Two-component polyurethanes for polycarbonate bonding

Abstract

The present invention relates to a two-component polyurethane composition for polycarbonate bonding, a method of bonding to a polycarbonate substrate using the composition, and a method of preparing the composition. The present invention relates to a two-component polyurethane composition comprising: 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 does not contain an aromatic isocyanate compound. The use of the composition in compositions based on adhesives, coatings, primers, paints and varnishes is also disclosed.

Description

Technical Field

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

[0002] The present 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 molding (SRIM), resin transfer molding (RTM), plastics, etc.) to a variety of similar and dissimilar substrates, particularly for use in the manufacture of automobiles, trucks, boats and many other products.

[0003] A typical class of structural adhesives that can be used to adhere composite parts to the same and different substrates is a two-part polyurethane adhesive. Combining a prepolymer and a curing agent just before use makes these materials usable as adhesives. The ratio of these material combinations will vary depending on the functionality of the prepolymer and the curing agent. The accurate combination of these materials requires a certain skill level of the worker, and unfortunately, even when using automatic pumping equipment, there is still a lot of adhesive waste during the mixing process. In addition, polyurethane adhesives generally have poor thermal properties and are not conducive to applications that require high temperature ovens.

[0004] Another common class of structural adhesives that can be used to adhere metal parts to the same and different substrates (e.g., composite materials) is epoxy adhesives. Epoxy adhesive compositions most often contain multifunctional epoxy resins and are cured by the addition of a curing agent, which is typically provided in a separate package. The cure rate and product characteristics are affected by the choice of curing agent, which itself is affected by the composition of the adhesive composition, as determined by the final properties desired by the user.

[0005] The structural polyurethane adhesive composition is used by applying to the surface of a part made of, for example, metal, plastic and positioning the surface of a second part (of the same or different material) on the adhesive-covered surface of the metal / plastic. Since parts often have uneven surfaces, it is desirable that the adhesive has the ability to fill voids of varying depths that are created.

[0006] Many of these polyurethane adhesive compositions also have some systemic disadvantages. One of the most serious disadvantages is the residual monomer content of isocyanates, especially more volatile diisocyanates. These are very dangerous to health and lead to the labeling obligation of MDI products to list the hazard classification R40 / H351 (suspected carcinogenicity). The labeling obligation involves special measures for packaging and transportation. The presence of unreacted monomeric diisocyanates often leads to problems in further processing. Therefore, such diisocyanates may migrate from the coating or bonded body to the coated or bonded material. In the future, MDI-containing products with a residual monomer content of more than 0.1% may no longer be available to DIY customers (DIY = "do it yourself") and may be prohibited from self-service. Therefore, there is a strong interest in reactive polymers with no or at least greatly reduced residual MDI content, so that there is no or at least reduced potential health hazards of the product for the user. An alternative to MDI is the use of hexamethylene diisocyanate (HDI) oligomers and polymers. Unlike MDI, these HDIs have the advantage of being non-carcinogenic and do not have the H351 hazard classification.

[0007] Having good adhesion to PC (polycarbonate) and PC blends is a difficult challenge for conventional polyurethanes, especially after hot and wet aging conditions (such as cataplasma testing). The present invention uses polycarbonate polyols as raw materials to improve adhesion to PC substrates, following the chemical principle of "like attracts like". PC can undergo hydrolysis when in contact with moisture at high temperatures, and this reaction is catalyzed by alkaline conditions, such as in the presence of amines. Many modern catalysts are amine-based; the present invention avoids the use of these amine catalysts to prevent hydrolysis of the PC substrate.

[0008] EP 2462177 describes mixtures of radiation-curable water-dispersible polyurethanes which comprise at least one radiation-curable water-dispersible polyurethane.

[0009] WO 2005 / 0007721 describes the use of mixtures of low-monomer NCO-terminated prepolymers, ie mixtures liberated from monomeric reaction products of polyols and a stoichiometric excess of diphenylmethane diisocyanate, de-monomerized polyphenylenepolymethylene polyisocyanates, trimerized hexamethylene diisocyanate, and diluents.

[0010] EP 285859 describes a reaction-curable composition comprising as reactive materials a polyisocyanate component comprising a diisocyanate and a tri- or higher-functional polyisocyanate and having an average equivalent molecular weight of 120 to 240, and a polyol component comprising a diol and a tri- or higher-functional polyol and having an average equivalent molecular weight of 100 to 550.

[0011] Bostik Pliogrip TM Impact Adhesive and Pliogrip TM Evolution adhesives are Bostik's MDI-free polyurethane structural adhesives. They provide excellent adhesion and eliminate the need for additional primers and pre-surface preparation.

