Two-component polyurethanes for polycarbonate bonding.

Abstract

The present invention relates to a two-component polyurethane composition for bonding polycarbonate, a method for bonding to polycarbonate substrates using the composition, and a method for preparing the composition. The two-component polyurethane composition includes: (i) at least one polycarbonate polyol, (ii) an amine-free catalyst, and (iii) optionally, at least one aliphatic monomeric isocyanate compound; and at least one isocyanate component. The polyurethane composition is free of aromatic isocyanate compounds. Also disclosed is the use of the composition in adhesive, coating, primer, paint, and varnish-based compositions.

Description

[Technical Field]

[0001] The processes, procedures, methods, reaction products, results, and / or concepts disclosed herein (hereinafter collectively referred to as "the present disclosure" or "the present invention") generally relate to two-component polyurethane adhesive compositions for bonding polycarbonate, methods of bonding to polycarbonate substrates using the compositions, and methods for preparing the compositions. [Background technology]

[0002] This invention relates to structural engineering adhesives for bonding metal, plastic, and fiber-reinforced composite parts (e.g., sheet molding compound (SMC), fiberglass reinforced polyester (FRP), structural reaction injection molded (SRIM), resin transfer molded (RTM), plastics, etc.) to a variety of homogeneous and heterogeneous substrates, which find use in the manufacture of cars, trucks, boats, and many other products.

[0003] One typical class of structural adhesives useful for bonding composite parts to homogeneous and heterogeneous substrates is two-component polyurethane adhesives. These materials are useful as adhesives when a prepolymer and a curing agent are combined immediately before use. The ratios at which these ingredients are combined will vary depending on the functionality of the prepolymer and the curing agent. Accurately combining these ingredients requires a certain skill level from the operator, and unfortunately, even with automated pumping equipment, substantial adhesive waste is produced. Additionally, polyurethane adhesives generally have poor thermal properties, making them unsuitable for applications requiring high-temperature ovens.

[0004] Another common class of structural adhesives useful for bonding metal parts to homogeneous and heterogeneous substrates (e.g., composites) are epoxy adhesives. Epoxy adhesive compositions most often contain a multifunctional epoxy resin and are cured by the addition of a curing agent, which typically comes in a separate package. The cure rate and properties of the reaction product are affected by the choice of curing agent, which itself is influenced by the makeup of the adhesive composition, which is dictated by the end performance desired by the user.

[0005] Structural polyurethane adhesive compositions are used, for example, by applying them to the surface of a metal or plastic component and then placing the surface of a second component (of the same or different material) on top of the metal / plastic adhesive-coated surface. Often, these components have uneven surfaces, and it is desirable for the adhesive to have the ability to fill voids resulting from varying depths.

[0006] Many of these polyurethane adhesive compositions also have several systematic drawbacks. One of the most serious is the residual monomer content of isocyanates, especially the more volatile diisocyanates. They are extremely hazardous to health and are subject to mandatory labeling with hazard classification R40 / H351 (suspected carcinogen). This labeling requirement also requires special packaging and transportation measures. The presence of unreacted monomeric diisocyanates often leads to problems in further processing. Therefore, such diisocyanates can migrate from the coating or joint into the coated or joined material. In the future, MDI-containing products with a residual monomer content higher than 0.1% may be unavailable to DIY (do-it-yourself) customers and may be subject to self-service bans. Therefore, there is strong interest in reactive polymers with no or at least extremely reduced residual MDI content, thereby eliminating or at least reducing the potential health risks of the product to users. An alternative to MDI is the use of oligomers and polymers of hexamethylene diisocyanate (HDI), which have the advantage of not being carcinogenic and do not have the H351 hazard classification as MDI.

[0007] For conventional polyurethanes, maintaining good adhesion to PC (polycarbonate) and PC blends, especially after high-temperature, high-humidity aging conditions, such as the cataplasma test, is a difficult challenge. In this invention, polycarbonate polyols are used as raw materials to improve adhesion to PC substrates, based on the chemical principle that "like attracts like." PC can be hydrolyzed when in contact with moisture at high temperatures, but this reaction can be catalyzed under basic conditions, such as in the presence of amines. While many currently used catalysts are amine-based, this invention avoids the use of these amine catalysts to prevent hydrolysis of PC substrates.

[0008] EP 2462177 describes a mixture of radiation-curable, water-dispersible polyurethanes, which comprises at least one radiation-curable, water-dispersible polyurethane.

[0009] WO 2005 / 0007721 describes the use of a mixture of low monomeric NCO, i.e. terminated prepolymers formed from the monomeric reaction product of a polyol with a stoichiometric excess of diphenylmethane diisocyanate, demonomerized polyphenylene polymethylene polyisocyanate, trimerized hexamethylene diisocyanate, and a diluent.

[0010] European Patent Specification No. 285859 describes a reaction-curable composition containing, as reactive raw materials, a polyisocyanate component containing a diisocyanate and a tri- or higher-functional polyisocyanate and having an average equivalent molecular weight of 120 to 240, and a polyol component containing a diol and a tri- or higher-functional polyol and having an average equivalent molecular weight of 100 to 550.

[0011] Bostik Pliogrip™ Impact Adhesive and Pliogrip™ Evolution Adhesive are MDI-free polyurethane structural adhesives from Bostik. They provide excellent adhesion and do not require additional primers or prior surface preparation.

