Double-curing adhesive composition

Abstract

Adhesive compositions are shown and described herein. These compositions comprise a silylated polyurethane, an epoxy-functional compound, and an amine-functional compound. These compositions are provided to control the molar ratio of the amine's active hydrogen (AH) to the epoxy (E) group. By controlling the molar ratio of the amine's active hydrogen to the epoxy, adhesives with excellent adhesion and strength to various types of substrates are provided.

Description

[Technical Field]

[0001] The present invention relates to an adhesive composition. More specifically, the present invention relates to a double-curing adhesive composition comprising a silylated polyurethane, an amine-functional compound, and an epoxy-functional compound. This composition exhibits high adhesion to a substrate and also exhibits high adhesion to different materials or different types of materials. [Background technology]

[0002] Silylated moisture-curing resins have a wide range of applications as adhesives for use in a variety of applications. These adhesives may be used, for example, in construction, transportation, and / or electronic applications. Silylated polyurethane (SPUR) can provide an isocyanate-free alternative to polyurethane resins, as isocyanates can potentially cause toxicity issues in some applications.

[0003] Although silylated polyurethanes offer isocyanate-free alternatives to polyurethane resins, they may still not be a viable solution for many applications. For example, silylated polyurethanes may not exhibit the appropriate bond strength required for many applications. Furthermore, silylated polyurethanes may not exhibit sufficient bond strength across a wide range of substrate types.

[0004] Two-component polyurethane adhesives are a potential solution for providing adhesives with desirable elasticity and strength requirements for specific applications. However, such adhesives typically require the use of a primer. Primers for such materials are often isocyanate-based primers, which do not achieve the goal of reducing or eliminating isocyanates from the adhesive composition. [Overview of the project]

[0005] The following is a summary of the disclosure, providing a basic understanding of several aspects. This summary is not intended to identify any important or essential elements, nor to impose any limitations on the embodiments or claims. Furthermore, this summary may provide a simplified overview of several aspects, which may be described in detail in other parts of the disclosure.

[0006] The provided product is an adhesive composition. This composition comprises a silylated polyurethane, an epoxy-functional compound, and an amine-functional compound. The composition is provided to control the molar ratio of the amine's active hydrogen (AH) to the epoxy (E) group. By controlling the molar ratio of the amine's active hydrogen to the epoxy, an adhesive with excellent adhesion and strength to various types of substrates is provided.

[0007] In one embodiment, a composition is provided comprising: a silylated polyurethane; an amine-functional compound; and an epoxy-functional compound; wherein the molar ratio of the active hydrogen of the amine to the epoxy in the composition is in the range of about 0.3 to less than 0.8.

[0008] In one embodiment, the molar ratio of the active hydrogen of the amine to the epoxy in this composition is about 0.3 to about 0.75.

[0009] In one embodiment, the molar ratio of the active hydrogen of the amine to the epoxy in this composition is in the range of about 0.4 to about 0.7.

[0010] In one embodiment, the molar ratio of the active hydrogen of the amine to the epoxy in this composition is about 0.5 to about 0.6.

[0011] In one embodiment according to any of the preceding embodiments, the amine-functionalized compound is selected from polyetheramines, aminosilanes, or combinations thereof.

[0012] In one embodiment, the polyetheramine has a weight average molecular weight of from about 150 to about 6000.

[0013] In one embodiment according to any of the preceding embodiments, the composition comprises the polyetheramine in an amount of from about 0.1 wt% to about 10 wt% and the aminosilane in an amount of from about 0.1 wt% to about 10 wt% based on the total weight of the composition.

[0014] In one embodiment according to any of the preceding embodiments, the aminosilane is selected from compounds of the following formula: (R 11 )(R 12 )N-R 13 -Si(OR 14 ) 3-h (R 15 ) h ; R 16 -NH-R 17 -Si(OR 18 ) 3-i (R 19 )i; (R 20 ) j (R 21 O) 3-j Si-R 22 -NH-R 23 -Si(OR 24 ) 3-k (R 25 )k; N-(R 26 -Si(OR 27 ) 3-m (R 28 m) 3; where R 11 , R 12 , and R 16 are independently selected from H or a monovalent C1-C20 hydrocarbon; R 14 , R 15 , R 18 , R 19 , R 20 , R 21 , R 24 , R 25 , R 27 , and R 28R is independently selected from C1-C20 monovalent hydrocarbons; 13 , R 17 , R 22 , and R 26 is independently selected from divalent C1-C20 hydrocarbons; h, i, j, k, and m are independently selected from 0-2.

[0015] In one embodiment according to any of the preceding embodiments, the composition further comprises additives selected from pigments, fillers, curing catalysts, dyes, plasticizers, thickeners, coupling agents, bulking agents, volatile organic solvents, wetting agents, tackifiers, crosslinking agents, thermoplastic polymers, moisture scavengers, and UV stabilizers.

[0016] In one embodiment, the catalyst is a tin catalyst.

[0017] In one embodiment according to any of the preceding embodiments, the filler is selected from an organic filler, an inorganic filler, a conductive filler, or a combination thereof.

[0018] In one embodiment according to any of the preceding embodiments, the conductive filler is a thermally conductive filler, and includes alumina, magnesia, ceria, hafnia, lanthanum oxide, neodymium oxide, samaria, praseodymium oxide, tria, urania, yttria, zinc oxide, zirconia, silicon aluminum oxynitride, borosilicate glass, barium titanate, silicon carbide, silica, boron carbide, titanium carbide, zirconium carbide, boron nitride, silicon nitride, aluminum nitride, titanium nitride, zirconium nitride, zirconium boride, titanium diboride, dodecaboride, barite, barium sulfate, asbestos, barite, diatomaceous earth, feldspar, gypsum, formite, kaolin, mica, nepheline syenite, perlite, phyllolith, smectite, talc, vermiculite, zeolite, calcite, calcium carbonate. Selected from wollastonite, calcium metasilicate, clay, aluminum silicate, talc, magnesium aluminum silicate, hydrated alumina, hydrated aluminum oxide, aluminum hydroxide, magnesium hydroxide, silica, silicon dioxide, titanium dioxide, glass fibers, glass flakes, clay, exfoliated clay, or other high aspect ratio fibers, rods, or flakes, calcium carbonate, zinc oxide, magnesia, titania, calcium carbonate, talc, mica, wollastonite, alumina, aluminum nitride, graphite, graphene, aluminum powder, copper powder, bronze powder, brass powder, carbon fibers or whiskers, graphite, silicon carbide, silicon nitride, alumina, aluminum nitride, zinc oxide, carbon nanotubes, boron nitride nanosheets, zinc oxide nanotubes, or two or more combinations of these.

[0019] In another embodiment, a composition comprising a first agent and a second agent is provided, wherein the first agent comprises (i) a silylated polyurethane and an amino-functional compound, and the second agent comprises (ii) an epoxy-functional compound.

[0020] Provided in yet another embodiment is a method for forming an adhesive, comprising: (i) exposing a composition of any of the preceding embodiments; and subsequently (ii) crosslinking at a temperature of about 50°C to about 130°C.

[0021] In one embodiment, the adhesive is formed on the substrate.

[0022] Provided in yet another embodiment is a method for bonding two substrates, comprising: applying a composition according to any of the preceding embodiments to a first substrate; bringing a second substrate into contact with the composition applied on the first substrate; and curing the composition at a temperature of about 50°C to about 130°C.

[0023] In one embodiment, the first and second substrates are each independently selected from metal, thermoplastic resin, thermosetting resin, glass, carbon substrate, ceramic, cement, and wood.

[0024] In one embodiment according to any of the prior embodiments, the first substrate and the second substrate are made of the same type of material.

[0025] In one embodiment according to any of the preceding embodiments, the first substrate is a thermoplastic substrate, and the second substrate is a metal substrate.

[0026] In one embodiment according to any of the prior embodiments, the first and second substrates each lack a primer coating.

[0027] In a further embodiment, an article is provided comprising a first substrate bonded to a second substrate, wherein the adhesive is formed from a composition according to any of the preceding embodiments.

[0028] In one embodiment, the first and second substrates are each independently selected from metals, thermoplastics, thermosetting resins, glass, carbonaceous substrates, ceramics, cement, wood, and two or more combinations thereof.

[0029] In one embodiment according to any of the prior embodiments, the first substrate and the second substrate are made of the same type of material.

[0030] In one embodiment according to any of the preceding embodiments, the first substrate is a thermoplastic substrate, and the second substrate is a metal substrate.

[0031] In one embodiment according to any of the prior embodiments, the first and second substrates do not include a primer coating.

[0032] In one embodiment according to any of the preceding embodiments, the article has a shear strength of about 3 MPa or more as defined in ASTM D1002.

