阅读说明：本技术 双组分涂层组合物 (Two-component coating composition ) 是由 A·G·康迪 中岛将行 周宏英 M·S·弗伦奇 于 2020-03-19 设计创作，主要内容包括：本发明公开了一种涂层组合物,所述涂层组合物包括第一组分和第二组分。所述第一组分包括稀释剂和碳二亚胺,按所述涂层组合物的总重量计,所述碳二亚胺以不超过50重量％的量存在。所述第二组分包括与所述碳二亚胺发生化学反应的固化剂,所述固化剂包括含活性氢的化合物。所述涂层组合物可以是粘合剂组合物或密封剂组合物。本发明还公开了一种用于处理基材的方法,所述方法包括使所述基材的表面的至少一部分与本发明的组合物接触。本发明还公开了一种基材,所述基材包括至少部分地涂覆有由本发明的组合物形成的层的表面。本发明还公开了一种制品,所述制品包括第一基材和第二基材以及定位在所述第一基材与所述第二基材之间的本发明的组合物。(A coating composition includes a first component and a second component. The first component includes a diluent and a carbodiimide, the carbodiimide being present in an amount of no more than 50 weight percent based on the total weight of the coating composition. The second component includes a curing agent that chemically reacts with the carbodiimide, the curing agent including an active hydrogen-containing compound. The coating composition may be an adhesive composition or a sealant composition. Also disclosed is a method for treating a substrate comprising contacting at least a portion of the surface of the substrate with the composition of the invention. Also disclosed is a substrate comprising a surface at least partially coated with a layer formed from the composition of the invention. Also disclosed is an article comprising a first substrate and a second substrate and the composition of the invention positioned between the first substrate and the second substrate.)

1. A two-component coating composition comprising:

a first component comprising a carbodiimide and a diluent, wherein the carbodiimide is present in an amount of no more than 50 weight percent based on the total weight of the coating composition; and

a second component comprising a curing agent that chemically reacts with the carbodiimide, the curing agent comprising an active hydrogen-containing compound.

2. The coating composition of claim 1, wherein the coating composition is substantially free of unreacted isocyanate functional groups.

3. The coating composition of claim 1, wherein the diluent comprises a reactive diluent.

4. The coating composition of claim 3, wherein the reactive diluent comprises an epoxy-containing compound.

5. The coating composition of claim 1, wherein the diluent comprises a non-reactive diluent.

6. The coating composition of claim 1, wherein the carbodiimide comprises polyurethane groups and/or urea groups.

7. The coating composition of claim 1, wherein the curing agent comprises an amine, a thiol, an acid, and/or an alcohol.

8. The coating composition of claim 7, wherein (a) the amine comprises a primary and/or secondary amine; (b) the thiol comprises at least two thiol functional groups; (c) the acid includes a difunctional acid; and/or (d) the alcohol comprises phenol.

9. The coating composition of claim 7, wherein the amine comprises an alkanolamine.

10. The coating composition of claim 7, wherein the thiol is substantially free of S-S bonds.

11. The coating composition of claim 1, wherein the coating composition further comprises an epoxy-containing compound other than a reactive diluent, elastomer particles, additives, and/or accelerators.

12. The coating composition of claim 1, wherein the coating composition comprises a binder composition.

13. The coating composition of claim 1, wherein the coating composition comprises a sealant composition.

14. A substrate comprising the coating composition of claim 1 positioned on at least a portion of a surface of the substrate.

15. The substrate of claim 14, wherein in an at least partially cured state, the coating composition:

(a) capable of withstanding a maximum load of at least 0.3MPa as measured using a dog bone specimen on an Instron (Instron) model 5569 at a pull rate of 50 mm/min according to ASTM D-412; and/or

(b) Has an elongation at break of at least 10% as measured using a dog bone specimen on an instron model 5569 at a pull rate of 50 mm/min according to ASTM D-412.

16. An article comprising the substrate of claim 14 and a second substrate, wherein the coating composition is positioned between the surface of the substrate and a surface of the second substrate.

17. The article of claim 16, wherein in an at least partially cured state, the coating composition:

(a) has a green strength of at least 0.1MPa, as measured by Instron model 5567 in tensile mode according to test method ASTM D1002-10; and/or

(b) After exposure to ambient temperature for 2 hours and heating at 175 ℃ for 30 minutes, has an adhesive strength of at least 10.0MPa, as measured by Instron model 5567 in tensile mode according to test method ASTM D1002-10.

18. A component comprising the substrate of claim 14.

19. The component of claim 18, wherein the component comprises a three-dimensional component.

20. A vehicle comprising the substrate of claim 14.

21. A method for forming a coating on a first substrate, the method comprising applying the coating composition of claim 1 to at least a portion of a surface of the first substrate, and at least partially curing the coating composition under ambient or slightly thermal conditions.

22. The method of claim 21, further comprising exposing the coating composition to a temperature of at least 70 ℃.

23. The method of claim 21, further comprising contacting a surface of a second substrate with the coating composition such that the coating composition is positioned between the surface of the first substrate and the surface of the second substrate.

24. A method of forming an article comprising extruding the coating composition of claim 1 onto a substrate.

25. The method of claim 25, wherein the extruding comprises three-dimensional printing.

26. The method of claim 25, further comprising combining and mixing the first component and the second component prior to extrusion.

27. The method of claim 25, wherein the forming comprises applying successive layers to build the article.

28. An article formed by the method of claim 24.

Technical Field

The present invention relates to adhesive and sealant compositions, and more particularly to 2K adhesive and sealant compositions.

Background

Coating compositions comprising sealants and adhesives are used to treat substrates in a variety of applications, including bonding two or more substrate materials together.

Disclosure of Invention

The present invention relates to a two-component coating composition comprising: a first component comprising a diluent and a carbodiimide, the carbodiimide present in an amount of no more than 50 weight percent based on the total weight of the coating composition; and a second component comprising a curing agent that chemically reacts with the carbodiimide, the curing agent comprising an active hydrogen-containing compound. The coating composition may be an adhesive composition or a sealant composition.

The present invention also relates to a method for forming a coating on a first substrate, the method comprising: applying a coating composition of the present invention to at least a portion of the surface of the first substrate; and at least partially curing the coating composition under ambient or slightly thermal conditions; and optionally exposing the composition to a temperature of at least 70 ℃.

The present invention also relates to a substrate comprising a coating composition of the present invention positioned on at least a portion of the surface of the substrate.

Drawings

Fig. 1 shows a schematic representation of a dog bone sample utilized in a tensile test on a sealant composition of the invention.

Detailed Description

For purposes of this detailed description, it is to be understood that the invention may assume alternative variations and step sequences, except where expressly specified to the contrary. Moreover, other than in any operating examples, or where otherwise indicated, all 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". Accordingly, unless indicated to the contrary, the numerical parameters set forth in the following specification and attached claims are approximations that may vary depending upon the desired properties to be obtained by the present invention. At the very least, and not as an attempt to limit the application of the doctrine of equivalents to the scope of the claims, each numerical parameter should at least be construed in light of the number of reported significant digits and by applying ordinary rounding techniques.

Notwithstanding that the numerical ranges and parameters setting forth the broad scope of the invention are approximations, the numerical values set forth in the specific examples are reported as precisely as possible. Any numerical value, however, inherently contains certain errors necessarily resulting from the standard deviation found in their respective testing measurements.

Moreover, it should be understood that any numerical range recited herein is intended to include all sub-ranges subsumed therein. For example, a range of "1 to 10" is intended to include all sub-ranges between (and including) the recited minimum value of 1 and the recited maximum value of 10, i.e., having a minimum value equal to or greater than 1 and a maximum value of equal to or less than 10.

As used herein, "comprising," "including," and similar terms, are understood in the context of this application to be synonymous with "including" and thus open-ended and do not exclude the presence of elements, materials, ingredients, or method steps not otherwise described or recited. As used herein, "consisting of … …" is understood in the context of the present application to exclude the presence of any non-specified elements, ingredients, or method steps. As used herein, "consisting essentially of … …" is understood in the context of the present application to include the named elements, materials, ingredients, or method steps "as well as those elements, materials, ingredients, or method steps that do not materially affect the basic characteristics and novel characteristics of the described content.

In this application, the use of the singular includes the plural and plural encompasses singular, unless specifically stated otherwise. For example, although reference is made herein to "a" carbodiimide, "a" curing agent, and "an" epoxy-containing compound, combinations of these components (i.e., a plurality of these components) can be used. In addition, in this application, the use of "or" means "and/or" unless specifically stated otherwise, even though "and/or" may be explicitly used in some cases.

As used herein, "composition" or "coating composition" refers to a solution, mixture, or dispersion in a medium that, in an at least partially dried or cured state, is capable of producing a film, layer, or the like, on at least a portion of the surface of a substrate.

As used herein, the term "dispersion" refers to a mixture of transparent, translucent, or opaque systems, either homogeneous or heterogeneous, that can be made by blending two or more compounds.

As used herein, the terms "adhesive composition" and "adhesive coating composition" mean a coating composition that, in an at least partially cured state, is capable of holding two surfaces together when the two surfaces are in contact.

As used herein, "green strength" or "green lap shear strength" means the ability of the adhesive coating composition, after at least partial curing under ambient or slightly hot conditions and prior to exposure to an external energy source, to produce a load-bearing joint having a lap shear strength of at least 0.1MPa as determined by ASTM D1002-10 in tensile mode using an instron 5567 machine with a pull rate of 1mm per minute.

As used herein, the term "structural adhesive" means an adhesive coating composition that, upon at least partial curing by the two-step curing process described herein, produces a load-bearing joint having a lap shear strength of greater than 5MPa as determined by using an instron 5567 machine in tensile mode according to ASTM D1002-10 at a pull rate of 1mm per minute.

As used herein, "sealant composition" and "sealant coating composition" refer to a coating composition that, upon at least partial curing by the two-step curing process described herein, forms a seal having the ability to resist atmospheric conditions such as moisture and temperature and at least partially block the transport of materials such as water, fuel, and other liquids and gases.

As used herein, the terms "cure", "curing" or similar terms as used in connection with the compositions described herein mean that at least a portion of the components forming the composition are crosslinked to form a layer or bond, such as by subjecting the composition to conditions (referred to as "curing conditions") that cause the reactive functional groups of the components of the composition to react and cause at least a portion of the components of the composition to crosslink.

As used herein, the terms "at least partially cured", or similar terms, as used in connection with the compositions described herein, mean subjecting the composition to curing conditions to form a layer or bond wherein at least a portion of the reactive groups of the components of the composition react.

As used herein, a "two-component composition" (or "2K composition") refers to a composition in which at least a portion of the reactive components readily react and at least partially cure upon mixing without activation from an external energy source, such as under ambient or slightly thermal conditions. It will be appreciated by those skilled in the art that the two components of the composition are stored separately from each other and are mixed just prior to application of the composition. As described in more detail below, the 2K coating composition of the present invention can be subjected to "curing conditions" that include: (1) a first step in which, when mixed, at least a portion of the first and second components chemically react in the absence of activation from an external energy source (i.e., under ambient or slightly hot conditions) to at least partially cure the binder composition, optionally followed by (2) a second step in which an external energy source is applied to the coating composition to further cure the coating composition. As further defined herein, ambient conditions generally refer to room temperature (about 23 ℃) and humidity conditions (e.g., about 50%) or temperature and humidity conditions typically found in the area where the adhesive is applied to a substrate, while slightly hot conditions are temperatures slightly above ambient temperature, e.g., 10% above, but generally below the curing temperature of the second step of the two-step curing process.

As used herein, "Mw" refers to weight average molecular weight and means experimental values determined by gel permeation chromatography using a Waters2695 separation module with a Waters 410 differential refractometer (RI detector) and polystyrene standards, Tetrahydrofuran (THF) was used as eluent at a flow rate of 1 ml/min and two PL gel mixed C columns were used for separation.

As used herein, "Mn" refers to number average molecular weight and means experimental values determined by gel permeation chromatography using a Waters2695 separation module with a Waters 410 differential refractometer (RI detector) and polystyrene standards, Tetrahydrofuran (THF) was used as eluent at a flow rate of 1 ml/min and two PL gel mixed C columns were used for separation.

As used herein, the term "accelerator" means a substance that increases the rate of a chemical reaction or reduces the activation energy of a chemical reaction. The promoter may be a "catalyst", i.e. does not itself undergo any permanent chemical change; or may be reactive, i.e., capable of chemical reaction and include any level of reaction from partial reaction to complete reaction of the reactants.

As used herein, unless otherwise specified, the term "substantially free" means that the particular material is not purposefully added to the mixture or composition, respectively, and is present only as a trace amount of impurities of less than 5% by weight, based on the total weight of the mixture or composition, respectively. As used herein, unless otherwise specified, the term "essentially free" means that the specified material is present only in an amount of less than 2 weight percent, based on the total weight of the mixture or composition, respectively. As used herein, unless otherwise specified, the term "completely free" means that the mixture or composition, respectively, does not include the specified material, i.e., the mixture or composition includes 0% by weight of such material.

As used herein, the term "glass transition temperature" ("Tg") refers to the temperature at which an amorphous material, such as glass or a polymer, changes from a brittle glass state to a plastic or rubbery state or from a plastic or rubbery state to a brittle glass state.

As used herein, the term "dog bone" or "dog bone sample" refers to the sample schematically illustrated in fig. 1 and utilized in the tensile testing of the sealant of the present invention. Dog bone samples were die cut from 3mm thick sealant films.

