Surface-resistant adhesive

Abstract

The present disclosure provides a composition comprising a curable resin, a curing agent, and a surface modifier (such as a reactive siloxane, a reactive fluoro compound, or a mixture thereof). The composition is resistant to various contaminants (such as silicones) typically found on the surface of a substrate, and therefore can adhere to substrates having such contaminants on their surface, providing improved adhesive performance.

Description

[Technical field]

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS This application claims the benefit of U.S. Provisional Patent Application No. 63 / 315,218, filed March 1, 2022, the entire contents of which are expressly incorporated herein by reference.

[0002] STATEMENT REGARDING FEDERALLY SPONSORED RESEARCH OR DEVELOPMENT This invention was made with United States Government support under Cooperative Agreement No. W911W6-13-2-0004 awarded by the Department of Defense Research, Development and Engineering Command (DOD-Army-AMC). The United States Government has certain rights in this invention.

[0003] The present disclosure relates generally to compositions for use as adhesives, sealants, or coatings that have a high degree of resistance to a variety of contaminants typically found on the surface of a substrate. Specifically, the present disclosure relates to compositions that include a curable resin, a curing agent, and a surface modifier selected from reactive siloxanes, reactive fluoro compounds, and mixtures thereof. [Background technology]

[0004] Since adhesives and sealants must function via surface adhesion, the nature and condition of the substrate surface is critical to the success of any joining or sealing operation. One of the most important parameters is surface cleanliness, or the absence of contaminants that may impair adhesion.

[0005] One such known contaminant is silicone. Silicone is an unusual material because it prevents the formation of a reliable bond. Silicone has a low surface energy, which makes it extremely wet to most surfaces. As a result, silicone-based adhesives and sealants exhibit a high degree of wetting and adhesion on most practical surfaces. Certain silicone materials are even used as adhesion promoters in many formulations. However, problems can arise when silicone is present on a substrate surface (either liquid or solid). Silicone has a low surface energy, which causes other adhesives, sealants, or coatings to not wet or bond to the silicone surface. The presence of silicone on a substrate creates a "weak boundary layer" that prevents direct contact between the adhesive or sealant and the substrate, which can cause adhesion failure. Silicone contamination problems are not limited to adhesives and sealants. Even trace amounts of silicone can cause "fish eyes," separation, and loss of adhesion in primers, paints, or other coatings.

[0006] There are many sources of silicone contamination, including release agents, tapes, lubricants, and other silicone adhesives and sealants. Even when silicone is present in such small amounts that it is difficult to detect, its presence can ruin other adhesive and coating systems. Direct physical contact with materials or equipment can also spread silicone contamination, since many creams, cosmetics, hair products, antiperspirants, and some eyeglass cleaning tissues contain silicone. The high volatility of certain silicone-containing compounds can also promote cross-contamination of mating surfaces, even without direct contact with the surfaces. For example, serious coating problems have arisen in auto-finishing operations, where silicone release agents used in one part of the plant can be delivered through air ducts to surfaces being painted in other parts of the plant.

[0007] Cleaning silicone-contaminated substrates using a solvent wipe generally results in improved subsequent bond performance, but rarely returns performance to baseline.

[0008] Grit blasting may be considered a promising method for cleaning silicone-contaminated surfaces. However, the blasting media may pick up silicone contamination and transmit it to other parts awaiting cleaning. If a strict sequence of solvent cleaning, then blasting, then another solvent cleaning is not followed, the contamination may penetrate deeper into the substrate and become much more difficult to remove, such that bond strength may appear adequate initially but may degrade with use.

[0009] CO2 jet spraying has also been considered for large surfaces such as solar cells. Jet spraying appears to be successful in achieving a visually clean surface, although some silicone is likely to remain, as it is partially soluble in CO2. Other known surface treatments to increase surface free energy include chemical / acid treatments, flame treatments, and plasma / corona treatments. However, weak boundary layers remain a concern, so cleaning or degreasing is still recommended as a surface pretreatment.

[0010] Therefore, there is a need to further improve on the state of the art by utilizing new adhesives or sealants that are silicone resistant and thus capable of providing reliable bonds even in the presence of silicone contaminants with minimal or no surface pretreatment. Summary of the Invention

[0011] The present disclosure generally provides compositions for use as adhesives, sealants, or coatings that include (a) a curable resin; (b) a curing agent; and (c) a surface modifier selected from reactive siloxanes, reactive fluoro compounds, and mixtures thereof.

[0012] The present disclosure also provides a laminate structure comprising a first substrate bonded to a second substrate and a cured structural adhesive film between the first substrate and the second substrate, the structural adhesive film being formed from a composition of the present disclosure. The laminate structure may be used in automotive and aerospace applications. [Brief description of the drawings]

[0013] [Figure 1] 1 shows lap shear strength of adhesives according to the present disclosure and control adhesives at room temperature. [Diagram 2] 1 shows lap shear strength of adhesives according to the present disclosure and control adhesives on contaminated (hatched bars) and non-contaminated composite adherends (solid bars) at high (ETD) and low (LT) temperatures. [Diagram 3] 1 shows the strain energy release rate (G1c) values ​​of adhesives according to the present disclosure and control adhesives on contaminated (hatched bars) and non-contaminated CFRP substrates (solid bars). DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0014] The present disclosure generally provides a composition comprising: (a) a curable resin; (b) a curing agent; and (c) a surface modifier selected from the group consisting of reactive siloxanes, reactive fluoro compounds, and mixtures thereof. Contaminants typically found on the surface of a substrate (such as silicones) are known to substantially degrade the adhesive bonding ability between the composition and the surface, but it has surprisingly been found that surface modifiers have the ability to modify the surface properties of the composition to make it chemically compatible with the contaminants. Specifically, the surface modifiers reduce the surface energy of the composition, so that it is less attractive than the force of attraction between the composition and the contaminated surface, allowing it to spread and come into intimate contact with the surface, thereby increasing the bond strength between the composition and the surface.

[0015] The following terms shall have the following meanings:

[0016] The term "surface modifier" refers to a surface active material in the composition that tends to appear on the surface of the composition, thereby changing the properties of the surface of the composition.For example, the surface modifier disclosed herein creates a hydrophobic surface, thereby controlling the compatibility of the composition with a wide variety of contaminants (such as silicones) that are typically found on the surface of the substrate to which the composition may be applied.

[0017] The term "(meth)acrylic" may mean acrylic or methacrylic, "(meth)acryloyl" may mean acryloyl or methacryloyl, and "(meth)acrylate" may mean acrylate or methacrylate. Furthermore, "acrylic resin" may mean a resin obtained by polymerizing monomer components including at least one type of (meth)acrylic monomer.

[0018] The term "perfluoro group" refers to a hydrocarbon group in which all hydrogen atoms bonded to carbon atoms are replaced with fluorine atoms. In some cases, the perfluoro group may contain an ether linkage. For example, the perfluoro group may be a perfluoroalkyl group having 1 to 14 carbon atoms, or 1 to 6 carbon atoms, or 1 to 3 carbon atoms, or a perfluoroalkylene group having 2 to 12 carbon atoms, or 2 to 6 carbon atoms. In some embodiments, the perfluoro group has the formula: [ka]

[0046] In the formula, L P1 represents a single bond, or a linking group having an alkyl group having 2 to 36 carbon atoms or 2 to 18 carbon atoms, which may be substituted with a halogen atom, or a linking group containing an oxygen atom in the alkyl group chain; L P2represents a single bond, or an alkyl group having 1 to 12 carbon atoms, or 1 to 6 carbon atoms, or 1 to 3 carbon atoms, or an alkenyl group having 2 to 12 carbon atoms, or 2 to 6 carbon atoms, or 2 or 3 carbon atoms, or an alkynyl group having 2 to 12 carbon atoms, or 2 to 6 carbon atoms, or 2 or 3 carbon atoms, or an aralkyl group having 7 to 15 carbon atoms, or 7 to 11 carbon atoms, or an aryl group having 6 to 14 carbon atoms, or 6 to 10 carbon atoms, or a hydroxyl group, or an alkoxy group having 1 to 6 carbon atoms, or 1 to 4 carbon atoms; R P1 represents a hydrogen atom, an alkyl group having 1 to 12 carbon atoms (eg, 1 to 6 carbon atoms or 1 to 3 carbon atoms), or a halogen atom (eg, a fluorine atom).

[0019] The term "comprising" and its derivatives are not intended to exclude the presence of any additional component, step, or procedure, whether or not disclosed herein. For the avoidance of doubt, all compositions claimed herein through the use of the term "comprising" may include any additional additive or compound, unless stated to the contrary. In contrast, "consisting essentially of" means The term "consisting of," when used herein, excludes any other component, step, or procedure from the scope of any succeeding recitation, except those that are not essential to operability. The term "consisting of," when used, excludes any component, step, or procedure not specifically recited or listed. The term "or," unless otherwise stated, refers to the listed members individually or in any combination.

[0020] The articles "a" and "an" are used herein to refer to one or to more than one (i.e., to at least one) of the grammatical object of the article. By way of example, "an epoxy resin" means one epoxy resin or more than one epoxy resin.

[0021] The phrases "in one embodiment," "according to one embodiment," and the like generally mean that the particular feature, structure, or characteristic that follows the phrase is included in at least one aspect of the present disclosure, and may be included in multiple embodiments of the present disclosure. Importantly, such phrases do not necessarily refer to the same embodiment.

[0022] When a statement in this specification states that an ingredient or feature "may," "can," "could," or "might" be included or have a property, it does not require that the particular ingredient or feature be included or have that property.

[0023] The term "about," as used herein, allows for a certain degree of variation in a value or range, for example, the degree of variation may be within 10%, within 5%, or within 1% of a stated value or a stated range limit.