[0033] In one embodiment according to any of the preceding embodiments, the article undergoes coagulation and delamination as defined in ASTM D1002.

[0034] In one embodiment according to any of the preceding embodiments, the article is cured at 50°C for 24 hours as defined in ASTM D1002, then immersed in water at 50°C for one week, and then coagulated and peeled off.

[0035] In one embodiment according to any of the preceding embodiments, the article has a shear strength of about 4 MPa or more, measured after being immersed in water at 50°C for one week as defined in ASTM D1002.

[0036] In one embodiment according to any of the preceding embodiments, the article has a shear strength of about 10 MPa or more, measured after being immersed in water at 50°C for one week as defined in ASTM D1002.

[0037] The following description discloses various exemplary embodiments. Some improvements and novel embodiments may be explicitly identified, while others may be evident from the detailed description. [Modes for carrying out the invention]

[0038] Referencing the following exemplary embodiments, examples are illustrated in the accompanying drawings. As will be understood, other embodiments may also be used, and structural and functional modifications may be made. Furthermore, features of various embodiments may be combined or modified. Thus, the following description is presented merely as an example and does not in any way limit the various alternatives or modifications that may be made to the exemplary embodiments. In this disclosure, several specific details will lead to a complete understanding of the disclosed subject matter. It should be understood that aspects of this disclosure may be implemented in other embodiments that do not necessarily include all aspects described in this application or elsewhere.

[0039] As used in this application, the terms “example” and “illustration” mean examples or illustrations. The terms “example” and “illustration” do not indicate essential or preferred embodiments or forms. The term “or” is intended to be inclusive, not exclusive, unless the context suggests otherwise. For example, the statement “A uses B or C” includes any inclusive substitution (e.g., A uses B; A uses C; or A uses both B and C). Separately, the articles “one” and “a” are generally intended to mean “one or more,” unless the context suggests otherwise.

[0040] Ranges for specific material categories or parameters can be combined to form new, unspecified ranges.

[0041] The provided product is an adhesive composition. This composition comprises a silylated polyurethane, an epoxy-functional compound, and an amine-functional compound. The composition is provided to control the molar ratio of the amine's active hydrogen to the epoxy group. By controlling the molar ratio of the amine's active hydrogen to the epoxy, an adhesive is provided that exhibits excellent adhesion and strength to various types of substrates. This composition provides adhesion to various substrates under different conditions, such as adhesion under dry or wet conditions.

[0042] Silylated polyurethane

[0043] Silylated polyurethanes are not particularly limited and generally include polyurethanes functionalized with silane groups. Silylated polyurethanes can be formed by reacting an isocyanate-terminated polyurethane (PUR) prepolymer or a hydroxy-terminated polyurethane prepolymer with a silane having a suitable functional group that reacts with an isocyanate group or a hydroxyl group in a manner suitable for yielding the desired silylated polyurethane.

[0044] In one embodiment, the moisture-curing resin is a SPUR resin, for example, but not limited to, one described in U.S. Patent No. 5,990,257, which can be produced by any of the methods described herein, the entirety of which is incorporated into this application by reference.

[0045] Isocyanate-terminated PUR prepolymers can be obtained by reacting one or more polyols, such as diols (but not limited to them), with one or more polyisocyanates, such as diisocyanates (but not limited to them), in a ratio such that the resulting prepolymer is isocyanate-terminated. When reacting diols with diisocyanates, a molar excess of diisocyanate is used.

[0046] Polyols that can be used to prepare isocyanate-terminated PUR prepolymers include polyether polyols such as hydroxyl-terminated polycaprolactone, polyether ester polyols such as those obtained from the reaction of a polyether polyol with ε-caprolactone, polyester ether polyols such as those obtained from the reaction of a hydroxyl-terminated polycaprolactone with one or more alkylene oxides such as ethylene oxide and propylene oxide, hydroxyl-terminated polybutadiene, and others.

[0047] Suitable polyols that can be used to prepare isocyanate-terminated PUR prepolymers include, but are not limited to, poly(oxyalkylene) ether diols (i.e., polyether diols), particularly poly(oxyethylene) ether diols, poly(oxypropylene) ether diols and poly(oxyethylene-oxypropylene) ether diols, poly(oxyalkylene) ether triols, poly(tetramethylene) ether glycols, polyacetals, polyhydroxypolyacrylates, polyhydroxypolyesteramides, polyhydroxypolythioethers, polycaprolactone diols and triols, and others. In one embodiment, the polyol used in the production of the isocyanate-terminated PUR prepolymer is a poly(oxyethylene) ether diol with equivalents of about 500 to about 25,000, about 1,000 to about 20,000, about 2,500 to about 15,000, or about 5,000 to about 10,000. Mixtures of polyols having various structures, molecular weights, and / or functionalities can also be used.

[0048] Polyether polyols can have up to about 8 functionalities. In embodiments, polyether polyols have 2 to 4 functionalities, and in one embodiment, the functionality is 2 (i.e., diol). Particularly suitable are polyether polyols prepared in the presence of a complex metal cyanide (DMC) catalyst, an alkali metal hydroxide catalyst, or an alkali metal alkoxide catalyst; see, for example, U.S. Patents 3,829,505, 3,941,849, 4,242,490, 4,335,188, 4,687,851, 4,985,491, 5,096,993, 5,100,997, 5,106,874, 5,116,931, 5,136,010, 5,185,420, and 5,266,681. The full contents of each of these patents are incorporated into this application by reference. In one embodiment, the polyether polyol preferably has a number-average molecular weight of about 1,000 to about 25,000, more preferably about 2,000 to about 20,000, and even more preferably about 4,000 to about 18,000. The number-average molecular weight may be determined using gel permeation chromatography (GPC). Examples of commercially available diols suitable for creating isocyanate-terminated PUR prepolymers include ARCOL R-1819 (number-average molecular weight 8,000), E-2204 (number-average molecular weight 4,000), and ARCOL E-2211 (number-average molecular weight 11,000), ACCLAIM8200 (number-average molecular weight 8,000), ACCLAIM12200 (number-average molecular weight 12,000), and ACCLAIM18200 (number-average molecular weight 18,000).

[0049] Without limitation, any of the numerous polyisocyanates, such as diisocyanates and mixtures thereof, can be used to provide isocyanate-terminated PUR prepolymers. In one embodiment, the polyisocyanate may be diphenylmethane diisocyanate ("MDI"), polymethylene polyphenyl isocyanate ("PMDI"), paraphenylenedi isocyanate, naphthylene diisocyanate, liquid carbodiimide-modified MDI and its derivatives, isophorone diisocyanate, dicyclohexylmethane-4,4'-diisocyanate, toluene diisocyanate ("TDI"), particularly 2,6-TDI isomers, and various other technically well-established aliphatic and aromatic polyisocyanates, and combinations thereof.

[0050] The silylation reactant for reacting with the isocyanate-terminated PUR prepolymer comprises a functional group reactive with the isocyanate and at least one readily hydrolyzable and subsequently crosslinkable group, such as an alkoxy. In one embodiment, the silylation reactant is a silane of the following general formula: XR 1 -Si(R 2 ) x (OR 3 ) 3-x In the formula, X is an active hydrogen-containing group that is reactive with isocyanates, such as -SH or -NHR. 4 Here, R 4 H is a monovalent hydrocarbon group of carbon atoms up to 8, or -R 5 -Si(R 6 ) y (OR 7 ) 3-y And R 1 and R 5 Each of these is a divalent hydrocarbon group of up to 12 identical or different carbon atoms, optionally containing one or more heteroatoms, R 2 and R 6 Each of them is a monovalent hydrocarbon group of up to 8 carbon atoms, either identical or different, R 3 and R 7x is an alkyl group of up to 6 identical or different carbon atoms, and each of x and y is independently 0, 1, or 2.

