glued laminated timber product is cross-laminated timber (CLT), a wood panel product made by gluing together layers of solid-sawn lumber. Each layer of the board is oriented perpendicular to the adjacent layers and is usually glued symmetrically on the broad faces of each board with the outer layers having the same orientation. Ordinary timber is an anisotropic material, which means that its mechanical properties change depending on the direction of applied force. By gluing the wood layers together at right angles, the panel achieves better structural rigidity in both directions. CLT is distinct from glued laminated timber, which is a product in which all laminae are uniformly oriented.

[0003] Adhesive compositions used in building materials, such as glued laminated timber products and other structured wood products (also known as engineered wood products), must meet stringent requirements for bond strength under indoor and outdoor conditions. Adhesives are needed that provide good bond strength even under conditions where wood is exposed to moisture and thermal stresses that cause it to swell and shrink and put under tension.

[0004] One-part moisture-curing polyurethane adhesives are known for bonding wood pieces to form structural wood products, such as glued laminated timber products. Such adhesive compositions contain an isocyanate-functional prepolymer that cures upon reaction with moisture. The isocyanate groups in the prepolymer react with water to form amine groups, which react with additional isocyanate groups to form urea bonds. When used for making structural laminated timber products, the adhesive composition is typically applied to the surface of the wood pieces, such as timber or lumber pieces, and then the different pieces are pressed together to cure the adhesive composition and form the structural wood product.

[0005] Such polyurethane adhesives are described, for example, in WO 99 / 19141, U.S. Patent Application Publication No. 2005 / 032972 and WO 2021 / 022470.

[0006] WO 99 / 19141 describes a polyisocyanate adhesive for use in the manufacture of lignocellulosic structural laminates (plywood production). The adhesive contains an isocyanate-containing prepolymer with an isocyanate content of 5-25%, obtained by reacting a mixture of polyols with an average nominal functionality of 2-4 and an average equivalent weight of 500-3000 with a stoichiometric excess of diphenylmethane diisocyanate. A particularly preferred polyol mixture is a polypropylene-polyethylene oxide polyol containing up to 5% of another polyol.

[0007] US Patent Application Publication No. 2005 / 032972 describes a one-component fast-curing polyurethane adhesive that contains a polyisocyanate prepolymer and one or more aminoether polyols, in which the molar ratio of ether groups to amino nitrogen in the aminopolyether polyol is 7 to 30. The polyurethane prepolymer is produced by the reaction of a polyisocyanate with a compound having an isocyanate-reactive functional group.

[0008] WO 2021 / 022470 describes a one-component polyurethane prepolymer composition for waterproof coating applications. The composition includes one or more polyisocyanates and a polyol blend having a weight average molecular weight of 3,000 to 5,000. 9,000 and a difunctional polyether polyol having a weight average molecular weight of 5,000 to 5,000 which is end-capped with 10 to 28% by weight of ethylene oxide. 8,000 and a polyol blend containing a trifunctional polyether polyol of.

[0009] The balance between the maximum deposition time (AT) and the minimum pressing time (PT) is very important for one-part moisture-curing polyurethane adhesive compositions. The maximum deposition time is the time during which the adhesive composition can be applied to the pieces of material before pressing. The applied adhesive composition must still be able to cure when the pieces are pressed together. The minimum pressing time is the time during pressing required to provide sufficient bonding of the pressed pieces of material to allow further processing of the structural product. An AT to PT ratio of 1:1 to 1:2.5 is often acceptable. Ideally, the AT / PT ratio should be close to 1.1, preferably 1:1 to 1:2, more preferably 1:1 to 1:2. Adhesive compositions with very good AT / PT ratios usually have poorer mechanical properties, such as wet and dry bond strength, than products with less favorable AT / PT ratios. Therefore, fibers are often added to one-part moisture-curing polyurethane adhesive compositions to improve mechanical properties, such as longitudinal tensile strength.