The present invention relates to a two-component coating composition comprising, consisting essentially of, or consisting of a first component and a second component. The first component may include, consist essentially of, or consist of a carbodiimide and a diluent, wherein the carbodiimide is present in an amount of no more than 50 weight percent based on the total weight of the coating composition. The second component may include, consist essentially of, or consist of a curing agent that chemically reacts with the carbodiimide of the first component, the curing agent including an active hydrogen-containing compound.

As discussed above, the composition of the present invention includes a first component. The first component includes a carbodiimide. As used herein, "carbodiimide" refers to an aliphatic and/or aromatic dinitrogen analog of carbonic acid having the following general structure: -RN ═ C ═ NR₁Wherein R and R₁Independently an aliphatic or aromatic group. The carbodiimide may be solid or liquid at ambient conditions (25 ℃, 1atm), or may be dissolved or dispersed in a reactive diluent or a non-reactive diluent, as discussed in more detail below.

In an example, a carbodiimide can be prepared by the following decarbonation reaction: (A) an isocyanate having at least two isocyanate groups bonded to carbons of a methylene group in the molecule ("diisocyanate"); (B) acyclic, aliphatic or aromatic diisocyanates other than the acyclic, aliphatic or aromatic diisocyanates defined in (a); and (C) a monofunctionalAn organic compound (hydroxyl, amine and/or monoisocyanate functional) to block the isocyanate groups of the resulting decarbonized condensation reaction product of components (A) and (B). Optionally, the decarbonization reaction may be performed in the presence of a catalyst for carbodiimidization. Useful diisocyanates include, for example, hexamethylene 1, 6-diisocyanate, tolylene diisocyanate, m-phenylene diisocyanate, p-phenylene diisocyanate, ditolyl diisocyanate, 4 '-diphenylmethane diisocyanate, 2,4' -diphenylmethane diisocyanate, 2,2 '-diphenylmethane diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, polymethylene polyphenyl diisocyanate, 3' -dimethyl-4, 4 '-biphenylene diisocyanate, 3' -dimethyl-4, 4 '-diphenylmethane diisocyanate, 3-dichloro-4, 4' -biphenylene diisocyanate, 1, 5-naphthalene diisocyanate, and the like. Useful monofunctional isocyanates include compounds such as cyclohexyl isocyanate, 3-isopropenyl- α, α -dimethylbenzyl isocyanate (m-TMI). In addition, exemplary useful carbodiimides based on isocyanates including those available from BASF under the trade nameSold, available from Angus Chemical Company (Angus Chemical Company) toSold, available from Rheinchemie Additives toSold, available from Nisshinbo for spinningAnd available from Stahl Polymers toThose isocyanates which are sold.

Optionally, the carbodiimide may include polyurethane groups and/or urea groups. As used herein, the term "polyurethane group" refers to any derivative of a carbamic acid having the following general structure:as used herein, the term "urea group" refers to any organic moiety having the following generalized structure:for example, the carbodiimide may be at least one of the following structures:

[ Structure I ]

WhereinOr

[ Structure 2]

WhereinOr

[ Structure 3]

In each of structures I-II, R¹-R⁵Is not hydrogen and is aliphatic or aromatic. In structures I-III, n>1。

The carbodiimide of the invention may have a weight average molecular weight of at least 1,000g/mol as determined by gel permeation chromatography using a Waters2695 separation module with a Waters 410 differential refractometer (RI detector) and polystyrene standards, Tetrahydrofuran (THF) being used as the eluent at a flow rate of 1 ml/min and two PL gel mixed C columns for separation, such as at least 1,500g/mol, such as at least 1,700g/mol, and in some cases the carbodiimide has a molecular weight of no more than 10,000g/mol as determined by gel permeation chromatography using a Waters2695 separation module with a Waters 410 differential refractometer (RI detector) and polystyrene standards, Tetrahydrofuran (THF) being used as the eluent at a flow rate of 1 ml/min and two PL gel mixed C columns for separation, such as no more than 5,000g/mol, such as not more than 3,500 g/mol. The molecular weight of the carbodiimides of this invention can be from 1,000g/mol to 10,000g/mol as determined by gel permeation chromatography using a Waters2695 separation module with a Waters 410 differential refractometer (RI detector) and polystyrene standards, Tetrahydrofuran (THF) is used as the eluent at a flow rate of 1 ml/min and two PL gel mixed C columns are used for separation, such as from 1,500g/mol to 5,000g/mol, such as from 1,700g/mol to 3,500 g/mol.

The carbodiimide may be present in the first component in an amount of at least 2.5 wt.%, such as at least 5 wt.%, such as at least 10 wt.%, such as at least 11 wt.%, based on the total weight of the composition, and may be present in the first component in an amount of no more than 50 wt.%, such as no more than 40 wt.%, such as no more than 30 wt.%, such as no more than 22 wt.%, based on the total weight of the composition. The carbodiimide may be present in the first component in an amount of from 2.5 to 50 weight percent, such as from 5 to 40 weight percent, such as from 10 to 30 weight percent, such as from 11 to 22 weight percent, based on the total weight of the composition.

The carbodiimide may be dispersed or dissolved in a diluent, such as a reactive diluent and/or a non-reactive diluent. As used herein, the term "diluent" refers to a compound having a viscosity of up to 20,000 mPa-s at 25 ℃, as measured according to ASTM D789. The diluent may reduce the viscosity of the carbodiimide-containing mixture.

As used herein, the term "reactive diluent" when used in relation to a diluent in which a carbodiimide may be dispersed means a diluent comprising an epoxy resin-containing compound capable of reacting through an epoxy moiety to crosslink, that is, an epoxy resin-containing compound that may be formed from a monomer capable of internal crosslinking, or an epoxy resin-containing compound that may be capable of reacting with its own species of compound or a different species of compound, an epoxy resin-containing compound that comprises a compound present in the first component that is not a reactive diluent (i.e., those compounds having a viscosity greater than 20,000 mPa-s at 25 ℃ as measured according to ASTM D789) and/or a curing agent of the second component. As used herein with respect to the reactive diluent, by way of non-limiting example, the term "its own species" means another epoxy-containing compound having the same chemical structure as the chemical structure of the reactive diluent, and the term "different species" means an epoxy-containing compound having a chemical structure different from the chemical structure of the reactive diluent or a compound having a functional group other than an epoxide functional group capable of reacting with the epoxide functional group of the reactive diluent, such as an amine functional group and/or a thiol functional group. The epoxy-containing compound may be any of the epoxy-containing compounds described below with respect to the epoxy-containing compound optionally present in the first component. As used herein, the term "non-reactive diluent" refers to a monomer or polymer that is not intended to react with a component of the first or second component of the two-component system (i.e., the non-reactive diluent is non-epoxidized).

As mentioned above, the viscosity of the diluent at 25 ℃ may be up to 20,000mPa s, as measured according to ASTM D789. By way of non-limiting example, the viscosity of the diluent at 25 ℃ can be at least 1mPa · s, such as at least 5mPa · s, such as at least 50mPa · s, such as at least 300mPa · s, such as at least 1,000mPa · s, such as at least 10,000mPa · s, as measured according to ASTM D789, and the viscosity of the diluent at 25 ℃ can be no more than 20,000mPa · s, such as no more than 17,000mPa · s, such as no more than 700mPa · s, such as no more than 100mPa · s, as measured according to ASTM D789. By way of non-limiting example, the viscosity of the diluent at 25 ℃ can be from 1 to 20,000 mPas, for example from 5 to 100 mPas, such as from 300 to 700 mPas, such as from 10,000 to 17,000 mPas, as measured according to ASTM D789.

The diluent may be present in the first component in an amount of at least 5 wt%, such as at least 7 wt%, such as at least 15 wt%, based on the total weight of the composition, and may be present in the first component in an amount of no more than 55 wt%, such as no more than 50 wt%, such as no more than 45 wt%, based on the total weight of the composition. The reactive diluent may be present in the first component in an amount of from 5 wt% to 55 wt%, such as from 7 wt% to 50 wt%, such as from 15 wt% to 45 wt%, based on the total weight of the composition.

Those skilled in the art will appreciate that the carbodiimide of the first component is substantially stable in the presence of the diluent until an external energy source, an accelerator (described below), or one of the curing agents of the second component (described below) is introduced.

The reactive diluent may be a monomer or a polymer, and may be monofunctional, difunctional, or polyfunctional. Suitable examples of reactive diluents may include any of the epoxy-containing compounds described below having a viscosity at 25 ℃ of up to 20,000 mPa-s as measured according to ASTM D789, including Cardura E10P (available from spain Inc., Hexion Inc.), polyglycidyl ethers of bisphenol a and bisphenol F, 1, 4-butanediol diglycidyl ether (available from spain as Heloxy modifier BD), 1, 6-hexanediol diglycidyl ether, monofunctional aliphatic diluents (Epotec 108, RD 109, RD 188 available from ediya berla groups (adiya Birla)), and monofunctional aromatic reactive diluents (Epotec 104, RD 105, and RD 136 available from ediya berla groups). Other suitable examples of reactive diluents include epoxidized oils, such as glycerol esters of polyunsaturated fatty acids, such as sunflower oil, safflower oil, soybean oil, linseed oil, castor oil, orange oil, rapeseed oil, tall oil, plant process oils, sulfurized vegetable oils, high oleic sunflower oil, cottonseed oil, nut oil, and combinations thereof. The reactive diluent of the present invention may also be an epoxy-functionalized homopolymer of 1, 2-butadiene or 1, 4-butadiene or combinations thereof, an epoxy-functionalized copolymer of butadiene and an acrylic or olefinic monomer, or combinations thereof.

The boiling point of the reactive diluent may be greater than 100 deg.C, such as greater than 130 deg.C, such as greater than 150 deg.C.

In an example, the ratio of the theoretical epoxide equivalent of the reactive diluent to the theoretical carbodiimide equivalent of the carbodiimide may be at least 1.1:1, such as at least 2:1, and in some cases may not exceed 100:1, such as 50: 1. In an example, the ratio of the theoretical epoxide equivalent of the reactive diluent to the theoretical carbodiimide equivalent of the carbodiimide can be from 1.1:1 to 100:1, such as from 2:1 to 50: 1. The theoretical epoxide equivalent weight can be determined by dividing the number average molecular weight of the epoxy-containing compound by the theoretical number of epoxide groups per molecule of the epoxy-containing compound. The theoretical carbodiimide equivalent can be determined by dividing the number average molecular weight of the carbodiimide by the theoretical number of carbodiimide groups per molecule of carbodiimide.

In an example, the non-reactive diluent can comprise a non-epoxidized oil, such as sunflower oil, safflower oil, soybean oil, linseed oil, castor oil, orange oil, rapeseed oil, tall oil, plant process oil, sulfurized vegetable oil, high oleic sunflower oil, cottonseed oil, nut oil, and combinations thereof. Other non-reactive diluents include homopolymers of 1, 2-butadiene or 1, 4-butadiene or combinations thereof, copolymers of butadiene and acrylic or olefinic monomers or combinations thereof. Other non-reactive diluents include diols or polyols as described above. Other non-reactive diluents include diisononyl phthalate (Jayflex DINP available from Exxon Mobile), diisodecyl phthalate (Jayflex DIDP available from Exxon Mobile), and alkyl benzyl phthalate (Santicizer 278 available from Valtris, Valtis); benzoate-based non-reactive diluents such as dipropylene glycol dibenzoate (available from Emerson Performance Materials, Inc.)) (ii) a And othersNon-reactive diluents, including terephthalate-based dioctyl terephthalate (DEHT available from Eastman Chemical Company), alkyl sulfonate esters of phenol (Mesamoll available from borsch (Borchers)), and 1, 2-cyclohexanedicarboxylic acid diisononyl ester (Hexamoll DINCH available from basf).

The total solids content of the carbodiimide dispersion or solution can be at least 40 weight percent, such as at least 60 weight percent, such as at least 80 weight percent, based on the total weight of the carbodiimide dispersion, and can be no more than 100 weight percent, such as no more than 95 weight percent, such as no more than 90 weight percent, based on the total weight of the carbodiimide dispersion. The carbodiimide dispersion can have a total solids content of 40 to 100 weight percent, such as 60 to 100 weight percent, such as 80 to 100 weight percent, based on the total weight of the carbodiimide dispersion. As used herein, "total solids," when used in relation to a carbodiimide dispersion, refers to the non-volatile content of the carbodiimide dispersion, i.e., the material that will not volatilize when heated to 30 ℃ for 30 minutes.

Optionally, according to the present invention, the first component may include one or more epoxy-containing compounds. As discussed above, the reactive diluent may be an epoxy-containing compound. The first component may further comprise an epoxy-containing compound that is not a reactive diluent (i.e., AS per AS)^TM D789, a viscosity of greater than 20,000mPa · s at 25 ℃).

Suitable epoxy-containing compounds that may be used in the first component may include polyepoxides. Suitable polyepoxides comprise polyglycidyl ethers of bisphenol A such as828 and 1001 epoxy resins and bisphenol F diepoxides such as862 (commercially available from hansen Specialty Chemicals, Inc.). OthersSuitable polyepoxides include polyglycidyl ethers of polyhydric alcohols, polyglycidyl ethers of polycarboxylic acids, polyepoxides derived from the epoxidation of an ethylenically unsaturated alicyclic compound, polyepoxides derived from the epoxidation of an ethylenically unsaturated non-aromatic cyclic compound, polyepoxides containing oxyalkylene groups in the epoxy resin molecule, and epoxy novolac resins. Other suitable epoxy resin-containing compounds include epoxidized bisphenol a novolac, epoxidized phenol novolac, epoxidized cresol novolac, and triglycidyl-p-aminophenol bismaleimide. The epoxy resin-containing compound may also include an epoxy resin dimer acid adduct. The epoxy resin dimer acid adduct may be formed as a reaction product of reactants comprising: diepoxide compounds (such as the polyglycidyl ethers of bisphenol a) and dimer acids (such as C36 dimer acid). The epoxy-containing compound may also include a carboxyl-terminated butadiene-acrylonitrile copolymer modified epoxy-containing compound. The epoxy resin-containing compound may also include epoxidized castor oil. Optionally, at least one of the epoxy-containing compounds may include elastomer particles (described below).