[0051] Examples of silanes that can be used as reactants for silylation of resins include, but are not limited to, mercaptosilanes, namely 2-mercaptoethyltrimethoxylane, 3-mercaptopropyltrimethoxylane, 2-mercaptoethyltriethoxylane, 3-mercaptopropyltriethoxylane, 2-mercaptoethyltripropoxysilane, 2-mercaptoethyltrisec-butoxysilane, 3-mercaptopropyltri-t-butoxysilane, 3-mercaptopropyltriisopropoxysilane, 3-mercaptopropyltrioctoxysilane, 2-mercaptoethyltri-2'-ethylhexoxysilane, 2-mercaptoethyldimethoxyethoxysilane, 3-mercaptopropylmethoxyethoxypropoxysilane, 3-mercaptopropyldimethoxymethylsilane, 3-mercaptopropylmethoxydimethylsilane, 3-mercaptopropylethoxydimethylsilane, 3-mercaptopropyldiethoxymethylsilane, 3-mercaptopropylcyclohexoxydimethylsilane, 4-mercaptobutyltrimethoxylane, 3-mercapto-3-methylpropyltrimethoxylane, 3-mercapto 3-Methylpropyl-Tripropoxysilane, 3-Mercapto-3-Ethylpropyl-Dimethoxymethylsilane, 3-Mercapto-2-Methylpropyltrimethoxylane, 3-Mercapto-2-Methylpropyldimethoxyphenylsilane, 3-Mercaptocyclohexyl-Trimethoxylane, 12-Mercaptododecyltrimethoxysilane, 12-Mercaptododecyl-Triethoxysilane, 18-Mercaptooctadecyltrimethoxylane, 18-Mercaptooctadecylmethoxydimethylsilane, 2-Mercapto-2-Methylethyl-Trip Ropoxysilane, 2-mercapto-2-methylethyl-trioctoxysilane, 2-mercaptophenyltrimethoxylane, 2-mercaptophenyltriethoxylan, 2-mercaptotolyltrimethoxylane, 2-mercaptotolyltriethoxylan, 1-mercaptomethyltolyltrimethoxylane, 1-mercaptomethyltolyltriethoxylan, 2-mercaptoethylphenyltrimethoxylane, 2-mercaptoethylphenyltriethoxylan, 2-mercaptoethyltolyltrimethoxylane, 2-mercaptoethyltolyltriethoxylan3-mercaptopropylphenyltrimethoxylane, and 3-mercaptopropylphenyltriethoxylan, as well as aminosilanes, namely 3-aminopropyltrimethoxylane, 3-aminopropyltriethoxylan, 4-aminobutyltriethoxylan, N-methyl-3-amino-2-methylpropyltrimethoxylane, N-ethyl-3-amino-2-methylpropyltrimethoxylane, N-ethyl-3-amino-2-methylpropyldiethoxymethylsilane, N-ethyl-3-amino-2-methylpropyltriethoxylan, N-ethyl-3-amino-2-methylpropylmethyldimethoxysilane, N-butyl-3-amino-2-methylpropyltrimethoxylane, 3-(N-methyl-2-amino-1- This includes methyl-1-ethoxy)-propyltrimethoxylane, N-ethyl-4-amino-3,3-dimethyl-butyldimethoxymethylsilane, N-ethyl-4-amino-3,3-dimethylbutyltrimethoxysilane, N-(cyclohexyl)-3-aminopropyltrimethoxylane, N-(2-aminoethyl)-3-aminopropyltrimethoxylane, N-(2-aminoethyl)-3-aminopropyltriethoxysilane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane, aminopropyltriethoxylan, bis-(3-trimethoxysilyl-2-methylpropyl)amine, and N-(3'-trimethoxysilylpropyl)-3-amino-2-methylpropyltrimethoxylane.

[0052] Catalysts are typically used to prepare isocyanate-terminated PUR prepolymers. Condensation catalysts are generally used for the preparation of PUR. These catalysts may also catalyze the curing (hydrolysis and subsequent crosslinking) of the SPUR resin component of moisture-curable compositions. Suitable condensation catalysts include, but are not limited to, dialkyltin dicarboxylates such as dibutyltin dilaurate and dibutyltin acetate, tertiary amines, tin salts of carboxylic acids such as tin octanoate and tin acetate, and others. In one embodiment of the present invention, a dibutyltin dilaurate catalyst is used for the production of PUR prepolymers. Other useful catalysts include titanium-containing complexes, zirconium-containing complexes, and bismuth-containing complexes, such as K-KAT supplied by King Industries. 登録商標 XC6212, K-KAT 登録商標 XC-A209 and K-KAT 登録商標 348. Aluminum chelate, for example, TYZOR, which is commercially available from Dorf Ketal. 登録商標 This includes the KR type, which is commercially available from Kenrich Petrochemicals, as well as other organometallic catalysts, such as those containing metals like Zn, Co, Ni, Fe, and others.

[0053] In another embodiment, moisture-curable SPUR resins can be obtained from hydroxyl-terminated PUR prepolymers. Moisture-curable SPUR resins can be prepared by reacting a hydroxyl-terminated PUR prepolymer with an isocyanate silane, as previously described. Hydroxyl-terminated PUR prepolymers can be obtained using substantially the same materials, namely the polyols, polyisocyanates, and optionally a catalyst (e.g., a condensation catalyst) described above for the preparation of isocyanate-terminated PUR prepolymers, and by substantially the same method. The main difference in these reactions is that the polyols and polyisocyanates are used in a ratio that produces hydroxyl terminus in the resulting prepolymer. Thus, for example, in the case of diols and diisocyanates, the former is used in molar excess, thereby yielding a hydroxyl-terminated PUR prepolymer.

[0054] Useful silylation reactants for hydroxyl-terminated SPUR resins are reactants containing an isocyanate terminus and readily hydrolyzable functional groups, such as 1 to 3 alkoxy groups. Suitable silylation reactants are isocyanate silanes of the following general formula: OCN-R 8 -Si(R 9 ) x (OR 10 ) 3-x In the formula, R 8 is an alkylene group of up to 12 carbon atoms, optionally containing one or more heteroatoms, R 9 Each of them is an identical or different alkyl or aryl group of up to 8 carbon atoms, R 10 Each of them is an identical or different alkyl group with up to 6 carbon atoms, and x is 0, 1, or 2. In one embodiment, R 8 It has 1 to 4 carbon atoms, R 10 Each of them is the same or different methyl, ethyl, propyl, or isopropyl group, and x is 0.

[0055] Specific isocyanate silanes that can be used to react with hydroxyl-terminated PUR prepolymers to yield moisture-curable SPUR resins include, but are not limited to, isocyanate propyltrimethoxysilane, isocyanate isopropyltrimethoxysilane, isocyanate-n-butyltrimethoxysilane, isocyanate-t-butyltrimethoxysilane, isocyanate propyltriethoxysilane, isocyanate isopropyltriethoxysilane, isocyanate-n-butyltriethoxysilane, isocyanate-t-butyltriethoxysilane, and others.

[0056] In various embodiments, the polymer has the following general formula: R z -[OC(O)NH-R 8 Si(R 9 ) x (OR 10) 3-x ] y In the formula, R z R is an organic polymer fragment, 8 , R 9 , and R 10 As described above, and y is from 1 to 6. In one embodiment, the organic polymer fragment is a polymer fragment containing at least one urethane group.

[0057] Examples of silyl-terminated polyurethane oligomers include, but are not limited to, Momentive Performance Materials' SPUR1010 and SPUR1050, and Covestro's commercially available Desmoseal 2458, 2636, 2662, and others.

[0058] Silylated polyurethane can be present in amounts of about 3% to about 70% by weight, about 5% to about 60% by weight, or about 10% to about 50% by weight, based on the total weight of the composition.

[0059] Amine-functional compounds

[0060] This composition contains an amine-functional compound. The amine-functional compound can be selected as desired. The amine-functional compound is provided to have at least one active hydrogen.

[0061] The hydrogen content of amine-functional compounds may be described in terms of amine hydrogen equivalents (AHEW). As used in this application, the AHEW of a molecule may be calculated by dividing its molecular weight by the number of hydrogen atoms bonded to the amino nitrogen atoms within the molecule.

[0062] In one embodiment, the amine-functional compound can be selected from compounds that function as epoxy curing agents. The epoxy curing agent may be an amine-functional compound, such as a polyamine like a diamine, or a blend of polyamines. As understood, this composition may include mixtures of two or more such compounds.

[0063] In one embodiment, the amine-functionalized compound is selected from polyetheramines. The polyetheramine can be selected from polyethers terminated with primary or secondary amines. In one embodiment, the polyetheramine has at least two amino groups, which may be the same or different. In this embodiment, each of the amino groups in the polyetheramine is a primary amine. In this embodiment, the polyetheramine is a primary diamine. The polyether group of the polyetheramine can be selected from any suitable alkylene oxide unit. In this embodiment, the polyetheramine is a poly(C2-C24 alkylene oxide) with an amine-functional group. In this embodiment, the polyether group is selected from an ethylene oxide group, a propylene oxide group, or a combination thereof.

[0064] In one embodiment, the amine compound is an aliphatic amine or an aromatic amine.

[0065] In one embodiment, polyetheramines have a number-average molecular weight of about 150 to about 6000, about 200 to about 2000, or about 230 to about 500. The number-average molecular weight may be determined using gel permeation chromatography (GPC).