[0024] Values ​​expressed in range format are to be interpreted in a flexible manner to include not only the numbers expressly recited as the limits of the range, but also all of the individual numbers or subranges subsumed within that range, as if each number and subrange were expressly recited. For example, a range (such as 1 to 6) shall be considered to have specifically disclosed subranges (such as 1 to 3, 2 to 4, 3 to 6, etc.) as well as individual numbers within that range (e.g., 1, 2, 3, 4, 5, and 6). This applies regardless of the breadth of the range.

[0025] The terms "preferred" and "preferably" refer to embodiments that may provide certain benefits, under certain circumstances, while other embodiments may also be preferred, under the same or other circumstances. Furthermore, the recitation of one or more preferred embodiments does not imply that other embodiments are not useful, and is not intended to exclude other embodiments from the scope of the present disclosure.

[0026] According to one embodiment, the present disclosure provides a composition generally comprising: (a) a curable resin; (b) a curing agent; and (c) a surface modifier selected from the group consisting of reactive siloxanes, reactive fluoro compounds, and mixtures thereof. In some embodiments, the composition is an adhesive (e.g., a structural adhesive) or a sealant or coating.

[0027] In one embodiment, the curable resin may be an epoxy resin, an acrylic resin, a polyurethane / polyurea resin, or a mixture thereof. In one particular embodiment, the curable resin is an epoxy resin.

[0028] Generally, any epoxy-containing compound is suitable for use as an epoxy resin in the present disclosure, such as those epoxy-containing compounds disclosed in U.S. Pat. No. 5,476,748, which is incorporated herein by reference in its entirety. According to one embodiment, the epoxy resin is selected from difunctional epoxy resins (thus having two epoxide groups), trifunctional epoxy resins (thus having three epoxide groups), tetrafunctional epoxy resins (thus having four epoxide groups), and mixtures thereof.

[0029] Illustrative non-limiting examples of difunctional epoxy resins are bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, tetrabromobisphenol A diglycidyl ether, propylene glycol diglycidyl ether, butylene glycol diglycidyl ether, ethylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, cyclohexanedimethanol diglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, polytetramethylene glycol diglycidyl ether, resorcinol diglycidyl ether, neopentyl glycol diglycidyl ether, bisphenol A polyethylene glycol diglycidyl ether, bisphenol A polypropylene glycol diglycidyl ether, 3,4-epoxycyclohexylmethyl carboxylate, hexahydrophthalic acid diglycidyl ester, methyltetrahydrophthalic acid diglycidyl ester, and mixtures thereof. In some embodiments, the difunctional epoxy resin includes, but is not limited to, p-tertiary butylphenol glycidyl ether, cresyl glycidyl ether, 2-ethylhexyl glycidyl ether, and C8-C 14 It may be modified with a monofunctional reactive diluent, such as a glycidyl ether.

[0030] Illustrative non-limiting examples of trifunctional epoxy resins include those based on bisphenol F, bisphenol A (optionally brominated), phenol and cresol epoxy novolacs, glycidyl ethers of phenol-aldehyde adducts, aromatic epoxy resins, dialiphatic triglycidyl ethers, aliphatic polyglycidyl ethers, epoxidized olefins, brominated resins, aromatic glycidyl amines, heterocyclic glycidyl imidines and amides, glycidyl ethers, fluorinated epoxy resins. Specific examples include triglycidyl ethers of para-aminophenol, triglycidyl ethers of meta-aminophenol, dicyclopentadiene-based epoxy resins, N,N,O-triglycidyl-4-amino-m- or -5-amino-o-cresol type epoxy resins, and 1,1,1-(triglycidyloxyphenyl)methane type epoxy resins.

[0031] Illustrative non-limiting examples of tetrafunctional epoxy resins are N,N,N',N'-tetraglycidylmethylenedianiline, N,N,N',N'-tetraglycidyl-m-xylylenediamine, tetraglycidyldiaminodiphenylmethane, sorbitol polyglycidyl ether, pentaerythritol tetraglycidyl ether, tetraglycidyl bisaminomethylcyclohexane, and tetraglycidyl glycoluril.

[0032] Examples of commercially available epoxy resins that may be used include, but are not limited to, ARALDITE® PY306 epoxy resin (unmodified bisphenol-F based liquid epoxy resin), ARALDITE® MY721 epoxy resin (tetrafunctional epoxy resin based on methylene dianiline), ARALDITE® MY0510 epoxy resin (trifunctional epoxy resin based on para-aminophenol), ARALDITE® MY0610 epoxy resin (trifunctional epoxy resin based on meta-aminophenol), ARALDITE® GY6005 epoxy resin (bisphenol-A based liquid epoxy resin modified with a monofunctional reactive diluent), ARALDITE® 6010 epoxy resin (bisphenol-A based liquid epoxy resin), ARALDITE® MY06010 epoxy resin (trifunctional epoxy resin based on meta-aminophenol), ARALDITE® GY285 epoxy resin (unmodified Bisphenol-F based liquid epoxy resins), ARALDITE® EPN 1138, 1139, and 1180 epoxy resins (epoxy phenol novolac resins), ARALDITE® ECN 1273 and 9611 epoxy resins (epoxy cresol novolac resins), ARALDITE® GY289 epoxy resin (epoxy phenol novolac resin), ARALDITE® PY307-1 epoxy resin (epoxy phenol novolac resin), and mixtures thereof.

[0033] In one embodiment, the amount of epoxy resin present in the composition may be from about 10 wt.% to about 90 wt.%, or from about 20 wt.% to about 75 wt.%, or from about 30 wt.% to about 60 wt.%, or from about 40 wt.% to about 50 wt.% based on the total weight of the composition. In another embodiment, the amount of epoxy resin present in the composition may be from about 50 wt.% to about 95 wt.%, or from about 65 wt.% to about 90 wt.% based on the total weight of the composition.

[0034] According to another embodiment, the curable resin is an acrylic resin. The acrylic resin is a resin obtained by copolymerizing at least one (meth)acrylic acid alkyl ester monomer (a1) as a main component and at least one functional group-containing monomer (a2) and optionally at least one other copolymerizable monomer (a3) ​​as necessary.

[0035] In one embodiment, the (meth)acrylic acid alkyl ester monomer (a1) is a monomer in which the number of carbon atoms in the alkyl group is from 1 to 20, or from 1 to 12, or from 1 to 8, or even from 4 to 8. Specific examples of (a1) include, but are not limited to, methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, iso-butyl (meth)acrylate, tert-butyl (meth)acrylate, n-propyl (meth)acrylate, n-hexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, n-octyl (meth)acrylate, iso-octyl acrylate, iso-decyl (meth)acrylate, lauryl (meth)acrylate, cetyl (meth)acrylate, stearyl (meth)acrylate, iso-stearyl acrylate, and mixtures thereof.

[0036] In some embodiments, the content of the (meth)acrylic acid alkyl ester monomer (a1) in the comonomer component may be about 10 to 100% by weight, or about 20 to 95% by weight, or about 40 to 95% by weight, or about 60 to 95% by weight, based on the total weight of the comonomer component.

[0037] Examples of functional group-containing monomers (a2) include, but are not limited to, hydroxyl group-containing monomers, carboxyl group-containing monomers, amino group-containing monomers, acetoacetyl group-containing monomers, isocyanate group-containing monomers, glycidyl group-containing monomers, and mixtures thereof. In some embodiments, hydroxyl group-containing monomers and carboxyl group-containing monomers are preferred.

[0038] Examples of hydroxyl group-containing monomers include, but are not limited to, hydroxyalkyl esters of acrylic acid (such as hydroxyethyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 5-hydroxypentyl (meth)acrylate, 6-hydroxyhexyl (meth)acrylate, and 8-hydroxyoctyl (meth)acrylate); caprolactone-modified monomers (such as caprolactone-modified 2-hydroxyethyl (meth)acrylate); oxyalkylene-modified monomers (such as diethylene glycol (meth)acrylate and polyethylene glycol (meth)acrylate); monomers containing primary hydroxyl groups (such as 2-acryloyloxyethyl-2-hydroxyethyl phthalate); monomers containing secondary hydroxyl groups (such as 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl(meth)acrylate, and 3-chloro-2-hydroxypropyl(meth)acrylate; and monomers containing tertiary hydroxyl groups, such as 2,2-dimethyl-2-hydroxyethyl(meth)acrylate.

[0039] Examples of carboxyl group-containing monomers include, but are not limited to, (meth)acrylic acid, acrylic acid dimer, crotonic acid, maleic acid, maleic anhydride, fumaric acid, citraconic acid, glutaconic acid, itaconic acid, acrylamido-N-glycolic acid, and cinnamic acid.

[0040] Examples of amino group-containing monomers include tert-butylaminoethyl (meth)acrylate, ethylaminoethyl (meth)acrylate, dimethylaminoethyl (meth)acrylate, and diethylaminoethyl (meth)acrylate.

[0041] Examples of acetoacetyl group-containing monomers include 2-(acetoacetoxy)ethyl (meth)acrylate and allyl acetoacetate.

[0042] Examples of the isocyanate group-containing monomer include 2-acryloyloxyethyl isocyanate, 2-methacryloyloxyethyl isocyanate, and alkylene oxide adducts thereof.

[0043] Examples of glycidyl group-containing monomers include glycidyl (meth)acrylate and allyl glycidyl (meth)acrylate.

[0044] The content of the functional group-containing monomer (a2) in the comonomer component may be about 0.01 to 30% by weight, or about 0.05 to 10% by weight, or about 0.1 to 10% by weight, or about 2 to 5% by weight, based on the total weight of the comonomer components.