[0012] Despite the above-described prior art for reducing monomeric diisocyanates, there remains a need for polyurethane adhesive compositions that are free of aromatic isocyanate compounds and that are useful as adhesives, coatings, primers, lacquers and clearcoats for sealants.

[0013] Therefore, a main object of the present invention is to provide a two-component polyurethane composition free of aromatic isocyanate compounds, which can be used as an adhesive for sealants, coatings, primers, paints and varnishes. Summary of the invention

[0014] The present disclosure provides a two-component polyurethane composition for thermosetting and thermoplastic bonding, a method of bonding to thermosetting plastics and / or thermoplastics using the composition, and a method of preparing the composition. Examples of thermosetting plastics and thermoplastics include, but are not limited to, polycarbonates, 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, which comprises: (A) a polyol component, which comprises: (i) at least one polycarbonate polyol, (ii) a catalyst that does not contain an amine, and (iii) optionally, at least one aliphatic monomeric isocyanate compound; (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 a combination thereof; and wherein the polyurethane composition does not contain an aromatic isocyanate compound.

[0016] Yet another object of the present disclosure relates to a two-component polyurethane composition that does not contain an aromatic isocyanate compound, wherein the aromatic isocyanate compound is 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 a two-component polyurethane composition which can be used as an adhesive, coating, primer, lacquer and clearcoat.

[0018] Yet another object of the present disclosure relates to a two-component polyurethane adhesive composition, comprising: (A) a polyol component, the polyol component comprising: (i) at least one polycarbonate polyol, (ii) a catalyst that does not contain an amine, and (iii) optionally, at least one aliphatic monomeric isocyanate compound; (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; and wherein the polyurethane composition does not contain an aromatic isocyanate compound.

[0019] These and other objects of the present disclosure will become apparent in view of the following disclosure. BRIEF DESCRIPTION OF THE DRAWINGS

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

[0021] Figure 1 : Description of lap shear failure mode.

[0022] Figure 2A : Lap shear strength of adhesive type with prepolymer.

[0023] Figure 2B : Adhesive type failure mode with prepolymer.

[0024] Figure 3A : Lap shear strength of adhesive type without prepolymer.

[0025] Figure 3B : Adhesive-type failure mode without prepolymer.

[0026] Figure 4A : Image of failure mode on PC-PET after 7D cataplasm – prepolymer type.

[0027] Figure 4B : Image of failure mode on PC-ABS after 7D poultice – prepolymer type.

[0028] Figure 4C : Image of failure mode on PC after 7D poultice – prepolymer type.

[0029] Figure 5A : Image of failure mode on PC-PET after 7D cataplasm – without prepolymer.

[0030] Figure 5B : Image of failure mode on PC-ABS after 7D poultice – No prepolymer type.

[0031] Figure 5C : Image of failure mode on PC after 7D poultice – No prepolymer type. DETAILED DESCRIPTION

[0032] Now refer to Figures 1 to 5C Describing Exemplary Embodiments of the Disclosure

[0033] Before explaining in detail at least one embodiment of the present disclosure, it should be understood that the application of the present disclosure is not limited to the construction details and arrangements of the parts or steps or methods set forth in the following description or shown in the accompanying drawings. The present disclosure can have other embodiments or can be practiced or implemented in various ways. In addition, it should be understood that the wording and terminology used herein are for descriptive purposes and should not be considered restrictive.

[0034] Unless otherwise defined herein, the technical terms used in conjunction with this disclosure shall have the meanings commonly understood by those of ordinary skill in the art. In addition, unless otherwise required by context, singular terms shall include plural meanings and plural terms shall include singular meanings.

[0035] All patents, published patent applications, and non-patent publications mentioned in the specification are indicative of the skill levels of those skilled in the art to which the present disclosure pertains. All patents, published patent applications, and non-patent publications cited in any part of this application are expressly incorporated herein 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.

[0036] In view of the present disclosure, all articles and / or methods disclosed herein can be made and performed without undue experimentation. Although the articles and methods of the present disclosure have been described in terms of preferred embodiments, it will be apparent to those of ordinary skill in the art that variations may be applied to the articles and / or methods described herein and the steps or sequence of steps of the methods without departing from the concept, spirit and scope of the present disclosure. All such similar substitutions and modifications apparent to those skilled in the art are considered to be within the spirit, scope and concept of the present disclosure.

[0037] As used in accordance with this disclosure, the following terms shall be understood to have the following meanings, unless otherwise indicated.

[0038] When used in conjunction with the term "comprising," the use of the word "a / an" can mean "one", but it is also consistent with the meaning of "one or more", "at least one", and "one or more than one". Unless explicitly stated that alternatives are meant only when the alternatives are mutually exclusive, the use of the term "or" is used to mean "and / or", although the present disclosure supports definitions that refer only to alternatives and "and / or". Throughout this application, the term "about" is used to indicate that a value includes the inherent error variation of the quantification device, the method used to determine the value, or the variation that exists between the subjects of study.