According to the present invention, the epoxy resin-containing compound may include an epoxy resin adduct. The first component may include one or more epoxy resin adducts. As used herein, the term "epoxy resin adduct" refers to a reaction product comprising the residue of an epoxy resin compound and at least one other compound that does not comprise an epoxide functional group. For example, the epoxy resin adduct may include the reaction product of reactants including: (1) epoxy resin compounds, polyols and anhydrides; (2) epoxy resin compounds, polyols and diacids; or (3) epoxy compounds, polyols, anhydrides, and diacids.

According to the present invention, the epoxy resin compound used to form the epoxy resin adduct may include any of the epoxy resin-containing compounds listed above that may be included in the first component.

According to the present invention, the polyol used to form the epoxy resin adduct may comprise diols, triols, tetrols and higher functional polyols. Combinations of such polyols may also be used. The polyols may be based on polyether chains derived from ethylene glycol, propylene glycol, butylene glycol, hexylene glycol, and the like, as well as mixtures thereof. The polyols may also be based on ring-opening polymerized polyester chains derived from caprolactone (hereinafter referred to as polycaprolactone-based polyols). Suitable polyols may also include polyether polyols, polyurethane polyols, polyurea polyols, acrylic polyols, polyester polyols, polybutadiene polyols, hydrogenated polybutadiene polyols, polycarbonate polyols, polysiloxane polyols, and combinations thereof. Polyamines corresponding to polyols may also be used and in this case will form amides with diacids and anhydrides rather than carboxylates.

The polyol may include a polycaprolactone-based polyol. The polycaprolactone-based polyol may include a diol, triol, or tetraol terminated by a primary hydroxyl group. Commercially available polycaprolactone-based polyols include those from the Pasteur Group (Perstorp Group) under the trade name Capa^TMThose polyols sold, for example, Capa 2054, Capa 2077A, Capa 2085, Capa 2205, Capa 3031, Capa 3050, Capa 3091 and Capa 4101.

The polyol may include a polytetrahydrofuran-based polyol. The polytetrahydrofuran-based polyol may include a diol, triol or tetraol terminated with primary hydroxyl groups. Commercially available polytetrahydrofuran-based polyols include those available from Invista under the trade name InvistaPolyols of the kind sold, e.g.PTMEG 250 andPTMEG 650, which is a blend of linear diols in which the hydroxyl groups are separated by repeating tetramethylene ether groups. In addition, those available from Corning Corporation (Cognis Corporation) under the trade name of Cognis may also be utilizedSolvermol^TMAnda dimer diol-based polyol sold or a BioBased polyol such as the tetrafunctional polyol Agrol 4.0 available from BioBased Technologies.

The anhydride used to form the epoxy resin adduct according to the present invention may include any suitable anhydride known in the art. For example, the anhydride may include hexahydrophthalic anhydride and derivatives thereof (e.g., methylhexahydrophthalic anhydride); phthalic anhydride and its derivatives (e.g., methylphthalic anhydride); maleic anhydride; succinic anhydride; trimellitic anhydride; pyromellitic dianhydride (PMDA); 3,3',4,4' -Oxydiphthalic Dianhydride (ODPA); 3,3',4,4' -Benzophenone Tetracarboxylic Dianhydride (BTDA); and 4,4' -diphthalic acid (hexafluoroisopropylidene) anhydride (6 FDA).

The diacids used to form the epoxy resin adduct according to the present invention may include any suitable diacids known in the art. For example, the diacid can include phthalic acid and its derivatives (e.g., methylphthalic acid), hexahydrophthalic acid and its derivatives (e.g., methylhexahydrophthalic acid), maleic acid, succinic acid, adipic acid, and the like.

According to the present invention, the epoxy resin adduct may include a diol, mono-anhydride or di-acid and a di-epoxy resin compound, wherein the molar ratio of diol, mono-anhydride (or di-acid) to di-epoxy resin compound in the epoxy resin adduct may vary from 0.5:0.8:1.0 to 0.5:1.0: 6.0.

According to the present invention, the epoxy resin adduct may include a triol, mono-anhydride or di-acid and a diepoxy resin compound, wherein the molar ratio of the triol, mono-anhydride (or di-acid) to the diepoxy resin compound in the epoxy resin adduct may vary from 0.5:0.8:1.0 to 0.5:1.0: 6.0.

According to the present invention, the epoxy resin adduct may include a tetraol, a mono-anhydride or a di-acid and a di-epoxy resin compound, wherein the molar ratio of the tetraol to the mono-anhydride (or di-acid) to the di-epoxy resin compound in the epoxy resin adduct may vary from 0.5:0.8:1.0 to 0.5:1.0: 6.0.

When used, the epoxy-containing compound that is not a reactive diluent may be present in the first component of the adhesive composition in an amount of at least 2 weight percent, such as at least 5 weight percent, such as at least 10 weight percent, based on the total weight of the composition, and may be present in an amount of no more than 40 weight percent, such as no more than 30 weight percent, such as no more than 25 weight percent, based on the total weight of the composition. The epoxy-containing compound, which is not a reactive diluent, may be present in the first component in an amount of from 2 to 40 weight percent, such as from 5 to 30 weight percent, such as from 10 to 25 weight percent, based on the total weight of the composition.

According to the invention, the composition further comprises a second component which reacts chemically with the first component. That is, the second component includes a curing agent. Curing agents may include amines, acids (including monomeric and polymeric acids, such as carboxylic acids), thiols, alcohols such as phenols, and/or other active hydrogen-containing compounds.

In mixing or combining the first and second components of the composition, the curing agent may be used to cure the composition by reacting the active hydrogen groups of the curing agent of the second component with the carbodiimide functionality of the carbodiimide, the epoxide functionality of the reactive diluent, and/or the epoxide functionality of the epoxy-containing compound that is not a reactive diluent of the first component to form the polymeric matrix. As will be discussed in more detail below, the curing conditions used to cure the composition optionally may include a two-step curing process.

The curing agent may include an active hydrogen-containing compound. For example, the curing agent may include amines, acids, alcohols, and/or thiols. Suitable amines for use in the present invention may be selected from a variety of known amines, such as primary and/or secondary amines. The amine may comprise a monoamine or a polyamine having at least two functional groups, such as a diamine, triamine, or higher functional amine; and mixtures thereof. The amines may be aromatic or aliphatic, such as cycloaliphatic, or mixtures thereof. Non-limiting examples of suitable amines may include aliphatic polyamines such as, but not limited to, ethylamine, isopropylamine, butylamine, pentylamine, hexylamine, cyclohexylamine, ethylenediamine, 1, 2-diaminopropane, 1, 4-diaminobutane, 1, 3-diaminopentane, 1, 6-diaminohexane, 2-methyl-1, 5-pentanediamine, 2, 5-diamino-2, 5-dimethylhexane, 2, 4-and/or 2,4, 4-trimethyl-1, 6-diamino-hexane, 1, 11-diaminoundecane, 1, 12-diaminododecane, 1, 3-cyclohexanediamine and/or 1, 4-cyclohexanediamine, 1-amino-3, 3, 5-trimethyl-5-aminomethyl-cyclohexane, 2, 4-and/or 2, 6-hexahydrotoluenediamine, 2,4 '-diamino-dicyclohexylmethane and/or 4,4' -diamino-dicyclohexylmethane and 3,3 '-dialkyl-4, 4' -diamino-dicyclohexylmethane (such as 3,3 '-dimethyl-4, 4' -diamino-dicyclohexylmethane and 3,3 '-diethyl-4, 4' -diamino-dicyclohexylmethane), 2, 4-diaminotoluene and/or 2, 6-diaminotoluene and 2,4 '-diaminodiphenylmethane and/or 4,4' -diaminodiphenylmethane or mixtures thereof.

The amine may comprise a primary amine, such as, but not limited to, a polyoxyalkylene amine. Suitable polyoxyalkylene amines may contain two or more primary amino groups attached to a backbone derived from, for example, propylene oxide, ethylene oxide, or mixtures thereof. Non-limiting examples of such amines may include those available from Hensman Corporation (Huntsman Corporation) under the name JEFFAMINE. Such amines may have molecular weights in the range of 200 to 7500, such as but not limited to JEFFAMINE D-230, D-400, D-2000, T-403, T-5000, XJS-616, and ED 600. Other suitable amines include aliphatic and cycloaliphatic polyamines, such as those available from Evonik corporation (Evonik)And (4) series.

The amine may comprise a secondary amine such as, but not limited to, dimethylamine, diethylamine, methylpropylamine, methylethanolamine, diethanolamine, N-allylmethylamine, Jeffamine series of secondary amines, such as SD-231, SD-401, and ST-404, cyclic secondary amines, such as aziridine, azepane, pyrrolidine, piperazine, morpholine, 1- (allyl) pyrrolidine-2-methylamine, and the like, and combinations thereof.

In an example, the amine may include an alkanolamine. As herein describedAs used, the term "alkanolamine" refers to a compound comprising a nitrogen atom bonded to at least one alkanol substituent comprising an alkyl group comprising a primary, secondary or tertiary hydroxyl group. The general structure of the alkanolamine may be R¹ _nN(R²-OH)_3-nWherein R is¹Including hydrogen or alkyl, R²Including alkanediyl, and n ═ 0, 1, or 2. When n is 2, there will be two R¹And these groups may be the same or different. When n is 0 or 1,2 or 3, R will be present²-OH groups, and these groups may be the same or different. Alkyl groups include aliphatic straight or branched carbon chains which may be unsubstituted or substituted with, for example, ether groups. Suitable alkanolamines include: monoalkanolamine such as ethanolamine, N-methylethanolamine, 1-amino-2-propanol, etc.; dialkanolamines such as diethanolamine, diisopropanolamine and the like; and trialkanolamines such as trimethanolamine, triethanolamine, tripropanolamine, tributanolamine, tripentanolamine, trihexanolamine, triisopropanolamine and the like.

Alkanolamines may serve a dual purpose in the composition. For one purpose, the alkanolamine may act as a catalyst during the first step, the second step, or both steps of the two-step curing process. For another purpose, the alkanolamine may be used as a reactant during the second step of the two-step curing process, as the hydroxyl groups of the alkanolamine may react with the epoxide groups of the epoxy-containing compound during curing.

Suitable examples of acids for use as curing agents include monomeric and polymeric acids, such as carboxylic acids. In an example, the acid may be a difunctional acid. Examples of carboxylic acids include, but are not limited to, formic acid, acetic acid, citric acid, propionic acid, dimer acids (fatty acids), trimer acids, butyric acid, benzoic acid, phenolic acids (e.g., cardanol), (meth) acrylic acid, terephthalic acid, suberic acid, sebacic acid, trimellitic acid, 4-bis (4-hydroxyphenyl) (valeric acid), polymeric acids, and the like, and combinations thereof. As used herein, the term "(meth) acrylic acid" refers to either or both (eiher/or) methacrylic acid and acrylic acid.

Suitable exemplary alcohols for use as curing agents include aromatic or aliphatic alcohols. Suitable examples of aromatic alcohols include phenol, resorcinol, catechol, bisphenol a (BPA), bisphenol f (bpf), diallyl BPA, lignin, and the like, and combinations thereof.

Suitable examples of aliphatic alcohols include, but are not limited to, methanol, ethanol, propanol, butanol, glycols, polyethylene oxide, polypropylene oxide, and the like, and combinations thereof.

The curing agent may include a thiol, such as a polythiol curing agent. As used herein, "polythiol curing agent" refers to a compound having at least two thiol functional groups (-SH).

Polythiol curing agents can include compounds comprising at least two thiol functional groups. Polythiol curing agents can include dithiol, trithiol, tetrathiol, pentathiol, hexanethiol, or higher functional polythiol compounds. The polythiol curing agent can include a dithiol compound comprising: 3, 6-dioxa-1, 8-octanedithiol (DMDO), 3-oxa-1, 5-pentanedithiol, 1, 2-ethanedithiol, 1, 3-propanedithiol, 1, 2-propanedithiol, 1, 4-butanedithiol, 1, 3-butanedithiol, 2, 3-butanedithiol, 1, 5-pentanedithiol, 1, 3-pentanedithiol, 1, 6-hexanedithiol, 1, 3-dithio-3-methylbutane, ethylcyclohexyl dithiol (ECHDT), methylcyclohexyl dithiol, methyl-substituted dimercapto diethyl sulfide, dimethyl-substituted dimercapto diethyl sulfide, 2, 3-dimercapto-1-propanol, bis (4-mercaptomethylphenyl) ether, 2' -thiodiethanol and ethylene glycol dimercapto acetate (available from Brunobo chemical plant) Co., Ltd (BRUNO BOCK Chemische Fabrik GmbH)&Co. kg) toGDMA commercially available). The polythiol curing agent can include a trithiol compound comprising: trimethylpropane trimercaptoacetate (available from Brunobock chemical plant Co., LtdTMPMA commercially available), trimethylpropane tri-3-mercaptopropionate (available from Brunobock chemical plant, Inc. asCommercially available from TMPMP), ethoxylated trimethylpropane tri-3-mercaptopropionate polymer (available from brunaoka chemical plant gmbh and available from brunauer corporationCommercially available from ETTMP), tris [2- (3-mercaptopropionyloxy) ethyl]Isocyanurate (available from brunaoka chemical plant gmbh and others)TEMPIC commercially available). The polythiol curing agent can include a tetrathiol compound comprising: pentaerythritol Tetramercaptoacetate (available from Brunobock chemical plant Co., LtdPETMA commercially available), pentaerythritol tetra-3-mercaptopropionate (available from brunaoka chemical plant gmbh and available from brunauer corporationPETMP commercially available) and polycaprolactone tetrakis (3-mercaptopropionate) (available from brunaoko chemical plant gmbh and available from brunauer corporationPCL4MP 1350 is commercially available). The higher functional polythiol curing agent can comprise dipentaerythritol hexa-3-mercaptopropionate (available from brunaoka chemical plant, inc. and/or co.)Petmp commercially available). Combinations of polythiol curing agents can also be used.