[0045] Examples of other copolymerizable monomers (a3) ​​include, but are not limited to, (meth)acrylate compounds containing an alicyclic structure (such as cyclohexyl (meth)acrylate and isobornyl (meth)acrylate); monomers containing one aromatic ring (such as phenyl (meth)acrylate, benzyl (meth)acrylate, phenoxyethyl (meth)acrylate, phenyldiethylene glycol (meth)acrylate, 2-hydroxy-3-phenoxypropyl (meth)acrylate, styrene, and α-methylstyrene); (meth)acrylic acid ester monomers containing a biphenyloxy structure (such as biphenyloxyethyl (meth)acrylate); (meth)acrylamide monomers (ethoxymethyl (meth)acrylamide, n-butoxymethyl (meth)acrylamide, (meth)acryloylmorpholine, dimethyl (meth)acrylamide, diethyl (meth)acrylamide, and (meth)acrylamides). monomers containing alkoxy or oxyalkylene groups, such as 2-methoxyethyl (meth)acrylate, 2-ethoxyethyl (meth)acrylate, methoxydiethylene glycol (meth)acrylate, ethoxydiethylene glycol (meth)acrylate, methoxypolyethylene glycol (meth)acrylate, and polypropylene glycol mono(meth)acrylate; and acrylonitrile, methacrylonitrile, vinyl acetate, vinyl propionate, vinyl stearate, vinyl chloride, vinylidene chloride, alkyl vinyl ethers, vinyl toluene, vinyl pyridine, vinyl pyrrolidone, itaconic acid dialkyl esters, fumaric acid dialkyl esters, allyl alcohol, acrylic chloride, methyl vinyl ketone, allyl trimethyl ammonium chloride, dimethyl allyl vinyl ketone, and mixtures thereof.

[0046] The content of other copolymerizable monomers (a3) ​​in the comonomer component is Based on the total weight, it may be about 0 to 40% by weight, or about 0 to 30% by weight, or about 0 to 25% by weight.

[0047] The acrylic resin can be produced by polymerizing (such as solution polymerization) an (meth)acrylic acid alkyl ester monomer (a1), a functional group-containing monomer (a2), and, if necessary, other copolymerizable monomers (a3) ​​as comonomer components.

[0048] For example, solution polymerization can be carried out by mixing monomer components including the (meth)acrylic acid alkyl ester monomer (a1), the functional group-containing monomer (a2), and other copolymerizable monomers (a3) ​​and a polymerization initiator with an organic solvent or dropping them dropwise into the organic solvent, and polymerizing the monomer components under reflux conditions or at a temperature of about 50 to 98° C. for about 0.1 to 20 hours.

[0049] Specific examples of the polymerization initiator include typical radical polymerization initiators such as azo-type polymerization initiators (e.g., azobisisobutyronitrile and azobisdimethylvaleronitrile) and peroxide-type polymerization initiators (e.g., benzoyl peroxide, lauroyl peroxide, di-tert-butyl peroxide, and cumene hydroperoxide).

[0050] In some embodiments, the weight average molecular weight of the acrylic resin can be about 100,000 to 5,000,000 daltons, or about 300,000 to 1,500,000 daltons, or about 500,000 to 900,000 daltons.

[0051] In some embodiments, the amount of acrylic resin present in the composition may be from about 10 wt.% to about 90 wt.%, or from about 20 wt.% to about 75 wt.%, or from about 30 wt.% to about 60 wt.%, or from about 40 wt.% to about 50 wt.% based on the total weight of the composition. In other embodiments, the amount of acrylic resin present in the composition may be from about 50 wt.% to about 95 wt.%, or from about 65 wt.% to about 90 wt.% based on the total weight of the composition.

[0052] In another embodiment, the curable resin is a polyurethane / polyurea resin having a urea bond (-R-NH-CO-NH-) in the molecular chain. Any known polyurethane / polyurea resin can be used. In one embodiment, the polyurethane / polyurea resin is a reaction product of (A) a urethane prepolymer having an isocyanate group at the end of the molecule, (B) a polyamine compound having at least two amino groups in the molecule, and (C) a compound having one group in the molecule that can react with an isocyanate group.

[0053] In one embodiment, (A) the urethane prepolymer having an isocyanate group in the molecule is a reaction product of (A1) at least one polyol compound having at least two hydroxyl groups (such as polycarbonate polyol, polyether polyol, polyester polyol, and polycaprolactone polyol) and (A2) a diisocyanate compound having two isocyanate groups in the molecule.

[0054] The number of hydroxyl groups contained in one molecule of the polyol compound (A1) may be 2 to 6 or 2 to 3. Furthermore, the polyether polyols, polyester polyols, polycarbonate polyols, and polycaprolactone polyols may be used alone or in combination of two or more thereof.

[0055] Examples of polycarbonate polyols include, but are not limited to, ethylene glycol, 1,2-propanediol, 1,3-propanediol, 2-methyl-1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, Mention may be made of polycarbonate polyols obtained by phosgenating at least one low molecular weight polyol such as 1,5-pentanediol, 1,6-hexanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 3-methyl-1,5-pentanediol, 2-ethyl-4-butyl-1,3-propanediol, diethylene glycol, dipropylene glycol, neopentyl glycol, cyclohexane-1,4-diol, cyclohexane-1,4-dimethanol, dimer acid diol, ethylene oxide or propylene oxide adduct of bisphenol A, bis(β-hydroxyethyl)benzene, xylylene glycol, glycerin, trimethylolpropane, or pentaerythritol, or by transesterifying a low molecular weight carbonate such as ethylene carbonate, diethyl carbonate, or diphenyl carbonate. The number average molecular weight of the polycarbonate polyol can be about 400 to 2,000 g / mol, or about 500 to 1,500 g / mol, or about 600 to 1,200 g / mol.

[0056] Examples of polyether polyols include, but are not limited to, polyether polyols obtained from the reaction between a compound having at least two active hydrogen-containing groups in the molecule and an alkylene oxide, polymer polyols which are modified products of polyether polyol compounds, urethane-modified polyether polyols, and polyether ester copolymer polyols.

[0057] Examples of compounds having at least two active hydrogen-containing groups in the molecule include polyols such as glycols and glycerin having at least one hydroxyl group in the molecule, exemplified by water, ethylene glycol, propylene glycol, butanediol, glycerin, trimethylolpropane, hexanetriol, triethanolamine, diglycerin, pentaerythrytol, trimethylolpropane, hexanetriol, and mixtures thereof.

[0058] Examples of such alkylene oxides include ethylene oxide, propylene oxide, and cyclic ether compounds such as tetrahydrofuran, and mixtures thereof.

[0059] The number average molecular weight of the polyether polyol can be about 400 to 2,000 g / mol, or about 500 to 1,500 g / mol, or about 600 to 1,200 g / mol.

[0060] Examples of polyester polyols include, but are not limited to, polyester polyols obtained from the condensation reaction between polyhydric alcohols and polybasic acids. Examples of the polyhydric alcohols include ethylene glycol, 1,2-propanediol, 1,3-butanediol, 1,4-butanediol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, 3,3'-dimethylolheptane, 1,4-cyclohexanedimethanol, neopentyl glycol, 3,3-bis(hydroxymethyl)heptane, diethylene glycol, dipropylene glycol, glycerin, trimethylolpropane, and mixtures thereof. Examples of the polybasic acids include succinic acid, adipic acid, azelaic acid, sebacic acid, dodecanedicarboxylic acid, cyclopentanedicarboxylic acid, cyclohexanedicarboxylic acid, orthophthalic acid, isophthalic acid, terephthalic acid, naphthalenedicarboxylic acid, and mixtures thereof.

[0061] The number average molecular weight of the polyester polyol can be about 400 to 2,000 g / mol, or about 500 to 1,500 g / mol, or about 600 to 1,200 g / mol.

[0062] Polycaprolactone polyol is a chemical compound obtained by ring-opening polymerization of ε-caprolactone. The number average molecular weight of the polycaprolactone polyol may be about 400 to 2,000 g / mol, about 500 to 1,500 g / mol, or about 600 to 1,200 g / mol.

[0063] In one embodiment, the diisocyanate compound (A2) may be an aliphatic diisocyanate compound, an alicyclic diisocyanate compound, an aromatic diisocyanate compound, or a mixture thereof. In some embodiments, among these, it may be preferable to use an aliphatic diisocyanate compound and / or an alicyclic diisocyanate compound, and the aliphatic diisocyanate compound accounts for about 30% by weight to about 100% by weight or about 50% by weight to about 100% by weight of the total weight of the component (A2).

[0064] Examples of diisocyanate compounds include, but are not limited to, aliphatic diisocyanate compounds (such as tetramethylene-1,4-diisocyanate, hexamethylene-1,6-diisocyanate, octamethylene-1,8-diisocyanate, and 2,2,4-trimethylhexane-1,6-diisocyanate); alicyclic diisocyanate compounds (such as cyclobutane-1,3-diisocyanate, cyclohexane-1,3-diisocyanate, cyclohexane-1,4-diisocyanate, 2,4-methylcyclohexyl diisocyanate, 2,6-methylcyclohexyl diisocyanate, isophorone diisocyanate, norbornene diisocyanate, and the like). isocyanates, isomeric mixtures of 4,4'-methylenebis(cyclohexyl isocyanate), hexahydrotoluene-2,4-diisocyanate, hexahydrotoluene-2,6-diisocyanate, hexahydrophenylene-1,3-diisocyanate, hexahydrophenylene-1,4-diisocyanate, 1,9-diisocyanato-5-methylnonane, 1,1-bis(isocyanatomethyl)cyclohexane, 2-isocyanato-4-[(4-isocyanatocyclohexyl)methyl]-1-methylcyclohexane, 2-(3-isocyanatopropyl)cyclohexyl isocyanate, and norbornane diisocyanate;and aromatic diisocyanate compounds (phenylcyclohexylmethane diisocyanate, isomeric mixture of 4,4'-methylene bis(phenylisocyanate), toluene-2,3-diisocyanate, toluene-2,4-diisocyanate, toluene-2,6-diisocyanate, phenylene-1,3-diisocyanate, phenylene-1,4-diisocyanate, 1,3-bis(isocyanatomethyl)benzene, xylylene diisocyanate, tetramethylxylylene diisocyanate, naphthalene diisocyanate, diphenyl ether diisocyanate, 1,3-diisocyanatomethylbenzene, 4,4'- Diisocyanato-3,3'-dimethoxy(1,1-biphenyl), 4,4'-diisocyanato-3,3'-dimethylbiphenyl, 1,2-diisocyanatobenzene, 1,4-bis(isocyanatomethyl)-2,3,5,6-tetrachlorobenzene, 2-dodecyl-1,3-diisocyanatobenzene, 1-isocyanato-4-[(2-isocyanatocyclohexyl)methyl]2-methylbenzene, 1-isocyanato-3-[(4-isocyanatophenyl)methyl]-2-methylbenzene, 4-[(2-isocyanatophenyl)oxy]phenyl isocyanate, and diphenylmethane diisocyanate. These compounds may be used alone or in combination of two or more.;