[0012] Despite the above-mentioned prior art techniques for reducing monomeric diisocyanates, there remains a need for polyurethane adhesive compositions that are free of aromatic isocyanate compounds and are useful as adhesives for sealants, coatings, primers, paints, and varnishes. Summary of the Invention [Problem to be solved by the invention]

[0013] Accordingly, it is a primary object of the present invention to provide a two-component polyurethane composition that is free of aromatic isocyanate compounds and is useful as an adhesive for sealants, coatings, primers, paints, and varnishes. [Means for solving the problem]

[0014] The present disclosure provides two-component polyurethane compositions for bonding thermosets and thermoplastics, methods for using the compositions to bond thermosets and / or thermoplastics, and methods for preparing the compositions. Examples of thermosets and thermoplastics include, but are not limited to, polycarbonate, polycarbonate blends such as polycarbonate / polyethylene terephthalate, polycarbonate / acrylonitrile / butadiene / styrene, and polycarbonate / acrylonitrile / styrene / acrylate.

[0015] One object of the present disclosure relates to a two-component polyurethane composition comprising: (A) a polyol component comprising: (i) at least one polycarbonate polyol, (ii) an amine-free catalyst, and (iii) optionally, at least one aliphatic monomeric isocyanate compound; and (B) at least one isocyanate component selected from the group consisting of: (i) an aliphatic oligomeric isocyanate compound, (ii) an aliphatic polymeric isocyanate compound, and combinations thereof, wherein the polyurethane composition is free of aromatic isocyanate compounds.

[0016] A further object of the present disclosure relates to a two-component polyurethane composition that is free of aromatic isocyanate compounds selected from the group consisting of diphenylmethane diisocyanate (MDI), toluene diisocyanate (TDI), naphthalene diisocyanate, diisocyanatobenzene, triisocyanatobenzene, triisocyanatomethylbenzene, bis(isocyanatomethyl)benzene, and combinations thereof.

[0017] Another object of the present disclosure relates to two-component polyurethane compositions useful as adhesives, coatings, primers, paints, and varnishes.

[0018] A further object of the present disclosure relates to a two-component polyurethane adhesive composition comprising: (A) a polyol component comprising: (i) at least one polycarbonate polyol, (ii) an amine-free catalyst, and (iii) optionally, at least one aliphatic monomeric isocyanate compound; and (B) at least one isocyanate component selected from the group consisting of: (i) an aliphatic oligomeric isocyanate compound, (ii) an aliphatic polymeric isocyanate compound, and combinations thereof, wherein the polyurethane composition is free of aromatic isocyanate compounds.

[0019] These and other objects of the present disclosure will become apparent from the disclosure that follows.

[0020] It is believed that the present disclosure will be better understood from the following description taken in conjunction with the accompanying drawings, in which: The referenced drawings should not be considered as limiting the scope of the invention. [Brief explanation of the drawings]

[0021] [Figure 1] 1 is a table illustrating lap shear failure modes. [Figure 2A] 1 is a graph showing the lap shear strength of adhesives using prepolymer versions. [Figure 2B]1 is a graph showing the failure mode of adhesives using the prepolymer version. [Figure 3A] 1 is a graph showing the lap shear strength of adhesives without the prepolymer version. [Figure 3B] 1 is a graph showing the failure mode of the adhesive without the prepolymer version. [Figure 4A] Photograph of the failure mode after 7 days of Cataplasma in the case of PC-PET (prepolymer version). [Figure 4B] Photograph of the failure mode after 7 days of Cataplasma for PC-ABS (prepolymer version). [Figure 4C] This is a photograph of the failure mode after 7 days of Cataplasma in the case of PC (prepolymer version). [Figure 5A] Photograph of the failure mode after 7 days of Cataplasma for PC-PET (non-prepolymer version). [Figure 5B] Photograph of the failure mode after 7 days of Cataplasma for PC-ABS (non-prepolymer version). [Figure 5C] Photograph of the failure mode after 7 days of Cataplasma in the case of PC (non-prepolymer version). DETAILED DESCRIPTION OF THE INVENTION

[0022] Exemplary embodiments of the present disclosure will now be described with reference to Figures 1-5C.

[0023] Before describing in detail at least one embodiment of the present disclosure, it is to be understood that the disclosure is not limited in its application to the precise arrangement and configuration of components or steps or methods set forth in the following description or illustrated in the drawings. The disclosure is capable of other embodiments and of being practiced or carried out in various ways. Moreover, it is to be understood that the language and terminology employed herein is for purposes of description and not of limitation.

[0024] Unless otherwise defined herein, technical terms used in connection with this disclosure shall have the meanings commonly understood by those of ordinary skill in the art. Further, unless otherwise required by context, singular terms shall include pluralities and plural terms shall include the singular.

[0025] All patents, published patent applications, and other publications mentioned in this specification are indicative of the level of skill of those skilled in the art to which this disclosure pertains. All patents, published patent applications, and other publications referenced throughout this application are expressly incorporated by reference in their entirety to the same extent as if each individual patent or publication was specifically and individually indicated to be incorporated by reference.

[0026] All of the articles and / or methods disclosed herein can be made and executed without undue experimentation in light of the present disclosure. While the articles and methods of the present disclosure have been described in terms of preferred embodiments, it will be apparent to those skilled in the art that various changes can be made to the articles and / or methods in the various steps or the order of those steps of the methods described herein without departing from the concept, spirit, and scope of the present disclosure. All such substitutions and modifications apparent to those skilled in the art are deemed to be within the spirit, scope, and concept of the present disclosure.

[0027] As used in this disclosure, the following terms, unless otherwise indicated, shall be understood to have the following meanings:

[0028] The use of the indefinite articles "a" and "an," when used in conjunction with the word "comprising," can mean "one," but is also compatible with the meanings of "one or more," "at least one," or "one or more than one." The use of the word "or" refers to alternatives only where the alternatives are mutually exclusive, and unless expressly stated otherwise, the disclosure dictates a definition that refers to alternatives only and "and / or." Throughout this application, the term "about" is used to indicate that a value includes the inherent variation of error in the quantitative device being employed to measure the value or variation that exists in the subject matter discussed.

