Hardening components

Abstract

The curable composition includes a diluent, an epoxy-functionalized resin derived from nutshell oil, an epoxy-rubber copolymer adduct, and a curing agent. Methods for making the curable composition, imparting improved flexibility to the curable composition, and improving the adhesion of the curable composition to oil-containing metals are described. The method for imparting improved flexibility to the curable composition includes providing the curable composition, adding the epoxy-functionalized resin derived from nutshell oil, and adding a liquid modified hydrocarbon resin derived from nutshell oil.

Description

[Technical Field]

[0001] The present disclosure relates generally to curable compositions. [Background technology]

[0002] Curable compositions undergo a change known as curing when heated or exposed to various reagents (usually acids or bases). The resulting product is a reaction product, usually a very hard solid. In some instances, it may be desirable to impart certain physical properties to the reaction product to make it more attractive for various commercial applications. Summary of the Invention [Problem to be solved by the invention]

[0003] However, modification of the composition frequently results in the loss of other desirable properties, such as loss of adhesion, rendering the modified composition unable to achieve its intended purpose.

[0004] There has been a need to provide a flexible composition that can adhere to oily metals in both high and low temperature environments, but the art to date has not provided an adequate solution. [Means for solving the problem]

[0005] According to the present disclosure, the curable composition includes a diluent, an epoxy-functionalized resin derived from nutshell oil, an epoxy-rubber copolymer adduct, and a curing agent.

[0006] According to the present disclosure, a method for imparting improved flexibility to a curable composition includes providing a curable composition comprising an epoxy-rubber copolymer adduct, a curing agent, a hydrophobic fumed silica additive, and an adhesion promoter, and adding thereto an epoxy-functionalized resin derived from nutshell oil and, optionally, a liquid modified hydrocarbon resin derived from nutshell oil.

[0007] According to the present disclosure, a method for making a curable composition includes combining an epoxy-rubber copolymer adduct and a curing agent to obtain a mixture, and combining therewith an epoxy-functionalized resin derived from nutshell oil and, optionally, a liquid modified hydrocarbon resin derived from nutshell oil to obtain a curable composition.

[0008] According to the present disclosure, a method for improving adhesion of a curable composition to oily metal includes providing a curable composition comprising an epoxy-rubber copolymer adduct, a curing agent, a hydrophobic fumed silica additive, and an adhesion promoter, and adding thereto an epoxy-functionalized resin derived from nutshell oil and, optionally, a liquid modified hydrocarbon resin derived from nutshell oil.

[0009] Other features and advantages of the present disclosure will become apparent from a consideration of the following non-limiting description of the embodiments. DETAILED DESCRIPTION OF THE INVENTION

[0010] According to the present disclosure, the curable composition includes a diluent, an epoxy-functionalized resin derived from nutshell oil, an epoxy-rubber copolymer adduct, and a curing agent.

[0011] The diluent or epoxy-functionalized resin may be derived from nutshell oil functionalized with at least one epoxy group.

[0012] Such nut shell oils include, for example, almond oil, pine nut oil, walnut oil, Brazil nut oil, hazelnut oil, pistachio oil, peanut oil, cashew nut oil, coconut oil, chestnut oil, sunflower seed oil, macadamia nut oil, butternut oil, walnut oil, and combinations thereof.

[0013] Nut shell oils, such as cashew nut shell oil, modified to contain epoxy functional groups are often referred to as epoxidized nut shell resins. Epoxidized vegetable oils are also commercially available and can be used. Some examples of vegetable oils that can be epoxidized include palm oil, rapeseed oil, sunflower oil, soybean oil, linseed oil, and castor oil.

[0014] The epoxidized cashew nut shell resin can be a monofunctional epoxy diluent, a difunctional epoxy resin, or a multifunctional epoxy resin.

[0015] Examples of monofunctional reactive epoxy diluents include the following:

[0016] [ka] [ka]

[0017] Examples of bifunctional reactive epoxy resins include the following:

[0018] [ka]

[0019] Examples of polyfunctional epoxy resins include the following:

[0020] [ka]

[0021] Mono- and di-functional reactive epoxy resins and diluents are commercially available from Cardolite Corporation, Monmouth Junction, NJ. Any of the mono-, di-, and multi-functional epoxies, as well as blends thereof, may be useful herein.

[0022] Another example of an epoxy-functionalized resin and diluent is a liquid modified hydrocarbon resin. The liquid modified hydrocarbon resin derived from epoxidized cashew nut shell oil can also be referred to as an epoxidized cashew nut shell diluent.

[0023] Similar to the epoxidized cashew nut shell resin, the epoxidized cashew nut shell diluent may be a monofunctional epoxy resin, a difunctional epoxy resin, or a multifunctional epoxy resin.

[0024] In some embodiments, the amount of epoxy-functionalized resin is greater than the amount of diluent, based on 100% by weight of the curable composition.

[0025] In some embodiments, the amount of diluent is in the range of about 50-70% of the amount of epoxy-functionalized resin, based on the weight of the curable composition, hi some embodiments, the amount of diluent is in the range of 55-65% of the amount of epoxy-functionalized resin, based on the weight of the curable composition.

[0026] Other epoxy resins include those derived from epoxidized dimer fatty acids, which may be included in the curable compositions of the present invention.

[0027] When the nutshell oil-derived epoxy-functionalized resin and the epoxidized dimer fatty acid-derived epoxy resin are present in the curable composition, they comprise from about 60 to about 80 weight percent of the composition.