[0066] Examples of suitable polyetheramines include, but are not limited to, JEFFAMINE from Huntsman Company in Woodland, Texas. 登録商標 This includes commercially available products.

[0067] In one embodiment, the amine-functional compound may have an AHEW in the range of 10 to about 300. In specific embodiments, the epoxy curing agent has an AHEW in the range of about 55 to about 65; or about 75 to about 90; or about 140 to about 160. Two commercially available examples of epoxy curing agents are from JEFFAMINE. 登録商標 D-230 amine (AHEW=60) and JEFFAMINE登録商標 It is T-403 amine (AHEW = 81). JEFFAMINE 登録商標 D-230 amine is a di-primary polyether amine with a molecular weight of approximately 230. JEFFAMINE 登録商標 T-403 amine is a tri-primary polyether amine with a molecular weight of approximately 403. Any of the amines is available from Huntsman in Woodlands, Texas.

[0068] The polyether amine can be present in an amount of from about 0.1 wt% to about 10 wt%, from about 0.2 wt% to about 5 wt%, or from about 0.4 wt% to about 4 wt% based on the total weight of the composition.

[0069] In another embodiment, the amine-functional compound can be selected from amino silanes. The amino silane can be a primary amino silane, a secondary amino silane, a tertiary amino silane, or a combination of two or more of these. In one embodiment, the adhesion promoter is selected from at least secondary amino silanes.

[0070] In one embodiment, the amino silane is selected from aminoalkyltrialkoxysilanes, aminoalkyldialkoxysilanes, bis(alkyltrialkoxysilyl)amines, tris(alkyltrialkoxysilyl)amines, tris(alkyltrialkoxysilyl)cyanurates, and tris(alkyltrialkoxysilyl)isocyanurates, or a combination of two or more of these.

[0071] In one embodiment, the amino silane can be selected from one or more compounds of the following formula: (R 11 )(R 12 )N-R 13 -Si(OR 14 ) 3-h (R 15 ) h R 16 -NH-R 17 -Si(OR 18) 3-i (R 19 )i (R 20 ) j (R 21 O) 3-j Si-R 22 -NH-R 23 -Si(OR 24 ) 3-k (R 25 )k N-(R 26 -Si(OR 27 ) 3-m (R 28 m)3 In the formula, R 11 , R 12 , and R 16 R is independently selected from H or monovalent C1-C20 hydrocarbons; 14 , R 15 , R 18 , R 19 , R 20 , R 21 , R 24 , R 25 , R 27 , and R 28 R is independently selected from C1-C20 monovalent hydrocarbons; 13 , R 17 , R 22 , and R 26 is independently selected from divalent C1-C20 hydrocarbons; h, i, j, k, and m are independently selected from 0-2. In one embodiment, R 11 , R 12 , R 16 , R 14 , R 15 , R 18 , R 19 , R 20 , R 21 , R 24 , R 25 , R 27 , and R 28 R is selected from C1-C20 alkyl, C2-C15 alkyl, C4-C10 alkyl, or C6-C8 alkyl. In one embodiment, R 11 , R 12 , R 16 , R 14 , R 15 , R18 , R 19 , R 20 , R 21 , R 24 , R 25 , R 27 , and R 28 R is independently selected from C1-C4 alkyl groups. In one embodiment, R 13 , R 17 , R 22 , and R 26 The alkylene is independently selected from C1-C20 alkylene, C2-C15 alkylene, C3-C10 alkylene, or C4-C8 alkylene.

[0072] Examples of suitable aminosilanes include, but are not limited to, N-(2-aminoethyl)aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, bis(γ-trimethoxysilylpropyl)amine, N-phenyl-γ-aminopropyltrimethoxysilane, triamino-functionalized trimethoxysilane, γ-aminopropylmethyldimethoxysilane, γ-aminopropylmethyldiethoxysilane, methylaminopropyltrimethoxysilane, α,ω-bis-(aminoalkyl-diethoxysilyl)-polydimethylsiloxane, α,ω-bis-(aminoalkyl-diethoxysilyl)-octamethyltetrasiloxane, 4-amino-3,3-dimethylbutyl-trimethoxysilane, and N-ethyl-3-tri-methoxysilyl-2-methylpropane This includes aminosilanes, 3-(diethyl-aminopropyl)-trimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxy-ethoxyethoxysilane, 3-aminopropyl-methyl-diethoxysilane, N-methyl-3-aminopropyltrimethoxysilane, N-butyl-3-aminopropyltrimethoxysilane, (N-cyclohexylaminomethyl)methyldiethoxysilane, (N-cyclohexylaminomethyl)triethoxysilane, (N-phenylaminomethyl)methyldimethoxysilane, (N-phenylaminomethyl)trimethoxysilane, N-ethyl-aminoisobutyltrimethoxysilane, 4-amino-3,3-dimethylbutyltrimethoxysilane, combinations of two or more of these, and others. Oligomers of aminosilanes and amino-functionalized oligosiloxanes can also be used.

[0073] Examples of suitable aminosilanes include, but are not limited to, N-(2-aminoethyl)aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, bis(γ-trimethoxysilylpropyl)amine, N-phenyl-γ-aminopropyltrimethoxysilane, triaminofunctionalized trimethoxysilane, γ-aminopropylmethyldimethoxysilane, γ-aminopropylmethyldiethoxysilane, methacryloxypropyltrimethoxysilane, methylaminopropyltrimethoxysilane, γ-glycidoxypropylethyldimethoxysilane, γ-glycidoxypropyltrimethoxysilane, and γ-glycidoxyethyltrimethoxysilane. N, γ-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, β-(3,4-epoxycyclohexyl)ethylmethyl-dimethoxysilane, epoxylimonyltrimethoxysilane, isocyanatetopropyltriethoxysilane, isocyanatetopropyltrimethoxysilane, isocyanatetopropylmethyldimethoxysilane, β-cyano-ethyl-trimethoxysilane, γ-acryloxypropyl-trimethoxysilane, γ-methacryloxypropyl-methyldimethoxysilane, α,ω-bis-(aminoalkyl-diethoxysilyl)-polydimethylsiloxane, α,ω-bis-(aminoalkyl-diethoxysilyl)-octamethyltetrasiloxane, 4-amino-3,3-Dimethyl-butyl-trimethoxysilane, and N-ethyl-3-tri-methoxysilyl-2-methylpropanamine, 3-(diethyl-aminopropyl)-trimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxyethoxyethoxysilane, 3-aminopropyl-methyl-diethoxysilane, N-methyl-3-aminopropyltrimethoxysilane, N-butyl-3-aminopropyltrimethoxysilane, 3-mercaptopropyltrimethoxy This includes silanes, 3-mercaptopropyltriethoxysilane, 3-mercaptopropyl-methyl-dimethoxysilane, (N-cyclohexylaminomethyl)methyldiethoxysilane, (N-cyclohexylaminomethyl)triethoxysilane, (N-phenylaminomethyl)methyldimethoxysilane, (N-phenylaminomethyl)trimethoxysilane, N-ethylaminoisobutyltrimethoxysilane, 4-amino-3,3-dimethylbutyltrimethoxysilane, combinations of two or more of these, and others.

[0074] Examples of suitable aminosilanes include, but are not limited to, Silquest, available from Momentive Performance Materials. 登録商標 A-1120 Silane, Silquest 登録商標 A-2120 Silane, Silquest 登録商標 This includes A-1170 silane, Silkquest A-Link600, and Silkquest A-Link235 silane.

[0075] The aminosilane may be present in amounts of about 0.1% to about 10% by weight, about 1% to about 5% by weight, or about 1.5% to about 4% by weight, based on the total weight of the composition.

[0076] Epoxy functional compounds

[0077] Epoxy-functionalized compounds are not particularly limited and can be selected as desired depending on the specific purpose or intended use. Generally, the term “epoxy resin” as used herein refers to a composition or compound having one or more vicinal epoxy groups per molecule, i.e., at least one 1,2-epoxy group per molecule. Generally, epoxy resin compounds may be saturated or unsaturated aliphatic, cyclic aliphatic, aromatic or heterocyclic compounds having at least one 1,2-epoxy group. Such compounds may be substituted, if desired, with one or more non-interfering substituents, such as halogen atoms, hydroxyl groups, ether radicals, lower alkyls, and others. Epoxy-functionalized compounds may include epoxy silicones, epoxy silanes, and epoxy silane oligomers.