[0029] References herein to "one embodiment" or "one aspect" or "one version" or "one objective" of the invention, or to "another embodiment" or "another aspect" or "another version" or "another objective" may include one or more of such embodiments, aspects, versions or objectives, unless the context clearly indicates otherwise.

[0030] The term "at least one" refers to one or any amount greater than one, including but not limited to, 1, 2, 3, 4, 5, 10, 15, 20, 30, 40, 50, 100, etc. The term "at least one" can extend to 100 or 1000 or more, depending on the term to which it is attached.

[0031] As used herein, all percentages, parts, proportions, and ratios are by weight of the total composition unless otherwise specified. All such weights, when referring to listed ingredients, are based on the active level unless otherwise specified, and therefore do not include solvents or by-products contained in commercially available ingredients.

[0032] All references to a single feature or limitation of the invention include multiple features or limitations, and vice versa, unless otherwise specified or clearly implied to the contrary by the context in which the reference is made.

[0033] As used herein, numerical ranges include all values ​​and subsets of values ​​contained within the range, whether or not specifically disclosed, and should be considered to provide a basis for claims directed to the various values ​​and subsets of values ​​within the range.

[0034] As used herein, the words "comprising" (and various forms of "comprising," e.g., "comprise" and "comprises"), "having" (and various forms of "have," e.g., "have" and "has"), "including" (and various forms of "including," e.g., "includes" and "include"), or "containing" (and various forms of "containing," e.g., "contains" and "contain") are all inclusive, i.e., open-ended, and do not exclude additional, unlisted elements or method steps. The terms "or combinations thereof" and "and / or combinations thereof," as used herein, refer to all permutations and combinations of the list of items preceding the term. For example, "A, B, C, or combinations thereof" is intended to include at least one of A, B, C, AB, AC, BC, or ABC, and, if order is important in the particular context, further include BA, CA, CB, CBA, BCA, ACB, BAC, or CAB. Continuing with this example, expressly included are combinations including repeats of one or more items or terms, e.g., BB, AAA, AAB, BBC, AAABCCCC, CBBAAA, CABABB, etc. Those of skill in the art will understand that typically there is no limit to the number of items or terms in various combinations, unless the context makes clear otherwise.

[0035] For purposes of the following detailed description, except in the various examples or where otherwise indicated, for example, the numbers expressing quantities of ingredients used in the specification and claims should be understood to be modified in all instances by the term "about." The numerical parameters set forth in the specification and appended claims are approximations that may vary depending upon the desired properties obtained in the practice of the present invention.

[0036] The terms "or combinations thereof," "and combinations thereof," and "combinations thereof," as used herein, refer to all permutations and combinations of the list of items preceding the term.

[0037] The term "about" refers to a range of values ​​of plus or minus 10% of a particular value. For example, the phrase "about 200" includes 200 plus or minus 10%, or 180 to 220.

[0038] The terms "polymerization" or "polymerizing" refer to a process for chemically reacting monomer compounds to form polymer chains. The type of polymerization process can be selected from a wide variety of methods, including, but not limited to, polycondensation, step-growth polymerization, and free-radical polymerization.

[0039] With respect to amine-free catalysts, the term "free of" refers to compositions having 0.05 wt. % or less amines, preferably 0.01 wt. % or less amines, more preferably trace amounts or less, and even more preferably below current detection limits.

[0040] The expression "a polyurethane composition is free of an aromatic isocyanate compound" means that the composition contains 1% by weight or less of an aromatic isocyanate compound, preferably 0.05% by weight or less, more preferably 0.1% by weight or less, even more preferably traces or less of aromatic isocyanate compounds, and even more advantageously below current detection limits.

[0041] The present disclosure is directed to a two-component polyurethane composition comprising: (A) a polyol component comprising: (i) at least one polycarbonate polyol, (ii) an amine-free catalyst, and (iii) optionally, at least one aliphatic monomeric isocyanate compound; and (B) at least one isocyanate component selected from the group consisting of: (i) an aliphatic oligomeric isocyanate compound, (ii) an aliphatic polymeric isocyanate compound, and combinations thereof, wherein the polyurethane composition is free of aromatic isocyanate compounds.

[0042] In one or more embodiments, the aliphatic monomeric isocyanate compound has the formula R(NCO) n where n=2, 3, or 4, and R=an aliphatic residue having from about 2 to about 20 carbon atoms. In one non-limiting embodiment of the present application, the number of carbon atoms present can range from 2 to 5; 6 to 10; 11 to 15; or 16 to 20.

[0043] In another embodiment, the aliphatic monomeric isocyanate compound is selected from the group consisting of isophorone diisocyanate (IPDI), dicyclohexylmethane-4,4'-diisocyanate, hexamethylene-1,6-diisocyanate (HDI), cyclohexylene diisocyanate, diisocyanatomethylcyclohexane, bis(isocyanatomethyl)cyclohexane, diisocyanatoethane, diisocyanatopropane, diisocyanatobutane, diisocyanatopentane, diisocyanatooctane, diisocyanatodecane, diisocyanatododecane, 4,4'-HMDI, lysine diisocyanate, and combinations thereof.

[0044] In one or more embodiments of the present disclosure, the aliphatic monomeric isocyanate compound is present in an amount of from about 0.5% w / w to about 5% w / w of the polyol component of the present application.

[0045] In other embodiments, the aliphatic monomeric isocyanate compound is present in an amount from about 0.5% to about 1%, from about 1.1% to about 2%, from about 2.1% to about 3%, from about 3.1% to about 4%, and from about 4.1% to about 5% by weight of the polyol component of the present application.