[0039] Unless the context clearly dictates otherwise, references herein to “one embodiment” or “one aspect” or “one version” or “one object” or “another embodiment” or “another aspect” or “another version” or “another object” of the present invention may include one or more of such embodiments, aspects, versions or objects.

[0040] The term "at least one" refers to one and any number more 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" may extend to 100 or 1000 or more, depending on the term to which it is attached.

[0041] All percentages, parts, proportions and ratios as used herein are by weight of the total composition, unless otherwise specified. All such weights as they pertain to listed ingredients are based on the active level and, therefore, do not include solvents or by-products that may be included in commercially available materials, unless otherwise specified.

[0042] All references to singular features or limitations of the invention shall include the corresponding plural features or limitations and vice versa unless otherwise stated or the context clearly implies otherwise.

[0043] As used herein, numerical ranges are intended to include every number and subset of numbers contained within the range, whether or not specifically disclosed. In addition, these numerical ranges should be interpreted as providing support for protection against any number or subset of numbers within the range.

[0044] As used herein, the words "comprising" (and any form of comprising, such as "comprise" and "comprises"), "having" (and any form of having, such as "have" and "has"), "including" (and any form of including, such as "includes" and "include"), or "containing" (and any form of containing, such as "contains" and "contain") are inclusive or open-ended and do not exclude additional, unrecited 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 items listed 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, BA, CA, CB, CBA, BCA, ACB, BAC, or CAB. Continuing with this example, combinations containing repetitions of one or more items or terms are expressly included, such as BB, AAA, AAB, BBC, AAABCCCC, CBBAAA, CABABB, etc. The skilled artisan will understand that unless otherwise apparent from the context, there is generally no limit to the number of items or terms in any combination.

[0045] For purposes of the following detailed description, except in any operating examples, or where otherwise indicated, the numbers expressing, for example, quantities of ingredients used in the specification and claims are to be understood as being 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 to be obtained in practicing the present invention.

[0046] As used herein, the terms "or combinations thereof," "combinations thereof," and "combinations thereof" refer to all permutations and combinations of the items listed preceding that term.

[0047] The term "about" refers to a range of values ​​of ±10% of the specified value. For example, the phrase "about 200" includes ±10% of 200, or 180 to 220.

[0048] The term "polymerization" or "polymerizing" refers to a process for chemically reacting monomeric compounds to form polymer chains. The type of polymerization process may be selected from a wide variety of methods and includes the following non-limiting examples: polycondensation, step-growth polymerization, and free radical polymerization.

[0049] With respect to amine-free catalysts, the term "free" refers to a composition of no more than 0.05 wt% amine, preferably no more than 0.01 wt% amine, further preferably no more than trace amounts and even more preferably below current detection limits. The expression "the polyurethane composition does not contain aromatic isocyanate compounds" means that the composition contains no more than 1 wt% of aromatic isocyanate compounds, preferably no more than 0.05 wt%, further preferably no more than 0.1 wt%, even more preferably no more than trace amounts of compounds, and even more advantageously below the current detection limit.

[0050] The present disclosure relates to a two-component polyurethane composition comprising: (A) a polyol component comprising: (i) at least one polycarbonate polyol, (ii) a catalyst that does not contain an amine, and (iii) optionally, at least one aliphatic monomeric isocyanate compound; (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; and wherein the polyurethane composition does not contain an aromatic isocyanate compound.

[0051] According to yet another embodiment, the aliphatic monomeric isocyanate compound has the formula R(NCO): n wherein n=2, 3 or 4; and R=an aliphatic moiety having about 2 to about 20 carbon atoms. In non-limiting embodiments of the present application, the number of carbon atoms present may be in the following ranges: 2 to 5; 6 to 10; 11 to 15; 16 to 20.

[0052] According to 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.

[0053] According to yet another embodiment of the present disclosure, the aliphatic monomeric isocyanate compound is present in an amount of about 0.5% w / w to about 5% w / w of the polyol component of the present application.

[0054] According to another embodiment, the aliphatic monomeric isocyanate compound is present in an amount of about 0.5 wt.% to about 1 wt.%, about 1.1 wt.% to about 2 wt.%, about 2.1 wt.% to about 3 wt.%, about 3.1 wt.% to about 4 wt.%, and about 4.1 wt.% to about 5 wt.% of the polyol component of the present application.

[0055] According to another embodiment of the present disclosure, the aliphatic oligomeric isocyanate compound has the formula R(NCO): n wherein n = 2, 3 or 4; R = an aliphatic moiety having from about 6 to about 21 carbon atoms, and containing at least 2 to 15 repeating monomer units.