[0010] There is a need in the art for a one-part, moisture-curable polyurethane adhesive composition that combines good fiber-free mechanical properties with a favorable AT / PT ratio. [Prior art documents] [Patent documents]

[0011] [Patent Document 1] International Publication No. 99 / 19141 [Patent Document 2] US Patent Application Publication No. 2005 / 032972 [Patent Document 3] International Publication No. 2021 / 022470 Summary of the Invention

[0012] Diphenylmethane Diisocyanate and uretonimine modified Diphenylmethane Diisocyanate It has now been found that one-part moisture-curable adhesive compositions containing an isocyanate-functional prepolymer impart good adhesion and have a favorable AT / PT ratio, when the prepolymer is prepared by reacting an excess of a polyisocyanate comprising the prepolymer with a particular polyol mixture, and the content of free isocyanate groups in the adhesive composition is within the range of 14-17 wt.%.

[0013] Thus, the present invention provides in a first aspect a method for producing a method for treating a cancer comprising the steps of: (a) a polyisocyanate mixture having an average nominal isocyanate functionality in the range of greater than 2.00 and less than 2.05; (a1) Diphenylmethane Diisocyanate and (a2) Uretonimine-modified polyisocyanate having three or more isocyanate functional groups Diphenylmethane Diisocyanate A polyisocyanate mixture containing (b) a polyol mixture; (b1) a linear butylene oxide-based diol having two primary hydroxyl groups; (b2) a polyether triol having three secondary hydroxyl groups, and (b3) amine-initiated polyether polyols; A polyol mixture containing A one-part moisture-curable polyurethane adhesive composition comprising an isocyanate-functional prepolymer obtained by reacting the equivalent ratio of the isocyanate group of (a) to the hydroxyl group of (b) is within the range of 3.5 to 7.0; The present invention provides a one-component moisture-curable polyurethane adhesive composition, wherein the adhesive composition has a free isocyanate group content in the range of 14 to 17% by weight.

[0014] The one-component moisture-curing polyurethane adhesive composition according to the first aspect, due to its excellent adhesive properties and its favourable AT / PT ratio, is particularly suitable for joining pieces of material, in particular pieces of wood such as pieces of wood or timber, to form structural wood products.

[0015] The present invention therefore provides in a second aspect a method for joining a first piece of material to a second piece of material, comprising the step of contacting a surface of said first material with a surface of said second material, wherein prior to said contacting step an adhesive composition according to the first aspect of the present invention is applied to at least one of said contacting surfaces.

[0016] In a final aspect, the invention provides an object, in particular a structural wood product, comprising a first piece of material and a second piece of material joined together using an adhesive composition according to the second aspect of the invention. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0017] The adhesive composition according to the present invention is a one-part moisture-curable composition. The composition preferably comprises at least 80% by weight of an isocyanate-functional prepolymer, more preferably at least 85% by weight, even more preferably at least 90% by weight. The adhesive composition may comprise up to 100% by weight of an isocyanate-functional prepolymer, preferably up to 99.8% by weight.

[0018] The isocyanate-functional prepolymer is (a) a polyisocyanate mixture having an average nominal isocyanate functionality in the range of greater than 2.00 to less than 2.05, (a1) Diphenylmethane Diisocyanate and (a2) Uretonimine-modified polyisocyanate containing three or more isocyanate functional groups Diphenylmethane Diisocyanate A polyisocyanate mixture containing (b) a polyol mixture comprising: (b1) a linear butylene oxide-based diol having two primary hydroxyl groups; (b2) a polyether triol having three secondary hydroxyl groups, and (b3) Amine-initiated polyol A polyol mixture containing can be obtained by reacting The equivalent ratio of the isocyanate groups of (a) to the hydroxyl groups of (b) is within the range of 3.5 to 7.0.