[0078] The epoxy resin may, for example, contain glycidyl polyethers of polyhydric phenols and polyhydric alcohols. Examples of known epoxy resins that may be used in the present invention include, for example, resorcinol, catechol, hydroquinone, bisphenol, bisphenol A, bisphenol AP (1,1-bis(4-hydroxyphenyl)-1-phenylethane), bisphenol F, bisphenol K, tetrabromobisphenol A, phenolformaldehyde novolac resin, alkyl-substituted phenolformaldehyde resin, phenol hydroxybenzaldehyde resin, cresol-hydroxybenzaldehyde resin, dicyclopentadiene-phenol resin, dicyclopentadiene-substituted phenol resin, tetramethylbisphenol, tetramethyl-tetrabromobisphenol, tetramethyltribromobisphenol, and diglycidyl ethers of tetrachlorobisphenol A; and any combination thereof. The epoxy resin may contain triglycidyl of para-aminophenol, for example, Araldite MY0510. The epoxy resin may contain epoxidized tallow oil or other naturally derived oily substances.

[0079] The epoxy resin may also include an epoxy resin prepared by either the reaction of a diglycidyl ether of a divalent phenol with a divalent phenol, or the reaction of a divalent phenol with epichlorohydrin (also known as "taffy resin").

[0080] Examples of suitable epoxy resins include, but are not limited to, bisphenol A; 4,4'-sulfonyldiphenol; 4,4-oxydiphenol; 4,4'-dihydroxybenzophenone; resorcinol; hydroquinone; 9,9'-bis(4-hydroxyphenyl)fluorene; diglycidyl ethers of 4,4'-dihydroxybiphenyl or 4,4'-dihydroxy-α-methylstilbene; and diglycidyl esters of the dicarboxylic acids mentioned above.

[0081] Epoxy resins may include bisphenol epoxy, ortho-cresol novolac, polyfunctional epoxy, amine epoxy, heterocyclic epoxy, substituted epoxy, and naphthol epoxy, specifically bisphenol A epoxy resin, bisphenol F epoxy resin, hydrogenated bisphenol type epoxy resin, alicyclic epoxy resin, aromatic epoxy resin, novolac, dicyclopentadiene type epoxy resin, and combinations thereof. Examples of suitable epoxy resins, but not limited to, bisphenol epoxy resins such as EPICLON830-S, EPICLON EXA-830CRP, EPICLON EXA-850S, EPICLON EXA-850CRP, and EPICLON EXA-835LY (Dainippon Ink and Chemicals, Inc.); EPIKOTE807, EPIKOTE815, EPIKOTE825, EPIKOTE827, EPIKOTE828, EPIKOTE834, EPIKOTE1001, EPIKOTE1004, EPIKOTE1007, and EPIKOTE1009 (Yuka Shell Epoxy Corporation); DER-330, DER-301, DER-361 (Dow Chemical Corporation), YD-128, YDF-170, and others (Kokudo Chemical Corporation); Ortho-cresol novolac epoxy Resins, e.g., YDCN-500-1P, YDCN-500-4P, YDCN-500-5P, YDCN-500-7P, YDCN-500-80P, YDCN-500-90P (Kokudo Chemical Co.), EOCN-102S, EOCN-103S, EOCN-104S, EOCN-1012, EOCN-1025, EOCN-1027, and others (Nippon Kayaku Co.); polyfunctional epoxy resins, e.g., Epon1031S (Yuka Shell Epoxy Co.), ALALDITE0163 (Chiba Specialty Chemicals), DENACOL EX-611, DENACOL EX-614, DENACOL EX-614B, DENACOL EX-622, DENACOL EX-512, DENACOL EX-521, DENACOL EX-421, DENACOL EX-411, DENACOL EX-321, and others (Nagase ChemteX Corporation);This includes amine-based epoxy resins, such as EPIKOTE604 (Yuka Shell Epoxy Co.), YH-434 (Kokudo Chemical Co.), TETRAD-X, TETRAD-C (Mitsubishi Gas Chemical Co.), ELM-120 (Sumitomo Chemical Co.), and others; heterocyclic epoxy resins, such as PT-810 (Chiba Specialty Chemicals); substituted epoxy resins, such as ERL-4234, ERL-4299, ERL-4221, ERL-4206 (Union Carbide Co.); and naphthol-based epoxy resins, such as EPICLON HP-4032, EPICLON HP-4032D, EPICLON HP-4700, EPICLON 4701 (Dainippon Ink & Chemicals). These may be used individually or in mixtures of two or more. To obtain excellent film coating properties, a phenoxy resin may be applied, and high molecular weight resins, such as EPIKOTE1256 (Nippon Epoxy Resin Manufacturing Co., Ltd.), PKHH (Inchem Co., Ltd.), YP-70 (Kokudo Chemical Co., Ltd.), and others, may also be applied. Epoxy resins derived from tall oil may include Altamer E125 from Injevity Co., Ltd.

[0082] The epoxy resin may include epoxy resins derived from wood pulp, wood waste, or other plant waste.

[0083] The epoxy resin may be present in an amount of about 3% to about 45% by weight, about 5% to about 40% by weight, or about 10% to about 35% by weight, based on the total weight of the composition.

[0084] In embodiments, the ratio of active hydrogen of the amine to epoxy is about 0.3 to less than 0.8, about 0.3 to about 0.75, or about 0.5 to about 0.7.

[0085] The molar ratio of active hydrogen to epoxy groups in an amine is calculated using the amine hydrogen equivalent (AHEW) value of the amine-functional compound and the epoxide equivalent (EEW) of the epoxy-functional compound. The total number of moles of active hydrogen (AHM) in an amine is calculated by taking the sum of the weights of each amine-functional compound divided by their AHEW. The total number of moles of epoxy (EM) is calculated by taking the sum of the weights of each epoxy-functional compound divided by their EEW. The molar ratio of active hydrogen to epoxy groups in an amine is calculated by taking the ratio of AHM to EM.

[0086] Amine-functionalized compounds and epoxy-functionalized compounds are provided such that the ratio of AHM to EM is about 0.3 to less than 0.8. In embodiments, the ratio of AHM to EM is about 0.3 to about 0.75, about 0.4 to about 0.7, or about 0.5 to about 0.6. By controlling the ratio of AHM to EM within this range, excellent adhesive and strength properties can be obtained for the adhesive.

[0087] The catalysts typically used in adhesive formulations may be selected as desired depending on the intended purpose or application. Suitable catalysts include, but are not limited to, organotin compounds and tertiary amines. Other suitable, non-limiting examples of catalysts used to cure adhesives are technically well known, including chelates of various metals, e.g., acetylacetone, benzoylacetone, trifluoroacetylacetone, ethyl acetacetate, salicylaldehyde, cyclopentanone-2-carboxylate, acetylacetoneimine, bis-acetylacetone-alkylenediimine, salicylaldehydeimine, and others, and various metals, e.g., Al, Be, Mg, K, Zn, Cd, Pb, Ti, Zr, Sn, As, Bi, Cr, Mo, Mn, Fe, C Chelates can be obtained from o, Ni, and metal oxide ions MoO2++, UO2++, and others; alcoholates and phenolates of various metals, e.g., Ti(OR)4, Sn(OR)4, Sn(OR)2, Al(OR)3, Bi(OR)3, and others, where R is alkyl or aryl of 1 to about 18 carbon atoms; and reaction products of various metal alcoholates with carboxylic acids, β-diketones, and 2-(N,N-dialkylamino)alkanols, e.g., well-known titanium chelates obtained by this procedure or a similar procedure. Further catalysts include trivalent tin, trivalent and pentavalent As, Sb, and Bi, and metal carbonyls of iron and cobalt; and organometallic derivatives of combinations thereof. In one specific embodiment, non-limiting examples of organotin compounds that are dialkyltin salts of carboxylic acids include dibutyltin diacetate, dibutyltin dilaurate, dibutyltin maleate, dilauryltin diacetate, dioctyltin diacetate, dibutyltin-bis(4-methylaminobenzoate), dibutyltin dilauryl mercaptide, dibutyltin-bis(6-methylaminocaproate), and others, as well as combinations thereof. Similarly, in another embodiment, trialkyltin hydroxides, dialkyltin oxides, dialkyltin dialkoxides, or dialkyltin dichlorides, and combinations thereof may be used.Non-exclusive examples of these compounds include trimethyltin hydroxide, tributyltin hydroxide, trioctyltin hydroxide, dibutyltin oxide, dioctyltin oxide, dilauryltin oxide, dibutyltin-bis(isopropoxide), dibutyltin-bis(2-dimethylaminopentylate), dibutyltin dichloride, dioctyltin dichloride, and others, as well as combinations thereof.

[0088] The catalyst can be present in amounts of approximately 0% to 4% by weight, approximately 0.02% to 3% by weight, or approximately 0.09% to 1% by weight.