[0056] According to another embodiment, the aliphatic oligomeric isocyanate compound has the formula R(NCO): n wherein n = 2, 3 or 4; R = an aliphatic moiety having from about 6 to about 10, from about 11 to about 15, from about 16 to about 20, or from about 20 to about 21 carbon atoms.

[0057] According to another embodiment, the aliphatic oligomeric isocyanate compound has a monomer unit of the formula R(NCO)n; wherein n=2, 3 or 4; R=an aliphatic moiety having from about 6 to about 21 carbon atoms, and having 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14 or 15 repeating monomer units.

[0058] According to one embodiment of the present disclosure, the aliphatic oligomeric isocyanate compound is selected from the group consisting of HDI trimer, HDI biuret, HDI uretidone, HDI allophanate, HDI iminooxadiazinedione, polyisocyanates based on PDI (pentamethylene diisocyanate) and IPDI, and combinations thereof.

[0059] According to another embodiment of the present disclosure, the aliphatic oligomeric isocyanate compound may be present in an amount of greater than about 0% w / w to about 100% w / w of the isocyanate component.

[0060] According to another embodiment of the present disclosure, the aliphatic oligomeric isocyanate compound may be present in an amount of greater than about 0 wt.% to about 5 wt.%, about 6 wt.% to about 10 wt.%, about 11 wt.% to about 15 wt.%, about 16 wt.% to about 20 wt.%, about 21 wt.% to about 25 wt.%, 26 wt.% to about 30 wt.%, 31 wt.% to about 35 wt.%, 36 wt.% to about 40 wt.%, 41 wt.% to about 50 wt.%, about 51 wt.% to about 60 wt.%, about 61 wt.% to about 70 wt.%, about 71 wt.% to about 80 wt.%, about 81 wt.% to about 90 wt.%, or 91 wt.% to about 100 wt.% of the isocyanate component.

[0061] According to another embodiment of the present disclosure, the aliphatic polymeric isocyanate compound has the formula R(NCO): n wherein n = 2, 3 or 4; R = an aliphatic moiety having from about 2 to about 20 carbon atoms, and having at least 3 to 10,000 repeating monomer units.

[0062] According to another embodiment, the aliphatic polymeric isocyanate compound has the formula R(NCO): n wherein n=2, 3 or 4; R=an aliphatic moiety having from about 2 to about 3, from about 4 to about 5, from about 6 to about 7, from about 8 to about 9, from about 10 to about 11, from about 12 to about 13, from about 14 to about 15, from about 16 to about 17, or from about 18 to about 20 carbon atoms, and having at least 3 to 10,000 repeating monomer units.

[0063] According to another embodiment of the present disclosure, the aliphatic polymeric isocyanate compound has the formula R(NCO): n wherein n=2, 3 or 4; R=an aliphatic moiety having from about 2 to about 20 carbon atoms, and having at least 3 to 1000, at least 1001 to 2000, at least 2001 to 3000, at least 3001 to 4000, at least 4001 to 5000, at least 5001 to 6000, at least 6001 to 7000, at least 7001 to 8000, at least 8001 to 9000, or at least 9001 to 10000 repeating monomer units.

[0064] According to yet another embodiment of the present disclosure, the aliphatic polymeric isocyanate compound may be present in an amount of greater than about 0% w / w to about 100% w / w of the isocyanate component.

[0065] According to yet another embodiment, the aliphatic polymeric isocyanate compound may be present in an amount of greater than about 0 wt.% to about 5 wt.%, about 6 wt.% to about 10 wt.%, about 11 wt.% to about 15 wt.%, about 16 wt.% to about 20 wt.%, about 21 wt.% to about 25 wt.%, 26 wt.% to about 30 wt.%, 31 wt.% to about 35 wt.%, 36 wt.% to about 40 wt.%, 41 wt.% to about 50 wt.%, about 51 wt.% to about 60 wt.%, about 61 wt.% to about 70 wt.%, about 71 wt.% to about 80 wt.%, about 81 wt.% to about 90 wt.%, or 91 wt.% to about 100 wt.% of the isocyanate component.

[0066] According to another embodiment of the present disclosure, the polycarbonate polyol has at least two active hydrogens to react with the isocyanate compound. In another non-limiting embodiment, the active hydrogens may be in the range of about 1 to 5. In a non-limiting embodiment of the present application, the carbonate bonds are 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%.

[0067] Furthermore, in certain non-limiting embodiments of the present application, the polycarbonate polyol may be a compound based on an aliphatic polycarbonate polyol or an aromatic polycarbonate polyol.