[0046] In another embodiment of the present disclosure, the aliphatic oligomeric isocyanate compound has the formula R(NCO) n where n=2, 3, or 4, R=an aliphatic residue having from about 6 to about 21 carbon atoms, and containing at least 2 to 15 repeating monomer units.

[0047] In another embodiment, the aliphatic oligomeric isocyanate compound has the formula R(NCO) n where n=2, 3, or 4, and R=an aliphatic residue having about 6 to about 10, about 11 to about 15, about 16 to about 20, or about 20 to about 21 carbon atoms.

[0048] In another embodiment, the aliphatic oligomeric isocyanate compound has the formula R(NCO) n where n=2, 3, or 4, and R=an aliphatic residue having from about 6 to about 21 carbon atoms, and includes 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, or 15 repeating monomer units.

[0049] In one embodiment of the present disclosure, the aliphatic oligomeric isocyanate compound is selected from the group consisting of HDI trimers, HDI biurets, HDI uretidones, HDI allophanates, HDI iminooxadiazinediones, PDI (pentamethylene diisocyanate) and IPDI based polyisocyanates, and combinations thereof.

[0050] In another embodiment of the present disclosure, the aliphatic oligomeric isocyanate compound may be present in an amount from greater than about 0% w / w to about 100% w / w of the isocyanate component.

[0051] In another embodiment of the present disclosure, the aliphatic oligomeric isocyanate compound may be present in the following amounts of the isocyanate component: from greater than about 0% to about 5% by weight, from about 6% to about 10% by weight, from about 11% to about 15% by weight, from about 16% to about 20% by weight, from about 21% to about 25% by weight, from 26% to about 30% by weight, from 31% to about 35% by weight, from 36% to about 40% by weight, from 41% to about 50% by weight, from about 51% to about 60% by weight, from about 61% to about 70% by weight, from about 71% to about 80% by weight, from about 81% to about 90% by weight, or from 91% to about 100% by weight.

[0052] In another embodiment of the present disclosure, the aliphatic polymeric isocyanate compound has the formula R(NCO) n where n=2, 3, or 4, R=an aliphatic residue having from about 2 to about 20 carbon atoms, and contains at least 3 to 10,000 repeating monomer units.

[0053] In another embodiment, the aliphatic polymeric isocyanate compound has the formula R(NCO) n where n=2, 3, or 4, and R=an aliphatic residue having about 2 to about 3, about 4 to about 5, about 6 to about 7, about 8 to about 9, about 10 to about 11, about 12 to about 13, about 14 to about 15, about 16 to about 17, or about 18 to about 20 carbon atoms, and contains at least 3 to 10,000 repeating monomer units.

[0054] In yet another embodiment of the present disclosure, the aliphatic polymeric isocyanate compound has the formula R(NCO) nwhere n=2, 3, or 4, and R=an aliphatic residue having from about 2 to about 20 carbon atoms, and contains at least 3 to 1,000, at least 1,001 to 2,000, at least 2,001 to 3,000, at least 3,001 to 4,000, at least 4,001 to 5,000, at least 5,001 to 6,000, at least 6,001 to 7,000, at least 7,001 to 8,000, at least 8,001 to 9,000, or at least 9,001 to 10,000 repeating monomer units.

[0055] In a further embodiment of the present disclosure, the aliphatic polymeric isocyanate compound may be present in an amount from greater than about 0% w / w to about 100% w / w of the isocyanate component.

[0056] In a further embodiment, the aliphatic polymeric isocyanate compound may be present in the following amounts of the isocyanate component: from greater than about 0% to about 5% by weight, from about 6% to about 10% by weight, from about 11% to about 15% by weight, from about 16% to about 20% by weight, from about 21% to about 25% by weight, from 26% to about 30% by weight, from 31% to about 35% by weight, from 36% to about 40% by weight, from 41% to about 50% by weight, from about 51% to about 60% by weight, from about 61% to about 70% by weight, from about 71% to about 80% by weight, from about 81% to about 90% by weight, or from 91% to about 100% by weight.

[0057] In one or more embodiments of the present disclosure, the polycarbonate polyol has at least two active hydrogens for reacting with an isocyanate compound. In another non-limiting embodiment, the number of active hydrogens is in the range of about 1 to 5. In one non-limiting embodiment of the present application, the number of carbonate bonds is in the range of about 3 to 90. In another non-limiting embodiment, the —OH content in the polycarbonate polyol is in the range of about 0.1 to about 80%.

[0058] Furthermore, in certain non-limiting embodiments of the present application, the polycarbonate polyol may be a compound based on either an aliphatic polycarbonate polyol or an aromatic polycarbonate polyol.

[0059] In other embodiments, the polycarbonate polyol is present in the following amounts by weight of the polyol component: from about 5% to about 10%, from about 11% to about 15%, from about 16% to about 20%, from about 21% to about 25%, from 26% to about 30%, from 31% to about 35%, from 36% to about 40%, from 41% to about 50%, from about 51% to about 60%, from about 61% to about 70%, from about 71% to about 80%, or from about 81% to about 90%.

[0060] In one embodiment of the present disclosure, the polyol component of the two-component polyurethane composition comprises at least one non-polycarbonate polyol.

[0061] In one or more embodiments, the non-polycarbonate polyol is a polyester polyol, a polyether polyol, a polybutadiene polyol, a polyacrylate, and combinations thereof.

[0062] In yet another embodiment, the non-polycarbonate polyol is present in an amount from about 10% w / w to about 90% w / w of the polyol component.

[0063] In other embodiments, the non-polycarbonate polyol is present in the following amounts by weight of the polyol component: from about 10% to about 15%, from about 16% to about 20%, from about 21% to about 25%, from 26% to about 30%, from 31% to about 35%, from 36% to about 40%, from 41% to about 50%, from about 51% to about 60%, from about 61% to about 70%, from about 71% to about 80%, or from about 81% to about 90%.