[0019] The polyisocyanate mixture (a) is Diphenylmethane Diisocyanate and a diisocyanate (a1) containing 3 or more isocyanate functional groups. Uretonimine Denaturation Diphenylmethane Diisocyanate (a2). The polyisocyanate mixture (a) comprises Uretonimine Denaturation Diphenylmethane Diisocyanate The polyisocyanate mixture (a) contains an excess of diisocyanate (a1) over (a2). The average nominal isocyanate functionality of the polyisocyanate mixture (a) is in the range of from greater than 2.00 to less than 2.05, preferably greater than 2.00 to 2.04, more preferably greater than 2.00 to less than 2.03. Generally, the average nominal isocyanate functionality of the polyisocyanate mixture (a) is greater than 2.001, preferably greater than 2.002, more preferably greater than 2.003, even more preferably greater than 2.004, and most preferably greater than 2.005. References herein to the average nominal isocyanate functionality refer to the number average of isocyanate groups per molecule.

[0020] Diisocyanate (a1) is Diphenylmethane Diisocyanate (MDI) included. Diphenylmethane Diisocyanate is 4,4'- Diphenylmethane Diisocyanate , 2,4'- Diphenylmethane Diisocyanate , 2,2'- Diphenylmethane Diisocyanate or a mixture of two or more of these. Preferably, the diisocyanate (a1) is Diphenylmethane Diisocyanate More preferably, 4,4'- Diphenylmethane Diisocyanate or 4,4'- Diphenylmethane Diisocyanate and 2,4'- Diphenylmethane Diisocyanate and / or a mixture of 2,2'- Diphenylmethane Diisocyanate Preferably, the 4,4'- of the polyisocyanate mixture (a) is Diphenylmethane Diisocyanate The content is in the range of 50-100% by weight. Such mixtures are commercially available, for example, as Suprasec 2004, Suprasec 6004 (e.g., manufactured by Huntsman Corporation), Lupranate MX 119 / 1 (e.g., manufactured by BASF), Cosmonate JG-50K, Cosmonate PI (e.g., manufactured by Kumho Mitsui Chemicals, Inc.), or Ongronat CO4050 (e.g., manufactured by Wanhua Chemicals).

[0021] For purposes of this specification: Diphenylmethane Diisocyanate The term Diphenylmethane Diisocyanate Refers to itself, polymeric Diphenylmethane Diisocyanate , oligomeric Diphenylmethane Diisocyanate Or denaturation Diphenylmethane Diisocyanate , e.g. carbodiimide modification Diphenylmethane Diisocyanate , uretonimine modified Diphenylmethane Diisocyanate Or isocyanurate modified Diphenylmethane Diisocyanate Does not include.

[0022] Uretonimine modification Diphenylmethane Diisocyanate (a2) comprises 3 or more isocyanate functional groups, preferably in the range of 3 to 10 isocyanate functional groups, more preferably in the range of 3 to 6 isocyanate functional groups, and even more preferably 3 or 4 isocyanate functional groups.

[0023] The polyisocyanate mixture (a) is Diphenylmethane Diisocyanate or uretonimine modified Diphenylmethane DiisocyanateIn addition, the polyisocyanate may preferably be present in an amount of up to 25% by weight, more preferably up to 10% by weight, based on the total weight of the polyisocyanate (a). In a particularly preferred embodiment, the polyisocyanate mixture (a) comprises Diphenylmethane Diisocyanate and uretonimine modified Diphenylmethane Diisocyanate and does not contain any other polyisocyanate.

[0024] The polyol mixture (b) comprises a linear butylene oxide-based diol (b1) having two primary hydroxyl groups, a polyether triol (b2) having three secondary hydroxyl groups, and an amine-initiated polyol (b3).

[0025] The butylene oxide-based diol (b1) is linear and has two primary hydroxyl groups. The two primary hydroxyl groups are terminal hydroxyl groups. Such a diol can be obtained by polymerizing butylene oxide, also known as tetrahydrofuran, also known as poly(tetrahydrofuran), poly(tetramethylene ether) glycol, poly(tetramethylene oxide) or poly(1,4-butanediol). The diol (b1) is preferably 500 to 1000 .mu.m. 2,500 More preferably, within the range of 500 to 1,500 Such diols (b1) are commercially available, for example, as PolyTHF 650, PolyTHF 1000, and PolyTHF 1400 (for example, manufactured by BASF).