The thiol curing agent may comprise a thiol-terminated polysulfide. Commercially available thiol-terminated polysulfides include those available under the trade name Torray Fine Chemicals Co., Ltd from Torray Fine Chemicals, IncThose sold by LP, include, but are not limited to, LP-3, LP-33, LP-23, LP-980, LP-2, LP-32, LP-12, LP-31, LP-55, and LP-56. The THIOKOL LP thiol-terminated polysulfide has the general structure HS- (C)₂H₄-O-CH₂-O-C₂H₄-S-S)_nC₂H₄-O-CH₂-O-C₂H₄-SH, wherein n is an integer from 5 to 50. Other commercially available thiol-terminated polysulfides include those available under the trade name Akzo Nobel Functional Chemicals GmbH from Akzo Nobel Functional chemical Co., LtdG^TMThose sold, including but not limited to G10, G112, G131, G1, G12, G21, G22, G44, and G4. Thioplast G thiol-terminated polysulfide is a di-and trifunctional thiol-functional polysulfide and has the structure HS- (R-S-S)_nDifunctional units of-R-SH (where n is an integer from 7 to 38) and having the structure HS- (R-S-S)_a-CH₂-CH((S-S-R)_c-SH)-CH₂-(S-S-R)_bBlends of trifunctional units of-SH (where a + b + c ═ n and n is an integer from 7 to 38).

The thiol curing agent may include a thiol-terminated polyether. Commercially available thiol-terminated polyethers include POLYTHIOL QE-340M available from Toray Fine chemical Co., Ltd.

The calculated molecular weight of the mercaptans optionally used in the composition of the invention may be at least 94g/mol, such as at least 490g/mol, and the calculated molecular weight may not exceed 2,000g/mol, such as not more than 780 g/mol. The calculated molecular weight of the inventive mercaptans can be 94g/mol to 2,000g/mol, such as 490g/mol to 780 g/mol.

Optionally, the thiol curing agent may be substantially free of disulfide (S-S) linkages. Substantially free, when used with respect to the absence of S-S bonds in the thiol curing agent, means in the Raman spectrum, for example at 500cm^-1There is no detectable signal above the noise at (a).

Optionally, the second component may be substantially free of thiol-containing compounds or essentially free of thiol-containing compounds or completely free of thiol-containing compounds.

The curing agent may be present in the second component of the composition according to the invention in an amount of at least 2 wt. -%, such as at least 5 wt. -%, such as at least 10 wt. -%, such as at least 12 wt. -%, and may be present in an amount of not more than 50 wt. -%, such as not more than 40 wt. -%, such as not more than 30 wt. -%, such as not more than 25 wt. -%, based on the total weight of the composition. The curing agent may be present in the second component of the composition in an amount of from 2 to 50 wt%, such as from 5 to 40 wt%, such as from 10 to 30 wt%, such as from 12 to 25 wt%, based on the total weight of the composition.

In some examples, the curing agent may include mercaptans and alkanolamines. In such examples, the thiol-containing compound may be present in the second component in any of the above amounts, and the alkanolamine may be present in the second component of the composition in an amount of at least 0.5 wt.%, such as at least 1 wt.%, such as at least 2 wt.%, such as at least 5 wt.%, based on the total weight of the composition, and may be present in an amount of no more than 40 wt.%, such as no more than 30 wt.%, such as no more than 20 wt.%, such as no more than 10 wt.%, based on the total weight of the composition. In such examples, the alkanolamine may be present in the second component of the composition in an amount of from 0.5 wt.% to 40 wt.%, such as from 1 wt.% to 30 wt.%, such as from 2 wt.% to 20 wt.%, such as from 5 wt.% to 10 wt.%, based on the total weight of the composition.

According to the present invention, the second component of the composition may comprise one or more accelerators. The accelerator can actively catalyze the reaction of the carbodiimide, reactive diluent and/or epoxy-containing compound that is not a reactive diluent with the curing agent under ambient or slightly thermal conditions and optionally during the second step of the optional two-step curing process. That is, the accelerator may maintain catalytic activity during the second step of the two-step curing process. The accelerator may include a tertiary amine, a cyclic tertiary amine, and/or a secondary amine that reacts at room temperature with the epoxide group of the reactive diluent or the epoxy-containing compound that is not a reactive diluent (if one or both are present) to form a tertiary amine. The accelerator may also include a secondary amine that reacts with the hydrogen functional groups of the curing agent to form ions that may further react with the epoxide groups of the reactive diluent and/or epoxy-containing compounds that are not reactive diluents to form tertiary amines. The secondary amine may also react with the epoxide group of the reactive diluent and/or an epoxy-containing compound that is not a reactive diluent to form a tertiary amine. Accelerators may include 1, 4-diazabicyclo [2.2.2] octane ("DABCO"), 1, 8-diazabicyclo [5.4.0] undec-7-ene ("DBU"), 1, 5-diazabicyclo [4.3.0] non-5-ene ("DBN"), 1,5, 7-triazabicyclo [4.4.0] dec-5-ene ("TBD"), and combinations thereof. Additional examples of suitable accelerators include pyridine, imidazole, dimethylaminopyridine, 1-methylimidazole, N' -carbonyldiimidazole, [2,2] bipyridine, 2,4, 6-tris (dimethylaminomethyl) phenol, 3, 5-dimethylpyrazole, and combinations thereof.

The accelerator may be present in the second component of the composition in an amount of at least 0.02 wt%, such as at least 0.05 wt%, such as at least 0.1 wt%, based on the total weight of the composition, and may be present in an amount of no more than 1 wt%, such as no more than 0.5 wt%, such as no more than 0.25 wt%, based on the total weight of the composition. The accelerator may be present in the second component of the composition in an amount of from 0.02 wt% to 1 wt%, such as from 0.05 wt% to 0.5 wt%, such as from 0.1 wt% to 0.25 wt%, based on the total weight of the composition.

According to the present invention, the composition may be substantially free of accelerators including aromatic amines. As used herein, the term "aromatic amine" refers to an amine compound having an aromatic group. Examples of aromatic groups include phenyl and benzyl. As used herein, a composition may be "substantially free" of an aromatic amine-containing accelerator if present in an amount of 0.1 wt.% or less, based on the total weight of the composition. The composition may be essentially free of accelerators including aromatic amines. As used herein, a composition may be "essentially free" of accelerators that include aromatic amines if the aromatic amine-containing accelerator is present in an amount of 0.01 weight percent or less based on the total weight of the composition. The composition may be completely free of accelerators including aromatic amines. As used herein, a composition may be "completely free" of an aromatic amine-containing accelerator if the aromatic amine-containing accelerator is not present in the composition, i.e., 0.00 weight percent.

According to the present invention, the composition may optionally include one or more latency enhancers. As used herein, the term "accelerator of the second step" refers to a thermally activated latent accelerator that catalyzes the curing reaction of the composition only during the second step of the curing process. As used herein, "heat-activated latent promoter" refers to a compound that needs to be activated by the application of heat to the composition before the heat-activated latent catalyst has a catalytic effect. For example, the heat-activated latent accelerator may be in solid form at room temperature and not have a catalytic effect until it is heated and melted, or the heat-activated latent accelerator may react reversibly with a second compound that retards any catalytic effect until the reversible reaction is reversed by the application of heat and the second compound is removed, thereby releasing the accelerator to catalyze the reaction.

Accelerators of the second step that may be used include guanidines, substituted ureas, melamine resins, guanamine derivatives, heat-activated cyclic tertiary amines, aromatic amines, and/or mixtures thereof. Examples of substituted guanidines are methylguanidine, dimethylguanidine, trimethylguanidine, tetramethylguanidine, methylisobiguanide, dimethylisobiguanide, tetramethylisobiguanide, hexamethylisobiguanide, heptamethylisobiguanide and more especially cyanoguanidine (dicyandiamide). Representative of suitable guanamine derivatives which may be mentioned are alkylated benzoguanamine resins, benzoguanamine resins or methoxymethylethoxymethylbenzguanamine. In addition, catalytically active substituted ureas may also be used. Suitable catalytically active substituted ureas include p-chlorophenyl-N, N-dimethyl urea, 3-phenyl-1, 1-dimethyl urea (fenuron) or 3, 4-dichlorophenyl-N, N-dimethyl urea (also known as Diuron).

The accelerator of the second step may also comprise the reaction product of reactants comprising (i) an epoxy resin compound and (ii) an amine and/or an alkaloid. For example, (b) the heat-activated latent accelerator may comprise the reaction product of reactants comprising (i) an epoxy compound and (ii) an amine or the reaction product of reactants comprising (i) an epoxy compound and (ii) an alkaloid. Such heat-activated latent accelerators are described in paragraphs [0098] through [0110] of U.S. publication No. 2014/0150970, the referenced section of which is incorporated herein by reference. Examples of non-limiting commercially available accelerators for the second step comprising reaction products of reactants comprising (i) an epoxy resin compound and (ii) an amine and/or an alkaloid include the products sold under the tradename Ajicure available from Ajinomoto Fine technology, Inc. (Ajinomoto Fine-Techno Co., Inc.), including Ajicure PN-23, Ajicure PN-H, Ajicure PN-31, Ajicure PN-40, Ajicure PN-50, Ajicure PN-23J, Ajicure PN-31J, Ajicure PN-40J, Ajicure MY-24 and Ajicure MY-2.

The accelerator of the second step may be present in the second component of the composition in an amount of at least 1 wt. -%, such as at least 5 wt. -%, such as at least 7 wt. -%, based on the total weight of the coating composition, and may be present in an amount of not more than 20 wt. -%, such as not more than 15 wt. -%, such as not more than 13 wt. -%, based on the total weight of the coating composition. The accelerator of the second step may be present in the second component of the composition in an amount of from 1 wt% to 20 wt%, such as from 5 wt% to 15 wt%, such as from 7 wt% to 13 wt%, based on the total weight of the coating composition.

According to the present invention, the composition may be substantially free, essentially free, or completely free of the accelerator of the second step. As used herein, a composition is "substantially free" of the accelerator of the second step if the accelerator of the second step is present in an amount of less than 1 weight percent, based on the total weight of the composition. As used herein, a composition is "substantially free" of the accelerator of the second step if the cure accelerator of the second step is present in an amount of less than 0.1 weight percent based on the total weight of the composition. As used herein, a composition is "completely free" of the accelerator of the second step if the cure accelerator of the second step is absent from the composition, i.e., 0.0 wt%.

According to the present invention, the accelerator of the first step and the accelerator of the second step may be present in the second component of the composition in a combined amount of at least 0.5 wt. -%, such as at least 5 wt. -%, such as at least 8 wt. -%, and may be present in an amount of not more than 17 wt. -%, such as not more than 15 wt. -%, such as not more than 13 wt. -%, based on the total weight of the coating composition. The accelerator of the first step and the accelerator of the second step may be present in the second component of the composition in a combined amount of from 0.5 wt% to 17 wt%, such as from 5 wt% to 15 wt%, such as from 8 wt% to 13 wt%, based on the total weight of the coating composition.

The first component and/or the second component of the composition optionally may further comprise elastomer particles. As used herein, "elastomeric particles" refers to particles having a glass transition temperature (Tg) of-70 ℃ to 0 ℃, as measured by DSC. The elastomer particles may have a core/shell structure. Suitable core-shell elastomer particles may be composed of: butadiene rubber or other synthetic rubbers, such as styrene-butadiene, silicone rubber, silicone and acrylonitrile-butadiene, etc., butyl acrylate and/or 2-ethylhexyl acrylate. The type of elastomer particles and their concentration are not limited as long as the particle size is within the specified range as set forth below. In an example, the elastomer particles may be undispersed. In an example, the elastomer particles may be dispersed in, for example, one of the epoxy-containing compounds described above.

The mean particle size of the elastomer particles may be, for example, 0.02 to 500 micrometers (20 to 500,000nm), which is the reported particle size of rubber particles provided by Kanekea Texas Corporation, as measured by standard techniques known in the industry (e.g., according to ISO 13320 and ISO 22412).