[0064] In one or more embodiments of the present disclosure, the polycarbonate polyol has a hydroxyl functionality of 1 to 5 with a weight average molecular weight between 100 Da and 8000 Da, and the non-polycarbonate polyol has a functionality of 1 to 6 with a weight average molecular weight between 100 Da and 12000 Da.

[0065] In one or more embodiments, the polycarbonate polyol has the following weight average molecular weight: about 100 Da to about 500 Da, about 501 Da to about 1000 Da, about 1001 Da to about 1500 Da, about 1501 Da to about 2000 Da, about 2001 Da to about 2500 Da, about 2501 Da to about 3000 Da, about 3000 Da to about 3500 Da, about 3501 Da to about 4000 Da, about 4001 Da to about 4500 Da, about 4501 Da to about 5000 Da, about 5001 Da to about 5500 Da, about 5501 Da to about 6000 Da, about 6001 Da to about 6500 Da, about 6501 Da to about 7000 Da, about 7001 Da to about 7500 Da, or about 7501 Da to about 8000 Da.

[0066] Examples of commercially available polycarbonate polyols under trade names include Aramaco, Eternacoll, Kuraray, Unoxol, and Desmophen. A known distributor of such materials is TriiSO.

[0067] In one or more embodiments, the non-polycarbonate polyol has a weight average molecular weight of from about 100 Da to about 500 Da, from about 501 Da to about 1000 Da, from about 1001 Da to about 1500 Da, from about 1501 Da to about 2000 Da, from about 2001 Da to about 2500 Da, from about 2501 Da to about 3000 Da, from about 3000 Da to about 3500 Da, from about 3501 Da to about 4000 Da, from about 4001 Da to about 4500 Da, from about 4501 Da to about 5000 Da, or from about 5001 Da to about 5500 Da. a, about 5501 Da to about 6000 Da, about 6001 Da to about 6500 Da, about 6501 Da to about 7000 Da, about 7001 Da to about 7500 Da, or about 7501 Da to about 8000 Da, about 8000 Da to about 8500 Da, about 8501 Da to about 9000 Da, about 9001 Da to about 9500 Da, about 9501 Da to about 10000 Da, about 10001 Da to about 10500 Da, about 10501 Da to about 11000 Da, about 11001 Da to about 11500 Da, or about 11501 Da to about 12000 Da.

[0068] In another embodiment, the polyol component further comprises a chain extender selected from the group consisting of ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, 1,4-butanediol, 2-methyl-1,3-propylene diol, and N,N'-bis(2-hydroxypropylaniline), 4,4'-methylene-bis-(3-chloro-2,6-diethylaniline), 1,4-di(2-hydroxyethyl)hydroquinone, diethanolamine, triethanolamine, 1,1,1-trimethylolpropane, glycerol, dimethylolbutanoic acid (DMBA), hydrazine, ethylenediamine (EDA), 1,4-cyclohexanediamine, isophoronediamine, 4,4'-bis(sec-butylamine)diol. Cyclohexylmethane, 4,4'-bis(sec-butylamine)diphenylmethane, diethyltoluenediamine, 4,4'-methylenebis(2-chloroaniline), 4-chloro-3,5-diamino-benzoic acid isobutyl ester, 3,5-dimethylthio-toluenediamine, trimethylene glycol-di-p-aminobenzoate, 4,4'-methylenebis(3-chloro-2,6-diethylaniline), 1-(α-naphthyl)-3,3-di(2-hydroxyethyl)-triazene-1, 1-phenyl-3,3-di(2-hydroxyethyl)-triazene-1PT-D, 1,4-bis(2-hydroxyethoxy)benzene, diethoxylated resorcinol, 1,4-butanediamine, diaminopropane, cyclohexanediphenylalanine, and 4,4'-methylene-bis-(2-chloroaniline).

[0069] In one or more embodiments of the present disclosure, the chain extender is present in an amount of from about 1% w / w to about 15% w / w of the polyol component.

[0070] In one or more embodiments, the chain extender is present in an amount of from about 1% w / w to about 5% w / w, from about 5% w / w to about 10% w / w, or from about 10% w / w to about 15% w / w of the polyol component.

[0071] In another embodiment of the present disclosure, the polyol component further includes an amine-free catalyst selected from the group consisting of zinc-based catalysts, tin-based catalysts, bismuth-based catalysts, and various other metal-based catalysts, and combinations thereof.

[0072] In one or more embodiments, the amine-free catalyst is selected from the group consisting of dioctyltin di(ethylhexanoate), dioctyltin dithioglycolate, dioctyltin dilaurate (dotl), dioctyltin oxide, dibutyltin dilaurate (dbtl), monobutyltin tris(2-ethylhexanoate), dioctyltin diketanoate, dioctyltin diacetate (dota), dioctyltin oxide (doto), dibutyltin diacetate (dbta), dibutyltin oxide (dbto), monobutyltin oxide (mbto), dioctyltin dicarboxylate, dioctyltin stannoxane, dimethyltin neodecanoate, stannase octoate, stannase oxalate, stannase oxide, bis(dodecylsulfanyl)dimethylstannane, bis(dodecylthio)dioctylstannane, methyltin mercaptide, zinc neodecanoate, zinc octoate, zinc acetylacetonate, zinc oxalate, zinc acetate, bismuth carboxylate, bismuth oxide, bismuth tris(2-ethylhexanoate), potassium octoate, potassium neodecanoate, aluminum ethylacetoacetate, and combinations thereof.

[0073] In another embodiment of the present disclosure, the catalyst is present in an amount from about 0.005% w / w to about 3% w / w of the polyol component.