[0026] The polyether triol (b2) has three secondary hydroxyl groups. The polyether triol (b2) is preferably polyethylene ether, polypropylene ether, polybutylene ether or a hybrid thereof, more preferably polyethylene ether, polypropylene ether or a hybrid thereof. The polyether triol (b2) is preferably 500 to 2,500 More preferably, within the range of 500 to 1,500Particularly suitable examples of polyether triols (b2) have a number average molecular weight in the range 1,000 The polypropylene ether triol is Voranol CP1050 (available from Dow).

[0027] The amine-initiated polyether polyol (b3) is a polyol prepared by using an amine, preferably an aliphatic amine, as the initiator molecule. Suitable amine initiator molecules include ethylenediamine, hexamethylenediamine, methylamine, isopropanolamine, diisopropanolamine, ethanolamine, diethanolamine, N-methyldiethanolamine, tetrahydroxyethylethylenediamine or mixtures thereof. The amine initiator preferably contains 1 to 18 carbon atoms, more preferably 1 to 6 carbon atoms. The amine-initiated polyether polyol (b3) is a polyether, preferably poly(ethylene oxide), poly(propylene oxide) or a hybrid thereof. The amine-initiated polyether polyol (b3) preferably contains 2 to 6 hydroxyl groups, more preferably 2 to 4 hydroxyl groups, even more preferably 3 or 4 hydroxyl groups. The number average molecular weight of the amine-initiated polyether polyol (b3) is preferably 1,000 to 1,000. 10,000 More preferably, within the range of 1,000 to 6,000 and more preferably within the range of 1,500 to 5,000 Preferably, at least a portion of the hydroxyl groups are primary hydroxyl groups. Primary hydroxyl groups can be obtained by end-capping the polyether chain with ethylene oxide. Such amine-initiated polyether polyols are commercially available, for example Lupranool 1002 / 1 (e.g., from BASF).

[0028] Typically, the amount of butylene oxide diol (b1) in the polyol mixture (b) is such that the hydroxyl groups derived from the butylene oxide diol (b1) are in the range of 45-85%, preferably in the range of 50-80%, more preferably in the range of 55-75%, and most preferably in the range of 60-70% of the hydroxyl groups in the polyol mixture (b). It has been found that when the content of hydroxyl groups derived from the butylene oxide diol (b1) in the polyol mixture (b) is in the range of 55-75%, the AT / PT ratio is improved compared to when the content is lower.

[0029] In general, the amount of polyether triol (b2) in the polyol mixture (b) is such that the hydroxyl groups derived from the polyether triol (b2) are in the range of 20 to 70%, preferably in the range of 30 to 60%, more preferably in the range of 35 to 55%, of the hydroxyl groups in the polyol mixture (b).

[0030] The polyol mixture (b) may contain polyols other than the butylene oxide-based diol (b1) and the polyether triol (b2), preferably in an amount of less than 50% by weight, more preferably less than 30% by weight, and even more preferably less than 10% by weight of the polyol mixture (b). In a particularly preferred embodiment, the polyol mixture (b) is substantially free of polyols other than (b1) and (b2). The phrase "substantially free of polyols other than (b1) and (b2)" in this specification means that the polyol mixture contains 1% by weight or less, preferably 0.5% by weight or less of polyols other than (b1) and (b2), and even more preferably, the polyol mixture does not contain any polyols other than (b1) and (b2).

[0031] Preferably, the amount of amine-initiated polyether polyol (b3) in polyol mixture (b) is such that the number of hydroxyl groups derived from amine-initiated polyether polyol (b3) is 50% or less, preferably 40% or less, even more preferably 20% or less, and even more preferably 15% or less of the total number of hydroxyl groups in polyol mixture (b). The amount of butylene oxide-based diol (b1) in polyol mixture (b) is preferably such that the number of hydroxyl groups derived from butylene oxide-based diol (b1) is 40% or more of the total number of hydroxyl groups in polyol mixture (b).