As noted above, the elastomer particles optionally may be included in an epoxy carrier resin for incorporation into the composition. Suitable finely divided core-shell elastomer particles having an average particle size in the range of from 50nm to 250nm may be masterbatched in an epoxy resin, such as an aromatic epoxide, a novolac epoxy resin, a bisphenol a and/or a bisphenol F diepoxide, and/or an aliphatic epoxide, including cycloaliphatic epoxides, at a rubber particle concentration in the range of from 5 wt% to 40 wt%, such as from 20 wt% to 35 wt%, based on the total weight of the rubber dispersion. Suitable epoxy resins may also comprise mixtures of epoxy resins. When utilized, the epoxy carrier resin can be an epoxy resin-containing compound of the present invention such that the weight of the epoxy resin-containing compound present in the composition comprises the weight of the epoxy carrier resin.

Exemplary non-limiting commercial core-shell elastomer particle products using poly (butadiene) rubber particles that can be used in the compositions of the present invention comprise a dispersion of core-shell poly (butadiene) rubber in bisphenol F diglycidyl ether (25 weight percent rubber) (commercially available as Kane Ace MX 136), core-shell poly (butadiene) rubber in828 dispersion (33 wt.% rubber) (commercially available as Kane Ace MX 153), dispersion of core-shell poly (butadiene) rubber in bisphenol a diglycidyl ether (commercially available as Kane Ace MX 257) (37 wt.% rubber), dispersion of core-shell poly (butadiene) rubber in bisphenol F diglycidyl ether (37 wt.% rubber) (commercially available as Kane Ace MX 267), and dispersion of core-shell poly (butadiene) rubber in bisphenol a diglycidyl ether (commercially available as Kane Ace MX 150) (40 wt.% rubber), each of which is available from Kaneka texas corporation.

An exemplary non-limiting commercial core-shell rubber particle product using styrene-butadiene rubber particles that can be used in the composition comprises a dispersion of core-shell styrene-butadiene rubber in low viscosity bisphenol a diglycidyl ether (33 wt.% rubber) (commercially available as Kane Ace MX 113), a dispersion of core-shell styrene-butadiene rubber in bisphenol a diglycidyl ether (25 wt.% rubber) (commercially available as Kane Ace MX 125), and a core-shell styrene-butadiene rubber in D.E.N.^TM-438 Dispersion in Novolac epoxy resin (25% by weight rubber) (commercially available as Kane Ace MX 215), core-shell styrene-butadiene rubber inDispersion of MY-721 multifunctional Epoxy resin (25 wt.% rubber) (commercially available as Kane Ace MX 416), dispersion of core-shell styrene-butadiene rubber in MY-0510 multifunctional Epoxy resin (25 wt.% rubber) (commercially available as Kane Ace MX 451), dispersion of core-shell styrene-butadiene rubber in a syn Epoxy 21 cycloaliphatic Epoxy resin from Synasia (25 wt.% rubber) (commercially available as Kane Ace MX 551), and dispersion of core-shell styrene-butadiene rubber in polypropylene glycol (MW 400) (25 wt.% rubber) (commercially available as Kane Ace MX 715), each of which is available from Kaneka texas corporation. Other commercially available core-shell rubber particle dispersions include Fortegra 352 (bisphenol a liquid epoxy resin containing 33% by weight of core-shell rubber particles) available from olympic Corporation (Olin Corporation). Other commercially available core-shell rubber particles include Paraloid^TMEXL 2650A (core-shell poly (butadiene) commercially available from Dow).

Other exemplary elastomer particles comprise silicone rubber with a dispersion of core-shell rubber in bisphenol a diglycidyl ether (25 wt.% rubber) (commercially available as Kane Ace MX 960).

The elastomer particles may be present in the first component and/or the second component of the composition in a total amount of at least 3 wt.%, such as at least 5 wt.%, such as at least 7 wt.%, such as at least 10 wt.%, based on the total weight of the composition, and may be present in an amount of no more than 40 wt.%, such as no more than 35 wt.%, such as no more than 30 wt.%, such as no more than 20 wt.%, based on the total weight of the composition. The elastomer particles may be present in the first component and/or the second component of the composition in an amount of from 3 wt% to 40 wt%, such as from 5 wt% to 35 wt%, such as from 7 wt% to 30 wt%, such as from 10 wt% to 20 wt%, based on the total weight of the composition.

Additives such as organic and/or inorganic fillers, reinforcing fillers, thixotropes, colorants, dyes, toners, and/or other materials (collectively "additives") may optionally be added to the first and/or second components of the coating composition. Useful additives that may be incorporated include cellulose, starch, Silica (SiO)₂) Borosilicate, aluminosilicate, calcium carbonate, mica, calcium oxide (CaO), wollastonite, carbon black, clay minerals, organoclay, castor wax, fiber, glass beads, grapheme carbon fiber, and the like, and combinations thereof.

The term "mica" generally refers to sheet silicate (phyllosilicate) minerals. The mica may comprise muscovite mica. The muscovite mica has the formula KAl₂(AlSi₃O₁₀)(F,OH)₂Or (KF)₂(Al₂O₃)₃(SiO₂)₆(H₂O) aluminum and potassium. Exemplary non-limiting commercially available muscovite includes those available from Persia Minerals (Pacer Minerals) under the tradename Dakotapure^TMProducts sold, e.g. Dakotapure^TM700、DakotaPURE^TM1500、DakotaPURE^TM2400、DakotaPURE^TM3000、DakotaPURE^TM3500 and Dakotapure^TM4000。

The silica may comprise fumed silica, including silica that has been flame treated to form a three-dimensional structure. Fumed silica can be untreated or surface treated with a siloxane, such as polydimethylsiloxane. Exemplary non-limiting commercially available fumed silicas include those available from Evonik Industries, Inc. (Evonik Industries), under the trade nameSuch asR 104、R 106、R 202、R208 product solder commercially available.

Wollastonite includes calcium inosilicate minerals (CaSiO) which may contain minor amounts of iron, aluminum, magnesium, manganese, titanium and/or potassium₃). The wollastonite may have a B.E.T. surface area of 1.5 to 2.1m²In g, e.g. 1.8m²And a median particle size of 6 microns to 10 microns, such as 8 microns. Non-limiting examples of commercially available wollastonite include NYAD 400, available from NYCO Minerals, Inc. Useful clay minerals comprise nonionic platy fillers such as talc, pyrophyllite, chlorite, vermiculite, or combinations thereof.

Useful fibers include acrylic fibers, engineered cellulose fibers, glass fibers, fibrous titanium dioxide, fibrous aluminum oxide, carbon fibers comprising graphite and carbon nanotubes. Examples of synthetic fibers includeFiber anda fiber.

The calcium carbonate may comprise precipitated calcium carbonate or ground calcium carbonate. The calcium carbonate may or may not be surface treated with stearic acid. Non-limiting examples of commercially available precipitated calcium carbonates include those available from Specialty Minerals (Specialty Minerals)And AlbacarAnd obtainable from SolvayAnd (4) SPT. Can be used forNon-limiting examples of commercially available ground calcium carbonate include Duramite available from England porcelain Inc. (IMERYS)^TMAnd available from specialty minerals

As used herein, the term "graphenic carbon particle" means a carbon particle having a structure comprising one or more layers of monoatomic, thick, planar sheets of sp 2-bonded carbon atoms that are tightly packed in a honeycomb lattice. The average number of stacked layers may be less than 100, for example, less than 50. The average number of stacked layers may be 30 or less, such as 20 or less, such as 10 or less, such as 5 or less. The grapheme carbon particles may be substantially planar; however, at least a portion of the planar sheet may be substantially curved, curled, crumpled, or buckled. The particles generally do not have a spherical or equiaxed morphology. Suitable grapheme carbon particles are described in U.S. publication No. 2012/0129980, at paragraphs [0059] - [0065], the cited portion of which is incorporated herein by reference. Other suitable grapheme carbon particles are described in paragraphs [0039] - [0054] in U.S. publication No. 2014/0299270, the cited portion of which is incorporated herein by reference.

Useful colorants, dyes or toners may comprise red iron pigments, titanium dioxide, calcium carbonate and phthalocyanine blue and combinations thereof.

Optionally, such additives (if present) may be present in an amount of at least 0.1 wt%, such as not more than 0.5 wt%, such as not more than 1 wt%, such as not more than 5 wt%, such as not more than 15 wt%, such as not more than 30 wt%, based on the total weight of the composition, and may be present in an amount of not more than 50 wt%, such as not more than 45 wt%, such as not more than 20 wt%, such as not more than 10 wt%, based on the total weight of the composition. Optionally, such additives (if present) may be present in an amount of from 0.1 to 50 wt%, such as from 0.5 to 45 wt%, such as from 30 to 45 wt%, such as from 15 to 20 wt%, such as from 1 to 10 wt%, based on the total weight of the composition.

Optionally, the composition may be substantially free or essentially free or completely free of platy fillers, such as mica, talc, pyrophyllite, chlorite, vermiculite, or combinations thereof.

According to the present invention, the composition may be substantially free of a color changing indicator. As used herein, the term "color changing indicator" refers to a compound that at least partially changes the color of a composition during the curing process. Examples of color changing indicators include inorganic and organic dyes, such as azo compounds or azo dyes, including Solvent Red 26(Solvent Red 26) (1- [ [2, 5-dimethyl-4- [ (2-methylphenyl) azo ] -phenyl ] azo ] -2-naphthol) and Solvent Red164 (Solvent Red164) (1- [ [4- [ phenylazo ] -phenyl ] azo ] -2-naphthol), and pH dependent color changing indicators, such as phenolphthalein. As used herein, a composition is "substantially free" of a color changing indicator if the color changing indicator is present in the composition in an amount of 0.05 weight percent or less, based on the total weight of the composition. The composition may be essentially free of color changing indicators. As used herein, a composition is "essentially free" of a color changing indicator if the color changing indicator is present in the composition in an amount of 0.01 weight percent or less based on the total weight of the composition. The composition may be completely free of color changing indicators.

As used herein, a composition is "completely free" of a color changing indicator if the color changing indicator is not present in the composition, i.e., 0.0 wt%.

According to the present invention, the composition may be substantially free of silane. As used herein, a composition is "substantially free" of silane if the silane is present in the composition in an amount of 0.5 weight percent or less, based on the total weight of the composition. The composition may be essentially free of silane. As used herein, a composition is "essentially free" of silane if the silane is present in the composition in an amount of 0.1 weight percent or less, based on the total weight of the composition. The composition may be completely free of silane. As used herein, a composition is "completely free" of silane if the silane is not present in the composition, i.e., 0.0 wt%.

According to the present invention, the composition may be substantially free, essentially free, or completely free of unreacted isocyanate functional groups. As used herein, a composition is "substantially free" of unreacted isocyanate functionality if the composition has an NCO functionality of >10,000g/Eq (as determined by titration as described in the examples). As used herein, a composition is "completely free" of unreacted isocyanate functionality if it has an NCO functionality of >12,000g/Eq (as determined by titration as described in the examples).

According to the invention, the weight ratio of the first component to the second component may be at least 1:10, such as at least 1:5, such as at least 1:3, and may not exceed 10:1, such as not exceeding 5:1, such as not exceeding 3: 1. The weight ratio of the first component to the second component may be from 1:10 to 10:1, such as from 1:5 to 5:1, such as from 1:3 to 3: 1.

Optionally, the compositions of the present invention may be subjected to a two-step curing process in which (1) upon mixing under ambient or slightly thermal conditions, at least a portion of the first component and the second component chemically react to partially cure the composition without activation from an external energy source, followed by (2) application of an external energy source to the composition to further cure the composition. As further defined herein, ambient conditions generally refer to room temperature (about 23 ℃) and humidity conditions (e.g., about 50%) or temperature and humidity conditions typically found in the area where the adhesive is applied to a substrate, while slightly hot conditions are temperatures slightly above ambient temperature, such as 10% above ambient temperature and/or humidity, such as 20% above, such as 30% above, but generally below the curing temperature of the second step of the two-step curing process.

In an example, the present invention relates to a two-part adhesive composition comprising or consisting essentially of a first component and a second component. The first component may comprise or consist essentially of a diluent such as a reactive diluent and a carbodiimide. The second component may include, consist essentially of, or consist of a curing agent that chemically reacts with the reactive diluent and/or carbodiimide of the first component, the curing agent including an active hydrogen-containing compound. The adhesive composition may be used to bond two substrate materials together for a variety of potential applications, where the bond between the substrate materials may provide specific mechanical properties related to lap shear strength. An adhesive may be applied to one or both of the materials being joined. The pieces may be aligned and pressure and spacers may be added to control the bond thickness. In an example, the "green strength" of the adhesive bond after at least partial curing under ambient conditions is greater than 0.1MPa as determined by using an instron 5567 machine at a pull rate of 1.0mm per minute in tensile mode according to ASTM D1002-10. The green strength of the adhesive bond may be achieved after allowing the adhesive composition to cure under ambient conditions for about 5 hours, such as about 1 hour, such as about 0.5 hours, such as about 0.3 hours. The composition may also be subjected to curing conditions, such as the two-step curing process described herein, such that substantially complete curing is obtained, and wherein further curing does not further significantly improve adhesive properties, such as lap shear strength. When the adhesive bonds a lap shear strength of greater than 5MPa as determined by using an instron 5567 machine in a tensile mode according to ASTM D1002-10 at a draw rate of 1mm per minute, the adhesive will be considered "cured" after the two-step curing process. Surprisingly, the adhesive composition of the invention can form an adhesive having a lap shear strength greater than 10MPa as determined in tensile mode according to ASTM D1002-10 using an instron 5567 machine at a pull rate of 1mm per minute.