[0068] According to another embodiment, the polycarbonate polyol is present in an amount of about 5 wt.% to about 10 wt.%, about 11 wt.% to about 15 wt.%, about 16 wt.% to about 20 wt.%, about 21 wt.% to about 25 wt.%, 26 wt.% to about 30 wt.%, 31 wt.% to about 35 wt.%, 36 wt.% to about 40 wt.%, 41 wt.% to about 50 wt.%, about 51 wt.% to about 60 wt.%, about 61 wt.% to about 70 wt.%, about 71 wt.% to about 80 wt.%, or about 81 wt.% to about 90 wt.% of the polyol component.

[0069] According to one embodiment of the present disclosure, the polyol component of the two-component polyurethane composition further comprises at least one non-polycarbonate polyol.

[0070] According to yet another embodiment, the non-polycarbonate polyol is a polyester polyol, a polyether polyol, a polybutadiene polyol, a polyacrylate, and combinations thereof.

[0071] According to another embodiment, the non-polycarbonate polyol is present in an amount of about 10% w / w to about 90% w / w of the polyol component.

[0072] According to another embodiment, the non-polycarbonate polyol is present in an amount of about 10 wt.% to about 15 wt.%, about 16 wt.% to about 20 wt.%, about 21 wt.% to about 25 wt.%, 26 wt.% to about 30 wt.%, 31 wt.% to about 35 wt.%, 36 wt.% to about 40 wt.%, 41 wt.% to about 50 wt.%, about 51 wt.% to about 60 wt.%, about 61 wt.% to about 70 wt.%, about 71 wt.% to about 80 wt.%, or about 81 wt.% to about 90 wt.% of the polyol component.

[0073] According to yet another embodiment of the present disclosure, the polycarbonate polyol has a weight average molecular weight between 100 Da and 8000 Da and a hydroxyl functionality of 1 to 5 and the non-polycarbonate polyol has a weight average molecular weight between 100 Da and 12000 Da and a functionality of 1 to 6.

[0074] According to yet another embodiment, the polycarbonate polyol has a weight average molecular weight of about 100 Da to 500 Da, about 501 Da to 1000 Da, about 1001 Da to 1500 Da, about 1501 Da to 2000 Da, about 2001 Da to 2500 Da, about 2501 Da to 3000 Da, about 3000 Da to 3500 Da, about 3501 Da to 4000 Da, about 4001 Da to 4500 Da, about 4501 Da to 5000 Da, about 5001 Da to 5500 Da, about 5501 Da to 6000 Da, about 6001 Da to 6500 Da, about 6501 Da to 7000 Da, about 7001 Da to 7500 Da, or about 7501 Da to 8000 Da.

[0075] Examples of trade names for commercially available polycarbonate polyols include Aramaco, Eternacoll, Kuraray, Unoxol and Desmophen. A known distributor of such materials is TriiSO.

[0076] According to yet another embodiment, the non-polycarbonate polyol has a molecular weight of 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, or about 6001 Da to about 7000 Da. A weight average molecular weight of 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.

[0077] According to 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-propanediol, and N,N′-bis(2-hydroxypropylaniline), 4,4′-methylene-bis-(3-chloro-2,6-diethylaniline), 1,4-bis(2-hydroxyethyl)hydroquinone, diethanolamine, triethanolamine, 1,1,1-trimethylolpropane, glycerol, dimethylolbutyric acid (DMBA), hydrazine, ethylenediamine (EDA), 1,4-cyclohexanediamine, isophoronediamine, 4,4′-bis(sec-butylamino)dicyclohexylmethane, 4,4′-bis(sec-butylamino)dicyclohexylmethane, 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-bis(2-hydroxyethyl)-triazene-1, 1-phenyl-3,3-bis(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).

[0078] According to yet another embodiment of the present disclosure, the chain extender is present in an amount of about 1% w / w to about 15% w / w of the polyol component.

[0079] According to yet another embodiment, the chain extender is present in an amount of about 1% w / w to about 5% w / w, about 5% w / w to about 10% w / w, or about 10% w / w to about 15% w / w of the polyol component.

[0080] According to another embodiment of the present disclosure, the polyol component further comprises an amine-free catalyst selected from the group consisting of a zinc-based catalyst, a tin-based catalyst, a bismuth-based catalyst, and any other metal-based catalyst and combinations thereof.

[0081] According to yet another embodiment, the amine-free catalyst is selected from the group consisting of: dioctyltin di(ethylhexanoate), dioctyltin dimercaptoacetate, dioctyltin dilaurate (DOTl), dioctyltin oxide, dibutyltin dilaurate (DBTL), monobutyltin tri(2-ethylhexanoate), dioctyltin diketanoate, dioctyltin diacetate (DOTA), dioctyltin oxide (DOTO), dibutyltin diacetate (DBTA), dibutyltin oxide (DBTO), monobutyltin oxide (MBTO), dioctyltin dicarboxylate, dioctyltin stannoxane (DIOCTYLT). stannoxane), dimethyltin neodecanoate, stannous octoate, stannous oxalate, stannous oxide, bis(dodecylsulfanyl)dimethyltinane, bis(dodecylsulfanyl)dioctyltinane, 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.