[0065] In one embodiment, the diisocyanate compounds include tetramethylene-1,4-diisocyanate, hexamethylene-1,6-diisocyanate, octamethylene-1,8-diisocyanate, 2,2,4-trimethylhexane-1,6-diisocyanate, cyclobutane-1,3-diisocyanate, cyclohexane-1,3-diisocyanate, cyclohexane-1,4-diisocyanate, 2,4-methylcyclohexyl diisocyanate, 2,6-methylcyclohexyl diisocyanate, isophorone diisocyanate, norbornane diisocyanate, isomeric mixtures of 4,4'-methylenebis(cyclohexyl isocyanate), hexahydrotoluene-2,4-diisocyanate, ... Examples of suitable isocyanates include hexahydrophenylene-2,6-diisocyanate, hexahydrophenylene-1,3-diisocyanate, hexahydrophenylene-1,4-diisocyanate, and mixtures thereof.

[0066] The polyamine compound (B) having at least two amino groups in the molecule may be a polyamine compound having at least two amino groups -NH2 or -NH(R), where R is an alkyl group (such as an alkyl group having 1 to 5 carbon atoms in the molecule). In some embodiments, the molecular weight of the polyamine compound having at least two amino groups is about 50 g / mol to about 300 g / mol, or about 50 g / mol to about 250 g / mol, or about 100 g / mol to about 220 g / mol.

[0067] Examples of the polyamine compound (B) include, but are not limited to, isophoronediamine, ethylenediamine, 1,2-diaminopropane, 1,3-diaminopropane, 1,2-diaminobutane, 1,3-diaminobutane, 1,4-diaminobutane, 1,5-diaminopentane, 1,6-diaminohexane, piperazine, N,N-bis-(2-aminoethyl)piperazine, bis-(4-aminocyclohexyl)methane, bis-(4-amino-3-butylcyclohexyl)methane, 1,2-diaminocyclohexane, 1,3-diamino and 1,4-diaminocyclohexane, norbornane diamine, hydrazine, dihydrazine adipate, phenylenediamine, 4,4'-diphenylmethanediamine, N,N'-diethylethylenediamine, N,N'-dimethylethylenediamine, N,N'-dipropylethylenediamine, N,N'-dibutylethylenediamine, N-methylethylenediamine, N-ethylethylenediamine, bis(hexamethylene)triamine, 1,2,5-pentanetriamine, and mixtures thereof.

[0068] To synthesize the polyurethane / polyurea resin, a compound (C) having one group capable of reacting with an isocyanate group in the molecule is also used. By using such a compound (C), a polyurethane / polyurea resin having a capped end of the molecular chain can be obtained. Examples of the group capable of reacting with an isocyanate group include an amino group, a hydroxyl group, a mercapto group, a carboxyl group, and an acid chloride group.

[0069] In one particular embodiment, the compound having one group in the molecule capable of reacting with an isocyanate group is represented by the formula (1): [ka] is a compound having the formula In the formula, R 1 , R 2 , R 3 , and R 4 are each independently an alkyl group having 1 to 4 carbon atoms; R 5 is an alkyl group having 1 to 10 carbon atoms or hydrogen, R 6 is an alkylene group having 1 to 20 carbon atoms or a polymethylene group having 3 to 20 carbon atoms, a is 0 or 1, and X is a group capable of reacting with an isocyanate group (such as an amino group or a hydroxy group). 1 ~R 4 is an alkyl group having 1 to 4 carbon atoms, so R 5 Even when R is hydrogen, 5 The nitrogen atom bonded to does not react with the isocyanate group due to the effect of steric hindrance. Examples of compounds represented by the above formula (1) include 1,2,2,6, These include 6-pentamethyl-4-hydroxypiperidine, 1,2,2,6,6-pentamethyl-4-aminopiperidine, 2,2,6,6-tetramethyl-4-hydroxypiperidine, 2,2,6,6-tetramethyl-4-aminopiperidine, 1,2,2,6,6-pentamethyl-4-aminomethylpiperidine, and 1,2,2,6,6-pentamethyl-4-aminobutylpiperidine.

[0070] In addition to the above compounds having the formula (1), common amines, alcohols, thiols, and carboxylic acids can also be used as compounds having one group in the molecule capable of reacting with an isocyanate group. For example, a compound having one group in the molecule capable of reacting with an isocyanate group can be represented by the formula (2): [ka] and In the formula, R 7 is an alkyl group having 1 to 20 carbon atoms, an aryl group, an aralkyl group, an alkyloxycarbonyl group, or hydrogen; R 8 is an alkyl group having 1 to 20 carbon atoms, an aryl group, an aralkyl group, or an ester group.

[0071] In one embodiment, R 7 is methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, pentyl, hexyl, heptyl, octyl, 1,1,3,3-tetramethylbutyl, phenyl, benzyl, 1,1-dimethylbenzyl, carboxymethyl, carboxyethyl, carboxypropyl, or hydrogen. 8 is a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a normal butyl group, a tert-butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a 1,1,3,3-tetramethylbutyl group, a phenyl group, a benzyl group, a 1,1-dimethylbenzyl group, a carboxymethyl group, a carboxyethyl group, or a carboxypropyl group.

[0072] In another embodiment, the compound having one group in the molecule capable of reacting with an isocyanate group is ZR 9 wherein R 9 is an alkyl group having 1 to 20 carbon atoms, an aryl group, an aralkyl group, or an alkyloxycarbonyl group, and Z is a hydroxyl group, a carboxyl group, or a thiol group. 9 is a methyl group, an ethyl group, a normal propyl group, an isopropyl group, a normal butyl group, a tert-butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a 1,1,3,3-tetramethylbutyl group, a phenyl group, a benzyl group, a 1,1-dimethylbenzyl group, a carboxymethyl group, a carboxyethyl group, or a carboxypropyl group.

[0073] Examples of the above compound (C) (i.e., a compound having one group in the molecule capable of reacting with an isocyanate group) include amines (methylamine, ethylamine, propylamine, isopropylamine, butylamine, tert-butylamine, pentylamine, hexylamine, heptylamine, 4-heptylamine, octylamine, 1,1-dipropylbutylamine, phenylamine, benzylamine, dimethylamine, diethylamine, dipropylamine, diisopropylamine, dibutylamine, di-tert-butylamine, dipentylamine, dihexylamine, diheptylamine, dioctylamine, methylethylamine, methylbutylamine, methylpentylamine, methylhexylamine, amine, methylheptylamine, methyloctylamine, ethylpropylamine, ethylbutylamine, ethylpentylamine, ethylhexylamine, ethylheptylamine, ethyloctylamine, propylbutylamine, isopropylbutylamine, propylpentylamine, propylhexylamine, propylheptylamine, and propyloctylamine; alcohols (methanol, ethanol, propanol, isopropanol, butanol, 2-butanol, tert-butyl alcohol, pentyl alcohol, hexyl alcohol, heptyl alcohol, octyl alcohol, nonyl alcohol, decanol, and 2-decanol); thiols (methane thiol, ethanethiol, 1-propanethiol, 2-propanethiol, 1-butanethiol, 2-butanethiol, propanethiol, hexanethiol, heptanethiol, octanethiol, dodecanethiol, 2-methyl-1-butanethiol, 2-methylpropanethiol, 3-methyl-2-butenethiol, 1,1-dimethylheptanethiol, cyclohexanethiol, cyclopentanethiol, benzenethiol, benzenemethanethiol, and 2,6-dimethylbenzenethiol; and carboxylic acids (acetic acid, propionic acid, butanoic acid, pentanoic acid, hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, and dodecanoic acid, etc.). Such compounds may be used alone or in combination of two or more.

[0074] The polyurethane / polyurea resin can be obtained by any method known to a person skilled in the art, such as by reacting the above components, optionally in the presence of an organic solvent, under an inert atmosphere at a temperature ranging from -10°C to 40°C for a certain period of time (such as 0.5 hours to 24 hours).

[0075] In some embodiments, the amount of polyurethane / polyurea resin present in the composition may be from about 10 wt.% to about 90 wt.%, or from about 20 wt.% to about 75 wt.%, or from about 30 wt.% to about 60 wt.%, or from about 40 wt.% to about 50 wt.% based on the total weight of the composition. In other embodiments, the amount of polyurethane / polyurea resin present in the composition may be from about 50 wt.% to about 95 wt.%, or from about 65 wt.% to about 90 wt.% based on the total weight of the composition.

[0076] In another embodiment, the curing agent is any chemical material(s) capable of curing the curable resin. Curing agents for the curable resin include, but are not limited to, aromatic amines, cyclic amines, aliphatic amines, alkylamines, polyetheramines (including polyetheramines that can be obtained from polypropylene oxide and / or polyethylene oxide), 9,9-bis(4-amino-3-chlorophenyl)fluorene (CAF), acid anhydrides, carboxylic acid amides, polyamides, polyphenols, cresol and phenol novolac resins, imidazoles, guanidines, substituted guanidines, substituted ureas, melamine resins, guanamine derivatives, tertiary amines, Lewis acid complexes (such as boron trifluoride and boron trichloride), and polymercaptans. Any epoxy-modified amine products, Mannich-modified products, and Michael-modified addition products of the above exemplary curing agents may also be used. All of the above-mentioned curing agents may be used alone or in any combination.