[0089] The composition may optionally contain silanes other than aminosilanes. Such silanes are used in the composition as adhesion promoters. Suitable non-aminosilanes include, but are not limited to, epoxysilanes, isocyanatesilanes, acryloxysilanes, mercaptosilanes, and others. Some specific examples of non-aminosilanes include, but are not limited to, methacryloxypropyltrimethoxysilane, γ-glycidoxypropylethyldimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxyethyltrimethoxysilane, γ-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, β-(3,4-epoxycyclohexyl)ethylmethyldimethoxysilane, epoxylimonyltrimethoxysilane, isocyanatetopropyltriethoxysilane, isocyanatetopropyltrimethoxysilane, isocyanatetopropylmethyldimethoxysilane, β-cyanoethyltrimethoxysilane, γ-acryloxypropyltrimethoxysilane, γ-methacryloxypropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-mercaptopropyl-methyldimethoxysilane, and others.

[0090] For practical applications, moisture-curable compositions may optionally contain additives such as pigments, fillers, curing catalysts, dyes, plasticizers, thickeners, coupling agents, bulking agents, volatile organic solvents, wetting agents, tackifiers, crosslinking agents, thermoplastic polymers, moisture scavengers, and / or UV stabilizers. Such additives may be used in any appropriate amount, as is well known to those skilled in the art, to be useful for a particular purpose or intended use.

[0091] Adhesive compositions may contain fillers. Suitable fillers include inorganic and organic fillers. Suitable inorganic fillers include, but are not limited to, heavy, precipitated, and colloidal calcium carbonate treated with compounds such as stearate or stearic acid, reinforced silica, e.g., fumed silica, precipitated silica, silica gel, and hydrophobized silica and silica gel; crushed and pulverized quartz, alumina, aluminum hydroxide, aluminum trihydrate, titanium hydroxide, titanium dioxide, diatomaceous earth, iron oxide, zinc sulfide, or clay, e.g., kaolin, bentonite or montmorillonite, talc, mica, and others.

[0092] In some embodiments, the filler includes a thermally conductive filler. Thermally conductive fillers include, but are not limited to, alumina, magnesia, ceria, hafnia, lanthanum oxide, neodymium oxide, samaria, praseodymium oxide, tria, urania, yttria, zinc oxide, zirconia, silicon aluminum oxynitride, borosilicate glass, barium titanate, silicon carbide, silica, boron carbide, titanium carbide, zirconium carbide, boron nitride, silicon nitride, aluminum nitride, titanium nitride, zirconium nitride, zirconium boride, titanium diboride, dodecaboride, barite, barium sulfate, asbestos, barite, diatomaceous earth, feldspar, gypsum, formite, kaolin, mica, nepheline syenite, perlite, phyllolith, smectite, talc, vermiculite, zeolite, calcite, calcium carbonate, wollastonite, and calcium metasilicate. It may contain clay, aluminum silicate, talc, magnesium aluminum silicate, hydrated alumina, hydrated aluminum oxide, aluminum hydroxide, magnesium hydroxide, silica, silicon dioxide, titanium dioxide, glass fibers, glass flakes, clay, exfoliation clay, or other high aspect ratio fibers, rods, or flakes, calcium carbonate, zinc oxide, magnesia, titania, calcium carbonate, talc, mica, wollastonite, alumina, aluminum nitride, graphite, graphene, aluminum powder, copper powder, bronze powder, brass powder, carbon fibers or whiskers, graphite, silicon carbide, silicon nitride, alumina, aluminum nitride, zinc oxide, carbon nanotubes, boron nitride nanosheets, zinc oxide nanotubes, or two or more combinations thereof. In the embodiments, the thermally conductive filler has an average particle size of 20 nanometers to 100 micrometers, about 50 nanometers to about 50 micrometers, about 100 nanometers to about 25 micrometers, or about 500 nanometers to about 10 micrometers. This average particle size is measured by dynamic light scattering techniques or image analysis techniques.In embodiments of the present invention, the treated calcium carbonate has a particle size ranging from approximately 0.07 micrometers (μm) to approximately 4 micrometers (μm) and is available from several companies under several trade names, including Ultra Pflex, Super Pflex, and Hi Pflex from Specialty Minerals; Winnofil SPM and SPT from Zeneca Resin; Hubercarb 1Qt, Hubercarb 3Qt, and Hubercarb W Martoxid, Magnifin, and Martinal from Huber; and Kotomite from ECC. Fillers commonly used in Japan include Shiraishi Kogyo's Shiratsuka CCR and Shiratsuka CC; and Maruo Calcium's KALFAIN200. These fillers can be used alone or in combination.

[0093] Organic fillers include carbon black, carbides, soot, graphene, graphite, carbon nanotubes, carbon nanofibers, and cellulose nanocrystals. To further enhance the physical strength of the curable resin-forming composition, reinforcing carbon black can be used as the main filler, leading to a black system. Several commercial grades of carbon black useful in this invention are commercially available, including, but are not limited to, "Corax" products (Degussa) and ELFTEX. 登録商標 A product (Cabot Corporation) exists. To obtain a translucent formulation, a high level of fumed silica or precipitated silica can be used as the primary filler, without carbon black.

[0094] Fillers can be used alone or in combination. Fillers may be present in the composition in amounts of about 3% to about 90% by weight, about 5% to about 80% by weight, or about 10% to about 50% by weight, based on the total weight of the composition.

[0095] In embodiments, the composition may contain a plasticizer. The plasticizer is not particularly limited and can be selected from any material suitable as a plasticizer. Examples of suitable plasticizers include, but are not limited to, carboxylic acid esters, e.g., phthalates, especially dioctyl phthalate, bis(2-ethylhexyl) phthalate, bis(3-propylheptyl) phthalate, diisononyl phthalate, or diisodecyl phthalate; diesters of orthocyclohexanedicarboxylic acid, especially diisononyl 1,2-cyclohexanedicarboxylate; adipates, especially dioctyl adipate, bis(2-ethylhexyl) adipate; azelaic acid esters, especially bis(2-ethylhexyl) azelate; sebacates, especially bis(2-ethylhexyl) sebacate or diisononyl sebacate; glycol ethers, glycol esters, organophosphate esters or organosulfonic acid esters, sulfonamides, polybutenes, or fatty acid methyl esters or fatty acid ethyl esters derived from natural oils and fats, also known as "biodiesel."

[0096] Other suitable plasticizers include, for example, polymeric plasticizers, which refer to polymeric additives that are liquid at room temperature and do not contain hydrolyzable silanes. Examples of suitable polymeric plasticizers include, but are not limited to, polyols, such as polyether polyols, polyester polyols, polyhydrocarbon polyols, polybutadiene polyols, poly(meth)acrylate polyols, and others.

[0097] Further examples of suitable plasticizer materials include, for example, trialkyl and / or triaryl phosphates. Examples of suitable phosphate plasticizers include, but are not limited to, triethyl phosphate, tricresyl phosphate, triphenyl phosphate, diphenylcresyl phosphate, isodecyldiphenyl phosphate, tris(1,3-dichloro-2-propyl) phosphate, tris(2-chloroethyl) phosphate, tris(2-ethylhexyl) phosphate, tris(chloroisopropyl) phosphate, tris(chloropropyl) phosphate, isopropylated triphenyl phosphate, mono-, bis-, or tris(isopropylphenyl) phosphate. An example of a trialkyl and / or triaryl phosphate plasticizer is tris-(2-ethylhexyl)-phosphate (trade name Disflamoll from Lanxess). 登録商標 (Commercially available under TOF), cresyl diphenyl phosphate, tricresyl phosphate, and triphenyl phosphate (all from Lanxess under the Disflamoll brand). 登録商標 This includes (commercially available under the following). Trialkyl and / or triaryl phosphate plasticizers also contribute to imparting flame retardancy to the composition.

[0098] In embodiments, the composition includes a moisture scavenger. Examples of moisture scavengers include, but are not limited to, vinyltrimethoxysilane, methyltrimethoxysilane, hexamethyldisilazane, p-toluenesulfonyl isocyanate (PTSI), toluene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), polymeric MDI, and others. Examples of suitable moisture scavengers include, but are not limited to, Silquest, available from Momentive Performance Materials. 登録商標 It's an A-171.

[0099] This composition may be provided as a two-component composition. In embodiments, the first component, which may optionally be referred to as part A in this application, comprises a silylated polyurethane, an amine-functionalized compound, and optionally a filler. The second component, which may optionally be referred to as part B in this application, may comprise an epoxy-functionalized material and a catalyst. In another embodiment, the first component comprises a silylated polyurethane, an epoxy-functionalized material, a catalyst, an aminosilane, and optionally a filler. The second component may comprise an amino-functionalized compound, water, and optionally a filler.