[0082] According to another embodiment of the present disclosure, the catalyst is present in an amount of about 0.005% w / w to about 3% w / w of the polyol component.

[0083] According to another embodiment, the catalyst is present in an amount of about 0.005% w / w to about 0.001% w / w, about 0.099% w / w to about 0.99% w / w, about 1% w / w to about 2% w / w, 2.1% w / w to about 3% w / w of the polyol component.

[0084] According to yet another embodiment of the present disclosure, the polyurethane composition further comprises an additive selected from the group consisting of fillers, antioxidants, waxes, UV inhibitors, plasticizers, thickeners, compatibilizers, dispersants, rheology modifiers, flame retardants, optical brighteners, pigments, and water scavengers.

[0085] According to another embodiment of the present disclosure, the polyurethane composition does not contain an aromatic isocyanate compound, and the aromatic isocyanate compound is selected from the group consisting of diphenylmethane diisocyanate (MDI), toluene diisocyanate (TDI), naphthalene diisocyanate, diisocyanatobenzene, triisocyanatobenzene, triisocyanatomethylbenzene, bis(isocyanatomethyl)benzene, and combinations thereof.

[0086] According to yet another embodiment of the present disclosure, the composition may be used as an adhesive composition, a coating composition, a primer composition, a paint composition, and a clear coat composition.

[0087] According to another embodiment of the present disclosure, the two-component polyurethane adhesive composition comprises: (A) a polyol component, the polyol component comprising: (i) at least one polycarbonate polyol, (ii) a catalyst that does not contain an amine, and (iii) optionally, at least one aliphatic monomeric isocyanate compound; (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 a combination thereof; and wherein the polyurethane composition does not contain an aromatic isocyanate compound.

[0088] An advantage of the present adhesive is that it is an aliphatic urethane adhesive with a suitable processing time. The disclosed adhesive may have a processing time of less than two (2) hours at substantially ambient temperature. Preferably, the processing time may be less than 90 minutes, and even more preferably no more than one (1) hour.

[0089] The present invention may further include other aspects, such as those listed below. Such embodiments disclosed herein may have less than 1 wt% of aromatic urethane compounds, preferably less than 0.1 wt% of such aromatic urethanes.

[0090] One aspect of the present invention includes a two-component polyurethane composition. The composition includes a polyol component. The polyol component includes (i) at least one polycarbonate polyol, (ii) a catalyst having an amine content of less than 0.05 wt%, and (iii) optionally, at least one aliphatic monomeric isocyanate compound. The polyol component also includes (B) at least one isocyanate component. These isocyanate components are at least one selected from the group consisting of (i) aliphatic oligomeric isocyanate compounds, (ii) aliphatic polymeric isocyanate compounds, and combinations thereof. Preferably, the polyurethane composition has an aromatic isocyanate compound content of less than 1 wt%.

[0091] In a second aspect, according to the two-component polyurethane composition of the above aspect, the polyol component further comprises at least one non-polycarbonate polyol.

[0092] In a third aspect, according to the two-component polyurethane composition of the first aspect or the second aspect, wherein the aliphatic monomer isocyanate compound has a formula R(NCO): n wherein n=2, 3, and 4; and R=an aliphatic moiety having from about 2 to about 20 carbon atoms.

[0093] In a fourth aspect, a two-component polyurethane composition according to any one of aspects 1 to 3, wherein the aliphatic monomer 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.

[0094] In a fifth aspect, the two-component polyurethane composition according to any one of aspects 1-4, wherein the aliphatic monomeric isocyanate compound is present in an amount of about 0.5% w / w to about 5% w / w of the polyol component.

[0095] In a sixth aspect, according to any one of aspects 1-5 of the two-component polyurethane composition, wherein the aliphatic oligomeric isocyanate compound has a formula R (NCO) n wherein n = 2, 3 and 4; R = an aliphatic moiety having from about 6 to about 21 carbon atoms, and having at least 2 to 15 repeating monomer units.

[0096] In a seventh aspect, a two-component polyurethane composition according to any one of aspects 1-6, wherein the aliphatic oligomeric isocyanate compound is selected from the group consisting of HDI trimers, HDI biuret, HDI uretone, HDI allophanate, HDI iminooxadiazinedione, polyisocyanates based on PDI and IPDI, and combinations thereof.

[0097] In an eighth aspect, the two-component polyurethane composition according to any one of aspects 1-7, wherein the aliphatic oligomeric isocyanate compound is present in an amount of greater than about 0% w / w to about 100% w / w of the isocyanate component.