[0077] Examples of aromatic amines include, but are not limited to, 1,8 diaminonaphthalene, m-phenylenediamine, diethylenetoluenediamine, diaminodiphenylsulfone, diaminodiphenylmethane, diaminodiethyldimethyldiphenylmethane, 4,4'-methylenebis(2,6-diethylaniline), 4,4'-methylenebis(2-isopropyl-6-methylaniline), 4,4'-methylenebis(2,6-diisopropylaniline), 4,4'-[1,4-phenylenebis(1-methyl-ethylindene)]bisaniline, 4,4'-[1,3-phenylenebis(1-methyl-ethylindene)]bisaniline, 1,3-bis(3-aminophenoxy)benzene, bis-[4-(3-aminophenoxy)phenyl] ... Bis-[4-(4-aminophenoxy)phenyl]sulfone, bis-[4-(4-aminophenoxy)phenyl]sulfone, 2,2'-bis[4-(4-aminophenoxy)phenyl]propane, and bis(4-amino-2-chloro-3,5-diethylphenyl)methane. Additionally, aromatic amines may include heterocyclic polyfunctional amine adducts as disclosed in U.S. Patent Nos. 4,427,802 and 4,599,413, both of which are incorporated herein by reference in their entireties.

[0078] Examples of cyclic amines include, but are not limited to, bis(4-amino-3-methyldicyclohexyl)methane, diaminodicyclohexylmethane, bis(aminomethyl)cyclohexane, N-aminoethylpyrazine, 3,9-bis(3-aminopropyl)-2,4,8,10-tetraoxaspiro(5,5)undecane, m-xylylenediamine, isophoronediamine, menthene diamine, 1,4-bis(2-amino-2-methylpropyl)piperazine, N,N'-dimethylpiperazine, pyridine, picoline, 1,8-diazabicyclo[5,4,0]-7-undecene, benzylmethylamine, 2-(dimethylaminomethyl)-phenol, 2-methylimidazole, 2-phenylimidazole, and 2-ethyl-4-methylimidazole.

[0079] Examples of aliphatic amines include, but are not limited to, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, 3-(dimethylamino)propylamine, 3-(diethylamino)-propylamine, 3-(methylamino)propylamine, tris(2-aminoethyl)amine; 3-(2-ethylhexyloxy)propylamine, 3-ethoxypropylamine, 3-methoxypropylamine, 3-(dibutylamino)propylamine, and tetramethyl-ethylenediamine; ethylenediamine; 3,3'-iminobis(propylamine), N-methyl-3,3'-iminobis(propylamine); allylamine, diallylamine, triallylamine, polyoxypropylenediamine, and polyoxypropylenetriamine.

[0080] Examples of alkylamines include, but are not limited to, methylamine, ethylamine, propylamine, isopropylamine, butylamine, sec-butylamine, t-butylamine, n-octylamine, 2-ethylhexylamine, dimethylamine, diethylamine, dipropylamine, diisopropylamine, dibutylamine, di-sec-butylamine, di-t-butylamine, di-n-octylamine, and di-2-ethylhexylamine.

[0081] Examples of acid anhydrides include, but are not limited to, cyclohexane-1,2-dicarboxylic anhydride, 1-cyclohexene-1,2-dicarboxylic anhydride, 2-cyclohexene-1,2-dicarboxylic anhydride, 3-cyclohexene-1,2-dicarboxylic anhydride, 4-cyclohexene-1,2-dicarboxylic anhydride, 1-methyl-2-cyclohexene-1,2-dicarboxylic anhydride, 1-methyl-4-cyclohexene-1,2-dicarboxylic anhydride, 3-methyl-4-cyclohexene-1,2-dicarboxylic anhydride, 4-methyl-4-cyclohexene-1,2-dicarboxylic anhydride, dodecenyl succinic anhydride, succinic anhydride, 4-methyl-1-cyclo Hexene-1,2-dicarboxylic anhydride, phthalic anhydride, hexahydrophthalic anhydride, methylnadic anhydride, dodecenylsuccinic anhydride, tetrahydrophthalic anhydride, maleic anhydride, pyromellitic dianhydride, trimellitic anhydride, benzophenonetetracarboxylic dianhydride, bicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic anhydride, methylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic anhydride, bicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic anhydride, dichloromaleic anhydride, chlorendic anhydride, tetrachlorophthalic anhydride, and any derivatives or adducts thereof.

[0082] Examples of imidazoles include, but are not limited to, imidazole, 1-methylimidazole, 2-methylimidazole, 2-ethylimidazole, 2-isopropylimidazole, 2-n-propylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 1-isopropyl-2-methylimidazole, 1-cyanoethyl 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-phenylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2-phenylimidazole, 2-phenyl-4,5-dihydroxymethylimidazole, 1,2-phenyl-4-methyl-5-hydroxymethylimidazole, 1-dodecyl-2-methylimidazole, and 1-cyanoethyl-2-phenyl-4,5-di(2-cyanoethoxy)methylimidazole.

[0083] Examples of substituted guanidines are methylguanidine, dimethylguanidine, trimethylguanidine, tetramethylguanidine, methylisobiguanidine, dimethylisobiguanidine, tetramethylisobiguanidine, hexamethylisobiguanidine, heptamethylisobiguanidine, and cyanoguanidine (dicyandiamide). Representatives of guanamine derivatives that may be mentioned are alkylated benzoguanamine resins, benzoguanamine resins, or methoxymethylethoxymethylbenzoguanamine. Substituted ureas may include p-chlorophenyl-N,N-dimethylurea (monuron), 3-phenyl-1,1-dimethylurea (fenuron), or 3,4-dichlorophenyl-N,N-dimethylurea (diuron).

[0084] Examples of tertiary amines include, but are not limited to, trimethylamine, tripropylamine, triisopropylamine, tributylamine, tri-sec-butylamine, tri-t-butylamine, tri-n-octylamine, N,N-dimethylaniline, N,N-dimethyl-benzylamine, pyridine, N-methylpiperidine, N-methylmorpholine, N,N-dimethylaminopyridine, derivatives of morpholine (bis(2-(2,6-dimethyl-4- Bis(2-(morpholino)ethyl)-(2-(4-morpholino)ethyl)amine, bis(2-(2,6-dimethyl-4-morpholino)ethyl)-(2-(2,6-diethyl-4-morpholino)ethyl)amine, tris(2-(4-morpholino)ethyl)amine, and tris(2-(4-morpholino)propyl)amine, diazabicyclooctane (DABCO), and heterocyclic compounds having an amidine bond (such as diazabicyclono).

[0085] In one embodiment, the curing agent is a polyfunctional amine. The term "polyfunctional amine" as used herein refers to an amine having at least two primary and / or secondary amino groups in the molecule. For example, the polyfunctional amine may be an aromatic polyfunctional amine having two amino groups attached to benzene in any one of ortho, meta, and para positions (such as phenylenediamine, xylylenediamine, 1,3,5-triaminobenzene, 1,2,4-triaminobenzene, and 3,5-diaminobenzoic acid), an aliphatic polyfunctional amine (such as ethylenediamine and propylenediamine), an alicyclic polyfunctional amine (such as 1,2-diaminocyclohexane, 1,4-diaminocyclohexane, piperazine, 1,3-bispiperidylpropane, and 4-aminomethylpiperazine), and the like. Such polyfunctional amines may be used alone or as a mixture.

[0086] Amine-epoxy adducts may also be used, which are well known in the art and are described, for example, in U.S. Pat. Nos. 3,756,984 and 4,066,626. Nos. 25, 4,268,656, 4,360,649, 4,542,202, 4,546,155, 5,134,239, 5,407,978, 5,543,486, 5,548,058, 5,430,112, 5,464,910, 5,439,977, 5,717,011, 5,733,954, 5,789,498, 5,798,399, and 5,801,218, each of which is incorporated herein by reference in its entirety. Such amine-epoxy adducts are the product of one or more amine compounds reacted with one or more epoxy compounds to a predetermined degree of polymerization. Preferably, the adducts are solids that are insoluble in the epoxy resin at room temperature but become soluble upon heating and function as accelerators to increase the cure rate. While any type of amine may be used (heterocyclic amines and / or amines containing at least one secondary nitrogen atom are preferred), imidazole compounds are particularly preferred. Exemplary imidazoles include 2-methylimidazole, 2,4-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, and the like. Other suitable amines include, but are not limited to, piperazine, piperidine, pyrazole, purine, and triazole. Any type of epoxy compound may be used as the starting material for the other adducts, including monofunctional and multifunctional epoxy compounds such as those previously described for the epoxy resin component.

[0087] In one embodiment, the composition of the present disclosure may include a curing agent in an amount of about 10 wt.% to about 60 wt.%, or about 20 wt.% to about 50 wt.%, or about 30 wt.% to about 50 wt.%, based on the total weight of the composition. In another embodiment, the composition of the present disclosure may include a curing agent in an amount of about 5 wt.% to about 50 wt.%, or about 10 wt.% to about 45 wt.%, or about 20 wt.% to about 40 wt.%, based on the total weight of the composition.