[0100] This composition can be cured by a double curing mechanism, involving an initial condensation curing reaction followed by heating of the mixture. The condensation curing step involves combining a silylated polyurethane, an amine-functionalized compound, an epoxy-functionalized compound, a catalyst, and optionally a filler, and then exposing this mixture to moisture. This mixture may contain some water, and the mixture may also be cured by exposure to atmospheric moisture at room temperature (e.g., about 20°C to 25°C) for a period of about 1 to about 24 hours. After curing for a selected time, the mixture is heated to a temperature of about 50°C to about 130°C. Alternatively, the composition can be crosslinked by combining a silylated polyurethane, an epoxy-functionalized compound, and an amine-functionalized compound under shear, and then performing the heating step first while keeping the mixture under anhydrous conditions. In the second step, water and a catalyst can be added to carry out condensation curing.

[0101] This composition can be used to bond substrates together. This composition exhibits excellent bonding across various substrates, thus the substrates can be identical or different materials. Substrates can be selected from a variety of materials, including, but are not limited to, metals and alloys, thermoplastics, thermosetting resins, glass, ceramics, carbonaceous materials (e.g., carbon fiber reinforced composites), cement, stone, wood, cellulose materials, composites and laminates thereof, and others. Examples of substrates, but are not limited to, polyester, polycarbonate, polyurethane, polypropylene, polyamide, polyvinyl chloride, polyolefin, polyvinyl acetate, polyetheretherketone, aluminum, aluminized plastics, and others. Substrates can be formed from identical or different materials, and may have identical or different mechanical properties, identical or different structural properties, dimensions, and other characteristics.

[0102] In one embodiment, the composition can adhere to a substrate and / or to two substrates without the use of a primer material, and preferably without the use of an isocyanate-based primer.

[0103] Materials bonded using this adhesive may, in embodiments, have a shear strength of 3 MPa or greater, 4 MPa or greater, 5 MPa or greater, or 6 MPa or greater, as measured using ASTM D1002. In embodiments, the bonded materials have a shear strength of 3 MPa to 9 MPa, 3.5 MPa to 8 MPa, 4 MPa to 7 MPa, or 5 MPa to 6 MPa.

[0104] In one embodiment, materials bonded with an adhesive may have a shear strength of 4 MPa or greater, 5 MPa or greater, 6 MPa or greater, 8 MPa or greater, 10 MPa or greater, 12 MPa or greater, or 14 MPa or greater after curing at 50°C for 24 hours and then immersing in 50°C water for one week, as measured using ASTM D1002. In one embodiment, the bonded materials may have a shear strength of 4 MPa to 18 MPa, 6 MPa to 16 MPa, 8 MPa to 14 MPa, or 10 MPa to 12 MPa after curing at 50°C for 24 hours and then immersing in 50°C water for one week, as measured using ASTM D1002.

[0105] The bonded material delaminates cohesively when evaluated with ASTM D1002 in the embodiment. In the embodiment, the bonded material is cured at 50°C for 24 hours, then immersed in 50°C water for one week, and then evaluated with ASTM D1002, resulting in cohesive delamination.

[0106] In one embodiment, the adhesive composition can be applied to the surface of a substrate and brought into contact with the surface of another substrate. This composition can undergo initial condensation curing over a period of about 1 to about 24 hours, after which the assembly can be heated for final curing.

[0107] Examples

[0108] Preparation of adhesive compositions

[0109] Part A of the adhesive composition contained a silylated polyurethane resin SPUR+1050 or SPUR+1070, amine curing agents Jeffamine D230 and Jeffamine T403, aminosilane Silquest 1120J, and carbon black filler Eltex 8. Part A was prepared by mixing these components.

[0110] Part B of the adhesive composition contained bisphenol A resin, a tin catalyst, and water.

[0111] The amount of amine-functional compound in part A and the amount of epoxy resin in part B are set so that the molar ratio of active hydrogen of the amine to epoxy groups (AHM / EM) is less than 0.8 and greater than 0.3.

[0112] Parts A and B were mixed before use for the bonding process.

[0113] Integration process

[0114] The adhesive was applied to an area of ​​aluminum or PET plastic substrate (1 inch x 3 inches), or carbon-reinforced composite material. Two 0.5 mm diameter copper wire spacers were placed on top of the adhesive layer. Another substrate (1 inch x 3 inches) was placed on top of the first substrate to form a lap shear sample. The bonded area was a 0.5 inch x 1 inch rectangle. Clamps were used to hold the two substrates together during the curing process. The bonded sample was then cured.

[0115] hardening

[0116] For the curing process, the wrapped shear samples were placed in the oven immediately after preparation for bonding with adhesive, or left at room temperature for a certain period of time before being placed in the oven. The time prior to the heating process varied from 1 hour to 24 hours. The oven temperature was varied from 50°C or 130°C. The duration of the heating process varied according to the oven temperature (from a few minutes to several days).

[0117] Evaluation of bond strength

[0118] After the heating process, the bonded samples (wrap shear or otherwise) were cooled, and the strength was tested by applying force to break the bond and measuring the bond strength (ASTM D1002). In addition, the failure mode was evaluated after the bond was broken. Cohesive failure mode means that the sample broke inside the adhesive itself, and a visible layer of adhesive was present on both substrates after the bond broke. Interfacial failure mode means that the sample broke at the interface with the substrate, and one of the substrates was left without any visible adhesive residue.

[0119] Adhesion to aluminum

[0120] The adhesive composition was prepared according to the composition shown in Table 1. The silylated polyurethane prepolymer, SPUR+1050 prepolymer, aminosilane Silquest A-1120J (AHEW=74), and tin catalyst Fomrez SUL11C were obtained from Momentive Performance Materials. Jeffamine 登録商標 D230 (AHEW=60) and T403 polyetheramine (AHEW=81) were obtained from Huntsman. Carbon black filler EltexE8 was obtained from Cabot. Bisphenol A resin DER330 (EEW=178) was obtained from Orlin. Part A was prepared, and then Part B was prepared separately. The compositions of Part A and Part B were mixed in a SpeedMixer by Flacktec. 登録商標 The mixture was placed inside. The adhesive composition obtained from the mixture of parts A and B was applied to an aluminum sample, AlCladAD2024T3C. The lapped shear sample was cured at 50°C for 24 hours.

[0121] [Table 1]

[0122] As shown in Table 1, the shear strength of the aluminum strips in Examples 1-5 was higher than 3 MPa, and cohesive failure (CF), a typical mode of failure, was obtained when the ratio AHM / EM was less than 0.8. In contrast, Comparative Examples 1 and 2 exhibited interfacial failure modes, indicating that adhesion was undesirable.

[0123] Adhesion to PET

[0124] Adhesion to polyethylene terephthalate (PET) was investigated using the compositions listed in Table 2. The adhesive compositions shown in Table 2 were prepared in the same manner as in Example A. Wrapped shear samples were cured at 50°C for 24 hours.

[0125] [Table 2]

[0126] Examples 6 and 7 exhibited shear strengths higher than 4 MPa on the PET substrate and showed cohesive failure. Comparative Example 3, which did not contain aminosilane, showed an interfacial failure mode, indicating that adhesion was undesirable.

[0127] Bonding onto carbon fiber reinforced composite materials (CFRC)

[0128] The substrate was prepared from a carbon fiber-reinforced composite material provided by the Institute of Mechanical Engineering Innovation (University of Porto). Silylated polyurethane SPUR+1070 was obtained from Momentive Performance Materials. The adhesive composition was prepared in the same manner as in Example A. The lap shear samples were cured at 50°C for 24 hours. The adhesive properties to the composite material are shown in Table 3.

[0129] [Table 3]

[0130] This composition exhibited a shear strength exceeding 4 MPa and showed cohesive failure.

[0131] Adhesion to aluminum

[0132] The compositions were prepared according to Table 4.

[0133] [Table 4]

[0134] AltaMer EP125 is an epoxidized oligomer of distilled tall oil. This composition exhibits excellent adhesion to aluminum (greater than 4 MPa) and cohesive failure.

[0135] Adhesion to dissimilar substrates

[0136] The adhesive composition shown in Example 8 was applied to an area of ​​an aluminum substrate (AlcladAD2024T3C). Another substrate made of PET plastic or acrylic plastic was placed on top of the first aluminum substrate to form a dissimilar material bonded lap shear sample. This lap shear sample was cured at 50°C for 24 hours.

[0137] Table 5 shows the shear strength of lap shear samples made of different materials.

[0138] [Table 5]

[0139] The bonding of dissimilar materials exhibited a shear strength exceeding 4 MPa.

[0140] Wet bonding: The following examples also evaluate and explain the bonding strength on various wet substrates.