[0098] In a ninth aspect, the two-component polyurethane composition according to any one of aspects 1-5, 7 or 8, wherein the aliphatic polymeric isocyanate compound has the formula R(NCO): n wherein n = 2, 3 and 4; R = an aliphatic moiety having from about 2 to about 20 carbon atoms, and having at least 3 to 10,000 repeating monomer units.

[0099] In a tenth aspect, the two-component polyurethane composition according to any one of aspects 1-9, wherein the polycarbonate polyol has at least two active hydrogens to react with the isocyanate compound.

[0100] In an eleventh aspect, the two-component polyurethane composition according to any of aspects 1-10, wherein the polycarbonate polyol is present in an amount of about 5% w / w to about 90% w / w of the polyol component. In a twelfth aspect, the two-component polyurethane composition according to any one of aspects 1 to 11, wherein the polyurethane composition has less than 0.1 wt % of the aromatic isocyanate compound. Examples

[0101] The present invention is described in a non-limiting manner with reference to the following examples. The following examples illustrate the water-based moisture-resistant adhesive composition described herein for bonding a sheet-like film to a substrate, a method for bonding the composition to a substrate, and a method for preparing the composition. These examples are for illustrative purposes only and are not intended to be limiting. Many variations will be apparent and are within the entire contemplated range.

[0102] Example 1

[0103] Example 2

[0104] Example 3

[0105] Lap Shear:

[0106] Lap shear according to EN 1465 (10 mm / min, using Zwick Universal Tensile Tester Z020)

[0107] The 7-day poultice-lap shear bonds were rolled in cotton sheets, 4-6 bonds were packed into each roll. The rolls were placed in sealed plastic bags, and water was added to the bags (10x cotton weight). All samples were stored at 70°C for 7 days, immediately followed by storage at -20°C for 2 hours, and then finally at 23°C for 4 hours before testing.

[0108] Lap Shear Treatment Time - Lap shear strength is measured shortly after the adhesive is applied and then the test is repeated after set time intervals until the desired strength is reached. This method shows the time and rate at which the adhesive builds strength.

[0109] Mechanical properties - test method ASTM D638 IV (50 mm / min, using Zwick universal tensile testing machine Z020)

[0110] Figure 1 It is a description of the lap shear failure mode. Figure 2A is a bar graph of the bond lap shear strength of the samples of Example 2 and Figure 2B is a bar graph of the failure mode of the sample of Example 2.

[0111] Conventional polyurethane adhesives typically fail adhesion on PC and PC blend substrates after heat / humidity conditioning, whereas ours maintained adhesion after 7d of poultice (heat / humidity aging conditions). Test results are shown in Figure 1 A, 2A and 2B

[0112] Figure 2A Lap shear adhesion results are shown at ambient temperature and at ambient temperature after aging the samples according to 7d of poultice as described above. Surprisingly enough, after 7d of poultice exposure, each sample exceeded a lap shear adhesion strength of at least 1 MPa. Surprisingly, each sample exhibited a lap shear strength of at least 15.MPa and 2.0MPa.

[0113] Regarding the damage mode, Figure 2B , adhesion failure was observed in only 2 instances and in less than 10% of the samples tested. Most impressively, after 7 days of poultice exposure, no more than 5% of the samples tested exhibited adhesion failure. Samples PC-PET and PC bonded exhibited 0 adhesion failures. The PC-ABS sample exhibited only one adhesion failure.

[0114] Figure 3A is a bar graph of the bond lap shear strength of the samples of Example 3 and Figure 3B is a bar graph of the failure mode of the sample of Example 3.

[0115] for Figure 3A , the adhesives without prepolymers exhibited similar lap shear strength results to the adhesives with prepolymers; i.e., after 7 days of poultice exposure, each sample exceeded a lap shear bond strength of at least 1 MPa. In addition, each sample exhibited a lap shear strength of at least 15.MPa and 2.0 MPa.

[0116] Figure 3B It is shown that samples coated with adhesive without prepolymer did not experience bond failure. In both cases, the example adhesives performed well.

[0117] Figures 4A-5C is the image of the test sample after testing. Figure 4BThe sample in the lower left corner of the center exhibited adhesive failure. All other samples shown did not exhibit adhesive failure.

[0118] Although the present invention has been described in detail with reference to certain preferred embodiments, it should be understood that the present invention is not limited to those precise embodiments. Rather, in light of this disclosure, many modifications and variations will present themselves to those skilled in the art without departing from the scope and spirit of the present invention.

Claims

1. A two-component polyurethane composition comprising: (A) a polyol component, the polyol component comprising: (i) at least one polycarbonate polyol, (ii) a catalyst that does not contain an amine, and (iii) optionally, at least one aliphatic monomeric isocyanate compound; (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; and wherein the polyurethane composition does not contain an aromatic isocyanate compound.