[0088] The composition also includes a surface modifier. In one embodiment, the surface modifier includes a reactive siloxane. The reactive siloxane is represented by the formula [ka] and any polymer, copolymer, or oligomer containing siloxane units in the backbone having the formula: a and R b are each independently hydrogen, alkyl, cycloalkyl, alkenyl, acyl, aryl, alkaryl, or aralkyl (having up to 100 carbon atoms or up to 20 carbon atoms), and x is the number of siloxane monomer units in the siloxane polymer, which comprises at least one reactive group on at least a portion of the siloxane monomer units that can chemically react with another reactive group on a different material (e.g., a curing agent and / or preferably a curable resin) to form a covalent or ionic reactive functionality. The backbone of the siloxane polymer can comprise alkyl and phenyl substitutions. In some embodiments, the reactive group on at least a portion of the siloxane monomer units can be an amino group, an epoxy group, a hydroxyl group, an anhydride group, an acrylate group, a perfluoro group, or a mixture thereof.

[0089] In one embodiment, the reactive siloxane has formula (3): [ka] Or equation (4): is a compound having the formula wherein each X is independently an alkyl group, an aryl group, or a cycloalkyl group; Y 1 , Y 2 , and Y 3 are each independently X or a reactive group (such as an amino group, an epoxy group, an anhydride group, an acrylate group, or a perfluoro group), with the proviso that Y 1 , Y 2 , or Y 3is not X, m is a number from about 1 to about 10,000, n is a number from 0 to about 10, and each p is independently a number from 0 to about 1,000, provided that at least one p is at least about 10. 1 and / or Y 3 is a reactive group, and Y 2 When is X, the reactive siloxane is a reactive group terminated siloxane. There are no internal reactive groups Y in the polysiloxane chain. 2 Since the functional groups Y can be randomly distributed, the siloxane notation in the above formula is 2 It will be understood that this should not be construed as requiring that all of the SiO groups having the formula be appended consecutively in a block.

[0090] In some embodiments, each X is independently an alkyl group, an aryl group, a cycloalkyl group, or an alkaryl group having up to 20 carbon atoms. Examples of X groups include methyl, ethyl, propyl, butyl, isopropyl, hexyl, dodecyl, octadecyl, 2-phenylpropyl, cyclopentyl, cyclohexyl, cyclooctyl, phenyl, benzyl, styryl, tolyl, and xylyl groups.

[0091] The values ​​of m, n, and p in formulas (3) and (4) can be varied to provide polysiloxanes having any desired molecular weight, such as from about 800 to about 20,000 Daltons. The value of n can also be varied to provide reactive siloxanes with greater or less reactive group content.

[0092] In one embodiment, the reactive siloxane is a compound having the formula (3) or (4), where each X is a methyl group and Y 1 , Y 2 , and Y 3 are each independently an alkyl group or a reactive group that includes an amino group, an epoxy group, a hydroxyl group, an anhydride group, an acrylate group, or a perfluoro group; m is a number from about 1 to about 10,000; n is a number from 0 to about 10, and each p is independently a number from 0 to about 1000, provided that at least one p is at least 10, and further provided that Y 1 , Y 2 , and Y 3 The condition is that at least one of the groups Y is not an alkyl group. In this case, too, there is no internal reactive group Y in the polysiloxane chain. 2 Since the functional groups Y can be randomly distributed, the siloxane notation in the above formula is 2 It will be understood that this should not be construed as requiring that all of the SiO groups having the formula be appended consecutively in a block.

[0093] In one embodiment, the reactive group is -R'N(R c where R′ is a divalent radical composed of carbon and hydrogen and optionally oxygen or nitrogen, which may further be an aliphatic or cycloaliphatic radical, and each R c are independently hydrogen or an alkyl group having 1 to 8 carbon atoms, or an aryl group having 6 to 8 carbon atoms. Thus, R' can be an alkylene group, a cycloalkylene group, an oxyalkylene group or an oxycycloalkylene group attached to a silicon atom, or an aminoalkylene group or an aminocycloalkylene group. Specific examples of R' include -CH2-, -CH2CH2-, -CH2-CH2-CH2-, -cyclohexylene, -OCH2CH2-, -OCH2CH2CH2-, -NCH2CH2-, -CH2CH2CH2N(H)CH2-CH2-. In one embodiment, R' is a divalent group containing 1 to about 3 carbon atoms. Amino groups also include the above amines and their salts, including quaternary salts that can be obtained by techniques known to those skilled in the art. Specific examples of amino groups that may be present on the reactive siloxane include -CH2NH2, -CH2N(H)CH3, -CH2N(H)C6H 11 , -CH2CH2CH2NH2, -CH2CH2CH2N(CH3)2, -cyclohexylamine, -OCH(CH3)CH2NH2, -OCH(CH3)CH2CH2NH2, -C3H6N(H)C2H4NH2, and -CH2CH2CH2N+ (CH3)HCH3-COO - Examples include:

[0094] In another embodiment, the reactive group is of the formula [ka] is an epoxy group having the formula In the formula, R d is an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 5 to 20 carbon atoms, an aryl group having 6 to 9 carbon atoms, a direct bond, or an alkyl-O-alkyl group having 3 to 10 carbon atoms. In another embodiment, the reactive group is of the formula [ka] is an epoxy group having the formula In the formula, R d is an alkyl group having 1 to 4 carbon atoms.

[0095] In yet another embodiment, the reactive group is -CH2CH2C(O)-OR e -[OC(O)CH=CH2] n-1 where n is from 2 to about 5. The number of 0s, R e is an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 10 carbon atoms.

[0096] In yet another embodiment, the reactive group is -R f is a hydroxyl group having the formula: OH, where R f is an alkyl group having 1 to about 20 carbon atoms or is a direct bond.

[0097] In another embodiment, the reactive group is of the formula [ka] is an anhydride group having the formula In the formula, Rg is an alkyl group having 1 to 10 carbon atoms.

[0098] In another embodiment, the surface modifier is a reactive fluoro compound. The reactive fluoro compound can be a fluorine-containing monomer or oligomer capable of polymerization, which can have 1 to 10 reactive groups, such as selected from (meth)acrylate, imide, amide, vinyl, urethane, ester, epoxy, and alcohol.

[0099] In one particular embodiment, the reactive fluorine is R 10 -CF3, where R 10 , CH2=CR 11 COOR 12 - and R 11 is hydrogen or an alkyl group having 1 to 3 carbon atoms, R 12 is an alkyl group having 1 to 6 carbon atoms (such as a methyl group, an ethyl group, a trimethyl group, a methylethyl group, a propyl group, a tetramethyl group, a pentamethyl group, and a hexamethyl group).

[0100] In another embodiment, the reactive fluoro compound is R 13 -R f -R 13 wherein R 13 , CH2=CR 14 COO- R 14 is hydrogen or an alkyl group having 1 to 3 carbon atoms, R f (a)~(e) [ka] is a compound selected from the group consisting of During the ceremony, * is R 13 is the binding site for R F1 is a perfluoroalkyl group having 1 to 14 carbon atoms, and R F2 , R F3 , R F4 , and R F5is each independently hydrogen or a perfluoroalkyl group having 1 to 14 carbon atoms.

[0101] Specific examples of reactive fluoro compounds include 6-perfluorohexanol, 3-perfluorobutylpropanol, 2-perfluoropropyltetrafluoropropanol, 2,5-ditrifluoromethyldioxaundecafluorononanol, octafluorohexanediol, perfluorobutylepoxypropane, perfluoromethylbutylepoxypropane, tetrafluoropropoxyepoxypropane, 1,4-bisepoxypropylperfluoro-n-butane, perfluorohexylethylene, 1-methoxyperfluoromethylpropane, 1,4-divinyldodecafluorohexane, 3-perfluorobutylhydroxypropylmethacrylate, 3-perfluorohexylhydroxypropylmethacrylate, trifluoroethylmethacrylate, tetrafluoropropylmethacrylate, 2-perfluorohexylethylacrylate, 3-perfluoromethylbutyl-2-hydroxypropylacrylate, methyltrifluoroacetate, ethyltrifluoroethyl. Fluoroacetate, trifluoroethyl methyl ether, tetrafluoroethyl methyl ether, hetafluorobutylamine, tridecafluoroheptylamine, and derivatives thereof may be mentioned.

[0102] The compositions of the present disclosure may include a surface modifier in an amount of about 0.01 wt.% to about 8.0 wt.%, or 0.01 wt.% to about 3.0 wt.%, or about 0.02 wt.% to about 2.0 wt.%, or about 0.03 wt.% to about 1.0 wt.%, or preferably about 0.05 wt.% to about 0.5 wt.%, based on the total weight of the composition [for wt.%, the initial weight fraction must be multiplied by 100]. In another embodiment, the compositions of the present disclosure may include a surface modifier in an amount of about 0.01 wt.% to about 1.0 wt.%, or about 0.03 wt.% to about 0.5 wt.%, or about 0.05 wt.% to about 0.3 wt.%, based on the total weight of the composition.

[0103] According to one embodiment, the curable resin includes (i) an epoxy resin (e.g., a difunctional epoxy resin, a trifunctional meta-glycidylamine, and / or N,N,N',N'-tetraglycidylmethylenedianiline), (ii) a curing agent (e.g., an aromatic amine, a cyclic amine, and / or a polyether amine), and (iii) a surface modifier (e.g., a reactive siloxane, such as an amine-terminated polysiloxane or an epoxy-terminated polysiloxane).