[0032] The isocyanate-functional prepolymer can be obtained by reacting an excess of polyisocyanate with a polyol. The equivalent ratio of the isocyanate groups in the polyisocyanate mixture (a) to the hydroxyl groups in the polyol mixture (b) is in the range of 3.5 to 7.0, preferably in the range of 4.0 to 6.5, more preferably in the range of 4.5 to 6.0. If the amount of polyisocyanate is further excessive, the molecular weight of the obtained prepolymer will be small, which may adversely affect the bond strength and AT / PT ratio.

[0033] The weight average molecular weight of the isocyanate-functional prepolymer is preferably 1,500 More preferably, 2,000 That's all. 2,000~ 5,000 Weight average molecular weights in the range of are particularly preferred.

[0034] The reaction conditions for preparing isocyanate-functional prepolymers from polyisocyanates and polyols are well known in the art. Any suitable reaction conditions may be used.

[0035] References herein to number average or weight average molecular weight refer to number average or weight average molecular weight as measured by size exclusion chromatography using polystyrene standards. A suitable method of measurement is the ISO 16014-1 standard.

[0036] The adhesive composition may contain components other than the isocyanate-functional prepolymer, such as organic solvents, reactive diluents, curing catalysts, pigments, fillers, and one or more additives, such as defoamers and thickeners.

[0037] The adhesive composition may contain an organic solvent, preferably in an amount of 10% by weight or less, more preferably 5% by weight or less, even more preferably 2% by weight or less of the total weight of the adhesive composition. If an organic solvent is present, the organic solvent is preferably a polar organic solvent, such as a ketone, ester or ether.

[0038] The adhesive composition may contain a curing catalyst for curing the moisture curing reactant, typically in an amount ranging from 0 to 0.4% by weight. Suitable curing catalysts are known in the art. Tertiary amines, organometallic compounds and strong bases are known to be suitable as curing catalysts. A particularly preferred curing catalyst is 2,2'-dimorpholine diethyl ether (DMDEE).

[0039] The adhesive composition may include any suitable additive commonly used in adhesive compositions, such as an antifoaming agent, a thickener, and / or a wetting agent. Preferably, the adhesive composition includes an antifoaming agent and / or a thickener.

[0040] The content of free isocyanate groups in the adhesive composition is in the range of 14 to 17% by weight based on the total weight of the adhesive composition. The free isocyanate groups are free isocyanate groups in the prepolymer and any unreacted polyisocyanate monomer. A further polyisocyanate, preferably a diisocyanate, more preferably Diphenylmethane Diisocyanate may be added to the prepolymer so that the content of free isocyanate groups in the adhesive composition reaches a range of 14 to 17% by weight.

[0041] More preferably, the content of free isocyanate groups in the adhesive composition is within the range of 15.0 to 16.5% by weight.

[0042] The content of free isocyanate groups is determined in accordance with the ASTM D2572-19 standard.

[0043] The adhesive composition preferably does not contain water or contains only trace amounts of water. Preferably, the adhesive composition contains less than 1.0 wt. %, more preferably less than 0.2 wt. %, even more preferably less than 0.01 wt. %, based on the total weight of the adhesive composition. Water is not specifically and precisely added, for example to adjust the viscosity of the coating composition, but is present only in trace amounts as part of a general adhesive additive, if present at all.

[0044] The adhesive composition is preferably fiber-free.

[0045] In a preferred embodiment, the adhesive composition does not contain any compounds other than the isocyanate-functional prepolymer, additional polyisocyanate, curing catalyst and additives.

[0046] One-part moisture curable adhesive compositions are particularly suitable for joining pieces of wood or other materials to form structural products.

[0047] The present invention therefore provides a method of joining a first piece of material to a second piece of material, comprising the step of contacting a surface of said first material with a surface of said second material, wherein prior to said contacting step an adhesive composition according to the first aspect of the present invention is applied to at least one of said contacting surfaces.