[0074] In other embodiments, the catalyst is present in an amount from about 0.005% w / w to about 0.001% w / w, from about 0.099% w / w to about 0.99% w / w, from about 1% w / w to about 2% w / w, or from 2.1% w / w to about 3% w / w of the polyol component.

[0075] In one or more embodiments of the present disclosure, the polyurethane composition further comprises an additive selected from the group consisting of fillers, antioxidants, waxes, ultraviolet light inhibitors, plasticizers, thickeners, compatibilizers, dispersants, rheology modifiers, flame retardants, optical brighteners, pigments, and water scavengers.

[0076] In another embodiment of the present disclosure, the polyurethane composition does not contain an aromatic isocyanate compound selected from the group consisting of diphenylmethane diisocyanate (MDI), toluene diisocyanate (TDI), naphthalene diisocyanate, diisocyanatobenzene, triisocyanatobenzene, triisocyanatomethylbenzene, bis(isocyanatomethyl)benzene, and combinations thereof.

[0077] In one or more embodiments of the present disclosure, the compositions are useful as adhesive compositions, coating compositions, primer compositions, paint compositions, and varnish compositions.

[0078] In another embodiment of the present disclosure, the two-component polyurethane adhesive composition comprises: (A) a polyol component comprising: (i) at least one polycarbonate polyol, (ii) an amine-free catalyst, and (iii) optionally, at least one aliphatic monomeric isocyanate compound; and (B) at least one isocyanate component selected from the group consisting of: (i) an aliphatic oligomeric isocyanate compound, (ii) an aliphatic polymeric isocyanate compound, and combinations thereof, wherein the polyurethane composition is free of aromatic isocyanate compounds.

[0079] An advantage of the adhesive under discussion is that it is an aliphatic urethane adhesive with a suitable pot life. The adhesive disclosed can have a pot life of less than 2 hours at substantially ambient temperatures. A pot life of less than 90 minutes is preferred, and even more preferred is one hour or less.

[0080] The present invention may further include other aspects, such as those listed below: The embodiments disclosed herein may contain less than 1% by weight of aromatic urethane compounds, preferably less than 0.1% by weight of aromatic urethane.

[0081] An embodiment of the present invention includes a two-component polyurethane composition, the composition including a polyol component, the polyol component including: The polyurethane composition comprises (i) at least one polycarbonate polyol, (ii) an amine-containing catalyst of less than 0.05 wt. %, and (iii) optionally at least one aliphatic monomeric isocyanate compound. The polyol component further comprises (B) at least one isocyanate component. The isocyanate component is at least one selected from the following group: (i) an aliphatic oligomeric isocyanate compound, (ii) an aliphatic polymeric isocyanate compound, and combinations thereof. Preferably, the polyurethane composition contains less than 1 wt. % aromatic isocyanate compound.

[0082] In a second embodiment, the two-component polyurethane composition is according to the previous embodiment, wherein the polyol component further comprises at least one non-polycarbonate polyol.

[0083] In a third aspect, there is provided a two-component polyurethane composition according to either the first or second aspect, wherein the aliphatic monomeric isocyanate compound is represented by the formula R(NCO) n where n=2, 3, and 4, and R=an aliphatic residue having from about 2 to about 20 carbon atoms.

[0084] In a fourth aspect, the two-component polyurethane composition of any one of aspects 1-3, wherein the aliphatic monomeric isocyanate compound is selected from the group consisting of isophorone diisocyanate (IPDI), dicyclohexylmethane-4,4′-diisocyanate, hexamethylene-1,6-diisocyanate (HDI), cyclohexylene diisocyanate, diisocyanatomethylcyclohexane, bis(isocyanatomethyl)cyclohexane, diisocyanatoethane, diisocyanatopropane, diisocyanatobutane, diisocyanatopentane, diisocyanatooctane, diisocyanatodecane, diisocyanatododecane, 4,4′-HMDI, lysine diisocyanate, and combinations thereof.

[0085] In a fifth embodiment, the two-component polyurethane composition of any of embodiments 1-4, wherein the aliphatic monomeric isocyanate compound is present in an amount of from about 0.5% w / w to about 5% w / w of the polyol component.

[0086] In a sixth embodiment, the two-component polyurethane composition of any of the first to fifth embodiments is provided, wherein the aliphatic oligomeric isocyanate compound is a compound of the formula R(NCO) n where n=2, 3, and 4, R=an aliphatic residue having from about 6 to about 21 carbon atoms, and having at least 2 to 15 repeating monomer units.

[0087] In a seventh aspect, the two-component polyurethane composition of any of aspects 1-6, wherein the aliphatic oligomeric isocyanate compound is selected from the group consisting of HDI trimers, HDI biurets, HDI uretidones, HDI allophanates, HDI iminooxadiazinediones, PDI and IPDI based polyisocyanates, and combinations thereof.

[0088] In an eighth embodiment, the two-component polyurethane composition of any of embodiments 1-7, wherein the aliphatic oligomeric isocyanate compound is present in an amount from greater than about 0% w / w to about 100% w / w of the isocyanate component.

[0089] In a ninth aspect, the two-component polyurethane composition of any of aspects 1-5, 7, or 8, wherein the aliphatic polymeric isocyanate compound is a compound of the formula R(NCO) n where n=2, 3, and 4, R=an aliphatic residue having from about 2 to about 20 carbon atoms, and has at least 3 to 10,000 repeating monomer units.

[0090] In a tenth embodiment, the two-component polyurethane composition is the two-component polyurethane composition of any of the first to ninth embodiments, wherein the polycarbonate polyol has at least two active hydrogens for reacting with an isocyanate compound.

[0091] In an eleventh embodiment, there is provided a two-component polyurethane composition according to any of the first to tenth embodiments, wherein the polycarbonate polyol is present in an amount from about 5% w / w to about 90% w / w of the polyol component.