[0104] In another embodiment, the composition may also include one or more other additives useful for its intended use. For example, useful optional additives include, but are not limited to, diluents, stabilizers, surfactants, flow improvers, release agents, matting agents, degassing agents, toughening agents (e.g., core-shell rubbers, liquid rubbers or functionalized rubbers (such as carboxyl terminated liquid butadiene acrylonitrile rubbers, amine terminated liquid butadiene acrylonitrile rubbers, hydroxyl terminated liquid butadiene acrylonitrile rubbers, acrylic terminated liquid butadiene acrylonitrile rubbers, epoxy terminated liquid butadiene acrylonitrile rubbers, hydroxyl terminated liquid butadiene acrylonitrile rubbers, and liquid epoxy resin (LER) adducts of elastomers)), cure inhibitors, wetting agents, processing aids, fluorescent compounds, UV stabilizers, antioxidants, impact modifiers, corrosion inhibitors, tackifiers, rheology modifiers (e.g., fumed silica, colloidal silica, hydroxyethyl cellulose, hydroxypropyl cellulose, fly ash (ASTM C618), polyoxyalkylenes, polysaccharides, natural rubber, various naturally occurring clays (such as kaolin, bentonite, montmorillonite or modified montmorillonite, attapulgate, and Buckminsterfuller's earth); other naturally occurring or derived materials (such as mica, calcium carbonate, and aluminum carbonate); various oxides (such as iron oxide, titanium dioxide, calcium oxide, and silicon dioxide (e.g., sand)); various man-made materials (such as precipitated calcium carbonate); and various waste materials (such as crushed blast furnace slag), conductive particles (e.g., silver, gold, copper, nickel, aluminum, and conductive grades of carbon and carbon nanotubes), and mixtures thereof.

[0105] When present, the amount of additive included in the composition may be at least about 0.1 wt.%, or at least 0.5 wt.%, or at least 2 wt.%, or at least 5 wt.%, or at least 10 wt.%, based on the total weight of the composition. In other embodiments, the amount of additive included in the composition may be about 30 wt.% or less, or 25 wt.% or less, or 20 wt.% or less, or 15 wt.% or less, based on the total weight of the composition.

[0106] The compositions may be prepared, for example, by premixing the individual components and then mixing such premixes, or by mixing all of the components together using conventional devices, such as a stirred vessel, a stirring rod, a ball mill, a roll mill, a sample mixer, a static mixer, a high shear mixer, a screw extruder, a ribbon blender, or by hot melt. It may be prepared by mixing.

[0107] Thus, according to another embodiment, the composition of the present disclosure can be prepared by mixing together about 10 wt.% to about 90 wt.% of a curable resin, and about 0.0001 wt.% to about 0.3 wt.% of a surface modifier, and about 10 wt.% to about 60 wt.% of a curing agent, where the wt.% are based on the total weight of the composition.

[0108] The composition of the present disclosure is preferably a one-part curable composition from the viewpoint of handling, and in some embodiments, it can be used as a structural adhesive for vehicles and aerospace structures, an adhesive for wind power generation structures, a paint, a lamination material using glass fiber, a material for printed wiring substrates, a solder resist, an interlayer insulating film, a build-up material, an adhesive for FPCs, an electrical insulating material including a sealing material for electronic components (such as semiconductors and LEDs), a die bonding material, an underfill, a semiconductor packaging material, a sealing material (such as a sealing material for display devices and lighting devices including liquid crystal panels, OLED lighting devices, and OLED displays).

[0109] In particular, the compositions of the present disclosure are useful in joining a variety of automotive and aerospace structural materials to form laminate structures, including metal-to-metal, metal-to-composite, metal-to-ceramic, composite-to-composite, composite-to-ceramic, and ceramic-to-ceramic.

[0110] Composite materials may include a wide variety of thermoplastic resins commonly used in the industry, including, but not limited to, thermoplastic polyetherimide, polypropylene (PP), polypropalene, polyetherimide (PEI), polyphenylene sulfide (PPS), polyetheretherketone (PEEK), polyaryletherketone (PAEK), and polyetherketoneketone (PEKK).

[0111] Ceramics may include, but are not limited to, metal oxides, nitrides, and carbides (such as aluminum oxide, aluminum nitride, boron oxide, boron nitride, boron carbide, titanium oxide, titanium nitride, titanium carbide, silicon oxide, calcium oxide, magnesium oxide, silicon nitride, beryllium oxide, silicon carbide, mullite-borosilicate glass, etc.).

[0112] Composite materials include fiber reinforced resin composites (such as prepregs or prepreg layups) used in the creation of automotive and aircraft composite structures. The term "prepreg," as used herein, refers to a sheet or thin layer of fiber impregnated with a matrix resin. The matrix resin may be in an uncured or partially cured state. The term "prepreg layup," as used herein, refers to a plurality of prepreg layers arranged in a stacked manner in contact with one another. The prepreg layers within the layup may be arranged with respect to one another in a selected orientation. For example, a prepreg layup may include prepreg layers having a unidirectional fiber configuration, with the fibers oriented at 0°, 90°, a selected angle θ, and combinations thereof, relative to the longest dimension (e.g., length) of the layup. It will be further understood that in certain embodiments, the prepreg may have any combination of fiber configurations, such as unidirectional and multi-dimensional fiber structures. Useful fibers include carbon or graphite fibers, glass fibers, and fibers formed from silicon carbide, alumina, boron, quartz, and the like, as well as fibers formed from organic polymers (such as, for example, polyolefins, poly(benzothiazoles), poly(benzimidazoles), polyarylates, poly(benzoxazoles), aromatic polyamides, polyarylethers, and the like), and can also include mixtures having two or more such fibers.

[0113] After the composition is mixed, it is applied, such as by beading or film application, onto the surface or surfaces to be bonded. A paste adhesive is formed that can be applied to metal and / or composite surfaces by conventional dispensing means known to those skilled in the art. In an alternative embodiment, the paste adhesive can be processed into a film format by conventional hot melt coating processes known to those skilled in the art. Examples of such coating processes include, but are not limited to, reverse roll coating, slot die coating, knife over roll coating, knife over plate coating, dip and squeeze coating, reverse gravure coating, microgravure coating, comma roll coating, and forward gravure coating. For structural bonding of metals and composites, the adhesive can be applied at a thickness of 5 to 100 mils, or 5 to 80 mils (0.254 mm to 2.032 mm), preferably 8 to 20 mils. The surfaces are then brought together to form a laminate, and the adhesive film is sandwiched between the substrates. The resulting laminate can then be cured at a temperature of about 80° C. or more, or about 140° C. or more, or about 220° C. or less, or about 180° C. or less, while being placed under high pressure to suppress deformation effects or void formation due to exhaust gases, at a pressure of up to 10 bar (1 MPa), preferably in the range of 2 bar (0.3 MPa) to 7 bar (0.7 MPa). In some embodiments, the curing temperature is achieved by heating at up to 5° C. / min, e.g., 2° C. / min to 3° C. / min, and maintained at the curing temperature for up to 9 hours or up to 6 hours (e.g., 2 hours to 4 hours). Pressure can be released throughout and the temperature can be reduced by cooling at up to 5° C. / min or less, preferably 3° C. / min or less. Post-curing can be carried out at atmospheric pressure, at a temperature in the range of about 190° C. to about 350° C., using an appropriate heating rate.

[0114] Accordingly, the present disclosure also provides a method of bonding a first substrate to a second substrate, the method comprising applying a composition of the present disclosure to a surface of at least one of the first substrate and the second substrate to form an adhesive film on the surface, contacting the first substrate and the second substrate such that there is an adhesive film therebetween, and curing the adhesive film to form an adhesive bond between the first substrate and the second substrate. EXAMPLES

[0115] General overview Five different structural film adhesives were tested, including an aerospace qualified structural film adhesive control (3M™ Scotch-Weld™ Structural Adhesive Film AF191) as well as four structural adhesives according to the present disclosure (HA-X1, HA-X2, HA-X3, and HA-X4) shown in Table 1 below. Each was designed and developed to be resistant to silicone contamination at the bond surface. The mechanical performance of these structural adhesives on pristine (uncontaminated-U) carbon fiber reinforced polymer (CFRP) adherends and silicone coated (contaminated-C) CFRP adherends was then determined. The results are presented in further detail below. [Table 1]

[0116] Composite Panel Production CFRP panels made from HexPly® 8552 epoxy matrix prepreg layers (IM7 / 8552 prepreg layers) were used to determine the performance of the HA-X1 to HA-X4 adhesives relative to the control adhesive. Specifically, CFRP panels were made from HexPly® 8552 epoxy matrix according to the autoclave cure cycle provided in the product technical data sheet. Laminates of 19 layers of carbon fiber-containing HexPly® 8552 epoxy matrix oriented in the 0° direction (IM) (i.e., [0°] 19Each panel was made from a 100% polyester 100% polyester laminate. The laminate was sandwiched between two HYSOL® EA9895 wet peel plies and bagged. The autoclave cure cycle for HexPly® 8552 epoxy matrix was performed (as per product data sheet) as follows: i) apply full vacuum and 15 psig pressure to the vacuum bag, ii) heat to 225°F at 3-5°F / min, iii) hold isothermal at 225°F for 30-60 minutes, iv) increase pressure to 85-100 psig, v) release vacuum when pressure reaches 30 psig, vi) hold isothermal at 350°F for 120±10 minutes, vii) cool to 150°F at 2-5°F / min and release autoclave pressure.

[0117] Surface Coating To consistently and repeatably coat the composite panels, a spray system equipped with a digital controller, stepper motor, linear actuator, and digital syringe pump was constructed and used for this study. The parameters of the spray system were precisely controlled to achieve a coating density of 30-40 μg / in on each composite panel. 2 The following parameters were precisely controlled to regulate the amount of deposition: i) nozzle to substrate distance (in), ii) N2 gas pressure at the atomizer inlet (psi), iii) liquid flow rate (ml / min), and iv) gas flow rate (standard cubic feet per minute, SCFM). To monitor the coating process, a witness coupon was used and its weight measured before and after coating to ensure that the desired amount of contaminant was deposited. The allowable variation in weight of deposited contaminant was approximately 10-15 μg / in 2 It is an aerospace-qualified release agent. LOCTITE® FREKOTE 44NC™ agent was used as the staining agent for the following tests.