In an example, the present invention is directed to a two-component sealant composition comprising or consisting essentially of a first component and a second component. The first component may comprise, consist essentially of, or consist of a non-reactive diluent and a carbodiimide. The second component may include, consist essentially of, or consist of a curing agent that chemically reacts with the carbodiimide of the first component, the curing agent including an active hydrogen-containing compound. The sealant can surprisingly be capable of withstanding a maximum load of at least 0.3MPa, such as at least 0.5MPa, as measured using a dog bone specimen (shown in fig. 1) on instron model 5569 at a pull rate of 50 millimeters/minute in accordance with ASTM D-412; and/or surprisingly may have an elongation at break of at least 10% as measured using a dog bone specimen (shown in figure 1) on an instron model 5569 at a pull rate of 50 mm/min in accordance with ASTM D-412. Such maximum load and elongation at break can be achieved when the sealant composition is at least partially cured by a two-step curing process as described herein comprising a second step, such as baking at 180 ℃ or less, such as 130 ℃ or less, such as 110 ℃ or less, such as 100 ℃ or less, such as 90 ℃ or less, such as 80 ℃ or less, such as 70 ℃ or less but greater than ambient, such as greater than 40 ℃, such as greater than 50 ℃, for any desired period of time sufficient to at least partially cure the composition, for example, 5 minutes to 5 hours, such as 0.3 hours to 2 hours, such as 0.4 hours to 1 hour.

The invention also relates to a process for preparing a coating composition, such as an adhesive composition or a sealant composition. The method may comprise, consist essentially of, or consist of: the carbodiimide and diluent are mixed with at least one of the curing agents described above and optionally one or more of the additional optional ingredients described above at a temperature of less than 50 ℃, such as from 0 ℃ to 50 ℃, such as from 15 ℃ to 35 ℃, such as at ambient or slightly elevated temperature. The method optionally may further comprise, consist essentially of, or consist of: the composition is subjected to the curing process of the second step described above.

The above compositions may be applied individually or as part of a system that can be deposited in a number of different ways onto a number of different substrates. The system may include a plurality of the same or different films, coatings or layers. A film, coating or layer is typically formed when the composition deposited onto at least a portion of the substrate surface is at least partially dried or cured by methods known to those of ordinary skill in the art (e.g., under ambient or slightly hot conditions and optionally by exposure to the second step of the two-step curing process described above, e.g., thermal heating).

The composition may be applied to the surface of the substrate in any number of different ways, non-limiting examples of which include brushes, rollers, films, pellets, trowels, scrapers, traps, spray guns, and applicator guns for forming a coating on at least a portion of the surface of the substrate. Alternatively, the composition may be cast, extruded, molded or machined to form a part or component in an at least partially dried or cured state.

After application to the substrate, the composition may be cured. For example, the composition may be at least partially cured under room temperature or slightly hot conditions and/or may be cured by baking and/or curing at elevated temperatures, such as at 180 ℃ or below, such as 130 ℃ or below, such as 110 ℃ or below, such as 100 ℃ or below, such as 90 ℃ or below, such as 80 ℃ or below, such as 70 ℃ or below but greater than ambient, such as greater than 40 ℃, such as greater than 50 ℃, for any desired period of time (e.g., 5 minutes to 1 hour) sufficient to at least partially cure the composition. Alternatively, the compositions of the present invention may be at least partially cured at ambient or slightly above ambient conditions.

The invention also relates to a method for treating a substrate, said method comprising or consisting essentially of or consisting of: contacting at least a portion of the surface of the substrate with one of the compositions of the invention described herein above. The composition may be cured to form a coating, layer or film on the surface of the substrate under ambient conditions or by exposure to an external energy source, for example by heating the substrate to a temperature of less than 180 ℃, such as less than 130 ℃, such as less than 90 ℃. The coating, layer or film may be, for example, a sealant or adhesive.

The present invention also relates to a method for forming a bond between two substrates for various potential applications, wherein the bond between the substrates provides specific mechanical properties related to lap shear strength. The method may comprise or consist essentially of or consist of: applying the composition described above to a first substrate; contacting the second substrate with the composition such that the composition is positioned between the first substrate and the second substrate; and curing the composition under ambient or slightly hot conditions and/or by exposure to an external energy source, for example by heating to a temperature of less than 180 ℃, such as less than 130 ℃, such as less than 90 ℃. For example, the composition may be applied to one or both of the substrate materials being bonded to form an adhesive bond therebetween, and the substrates may be aligned, and pressure and/or spacers may be added to control the bond thickness. The composition may be applied to a cleaned or uncleaned (i.e., containing oily or oiled) substrate surface.

Optionally, the composition may be cured after application to the substrate. Curing may be achieved by a two-step curing process as described herein. For example, the adhesive may be allowed to cure at room temperature or slightly hot conditions during the first step. Next, the adhesive may be cured during the second step by baking and/or curing at an elevated temperature, such as at a temperature of at least 70 ℃, such as at least 80 ℃, such as at least 110 ℃, such as at least 120 ℃, such as at least 125 ℃, such as at least 130 ℃, and in some cases, at a temperature of no more than 200 ℃, such as no more than 180 ℃, such as no more than 170 ℃, such as no more than 165 ℃, and in some cases, at a temperature of 70 ℃ to 200 ℃, 120 ℃ to 180 ℃, 125 ℃ to 170 ℃, 130 ℃ to 165 ℃ and for any desired period of time (e.g., 5 minutes to 1 hour) sufficient to at least partially cure the adhesive composition on the substrate.

The coating composition of the present invention may be applied to a substrate surface comprising a component that is a non-limiting example of a vehicle body or an automobile frame or an aircraft. The coating composition may be applied to a cleaned or uncleaned (i.e., containing oily or oiled) substrate surface. The coating composition can also be applied to a substrate that has been pretreated, has been coated with an electrodepositable coating, has been coated with additional layers such as a primer, basecoat, or topcoat. The coating composition, once applied to the substrate, can be dried or cured at ambient conditions, and/or the substrate coated with the coating composition can optionally be subsequently baked in an oven to cure the coating composition.

After applying the adhesive composition to a substrate and at least partially curing it to form an adhesive:

(a) surprisingly, the green strength of the binder that bonds the substrates together can be at least 0.1MPa, such as at least 0.5MPa, such as at least 1MPa, such as at least 2MPa, such as at least 3MPa, such as at least 4MPa, as measured in tensile mode according to test method ASTM D1002-10 by instron model 5567, and the green strength can be from 0.1MPa to less than 5MPa, such as from 0.5MPa to less than 5MPa, such as from 1MPa to less than 5MPa, such as from 2MPa to less than 5MPa, such as from 3MPa to less than 5MPa, such as from 4MPa to less than 5MPa, as measured in tensile mode according to test method ASTM D1002-10 by instron model 5567; and/or

(b) The adhesive that bonds the substrates together surprisingly may have an adhesive strength of at least 10.0MPa, such as an adhesive strength of at least 15MPa, such as an adhesive strength of at least 20MPa, measured in tensile mode according to test method ASTM D1002-10 by instron model 5567 after exposure to ambient temperature for 2 hours and heating at 175 ℃ for 30 minutes.

After applying the sealant composition to a substrate and at least partially curing as described herein:

(a) the sealant surprisingly can withstand a maximum load of at least 0.3MPa, such as at least 0.5MPa, such as at least 1MPa, measured using a dog bone specimen (as shown in fig. 1) on instron model 5569 at a pull rate of 50 mm/min according to ASTM D-412; and/or

(b) The sealant surprisingly can have an elongation at break of at least 10%, such as at least 15%, such as at least 20%, as measured using a dog bone specimen (as shown in fig. 1) on instron model 5569 at a pull rate of 50 millimeters/minute in accordance with ASTM D-412.

The substrate that can be coated with the composition of the present invention is not limited. Suitable substrates useful in the present invention include, but are not limited to, materials such as metals or metal alloys, polymeric materials such as hard plastics (including filled or unfilled thermoplastic materials or thermoset materials), or composites. Other suitable substrates useful in the present invention include, but are not limited to, glass or natural materials such as wood. For example, suitable substrates include rigid metal substrates such as ferrous metal, aluminum alloys, magnesium titanium, copper, and other metal and alloy substrates. Ferrous metal substrates used in the practice of the present invention may comprise iron, steel and alloys thereof. Non-limiting examples of useful steel materials include cold rolled steel, galvanized (zinc coated) steel, electrogalvanized steel, stainless steel, acid dipped steel, zinc-iron alloys such as GALVANNEAL, and combinations thereof. Combinations or composites of ferrous and non-ferrous metals may also be used. Also, aluminum alloys of the 1XXX, 2XXX, 3XXX, 4XXX, 5XXX, 6XXX, 7XXX or 8XXX series, as well as clad aluminum alloys and cast aluminum alloys of the a356, 1xx.x, 2xx.x, 3xx.x, 4xx.x, 5xx.x, 6xx.x, 7xx.x or 8xx.x series, may be used as the base material. Magnesium alloys of AZ31B, AZ91C, AM60B or EV31A series may also be used as the base material. The substrates useful in the present invention may also include grade 1-36 titanium and/or titanium alloys, including grade H variants. Other suitable non-ferrous metals include copper and magnesium and alloys of these materials. Suitable metal substrates for use in the present invention include metal substrates used in assemblies of vehicle bodies (such as, but not limited to, doors, body panels, trunk lids, roof panels, hoods, roofs and/or stringers, rivets, landing gear components and/or skins used on aircraft), vehicle frames, vehicle parts, motorcycles, wheels, and industrial structures and components. As used herein, "vehicle" or variations thereof include, but are not limited to, civil, commercial, and military aircraft, land vehicles such as automobiles, motorcycles, and/or trucks, agricultural equipment such as tractors, plows, rakes, and/or heavy equipment such as excavators, backhoes, forklifts, and the like. The metal substrate may also be in the form of, for example, a metal sheet or a fabricated part. It should also be understood that the substrate may be pretreated with a pretreatment solution comprising: a zinc phosphate pretreatment solution, such as those described in U.S. Pat. nos. 4,793,867 and 5,588,989, or a zirconium-containing pretreatment solution, such as those described in U.S. Pat. nos. 7,749,368 and 8,673,091. The substrate may comprise a composite material, such as a plastic or fiberglass composite. The substrate may be a glass fiber and/or carbon fiber composite. The compositions of the present invention are particularly useful in a variety of industrial or transportation applications, including automotive, light and heavy commercial vehicles, marine or aerospace.

The 2K compositions disclosed herein surprisingly can be used in any suitable additive manufacturing technique (e.g., extrusion, jetting, and adhesive jetting).

The present disclosure relates to the use of three-dimensional printing to produce structural articles, such as, by way of non-limiting example, acoustic damping mats. The three-dimensional article may be produced by: successive portions or layers of the article are formed by depositing the composition of the present invention onto a substrate, and then depositing additional portions or layers of the composition over and/or adjacent to the previously deposited portions or layers. Layers may be deposited successively adjacent to previously deposited layers to build up a printed article. The first and second components of the composition may be mixed and then deposited, or the first and second components of the composition may be separately deposited. When deposited separately, the first component and the second component may be deposited simultaneously, sequentially, or both simultaneously and sequentially.

By "portion of the article" is meant a subunit of the article, such as a layer of the article. The layers may lie in successive horizontal parallel planes. The portion may be parallel planes of deposited material or beads of deposited material produced in the form of discrete droplets or a continuous stream of material. The first and second components may each be provided neat or may further comprise a solvent (organic and/or water) and/or other additives as described below. The first and second components provided by the present disclosure may be substantially free of solvent. By substantially free it is meant that the first and second components comprise less than 5 wt%, less than 4 wt%, less than 2 wt%, or less than 1 wt% solvent, as the case may be, wherein wt% is based on the total weight of the first or second component. Similarly, the compositions provided by the present disclosure can be substantially free of solvent, such as having less than 5 wt.%, less than 4 wt.%, less than 2 wt.%, or less than 1 wt.% solvent, where wt.% is by total weight of the composition.

The first and second components may be mixed together and subsequently deposited as a mixture of components that react to form portions of the article. For example, the components may be mixed together and deposited as a mixture of components that react to form a thermoset by delivering at least two separate streams of the two components to a mixer, such as a static mixer and/or a dynamic mixer, to produce a single stream that is then deposited. The components may be at least partially reacted upon deposition of the composition comprising the reaction mixture. The deposited reaction mixture may at least partially react after deposition and may also react with previously deposited portions of the article and/or subsequently deposited portions (such as underlying layers or capping layers of the article).

Any suitable apparatus may be used to deposit the two or more components. The selection of a suitable deposition apparatus depends on a number of factors, including the deposition volume, the viscosity of the composition, and the complexity of the part being manufactured. Each of the two or more components may be introduced into a separate pump and injected into a mixer to combine and mix the two components. A nozzle may be coupled to the mixer, and the mixed composition may be pushed out under pressure or extruded through the nozzle.

The pump may be, for example, a positive displacement pump, a syringe pump, a piston pump, or a progressive cavity pump. The two pumps delivering the two components may be placed in parallel or in series. Suitable pumps may be capable of pushing a liquid or viscous liquid through the nozzle orifice. This process may also be referred to as extrusion. The components can be introduced into the mixer using two pumps in series.

For example, the first component and the second component may be deposited by dispensing the material through a disposable nozzle attached to a progressive cavity two-component feed system, such as a ViscoTec eco-DUO 450 precision feed system, in which the first component and the second component are mixed in-line. The two-component feed system may include, for example, two screw pumps that respectively dose the reactants into a disposable static mixer dispenser or dynamic mixer. Other suitable pumps include positive displacement pumps, syringe pumps, piston pumps, and progressive cavity pumps. Upon dispensing, the materials of the first and second components form an extrudate that can be deposited onto a surface to provide an initial layer and a continuous layer of material on a substrate. The deposition system may be positioned orthogonal to the base, but may be disposed at any suitable angle to form an extrudate such that the extrudate and the deposition system form an obtuse angle, wherein the extrudate is parallel to the base. By extrudate is meant the combined components, i.e. the composition that has been mixed, for example, in a static mixer or a dynamic mixer. The extrudate may be shaped as it passes through the nozzle.