[0092] In a twelfth embodiment, the two-component polyurethane composition of any of embodiments 1-11, wherein the polyurethane composition has less than 0.1 wt. % of aromatic isocyanate compounds. [Example]

[0093] The present invention will be described in a non-limiting manner with reference to the following examples.The following examples demonstrate the water-based moisture-resistant adhesive composition for bonding a sheet film to a substrate, the method for bonding a substrate with the composition, and the method for preparing the composition described herein.These examples are for illustrative purposes only and are not intended to be limiting.Many variations are known per se and are within the broadest scope.

[0094] Example 1

[0095] [Table 1]

[0096] Example 2

[0097] [Table 2]

[0098] Example 3

[0099] [Table 3]

[0100] Lap shear: Lap shear was carried out according to standard EN 1465 (10 mm / min using a Zwick Universal Tensile Tester Z020).

[0101] Cataplasma 7 Days: The overlap shear binder is rolled into a cotton sheet. 4-6 binders per roll. The rolls are sealed in a plastic bag and water is added to the bag (10 times the weight of the cotton). All samples are stored at 70°C for 7 days, followed immediately by 2 hours at -20°C and then a final 4 hours at 23°C before testing.

[0102] Lap Shear, Pot Life: Lap shear strength is measured immediately after application of the adhesive, followed by repeated testing at specified intervals until the desired strength is reached. This method indicates the time and rate at which the adhesive builds strength.

[0103] Mechanical strength: Test method ASTM D638IV (using Zwick Universal Tensile Tester Z020 at 50 mm / min)

[0104] Figure 1 is a representation of the lap shear failure mode. Figure 2A is a bar graph of adhesive lap shear strength for the samples of Example 2, and Figure 2B is a bar graph of failure mode for the samples of Example 2.

[0105] Conventional polyurethane adhesives typically fail to bond to PC and PC blend substrates after high temperature / humidity conditions, whereas the adhesives of the present invention maintain adhesion even after 7 days of Cataplasma (high temperature / humidity aging conditions). The test results are shown in Figures 1A, 2A, and 2B.

[0106] Figure 2A shows the lap shear bond results at ambient temperature and after the samples were aged in Cataplasma for 7 days as described above. Quite surprisingly, each sample exceeded a lap shear bond strength of at least 1 MPa even after 7 days of Cataplasma exposure. Surprisingly, each sample exhibited a lap shear strength of at least 15 MPa and 2.0 MPa, respectively.

[0107] Regarding failure modes, Figure 2B, only two instances of adhesive failure were observed, representing less than 10% of the samples tested. Most strikingly, after 7 days of Cataplasma exposure, less than 5% of the samples tested showed adhesive failure. The PC-PET and PC bonded samples showed zero adhesive failures. The PC-ABS sample showed only one adhesive failure.

[0108] FIG. 3A is a bar graph of adhesive lap shear strength for the samples of Example 3, and FIG. 3B is a bar graph of failure mode for the samples of Example 3.

[0109] 3A, the adhesives without prepolymer exhibited similar lap shear strength results as the adhesives with prepolymer, i.e., each sample exceeded a lap shear bond strength of at least 1 MPa after 7 days of Cataplasma exposure. Additionally, each sample exhibited a lap shear strength of at least 15 MPa and 2.0 MPa.

[0110] Figure 3B shows that there was no adhesive failure in any of the samples coated with the adhesive without the prepolymer. At both cures, the example adhesive performed well.

[0111] Figures 4A-5C are images of the tested samples after testing. The sample on the bottom left of Figure 4B showed adhesion failure. All other samples shown did not show adhesion failure.

[0112] While the present invention has been described in detail with reference to certain preferred embodiments, it is to be understood that the invention is not limited to these detailed embodiments. Rather, many modifications and variations will become apparent to those skilled in the art in light of this disclosure without departing from the scope and spirit of the invention.

Claims

1. 1. A two-component polyurethane composition comprising: (A) a polyol component comprising: (i) at least one polycarbonate polyol; (ii) an amine-free catalyst, and (iii) optionally, at least one aliphatic monomeric isocyanate compound; and (B) at least one isocyanate component selected from the group consisting of: (i) aliphatic oligomeric isocyanate compounds, (ii) aliphatic polymeric isocyanate compounds, and combinations thereof; Including, The polyurethane composition is free of aromatic isocyanate compounds. Two-component polyurethane compositions.

2. The two-component polyurethane composition of claim 1 , wherein the polyol component further comprises at least one non-polycarbonate polyol.

3. The aliphatic monomeric isocyanate compound has the formula R(NCO) n 3. The two-component polyurethane composition of claim 1, having monomer units of the formula: where n=2, 3, and 4, and R=an aliphatic residue having from about 2 to about 20 carbon atoms.

4. 4. The two-component polyurethane composition of claim 1, wherein the aliphatic monomeric isocyanate compound is selected from the group consisting of isophorone diisocyanate (IPDI), dicyclohexylmethane-4,4'-diisocyanate, hexamethylene-1,6-diisocyanate (HDI), cyclohexylene diisocyanate, diisocyanatomethylcyclohexane, bis(isocyanatomethyl)cyclohexane, diisocyanatoethane, diisocyanatopropane, diisocyanatobutane, diisocyanatopentane, diisocyanatooctane, diisocyanatodecane, diisocyanatododecane, 4,4'-HMDI, lysine diisocyanate, and combinations thereof.

5. 5. The two-component polyurethane composition of claim 1, wherein the aliphatic monomeric isocyanate compound is present in an amount of from about 0.5% w / w to about 5% w / w of the polyol component.

6. The aliphatic oligomeric isocyanate compound has the formula R(NCO) n where n=2, 3, and 4, R=an aliphatic residue having from about 6 to about 21 carbon atoms, and having at least 2 to 15 repeating monomer units.