[0118] Preparation of test specimens A layer of film adhesive was sandwiched between two subpanels that had been pre-treated with one of the following surface treatments: Surface Preparation (SP)-1 or SP-2 (with or without contamination): i. Surface Preparation for Carbon-Epoxy #1 (SP-1): Remove Peel Ply (Wet) / Apply Spray Contamination (if applicable) ii. Surface Preparation for Carbon-Epoxy #2 (SP-2): Remove peel ply (wet) / Apply spray contamination (if applicable) / 3M Scotch-Brite™ polish treatment (light uniform polish with Scotch-Brite™ for 30 seconds) / Acetone solvent wipe.

[0119] Stainless steel (SS) wire (7 mil diameter) was used to control bond line thickness. Each assembly was properly bagged and each assembly included a quadrant mold, dam tape, and breathers to reinforce areas that could cause risk of bridging or puncturing the vacuum bag, especially the corners of the fixture. Three thermocouples were used per cowl plate and attached directly to the bond fixture to ensure good coverage of the entire area. The assemblies were processed in an autoclave using a cure cycle as follows: i) a vacuum level in the range of 5-8 in Hg was applied to the vacuum bag, ii) the autoclave pressure was increased to 45 psi before heating and the vacuum bag was released to atmospheric pressure when the autoclave pressure reached 10 psi, iii) the assembly was heated to 350°F with a heating ramp rate of 5°F / min and held isothermal at 350°F for 1 hour with an autoclave pressure of 45 psi. Single lap shear specimens were obtained by joining two 4" x 7" subpanels together with a 1" overlap along the length of the subpanels, in accordance with ASTM D5868. Upon curing, the joined panels were machined using a diamond wet saw. Single lap shear specimens were cut to approximately 1.0 in. 2The specimens were 1” x 7” with a bonded overlap area of ​​2.5” from one end. Additionally, double cantilever beam (DCB) specimens were prepared by bonding 8” x 14” sub-panels together. The bonded DCB panels were then cut using a water jet machine to form 1” x 14” DCB specimens with 2.5” of unbonded area from one end. For the DCB specimens, 0.5 mil thick PTFE inserts were placed to create a natural split as per ASTM D5528 standard.

[0120] mechanical performance Tests were performed including conventional single lap shear (per ASTM D1002 / ASTM D5868) and Mode I fracture toughness (per ASTM D5528) at ambient room temperature (RTA), sub-ambient temperature (LT) of -67°F, dry hot (ETD) of 180°F, and wet hot (ETW) at 180°F wet conditions.

[0121] (A) Single lap shear i) Lap Shear Strength - Figure 1 shows the adhesive bond strength in shear mode of adhesives according to the present disclosure (HA-X1-HA-X4) and controls on both contaminated (SP-1 / C) and uncontaminated (SP-1 / U) composite adherends. All specimens were tested at ambient room temperature (RTA) conditions. The solid bars in Figure 1 represent strength values ​​of the corresponding adhesives with uncontaminated composite adherends (SP-1 / U) and the shaded bars represent strength values ​​of the corresponding adhesives with contaminated composite adherends (SP-1 / C). Each average and corresponding error is from at least six replicates. The results demonstrate that the adhesives according to the present disclosure have significantly improved performance when compared to the control on both uncontaminated (SP-1 / U) and more importantly, on contaminated (SP-1 / C) composite adherends. Furthermore, the adhesive bond strength on the composite adherends was significantly improved. Lap shear strength was measured at dry elevated temperature (ETD) and low temperature (LT) according to the standard MMM-A-132B. Figure 2(a) shows the shear strength in single lap shear mode (per ASTM D5868) for the adhesives (HA-X1-HA-X4) and the control with contaminated (hatched bars) and non-contaminated (solid bars) composite adherends at elevated temperature (ETD) and low temperature (LT). The results shown in Figure 2 show that the mechanical performance of the adhesives according to the present disclosure with non-contaminated composite adherends was not adversely affected when tested at ETD conditions (180°F) and LT conditions (-67°F). It is also evident from the results that the adhesives according to the present disclosure performed better than the control adhesive with silicone contaminated composite adherends at both ETD (180°F) and LT (-67°F). ii) Strength retention - The surface resistance properties of each adhesive were further investigated using strength retention (defined as the ratio of the adhesive shear strength in the silicone-contaminated joint to the same amount in the initial joint). For the control adhesive, the strength retention was found to be 21%, while for HA-X1 to HA-X4, this value was 56%, 55%, 79%, and 76%, respectively. The strength retention also clearly demonstrated that the adhesives according to the present disclosure have significantly improved silicone resistance properties compared to the control adhesive.

[0122] (B) Fracture toughness FIG. 3 shows the mode I fracture toughness G of the adhesives (HA-X1 to HA-X4) and the control adhesive on contaminated (hatched bars) and non-contaminated (solid bars) C / C adherends. 1c Values ​​are shown. Each mean and corresponding error are from at least six replicates. Compared to the control adhesive, HA-X1 and HA-X2 showed slightly higher resistance to fracture in the presence of silicone contamination, while the G 1cThe values ​​were relatively small. The further improvement in the performance of HA-X3 and HA-X4 on uncontaminated and contaminated composite adherends is evident in Figure 3. An additional batch of DCB specimens bonded with HA-X4 (HA-X4-2) was prepared and the G 1c From the results shown in Figure 3, it was found that the G 1c The reproducibility of the values ​​was confirmed.

[0123] Adhesive Surface Energy and Polarity Advancing contact angles of DI water and tricresyl phosphate (TCP) at room temperature were used to calculate the surface energy and polar and dispersive components of the control and adhesives according to the present disclosure (HA-X1-HA-X4) based on Wu's harmonic model (see Wu, Souheng, "Polymer Interface and Adhesion", New York: Marcel Dekker, 1982). Additionally, these quantities were determined for epoxy surfaces coated with the same solutions of LOCTITE® FREKOTE 44NC™ agent. The calculation results are shown in Table 2 and indicate that the surface polarity of the adhesives according to the present disclosure is successfully controlled, especially for HA-X2-HA-X4. [Table 2]

[0124] While the making and using of various embodiments of the invention have been described in detail above, it should be understood that the invention provides many applicable inventive concepts that can be embodied in a wide variety of specific contexts. The specific embodiments discussed herein are merely illustrative of specific ways to make and use the invention and do not limit the scope of the invention.

Claims

1. A composition comprising: (a) a curable resin; (b) a curing agent; and (c) a surface modifier selected from the group consisting of reactive siloxanes, reactive fluoro compounds, and mixtures thereof.

2. The composition of claim 1 , wherein the curable resin is an epoxy resin.

3. 3. The composition of claim 2, wherein the epoxy resin is selected from difunctional epoxy resins, trifunctional epoxy resins, tetrafunctional epoxy resins, and mixtures thereof.

4. The composition of claim 1 , wherein the curable resin is an acrylic resin.

5. The composition of claim 1 , wherein the curable resin is a polyurethane / polyurea resin.

6. The surface improver is represented by the formula (3) 【Chemistry 1】 is a reactive siloxane having the formula wherein each X is independently an alkyl group, an aryl group, or a cycloalkyl group; １ , Y ２ , and Y ３ are each independently X or a reactive group that includes an amino group, an epoxy group, an anhydride group, an acrylate group, or a perfluoro group, with the proviso that Y １ , Y ２ , or Y ３ is not X; m is a number from about 1 to about 10,000; n is a number from 0 to about 10; and each p is independently a number from 0 to about 1000, with the proviso that at least one p is at least about 10.

7. The composition of claim 6 wherein X is methyl.

8. Y １ , Y ２ , and Y ３ The composition of claim 7, wherein at least one of is an amino group.

9. Y １ , Y ２ , and Y ３ The composition of claim 7, wherein at least one of the groups is an epoxy group.

10. Y １ , Y ２ , and Y ３ The composition of claim 7, wherein at least one of is an acrylate group.

11. Y １ , Y ２ , and Y ３ The composition of claim 7, wherein at least one of the groups is a perfluoro group.

12. The surface modifier is represented by the formula R １０ -CF ３ is a reactive fluoro compound having the formula １０ But, CH ２ =CR １１ COOR １２ - and R １１ is hydrogen or an alkyl group having 1 to 3 carbon atoms; R １２ The composition of claim 1, wherein is an alkyl group having 1 to 6 carbon atoms.

13. The surface modifier is represented by the formula R １３ -R ｆ -R １３ is a reactive fluoro compound having the formula １３ But, CH ２ =CR １４ COO- and R １４ is hydrogen or an alkyl group having 1 to 3 carbon atoms; R ｆ However, (a) to (e) 【Chemistry 2】 is a compound selected from the group consisting of During the ceremony, ＊ But, R １３ is a binding site for Ｆ１ is a perfluoroalkyl group having 1 to 14 carbon atoms, R Ｆ２ , R Ｆ３ , R Ｆ４ , and R Ｆ５ The composition of claim 1, wherein each is independently hydrogen or a perfluoroalkyl group having 1 to 14 carbon atoms.

14. 10. The composition of claim 1, wherein the surface modifier is present in an amount of about 0.0001 wt. % to about 8.0 wt. %, based on the total weight of the composition.

15. The composition of claim 1 further comprising at least one of a rheology modifier or an enhancer.

16. 10. A laminate structure comprising a first substrate bonded to a second substrate and a structural adhesive film cured between the first substrate and the second substrate, the structural adhesive film being formed from the composition of claim 1.

17. 20. The laminate structure of claim 16, wherein the first substrate and the second substrate are independently selected from metals, composites, ceramics, and thermoplastics.

18. 11. A method of bonding a first substrate to a second substrate comprising: applying the composition of claim 1 to a surface of at least one of the first substrate and the second substrate to form an adhesive film on said surface; contacting the first substrate and the second substrate such that the adhesive film is therebetween; and curing the adhesive film to form an adhesive bond between the first substrate and the second substrate.

19. 20. The method of claim 18, wherein the first substrate and the second substrate are independently selected from metals, composites, ceramics, and thermoplastics.

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