[0048] In a third aspect, the present invention provides an object comprising a first piece of material and a second piece of material joined using an adhesive composition according to the first aspect of the present invention.

[0049] The material may be any suitable material, for example wood, metal, plastic, paper, glass, concrete, plaster or other mineral material, for example stone or brick. The first piece of material and the second piece of material may be dissimilar materials. Preferably, the piece of material is a piece of wood.

[0050] The object may be any suitable object. Preferably, the material is wood and the object is a structural wood product.

[0051] The invention is further illustrated by the following non-limiting examples. EXAMPLES

[0052] The polyisocyanates and polyols used in the examples are shown in Table 1.

[0053] [Table 1]

[0054] Preparation of isocyanate-functional prepolymers The polyisocyanate and polyol were added to a three-necked reactor equipped with a mechanical stirrer and a condenser under a nitrogen blanket. The amounts and types are as shown in Table 2. The reactor contents were mixed and once the exothermic reaction was complete (without any further temperature increase), the reactor was heated to a temperature of 50°C and maintained at this temperature until all the polyol had reacted (until the free isocyanate content, measured according to the ASTM D2572-19 standard, was equal to the theoretically achievable isocyanate content), which usually took 1.5 to 2 hours. The reactor was then cooled to room temperature and the resulting prepolymer was taken from the reactor. The molecular weight and free isocyanate content of the prepolymer thus prepared were determined.

[0055] Preparation of Adhesive Composition An adhesive composition was prepared by adding 0.2 wt% of a curing catalyst (Jeffcat DMDEE), 0.05 wt% of an antifoaming agent (Formaster MO 2115) and 0.8 wt% of a thickener (Carbosil TS 720) to the prepolymer. Diphenylmethane Diisocyanate (Suprasek 2004) was added until the content of free isocyanate groups reached 14.5–16.5 wt. %, based on the total weight of the adhesive composition.

[0056] Test Method

[0057] Longitudinal Tensile Shear Strength Each adhesive composition was used to prepare an assembly of beech panels with a thick adhesive layer (gap joint 0.5 mm) according to the EN302-1:2013 standard. The amount of adhesive composition applied was in excess (applied on both sides). The period between adhesive application and testing was 13 days (at 65% relative humidity and 20°C). The assembly time was about 4 minutes, the pressing time was 16 hours, and the applied pressure was 8.0 kg / cm 2 It was decided. The longitudinal tensile shear strength of bonded stacks with thick adhesive layers was measured after A4 treatment according to EN302-1:2013:A4 (immersion in boiling water for 6 hours followed by immersion in cold water (20 °C) for 2 hours). The samples were tested in wet condition.

[0058] Closure accumulation time (AT) The closed assembly time of the adhesive composition was determined according to the EN14080:2013 standard. An assembly was prepared by laminating five spruce lamellae with dimensions 285 x 145 x 30 mm with each adhesive composition. The applied amount of adhesive composition was 120 g / m 2 Immediately after application of the adhesive composition, the lamellae were stacked into a stack. After various time intervals (stack times), the stack was pressed for 16 hours. The applied pressure was 8.0 kg / cm. 2 It was decided. After 5 days at 20° C. and 65% relative humidity, the delamination of the adhesive layer was measured using method B according to Annex C of the EN14080:2013 standard. The closed lay time is the maximum applicable lay time that does not exceed the delamination values ​​in Table 9 of the EN14080:2013 standard.

[0059] Minimum pressing time (PT) The minimum clamping time of the adhesive composition was determined according to the EN14080:2013 standard. An assembly was prepared by laminating five spruce lamellae with dimensions 285 x 145 x 30 mm with each adhesive composition. The applied amount of adhesive composition was 120 g / m 2 After 2 minutes of deposition time, the deposit was pressurized at 8 kg / cm 2 The pressing time was varied. After 5 days at 20° C. and 65% relative humidity, the delamination of the adhesive layer was measured using method B according to Annex C of the EN14080:2013 standard. The minimum clamping time is the minimum clamping time required not to exceed the delamination value in Table 9 of the EN14080:2013 standard.