7. 7. The two-component polyurethane composition according to claim 1, wherein the aliphatic oligomeric isocyanate compound is selected from the group consisting of HDI trimer, HDI biuret, HDI uretidones, HDI allophanates, HDI iminooxadiazinediones, PDI and IPDI-based polyisocyanates, and combinations thereof.

8. 8. The two-component polyurethane composition of claim 1, wherein the aliphatic oligomeric isocyanate compound is present in an amount from greater than about 0% w / w to about 100% w / w of the isocyanate component.

9. The aliphatic polymeric isocyanate compound has the formula R(NCO) n where n=2, 3, and 4, R=an aliphatic residue having from about 2 to about 20 carbon atoms, and having at least 3 to 10,000 repeating monomer units.

10. The two-component polyurethane composition according to any one of claims 1 to 9, wherein the polycarbonate polyol has at least two active hydrogens for reacting with the isocyanate compound.

11. The two-component polyurethane composition of any of claims 1 to 10, wherein the polycarbonate polyol is present in an amount of from about 5% w / w to about 90% w / w of the polyol component.

12. The two-component polyurethane composition of any of claims 2 to 11, wherein the non-polycarbonate polyol is a polyester polyol, a polyether polyol, a polybutadiene polyol, a polyacrylate, or a combination thereof.

13. The two-component polyurethane composition of any of claims 2 to 12, wherein the non-polycarbonate polyol is present in an amount of from about 10% w / w to about 90% w / w of the polyol component.

14. 14. The two-component polyurethane composition of any of claims 1 to 13, wherein the polycarbonate polyol has a hydroxyl functionality of 1 to 5 with a weight average molecular weight of between 100 Da and 8000 Da, and the non-polycarbonate polyol has a functionality of 1 to 6 with a weight average molecular weight of between 100 Da and 12000 Da.

15. The polyol component is selected from the group consisting of ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, 1,4-butanediol, 2-methyl-1,3-propylene diol, and N,N'-bis(2-hydroxypropylaniline), 4,4'-methylene-bis-(3-chloro-2,6-diethylaniline), 1,4-di(2-hydroxyethyl)hydroquinone, diethanolamine, triethanolamine, 1,1,1-trimethylolpropane, glycerol, dimethylolbutanoic acid (DMBA), hydrazine, ethylenediamine (EDA), 1,4-cyclohexanediamine, isophoronediamine, 4,4'-bis(sec-butylamine)dicyclohexylmethane, 4,4'-bis(sec-butylamine)diphenylmethane, diethyltoluenediamine, 15. The two-component polyurethane composition of any of claims 1 to 14, further comprising a chain extender selected from the group consisting of benzene, 4,4'-methylenebis(2-chloroaniline), 4-chloro-3,5-diamino-benzoic acid isobutyl ester, 3,5-dimethylthio-toluenediamine, trimethylene glycol-di-p-aminobenzoate, 4,4'-methylenebis(3-chloro-2,6-diethylaniline), 1-(α-naphthyl)-3,3-di(2-hydroxyethyl)-triazene-1,1-phenyl-3,3-di(2-hydroxyethyl)-triazene-1PT-D, 1,4-bis(2-hydroxyethoxy)benzene, diethoxylated resorcinol, 1,4-butanediamine, diaminopropane, cyclohexanediphenylalanine, and 4,4'-methylene-bis-(2-chloroaniline).

16. 16. The two-component polyurethane composition of claim 15, wherein the chain extender is present in an amount of from about 1% w / w to about 15% w / w of the polyol component.

17. 17. The two-component polyurethane composition of any of claims 1 to 16, wherein the amine-free catalyst is selected from the group consisting of zinc-based catalysts, tin-based catalysts, bismuth-based catalysts, and various other metal-based catalysts, and combinations thereof.

18. The amine-free catalyst may be selected from the group consisting of dioctyltin di(ethylhexanoate), dioctyltin dithioglycolate, dioctyltin dilaurate (dotl), dioctyltin oxide, dibutyltin dilaurate (dbtl), monobutyltin tris(2-ethylhexanoate), dioctyltin diketanoate, dioctyltin diacetate (dota), dioctyltin oxide (doto), dibutyltin diacetate (dbta), dibutyltin oxide (dbto), monobutyltin oxide (mbto), dioctyltin dicarboxylate, dioctyltin stannoxane, and dimethyltin neodecanoate.

18. The two-component polyurethane composition of any of claims 1 to 17, wherein the bis(2-ethylhexanoate)-containing alkyl ester is selected from the group consisting of bis(2-ethylhexanoate), ...

19. The two-component polyurethane composition of any of claims 1 to 18, wherein the catalyst is present in an amount of from about 0.005% w / w to about 3% w / w of the polyol component.

20. 20. The two-component polyurethane composition of any of claims 1 to 19, wherein the polyurethane composition further comprises an additive selected from the group consisting of fillers, antioxidants, waxes, ultraviolet light inhibitors, plasticizers, thickeners, compatibilizers, dispersants, rheology modifiers, flame retardants, optical brighteners, pigments, water scavengers, and combinations thereof.

21. 21. The two-component polyurethane composition according to any one of claims 1 to 20, wherein the polyurethane composition is free of aromatic isocyanate compounds selected from the group consisting of diphenylmethane diisocyanate (MDI), toluene diisocyanate (TDI), naphthalene diisocyanate, diisocyanatobenzene, triisocyanatobenzene, triisocyanatomethylbenzene, bis(isocyanatomethyl)benzene, and combinations thereof.

22. The two-component polyurethane composition according to any one of claims 1 to 21, wherein the composition is useful as an adhesive composition, a coating composition, a primer composition, a paint composition, and a varnish composition.

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