[0141] Wet bonding on polypropylene substrate

[0142] Polypropylene substrates were treated with corona for 20 seconds using equipment from Tantec Lab-Tec. The adhesion to the corona-treated polypropylene substrates was investigated using the compositions listed in Table 6. The adhesive compositions shown in Table 6 were prepared as described above for the previous examples. The lap shear samples were cured at 50°C for 24 hours and then immersed in 50°C water for one week. The lap shear strength was measured immediately after immersion. The lap shear strength was observed to be 4.8 MPa. Comparative examples with an AHM / EM ratio greater than 0.8 showed significantly lower lap shear strength.

[0143] [Table 6]

[0144] Wet bonding on aluminum

[0145] Adhesion to aluminum substrates was investigated using the compositions listed in Table 7. The adhesive compositions shown in Table 7 were prepared as described above for the previous examples. The lap shear samples were cured at 50°C for 24 hours and then immersed in 50°C water for one week. The lap shear strength was measured immediately after immersion. The lap shear strength was observed to be 14.2 MPa. Comparative examples with an AHM / EM ratio greater than 0.8 showed significantly lower lap shear strength.

[0146] [Table 7]

[0147] The above description includes the examples of this specification. Of course, for the purposes of this specification, it is impossible to describe all recognizable combinations of components or methodologies, but those skilled in the art will recognize that many further combinations and substitutions of this specification are possible. Thus, this specification is intended to encompass all such changes, modifications and variations that are included in the idea and scope of the appended claims. Furthermore, wherever the term “encompasses” is used in the detailed description or claims, such term is intended to be as comprehensive as “includes,” as is interpreted when “includes” is used as a substitute in the claims.

[0148] The above description illustrates various non-limiting embodiments of the adhesive composition. Modifications may be conceived by those skilled in the art and those who create and use the present invention. The disclosed embodiments are for illustrative purposes only and are not intended to limit the scope of the invention or subject matter described in the claims.

Claims

1. A composition: Silylated polyurethane; Amine-functionalized compounds; and Contains epoxy-functional compounds; Herein, the composition has a molar ratio of active hydrogen of the amine to epoxy in the range of approximately 0.3 to less than 0.

8.

2. The composition according to claim 1, wherein the molar ratio of the active hydrogen of the amine to the epoxy in the composition is about 0.3 to about 0.

75.

3. The composition according to claim 1, wherein the molar ratio of the active hydrogen of the amine to the epoxy in the composition is in the range of about 0.4 to about 0.

7.

4. The composition according to claim 1, wherein the molar ratio of the active hydrogen of the amine to the epoxy in the composition is about 0.5 to about 0.

6.

5. The amine-functional compound is selected from polyetheramines, aminosilanes, or combinations thereof, in any composition of claims 1 to 4.

6. The composition according to claim 5, wherein the polyetheramine has a weight-average molecular weight of about 150 to about 6000.

7. The composition according to claim 5 or 6, wherein the composition contains polyetheramine in an amount of about 0.1% to about 10% by weight, based on the total weight of the composition, and aminosilane in an amount of about 0.1% to about 10% by weight.

8. The formula for aminosilane is: (R １１ )(R １２ )N-R １３ -Si(OR １４ ) ３－ｈ (R １５ ) ｈ ; R １６ -NH-R １７ -Si(OR １８ ) ３－ｉ (R １９ )i; (R ２０ ) ｊ (R ２１ O) ３－ｊ Si-R ２２ -NH-R ２３ -Si(OR ２４ ) ３－ｋ (R ２５ )k; N-(R ２６ -Si(OR ２７ ) ３－ｍ (R ２８ m) ３； Selected from the compounds, where R １１ , R １２ , and R １６ R is independently selected from H or monovalent C1-C20 hydrocarbons; １４ , R １５ , R １８ , R １９ , R ２０ , R ２１ , R ２４ , R ２５ , R ２７ , and R ２８ R is independently selected from C1-C20 monovalent hydrocarbons; １３ , R １７ , R ２２ , and R ２６ The composition according to any one of claims 5 to 7, wherein is independently selected from divalent C1-C20 hydrocarbons; and h, i, j, k, and m are independently selected from 0 to 2.

9. A composition according to any one of claims 1 to 8, further comprising additives selected from pigments, fillers, curing catalysts, dyes, plasticizers, thickeners, coupling agents, bulking agents, volatile organic solvents, wetting agents, tackifiers, crosslinking agents, thermoplastic polymers, moisture scavenging agents, and UV stabilizers.

10. The composition according to claim 9, wherein the catalyst is a tin catalyst.

11. The composition of claim 9, wherein the filler is selected from organic fillers, inorganic fillers, conductive fillers, or combinations thereof.

12. Conductive fillers are thermally conductive fillers, including alumina, magnesia, ceria, hafnia, lanthanum oxide, neodymium oxide, samaria, praseodymium oxide, tria, urania, yttria, zinc oxide, zirconia, silicon aluminum oxynitride, borosilicate glass, barium titanate, silicon carbide, silica, boron carbide, titanium carbide, zirconium carbide, boron nitride, silicon nitride, aluminum nitride, titanium nitride, zirconium nitride, zirconium boride, titanium diboride, dodecaboride, barite, barium sulfate, asbestos, barite, diatomaceous earth, feldspar, gypsum, formite, kaolin, mica, nepheline syenite, perlite, phyllolith, smectite, talc, vermiculite, zeolite, calcite, calcium carbonate, wollastonite, calcium metasilicate, clay, silica The composition of claim 11, selected from aluminum oxide, talc, magnesium aluminum silicate, hydrated alumina, hydrated aluminum oxide, aluminum hydroxide, magnesium hydroxide, silica, silicon dioxide, titanium dioxide, glass fibers, glass flakes, clay, exfoliated clay, or other high aspect ratio fibers, rods, or flakes, calcium carbonate, zinc oxide, magnesia, titania, calcium carbonate, talc, mica, wollastonite, alumina, aluminum nitride, graphite, graphene, aluminum powder, copper powder, bronze powder, brass powder, carbon fibers or whiskers, graphite, silicon carbide, silicon nitride, alumina, aluminum nitride, zinc oxide, carbon nanotubes, boron nitride nanosheets, zinc oxide nanotubes, or two or more combinations thereof.

13. A composition comprising a first agent and a second agent, wherein the first agent comprises (i) a silylated polyurethane and an amino-functional compound, and the second agent comprises (ii) an epoxy-functional compound.

14. A method for forming an adhesive, comprising: (i) exposing any composition from claims 1 to 12 to moisture; and subsequently (ii) crosslinking the composition at a temperature of about 50°C to about 130°C.

15. The method of claim 14, wherein the adhesive is formed on the substrate.

16. A method for joining two substrates: Apply any composition from claims 1 to 12 to a first substrate; The second substrate is brought into contact with the composition applied to the first substrate; and A method comprising curing a composition at a temperature of about 50°C to about 130°C.

17. The method of claim 16, wherein the first and second substrates are each independently selected from metal, thermoplastic resin, thermosetting resin, glass, carbon substrate, ceramic, cement, and wood.

18. The method of claim 16 or 17, wherein the first substrate and the second substrate are made of the same type of material.

19. The method of claim 17, wherein the first substrate is a thermoplastic substrate and the second substrate is a metal substrate.

20. The method according to any one of claims 16 to 19, wherein the first and second substrates each have no primer coating.

21. An article comprising a first substrate bonded to a second substrate, wherein the adhesive is formed from a composition according to any one of claims 1 to 12.

22. The article of claim 21, wherein the first and second substrates are each independently selected from metal, thermoplastic resin, thermosetting resin, glass, carbonaceous substrate, ceramic, cement, wood, and two or more combinations thereof.

23. The article according to claim 21 or 22, wherein the first base material and the second base material are made of the same type of material.

24. The article according to claim 21, wherein the first substrate is a thermoplastic substrate and the second substrate is a metal substrate.

25. An article according to any one of claims 21 to 24, wherein the first and second substrates each do not contain a primer coating.

26. The article according to any one of claims 21 to 25, wherein the article has a shear strength of about 3 MPa or more as defined in ASTM D1002.

27. The article according to any one of claims 21 to 26, wherein the article is agglomerated and detached as defined in ASTM D1002.

28. The article according to any one of claims 21 to 27, wherein the article is cured at 50°C for 24 hours as defined in ASTM D1002, and then immersed in water at 50°C for one week before being coagulated and peeled off.

29. The article according to claim 28, wherein the article has a shear strength of about 4 MPa or more, as measured after being immersed in water at 50°C for one week as defined in ASTM D1002.

30. The article according to claim 28, wherein the article has a shear strength of about 10 MPa or more, as measured after being immersed in water at 50°C for one week as defined in ASTM D1002.

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