[0060] The longitudinal tensile shear strengths, AT and PT, are shown in Table 2.

[0061] [Table 2A]

[0062] [Table 2B]

[0063] As the examples show, adhesive compositions having prepolymers prepared by reacting a polyol mixture containing poly(tetrahydrofuran), a triol having secondary hydroxyl groups, and an amine-initiated polyether diol with a polyisocyanate containing uretonimine-modified MDI have very good AT / PT ratios (1:1 to 1:2) and allow bonds with very good shear strength. The present specification includes the following aspects. Section 1. (a) a polyisocyanate mixture having an average nominal isocyanate functionality in the range of greater than 2.00 and less than 2.05; (a1) Diisocyanates, including diphenylmethane diisocyanate, and (a2) uretonimine-modified diphenylmethane diisocyanates having three or more isocyanate functional groups; A polyisocyanate mixture containing (b) a polyol mixture; (b1) a linear butylene oxide-based diol having two primary hydroxyl groups; (b2) a polyether triol having three secondary hydroxyl groups, and (b3) amine-initiated polyether polyols; A polyol mixture containing A one-component moisture-curable adhesive composition comprising 80 to 100% by weight of an isocyanate-functional prepolymer obtainable by reacting the equivalent ratio of the isocyanate group of (a) to the hydroxyl group of (b) is within the range of 3.5 to 7.0; The content of free isocyanate groups in the adhesive composition is within the range of 14 to 17% by weight, as measured in accordance with the ASTM D2572-19 standard; The polyisocyanate mixture (a) contains an excess of diisocyanate (a1) over uretonimine-modified diphenylmethane diisocyanate (a2), which is a one-component moisture-curable adhesive composition. Section 2. Item 2. The one-component moisture-curable adhesive composition according to item 1, wherein the linear butylene oxide diol (b1) has a number average molecular weight in the range of 500 to 1,500 as measured by size exclusion chromatography using a polystyrene standard in accordance with ISO 16014-1. Section 3. Item 3. The one-component moisture-curable adhesive composition according to item 1 or 2, wherein the polyether triol (b2) has a number average molecular weight in the range of 500 to 1,500 as measured by size exclusion chromatography using a polystyrene standard in accordance with ISO 16014-1. Section 4. The one-component moisture-curable adhesive composition according to any one of items 1 to 3, wherein the polyol mixture (b) does not substantially contain any polyol other than (b1), (b2) and (b3). Section 5. Item 5. The one-component moisture-curable adhesive composition according to any one of items 1 to 4, wherein the equivalent ratio of the isocyanate group (a) to the hydroxyl group (b) is within the range of 4.0 to 6.5, preferably within the range of 4.5 to 6.0. Section 6. Item 6. The one-component moisture-curable adhesive composition according to any one of items 1 to 5, wherein the content of free isocyanate groups in the adhesive composition is within the range of 15.0 to 16.5% by weight, as measured in accordance with the ASTM D2572-19 standard. Section 7. Item 7. The one-component moisture-curable adhesive composition according to any one of items 1 to 6, wherein the diisocyanate (a1) is diphenylmethane diisocyanate. Section 8. Item 8. The one-component moisture-curable adhesive composition according to item 7, wherein the polyisocyanate mixture (a) essentially consists of diphenylmethane diisocyanate and uretonimine-modified diphenylmethane diisocyanate. Section 9. The one-component moisture-curable adhesive composition according to any one of items 1 to 8, wherein the uretonimine-modified diphenylmethane diisocyanate (a2) comprises an isocyanate functional group in the range of 3 to 10, preferably an isocyanate functional group in the range of 3 to 6, and even more preferably 3 or 4 isocyanate functional groups. Section 10. Item 10. The one-component moisture-curable adhesive composition according to any one of items 1 to 9, comprising 85 to 99.8% by weight of the isocyanate-functional prepolymer. Section 11. Item 11. The one-part moisture-curable adhesive composition according to any one of items 1 to 10, further comprising a curing catalyst, preferably 2,2'-dimorpholine diethyl ether. Section 12. Item 12. The one-component moisture-curable adhesive composition according to any one of items 1 to 11, further comprising one or more additives, preferably an antifoaming agent and / or a thickener. Section 13. A method for joining a first piece of material to a second piece of material, comprising a step of contacting a surface of the first piece of material with a surface of the second piece of material, wherein the one-part moisture-curable adhesive composition according to any one of claims 1 to 12 is applied to at least one of the contacting surfaces prior to the contacting step. Section 14. Item 13. An object comprising a first piece of material and a second piece of material bonded together using the one-component moisture-curable adhesive composition according to any one of items 1 to 12. Section 15. Item 15. The object of item 14, wherein the piece of material is wood and the object is a structural wood product.