The substrate, the deposition system, or both the substrate and the deposition system may be moved to build the three-dimensional article. The movement may be performed in a predetermined manner, which may be accomplished using any suitable CAD/CAM method and apparatus, such as a robotic and/or computerized machine interface.

The extrudate may be continuously or intermittently dispensed to form an initial layer and a continuous layer. For intermittent deposition, the feed system may interface with a relay switch to turn off the pump (e.g., a progressive cavity pump) and stop the flow of reactive material. Any suitable switch may be used, such as an electromechanical switch which may be conveniently controlled by any suitable CAD/CAM method.

The deposition system may comprise an in-line static and/or dynamic mixer and separate pressurized pumping compartments for holding at least two components and feeding the materials into the static and/or dynamic mixer. Mixers such as active mixers may include a variable speed central impeller with high shear blades in a conical nozzle. A series of conical nozzles may be used, the outlet orifice size of which is for example 0.2mm to 50mm, 0.5mm to 40mm, 1mm to 30mm or 5mm to 20 mm.

A series of static and/or dynamic mixing nozzles may be used, having outlet orifice sizes of, for example, 0.6mm to 2.5mm and lengths of 30mm to 150 mm. For example, the outlet orifice diameter may be 0.2mm to 4.0mm, 0.4mm to 3.0mm, 0.6mm to 2.5mm, 0.8mm to 2mm, or 1.0mm to 1.6 mm. The length of the static mixer and/or the dynamic mixer may be, for example, 10mm to 200mm, 20mm to 175mm, 30mm to 150mm, or 50mm to 100 mm. The mixing nozzle may comprise a static and/or dynamic mixing section and a distribution section coupled to the static and/or dynamic mixing section. The static and/or dynamic mixing section may be configured to combine and mix the first component and the second component. The distribution section may be, for example, a straight tube having any of the above orifice diameters. The length of the dispensing section may be configured to provide a region in which the components may begin to react and build viscosity prior to deposition on the article. The length of the dispensing section may be selected, for example, based on the rate of deposition, the rate of reaction of the first and second components, and the desired viscosity.

The residence time of the first component and the second component in the static and/or dynamic mixing nozzle may be, for example, 0.25 seconds to 5 seconds, 0.3 seconds to 4 seconds, 0.5 seconds to 3 seconds, or 1 second to 3 seconds. Other residence times may be used as appropriate based on the cure chemistry and cure rate.

Generally, a suitable residence time is less than the gel time of the composition. Suitable gel times may be less than 10 minutes, less than 8 minutes, less than 6 minutes, less than 5 minutes, less than 4 minutes, less than 3 minutes, less than 2 minutes, or less than 1 minute. The gel time of the composition may be, for example, 0.5 minutes to 10 minutes, 1 minute to 7 minutes, 2 minutes to 6 minutes, or 3 minutes to 5 minutes.

The compositions provided by the present disclosure can have a volumetric flow rate of, for example, 0.1 ml/min to 20,000 ml/min, such as 1 ml/min to 12,000 ml/min, 5 ml/min to 8,000 ml/min, or 10 ml/min to 6,000 ml/min. The volumetric flow rate may depend on, for example, the viscosity of the composition, the extrusion pressure, the nozzle diameter, and the reaction rate of the first component and the second component.

The composition may be used at a printing speed of, for example, 1 mm/sec to 400 mm/sec, such as 5 mm/sec to 300 mm/sec, 10 mm/sec to 200 mm/sec, or 15 mm/sec to 150 mm/sec. The printing speed may depend on, for example, the viscosity of the composition, the extrusion pressure, the nozzle diameter, and the reaction rate of the components. The printing speed refers to the speed at which the nozzle used to extrude the composition is moved relative to the surface on which the composition is deposited.

The gel time of the composition can be, for example, less than 5 minutes, less than 4 minutes, less than 3 minutes, less than 2 minutes, less than 1 minute, less than 45 seconds, less than 30 seconds, less than 15 seconds, or less than 5 seconds. The gel time of the composition can be, for example, from 0.1 second to 5 minutes, from 0.2 second to 3 minutes, from 0.5 second to 2 minutes, from 1 second to 1 minute, or from 2 seconds to 40 seconds. Gel time is considered to be the time after mixing when the composition can no longer be stirred by hand.

The static and/or dynamic mixing nozzle may be heated or cooled to control, for example, the rate of reaction between the first component and the second component and/or the viscosity of the first component and the second component. The orifices of the deposition nozzles may be of any suitable shape and size. The system may include a plurality of deposition nozzles. The nozzle may have a fixed orifice size and shape, or the nozzle orifice may be controllably adjustable. The mixer and/or nozzle may be cooled to control the exotherm produced by the reaction of the first component and the second component.

The present disclosure provides methods comprising printing a composition on a manufactured part. The method provided by the present disclosure includes a direct printing component.

The components can be manufactured using the methods provided by the present disclosure. The entire component can be formed from one of the compositions disclosed herein, one or more portions of the component can be formed from one of the compositions disclosed herein, one or more different portions of the component can be formed using the compositions disclosed herein, and/or one or more surfaces of the component can be formed from the compositions provided by the present disclosure. Additionally, the interior region of the component can be formed from the compositions provided by the present disclosure.

While specific aspects of the invention have been described in detail, it will be appreciated by those skilled in the art that various modifications and alternatives to those details could be developed in light of the overall teachings of the disclosure. Accordingly, the particular arrangements disclosed are meant to be illustrative only and not limiting as to the scope of the invention which is to be given the full breadth of the claims appended and any and all equivalents thereof.

Aspect(s)

In view of the foregoing, the present invention therefore relates particularly, but not exclusively, to the following:

1. a two-component coating composition comprising:

a first component comprising a carbodiimide and a diluent, wherein the carbodiimide is present in an amount of no more than 50 weight percent based on the total weight of the coating composition; and

a second component comprising a curing agent that chemically reacts with the carbodiimide, the curing agent comprising an active hydrogen-containing compound.

2. The coating composition of aspect 1, wherein the composition is substantially free of unreacted isocyanate functional groups.

3. The coating composition of any one of the preceding aspects, wherein the diluent comprises a reactive diluent.

4. The coating composition of aspect 3, wherein the reactive diluent comprises an epoxy-containing compound.

5. The coating composition of any one of aspects 1 or 2, wherein the diluent comprises a non-reactive diluent.

6. The coating composition of any one of the preceding aspects, wherein the carbodiimide comprises polyurethane groups and/or urea groups.

7. The coating composition of any one of the preceding aspects, wherein the carbodiimide is present in the composition in an amount of from 5 weight percent to 50 weight percent, based on the total weight of the composition.

8. The coating composition according to any one of the preceding aspects, wherein the carbodiimide has a Mw of 1,000 to 10,000g/mol as measured by GPC using polystyrene standards in THF solvent and waters Styragel columns.

9. The coating composition according to any one of the preceding aspects, wherein the active hydrogen-containing compound comprises an amine, an acid, an alcohol and/or a thiol.

10. The coating composition of aspect 9, wherein the amine comprises a primary amine and/or a secondary amine.

11. The coating composition of any of the preceding aspects 9 or 10, wherein the acid comprises a difunctional acid.

12. The coating composition of any one of the preceding aspects 9-11, wherein the thiol comprises at least two thiol functional groups.

13. The coating composition of aspect 12, wherein the thiol comprises pentaerythritol tetra-3-mercaptopropionate.

14. The coating composition of any one of the preceding aspects 9-13, wherein the thiol is substantially free of S-S bonds.

15. The coating composition of any of the preceding aspects 9-14, wherein the calculated molecular weight of the thiol is 94g/mol to 2,000 g/mol.

16. The coating composition of any one of the preceding aspects 1-11, wherein the second component is substantially free of mercaptans.

17. The coating composition of aspect 9, wherein the amine comprises an alkanolamine.

18. The coating composition of aspect 17, wherein the alkanolamine comprises triethanolamine.

19. The coating composition of any one of aspects 17 or 18, wherein the alkanolamine is present in the second component of the composition in an amount of at least 0.5 wt.% based on the total weight of the coating composition.

20. The coating composition of any one of aspects 17-19, wherein the curing agent comprises the alkanolamine and a thiol, acid, and/or alcohol.

21. The coating composition of aspect 20, wherein the weight ratio of the thiol, the acid, and/or the alcohol to the alkanolamine is from 1:1 to 22: 1.

22. The coating composition of any one of the preceding aspects, wherein the weight ratio of the first component to the second component is from 1:10 to 10: 1.

23. The coating composition according to any one of the preceding aspects, wherein the coating composition further comprises an epoxy-containing compound that is not a reactive diluent, elastomer particles, additives and/or accelerators.

24. The coating composition of any one of the preceding aspects, wherein the coating composition is substantially free of a color changing indicator, an aromatic amine curing catalyst, and/or a silane.

25. The coating composition of any one of the preceding aspects, wherein the coating composition comprises a binder composition.

26. The coating composition of any one of the preceding aspects, wherein the coating composition comprises a sealing composition.

27. A substrate comprising a coating composition according to any one of the preceding aspects 1-26 positioned on at least a portion of a surface of the substrate.

28. The substrate of the foregoing aspect 27, wherein in an at least partially cured state, the composition:

(a) capable of withstanding a maximum load of at least 0.3MPa as measured using a dog bone specimen according to ASTM D-412 on an instron model 5569 at a pull rate of 50 mm/min; and/or

(b) Has an elongation at break of at least 10% as measured using a dog bone specimen on an instron model 5569 at a pull rate of 50 mm/min according to ASTM D-412.

29. An article comprising the substrate of any one of the preceding aspects 27 or 28 and a second substrate, wherein the coating composition is positioned between the surface of the substrate and a surface of the second substrate.

30. The article of the preceding aspect 29, wherein in the at least partially cured state, the composition:

(a) has a green strength of at least 0.1MPa, as measured by Instron model 5567 in tensile mode according to test method ASTM D1002-10; and/or

(b) After exposure to ambient temperature for 2 hours and heating at 175 ℃ for 30 minutes, has an adhesive strength of at least 10.0MPa, as measured by Instron model 5567 in tensile mode according to test method ASTM D1002-10.

31. A component comprising the substrate of any one of the preceding aspects 27 or 28.

32. The component of the preceding aspect 31, wherein the component comprises a three-dimensional component.

33. A vehicle comprising a substrate according to any of the preceding aspects 27 or 28, an article according to any of the preceding aspects 29 or 30, and/or an article according to any of the preceding aspects 31 or 32.

34. A method for forming a coating on a first substrate, the method comprising applying a coating composition according to any one of the preceding aspects 1 to 26 to at least a portion of a surface of the first substrate, and at least partially curing the coating composition under ambient or slightly thermal conditions.

35. The method of the preceding aspect 34, further comprising exposing the composition to a temperature of at least 70 ℃.

36. The method of any one of the preceding aspects 34 or 35, further comprising contacting a surface of a second substrate with the coating composition such that the coating composition is positioned between the surface of the first substrate and the surface of the second substrate.

37. A method of forming an article, the method comprising extruding the coating composition of any of the preceding aspects 1-26 onto a substrate.

38. The method of the preceding aspect 37, wherein the extruding comprises three-dimensional printing.

39. The method of any one of the preceding aspects 37 or 38, further comprising combining and mixing the first component and the second component prior to extruding.

40. The method of any one of the preceding aspects 37-39, wherein the shaping comprises applying successive layers to build the article.

41. An article formed by the method of any one of the preceding aspects 37-40.

Examples of the invention

Example a: synthesis of carbodiimides in epoxy resins

1049.4g Desmodur W (commercially available from Cornstarch LLC) and 7.9g 1-methyl-1-oxo-phosphole (commercially available from Clariant Co.) were added to a3 liter 4-neck kettle equipped with a motor driven stainless steel stirring blade, a water cooled condenser, a nitrogen sparge and a heating mantle with a thermometer connected by a temperature feedback control device. The contents of the kettle were heated to 160 ℃ and held for 5 hours until the NCO equivalent weight was about 451 as measured by using Metrohm 888Titrando as described below. The reaction mixture was cooled to 100 ℃, and 486.1g of Epon 828 (commercially available from spain specialty chemicals) was added to the reaction mixture. 0.09g of dibutyltin dilaurate (commercially available from Air Products & Chemicals) and 155.2g of butanol were added to the reaction mixture at 100 ℃. The reaction mixture was kept at 100 ℃ until the NCO peak disappeared, as measured by infrared spectroscopy (IR spectrometer, ThermoScientific Nicolet iS5 FT-IR). 681.4g of Epon 828 was then added to the reaction mixture and held for 30 minutes. The weight average molecular weight (Mw) was 1776g/mol as determined by gel permeation chromatography using a Waters2695 separation module with a Waters 410 differential refractometer (RI detector) and polystyrene standards, Tetrahydrofuran (THF) was used as eluent at a flow rate of 1 ml/min and two PL gels were mixed with a C-column for separation.

Isocyanate equivalent weight was measured by titration by dissolving a sample of a size appropriate to weight 0.003x the theoretical isocyanate equivalent weight in 30mL of a solution of 20mL of dibutylamine and 980mL of either n-methylpyrrolidone. The mixture was then titrated with a titrant of isopropanol solution containing 0.2N HCl.