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

3. The two-component polyurethane composition according to any one of claims 1 or 2, wherein The aliphatic monomeric isocyanate compound has the formula R(NCO) n wherein n=2, 3, and 4; and R=an aliphatic moiety having from about 2 to about 20 carbon atoms.

4. The two-component polyurethane composition according to any one of claims 1 to 3, wherein The aliphatic monomer 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. The two-component polyurethane composition according to any one of claims 1 to 4, wherein The aliphatic monomeric isocyanate compound is present in an amount of about 0.5% w / w to about 5% w / w of the polyol component.

6. The two-component polyurethane composition according to any one of claims 1 to 5, wherein The aliphatic oligomeric isocyanate compound has the formula R(NCO) n wherein n = 2, 3 and 4; R = an aliphatic moiety having from about 6 to about 21 carbon atoms, and having at least 2 to 15 repeating monomer units.

7. The two-component polyurethane composition according to any one of claims 1 to 6, wherein The aliphatic oligomeric isocyanate compound is selected from the group consisting of HDI trimer, HDI biuret, HDI uretone, HDI allophanate, HDI iminooxadiazinedione, polyisocyanates based on PDI and IPDI, and combinations thereof.

8. The two-component polyurethane composition according to any one of claims 1 to 7, wherein The aliphatic oligomeric isocyanate compound is present in an amount of greater than about 0% w / w to about 100% w / w of the isocyanate component.

9. The two-component polyurethane composition according to any one of claims 1 to 8, wherein The aliphatic polymeric isocyanate compound has the formula R(NCO) n wherein n = 2, 3 and 4; R = an aliphatic moiety 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 to react with the isocyanate compound.

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

12. The two-component polyurethane composition according to any one of claims 2 to 11, wherein The non-polycarbonate polyols are polyester polyols, polyether polyols, polybutadiene polyols, polyacrylates, and combinations thereof.

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

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

15. The two-component polyurethane composition according to any one of claims 1 to 14, wherein 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-propanediol, and N,N′-bis(2-hydroxypropylaniline), 4,4′-methylene-bis-(3-chloro-2,6-diethylaniline), 1,4-bis(2-hydroxyethyl)hydroquinone, diethanolamine, triethanolamine, 1,1,1-trimethylolpropane, glycerol, dimethylolbutyric acid (DMBA), hydrazine, ethylenediamine (EDA), 1,4-cyclohexanediamine, isophoronediamine, 4,4′-bis(sec-butylamino)dicyclohexylmethane, 4,4′-bis(sec-butylamino)diphenylmethane alkane, 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-bis(2-hydroxyethyl)-triazene-1, 1-phenyl-3,3-bis(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. The two-component polyurethane composition according to claim 15, wherein: The chain extender is present in an amount of about 1% w / w to about 15% w / w of the polyol component.

17. The two-component polyurethane composition according to any one 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 any other metal-based catalysts and combinations thereof.

18. The two-component polyurethane composition according to any one of claims 1 to 17, wherein The amine-free catalyst is selected from the group consisting of: dioctyltin di(ethylhexanoate), dioctyltin dimercaptoacetate, dioctyltin dilaurate (DOTl), dioctyltin oxide, dibutyltin dilaurate (DBTL), monobutyltin tri(2-ethylhexanoate), dioctyltin diketonate, dioctyltin diacetate (DOTA), dioctyltin oxide (DOTO), dibutyltin diacetate (DBTA), dibutyltin oxide (DBTO), Monobutyltin oxide (MBTO), dioctyltin dicarboxylate, dioctyltin stannoxane, dimethyltin neodecanoate, stannous octoate, stannous oxalate, stannous oxide, bis(dodecylsulfanyl)dimethyltin stanane, bis(dodecylsulfanyl)dioctyltin stanane, methyltin mercaptide, zinc neodecanoate, zinc octoate, zinc acetylacetonate, zinc oxalate, zinc acetate, bismuth carboxylate, bismuth oxide, bismuth tri(2-ethylhexanoate), potassium octoate, potassium neodecanoate, aluminum ethylacetoacetate, and combinations thereof.

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

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

21. The two-component polyurethane composition according to any one of claims 1 to 20, wherein The polyurethane composition does not contain an aromatic isocyanate compound, and the aromatic isocyanate compound is selected from the group consisting of diphenylmethane diisocyanate (MDI), toluene diisocyanate (TDI), naphthalene diisocyanate, diisocyanatobenzene, triisocyanatobenzene, triisocyanatomethylbenzene, bis(isocyanatomethyl)benzene, and combinations thereof.

22. A two-component polyurethane composition according to any one of claims 1 to 21, wherein The composition can be used as an adhesive composition, a coating composition, a primer composition, a lacquer composition and a clear coat composition.

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