Claims

1. (a) a polyisocyanate mixture having an average nominal isocyanate functionality in the range of greater than 2.00 to less than 2.05; (a1) a diisocyanate which is diphenylmethane diisocyanate, and (a2) uretonimine-modified diphenylmethane diisocyanates having three or more isocyanate functional groups; a polyisocyanate mixture consisting essentially of (b) a polyol mixture; (b1) a linear butylene oxide-based diol having two primary hydroxyl groups; (b2) a polyether triol having three secondary hydroxyl groups, and (b3) amine-initiated polyether polyols; a polyol mixture consisting essentially of A one-part moisture-curable adhesive composition comprising 80 to 100% by weight of an isocyanate-functional prepolymer obtainable by reacting the equivalent ratio of the isocyanate groups of (a) to the hydroxyl groups of (b) is in the range of 3.5 to 7.0; the content of free isocyanate groups in the adhesive composition is within the range of 14 to 17% by weight, as measured in accordance with the ASTM D2572-19 standard; The polyisocyanate mixture (a) contains an excess of diisocyanate (a1) over uretonimine-modified diphenylmethane diisocyanate (a2), which is a one-component moisture-curable adhesive composition.

2. 2. The one-component moisture-curable adhesive composition according to claim 1, wherein the linear butylene oxide-based diol (b1) has a number average molecular weight in the range of 500 to 1,500, as measured by size exclusion chromatography using polystyrene standards in accordance with ISO 16014-1.

3. The one-component moisture-curable adhesive composition according to claim 1, wherein the polyether triol (b2) has a number average molecular weight in the range of 500 to 1,500, as measured by size exclusion chromatography using polystyrene standards in accordance with the ISO 16014-1 standard.

4. 2. The one-part moisture-curable adhesive composition according to claim 1, wherein the equivalent ratio of the isocyanate groups of (a) to the hydroxyl groups of (b) is within the range of 4.0 to 6.

5.

5. The one-component moisture-curable adhesive composition according to claim 1, wherein the content of free isocyanate groups in the adhesive composition is in the range of 15.0 to 16.5% by weight, as measured in accordance with the ASTM D2572-19 standard.

6. 2. The one-part moisture-curable adhesive composition of claim 1, wherein the uretonimine-modified diphenylmethane diisocyanate (a2) contains in the range of 3 to 10 isocyanate functional groups.

7. 10. The one-part moisture-curable adhesive composition of claim 1 comprising 85 to 99.8 weight percent of said isocyanate-functional prepolymer.

8. The one-component moisture-curable adhesive composition of claim 1, further comprising a curing catalyst.

9. 10. The one-part moisture-curable adhesive composition of claim 1, further comprising one or more additives.

10. 10. A method of joining a first piece of material to a second piece of material, comprising the step of contacting a surface of the first piece of material with a surface of the second piece of material, the method comprising the step of applying a one-part moisture-curable adhesive composition according to any one of claims 1 to 9 to at least one of the contacting surfaces prior to said contacting step.

11. 10. An object comprising a first piece of material and a second piece of material joined using the one-part moisture-curable adhesive composition of any one of claims 1 to 9.

12. The object of claim 11 , wherein the first and second pieces of material are wood and the object is a structural wood product.

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