Example B: synthesis of carbodiimide in DINP

262.2g Desmodur W (commercially available from Corsaikow) and 2.0g 1-methyl-1-oxo-phosphole (commercially available from Clevelet) were added to a 1 liter 4-neck kettle equipped with a motor driven stainless steel stirring blade, a water cooled condenser, a nitrogen sparge and a heating mantle with a thermometer connected by a temperature feedback control device. The contents of the kettle were heated to 160 ℃ and held for 4 hours until the NCO equivalent weight was 461.9, as determined in example a. The reaction mixture was cooled to 100 ℃ and 121.1g DINP (diisononyl phthalate, commercially available from BASF) was added to the reaction mixture. 0.02g of dibutyltin dilaurate (commercially available from air chemical) and 37.6g of butanol were added to the reaction mixture at 100 ℃. The reaction mixture was kept at 100 ℃ until the NCO peak disappeared, as described in example a. Then 40g DINP was added to the reaction and held for 30 minutes. The weight average molecular weight was 2876g/mol as determined by the procedure described in example a.

Example C: synthesis of carbodiimide in DINP

262.2g Desmodur W (commercially available from Corsaikow) and 2.0g 1-methyl-1-oxo-phosphole (commercially available from Clevelet) were added to a 1 liter 4-neck kettle equipped with a motor driven stainless steel stirring blade, a water cooled condenser, a nitrogen sparge and a heating mantle with a thermometer connected by a temperature feedback control device. The contents of the kettle were heated to 160 ℃ and held for 4 hours until the NCO equivalent weight was 469.4, as determined as described in example a. The reaction mixture was cooled to 100 ℃, and 65.8DINP (diisononyl phthalate, commercially available from basf) was added to the reaction mixture. 0.02g of dibutyltin dilaurate (commercially available from air chemical) and 223.0g of dibutyltin dilaurate were mixed at 100 deg.CLBH-P2000 (available from Claraviri USA Limited)Commercially available from Cray Valley USA, LLC) was added to the reaction mixture. After 30 minutes at 100 ℃, 15.0g of butanol was added to the reaction mixture. The reaction mixture was kept at 100 ℃ until the NCO peak disappeared, as described in example a. 37.5g DINP was then added to the reaction and held for 30 minutes. The weight average molecular weight was 11986g/mol, as determined by the procedure described in example A.

Example D: synthesis of polycaprolactone diol-modified epoxy resin

948g of methylhexahydrophthalic anhydride ("MHHPA", commercially available from Dixie Chemical) and 4,054.7g of Epon 828 (bisphenol A diglycidyl ether epoxy resin, commercially available from Vast specialty Chemicals) were added to a 12 liter 4-neck kettle equipped with a motor-driven stainless steel stirring blade, a water-cooled condenser, a nitrogen blanket, and a heating mantle with a thermometer connected by a temperature feedback control device. The contents of the kettle were heated to 90 ℃ and held for 30 minutes. 2,064.0g of Capa 2077A (a polycaprolactone-based diol, commercially available from Pasteur group) was added and the reaction mixture was held at 90 ℃ for 30 minutes. 395.9g Epon 828 and 46.4g triphenylphosphine (available from Sigma Aldrich) were added and the mixture was exothermic and after this the mixture was heated to 120 ℃. The reaction mixture was kept at 120 ℃ until an acid value of less than 2mg KOH/g was achieved by titration using Metrohm 888Titrando and a 0.1N KOH in methanol solution as titration reagent. The reaction temperature was cooled to 80 ℃ and the resin was poured out of the kettle. The epoxy equivalent weight of this epoxy resin adduct was 424 g/epoxide as determined by titration using Metrohm 888Titrando and glacial acetic acid containing 0.1N perchloric acid. The weight average molecular weight was 3,670g/mol, as determined by the method described in example A. The epoxy resin adduct prepared by this procedure is referred to in the following examples as CAPA di-/MHHPA/Epon 828.

Example E: synthesis of polycaprolactone tetraol modified epoxy resin

1,038.6g of MHHPA and 4,439.3g of Epon 828 were added to a 12 liter 4-neck kettle equipped with a motor driven stainless steel stirring blade, a water cooled condenser, a nitrogen blanket, and a heating mantle with a thermometer connected by a temperature feedback control device. The contents of the kettle were heated to 90 ℃ and held for 30 minutes. 1,589.1g of Capa 4101 (polycaprolactone-based tetraol, commercially available from Pasteur group) was added and the reaction mixture was held at 90 ℃ for 30 minutes. 433.5g Epon 828 and 43.6g triphenylphosphine were added and the mixture was allowed to exotherm and after this the mixture was heated to 120 ℃. The reaction mixture was held at 120 ℃ until the acid number was less than 2mg KOH/g, as determined by the procedure described in example C. The reaction mixture was cooled to 80 ℃ and the resin was poured out of the kettle. The epoxy equivalent weight of this epoxy resin adduct was 412 grams per epoxide as determined by the method described in example C. The weight average molecular weight was 18,741g/mol, as determined by the procedure described in example A. The epoxy resin adduct prepared by this procedure is referred to in the following examples as CAPA tetra-/MHHPA/Epon 828.

Adhesive compositions-examples 1-9

The two-component adhesive compositions described below were prepared according to the following procedure, wherein all non-manual mixing was performed using a Speedmixer DAC600FVZ (commercially available from FlackTek Inc. In each example, the "resin" ingredients listed under "part a" in tables 1-3 were warmed to 60 ℃, and then combined and mixed at 2,350 revolutions per minute ("RPM") for 25 seconds. Then, the "filler" ingredients listed under part a in tables 1 and 2 were added and mixed at 2,350RPM for 25 seconds. The mixture was checked with a spatula and mixed manually. If necessary, high speed mixing is repeated to ensure homogeneity. In a separate container, all liquid ingredients listed under "part B" were combined and then all solid ingredients were combined and the ingredients were mixed at 2,350RPM for 15 seconds. The mixture was checked with a spatula and mixed manually. If necessary, high speed mixing is repeated to ensure homogeneity.

In examples 1 to 9, hot-dip galvanized (HDG) steel sheets (0.8 mm. times.25 mm. times.100 mm; "Test pieces") were available from ACT Test Board LLC (project No. 55538). The substrate was cleaned using an acetone wipe. A thin oil coating (Platinol B804/3 COW-1) was applied uniformly to the test piece in the bonding area. The adhesive composition of one of examples 1-9 was then applied to the size six oiled area of the combined test pieces. The length of the bonded area was 13mm, and the length of the unbonded area was 87 mm. Uniformity of bond thickness was ensured by the addition of 0.25mm glass spacer beads. The oiled side of another test strip was placed on the bonding area and spring-loaded clips (one on each side of the bond) were attached to hold the assembly together. The excess adhesive squeezed out was removed with a spatula. The bonded assembly was allowed to cure at ambient temperature for 2 hours. For each adhesive, three bonded assemblies were tested by lap shear (described below) and the three bonded assemblies were baked at 175 ℃ for 30 minutes. The baked samples were conditioned at ambient conditions for at least 16 hours prior to lap shear testing. The data are presented in tables 1 and 2. Each data point is the average of triplicate runs for each example and cure condition.

The lap shear test was performed by inserting the unbonded portion of the bonded assembly into a wedge action jig and pulling it apart in a tensile mode at a rate of 1 mm/min using an instron model 5567. The lap shear test was performed according to ASTM D1002-10, unless otherwise noted. Shear strength was calculated by the Blue Hill software package of instron. The data are reported in tables 1 and 2.

Open time was used to qualitatively assess how long the coating composition took to harden after uniformly mixing components a and B, where "hardening" refers to the point at which the coating composition was no longer deformable under manual pressure. Components a and B were mixed and held in plastic screw top cups at ambient temperature and humidity. The free flowing material is considered unhardened. A slightly to moderately resistant material that may deform and expand under slight manual force is considered to be slightly hardened. A material that cannot deform or expand and feels hard is considered to have completely hardened.

Rheological data were collected on an Anton-Paar MCR301 rheometer with parallel plates in rotating mode. The gap width was 500 μm. The viscosity was measured every 1 second for 71 seconds under a linear shear stress of 0 to 3,500 Pa. Viscosity data is reported as a function of shear stress.

Table 1: 2K adhesive compositions (examples 1-3) and curing under ambient conditions or after curing in a 2-step curing Process Lap shear strength of the adhesive

The data in table 1 shows the effect of including a carbodiimide in the adhesive composition on the lap shear strength of the adhesive after curing at ambient conditions or subsequent baking (i.e., a two-step curing process) at ambient conditions. Example 1 (comparative) contained no carbodiimide, whereas example 2 contained 10 wt% carbodiimide, based on the total weight of the composition, and example 3 contained 10 wt% carbodiimide and a phenolic curing agent (bisphenol a as phenolic acid), based on the total weight of the composition. These data indicate that the inclusion of a carbodiimide in the adhesive composition improves strength and that the strength can be further improved by the synergistic effect of the carbodiimide and the acid.

Table 2: 2K adhesive compositions (examples 4-9) and curing under ambient conditions or after curing in a 2-step curing Process Lap shear strength of the adhesive

The data in table 2 shows the effect of increasing the amount of carbodiimide resin in the adhesive composition on the lap shear strength of the adhesive after curing at ambient conditions or after curing at ambient conditions followed by baking. Increasing the amount of carbodiimide in the adhesive composition improves the lap shear strength of the adhesive after ambient cure (green strength) and ambient cure followed by baking (full bake). As shown in table 2, the maximum green strength (15 wt% carbodiimide, and 20 wt% based on the total weight of the composition) was achieved in examples 7 and 8, and the maximum lap shear strength (10 wt% carbodiimide, based on the total weight of the composition) of the adhesive exposed to full bake was achieved in example 6. In examples 4-9, the amount of bisphenol a in each composition was increased proportionally with the amount of carbodiimide in the composition, so as to match the hydroxyl equivalent weight of bisphenol a with the-N ═ C ═ N-equivalent weight of the carbodiimide.

Sealant compositions-examples 10-18

The sealant compositions described below were prepared according to the following procedure, wherein all non-manual mixing was performed using a Speedmixer DAC600FVZ (commercially available from FlackTek corporation).

In each example, the "resin" ingredients and "plasticizer" ingredients listed under part a in table 3 were combined and mixed at 2,350RPM for 10-15 seconds. The "filler" ingredients listed under part a in table 3 were then added and mixed at 2,350RPM for 10-15 seconds. The mixture was checked with a spatula and additional mixing time was given as necessary to ensure homogeneity. In a separate container, the "curing agent" ingredients and "plasticizer" ingredients listed under part B in table 3 were combined and mixed at 2,350RPM for 10-15 seconds. Then, the "filler" ingredients listed under part B in table 3 were then added and mixed at 2,350RPM for 10-15 seconds. The mixture was checked with a spatula and additional mixing time was given as necessary to ensure homogeneity. For each of examples 10-17, parts a and B were combined in the ratios shown in table 3 and then mixed at 2,350RPM for 15 seconds. Test specimens were prepared within five minutes of mixing (as described below).

For the PVC-based comparative example (example 18, table 4), Jayflex DINP, Santicizer 278 and Admex525 were combined and mixed at 2,350RPM for 5 seconds. The solids were then added and the mixture was mixed at 2,350RPM for 15 seconds. Mineral spirits and Nourybond were added and mixed at 2,350RPM for 15 seconds. The mixture was checked with a spatula and additional mixing time was given as necessary to ensure homogeneity.

In examples 10-17, the sealant composition was pulled down over a woven Teflon (Teflon) bake plate fixed to a 4 "x 12" steel plate with a 3mm thick pull-down bar. The sealant was baked in an electric oven at 80 ℃ for 30 minutes. As shown in fig. 1, the free film dog bone sample was allowed to cool and held at ambient conditions for at least 16 hours prior to die cutting into dog bones. The dog bone sample was pulled (the clamps clamped the ends of the sample 10mm) over an instron model 5567 at a pull rate of 50 mm/min and a grip distance of 30 mm. Five dog bones were tested for each sealant and the average of the five dog bones was reported. The elongation (%) and the maximum load (MPa) were determined from a plot of tensile stress versus strain. The data are reported in table 3.

The data in table 3 shows the effect of increasing acid functionality (i.e., crosslink density) (example 11) and increasing amine chain length (i.e., flexibility) compared to comparative example 10 (example 12, which contains long chain length amines) and example 13, which contains both short chain length amines and long chain length amines), example 14 is not cured, making it impossible to measure maximum load or elongation, and shows that the carbodiimide is critical to cure and cannot be replaced by amine-or acid-reactive materials, such as epoxy resins example 15-17 shows that cure can be achieved with amine curing agents comparative example 18 uses PVC chemistry and demonstrates that the carbodiimide-containing compositions of the invention (examples 10-13 and 15-17) when cured by a two-step curing process produce sealants with improved strength and elongation.

Table 3: examples of 2K carbodiimide-based sealants.

Table 3: comparative examples of PVC sealants showing properties after 30 minutes baking at 80 ℃.

It will be appreciated by persons skilled in the art that numerous modifications and variations are possible in light of the above disclosure without departing from the broad inventive concept thereof as described and illustrated herein. It should be understood, therefore, that the foregoing disclosure is merely illustrative of various exemplary aspects of the application and that numerous modifications and variations within the spirit and scope of the application and appended claims may be readily made by those skilled in the art.