[0028] When both the nutshell oil-derived epoxy-functionalized resin and the epoxidized dimer fatty acid-derived epoxy resin are present in the curable composition, the ratio of the nutshell oil-derived epoxy-functionalized resin to the epoxidized dimer fatty acid-derived epoxy resin is in the range of 0.5:1 to 2:1.

[0029] In some embodiments, the ratio of epoxy-functionalized resin derived from nut shell oil to epoxy resin derived from epoxidized dimer fatty acid is from 0.5:1 to 0.9:1.

[0030] In some embodiments, it may be desirable to react suitable polymers and copolymers with epoxy resins derived from epoxidized dimer fatty acids to form epoxy-rubber copolymer adducts, and then add the adduct to the curable composition.

[0031] In this regard, copolymers that may be used include acrylonitrile butadiene styrene (ABS), styrene / butadiene copolymer (SBR), nitrile rubber, styrene-acrylonitrile, styrene-isoprene-styrene (SIS), and ethylene-vinyl acetate. The copolymers may be constructed as block, random, graft, or alternating copolymers.

[0032] Nitrile rubber is also known as acrylonitrile-butadiene rubber, Buna-N, and Perbunan, or under the product names Nipol®, Krynac®, and Europrene®, among others.

[0033] Acrylonitrile-butadiene rubber is a copolymer of acrylonitrile and butadiene, and typically exhibits resistance to non-polar solvents, fats, oils, and motor fuels, in addition to other desirable physical properties.

[0034] The ratio of acrylonitrile and butadiene residues in the nitrile rubber may vary, for example, in one embodiment, the acrylonitrile-butadiene copolymer contains 1 to 26 weight percent acrylonitrile and 74 to 99 weight percent butadiene.

[0035] Carboxyl-terminated acrylonitrile-butadiene copolymers (e.g., those available under the product names Hypro® Reactive Liquid Polymers 1300X8 CTBN and 1300X8F CTBN) are liquid polymers having Brookfield viscosities in the range of 110,000 to 160,000 mPa·s or cP at 27° C., wherein the weight percent of acrylonitrile is from slightly more than 0 to about 25 weight percent, e.g., from about 15.5 to about 19.5 weight percent, and the weight percent of butadiene is from slightly less than 100 to about 75 weight percent, e.g., from about 80.5 to about 84.5 weight percent.

[0036] The reactivity of these carboxyl-terminated acrylonitrile-butadiene copolymers is due to the functionality at the chain ends. The acrylonitrile content affects the viscosity and glass transition temperature of the copolymer.

[0037] Other liquid polymers for use in the curable composition are also contemplated, such as those listed in the table below.

[0038] [Table 1]

[0039] These materials are commercially available from CVC Thermoset Specialties, Moorestown, NJ.

[0040] In some embodiments, the carboxyl-terminated acrylonitrile-butadiene copolymer is epoxy-functionalized, often by a "pre-react" method, which allows the copolymer to impart additional (or improved) toughness to the composition to which it is added.

[0041] The pre-react method includes the steps of providing a carboxyl-terminated acrylonitrile-butadiene copolymer, a liquid epoxy resin (e.g., DER331), and a triphenylphosphine (TPP) catalyst; providing a kettle; adding the liquid epoxy resin (DER331) to the kettle; adding the carboxyl-terminated acrylonitrile-butadiene copolymer to the kettle; purging the kettle containing the carboxyl-terminated acrylonitrile-butadiene copolymer and the liquid epoxy resin (DER331) with N2 gas; heating the kettle to at least 80°C while stirring the carboxyl-terminated acrylonitrile-butadiene copolymer and the liquid epoxy resin (DER331); and adding the triphenylphosphine (TPP) catalyst and continuing stirring. The liquid polymer (e.g., Hypro™ Reactive Liquid Polymer 1300X8 CTBN) can thus react with the epoxy resin to form an adduct. The adduct thus formed can be diluted with epoxy to produce a shelf-stable epoxy composition having the desired epoxy / adduct ratio.

[0042] A typical pre-reactant preparation typically uses 8-10 equivalents of epoxy per equivalent of Hypro™ Reactive Liquid Polymer 1300X8 CTBN along with a catalyst. Under these conditions, the Hypro™ Reactive Liquid Polymer 1300X8 CTBN reacts with the catalyst to produce a carboxylate salt, which subsequently reacts very rapidly with the epoxy group. In some embodiments, Hypro™ Reactive Liquid Polymer 1300X8 CTBN, in its epoxy-capped form, provides a pre-reactant with significant epoxide activity.

[0043] In some embodiments, the amount of the epoxy-rubber copolymer adduct is greater than the combined amount of the epoxidized cashew nut shell diluent and the epoxidized cashew nut shell resin based on the weight of the curable composition, ie, the amount of the epoxy-rubber copolymer adduct is in the range of 50 to 90 weight percent of the curable composition.

[0044] The curing agent for one or more of the curable compositions may be selected from conventional and / or commercially available curing agents including amines (aliphatic amines (e.g., tertiary amines), Jeffamines, cycloaliphatic amines, aromatic amines, polyamides, amidoamines, amine adducts, Mannich bases), polymeric captans, latent curing agents (dicyandiamide, imidazoles, substituted ureas), anhydrides, and organic acids.

[0045] A variety of therapeutic agents, rheology modifiers, and other compatible additives may be provided in the hardenable composition.

[0046] Some of the additives include a hydrophobic fumed silica additive, an adhesion promoter, and a non-ionic silane dispersant.

[0047] In some embodiments, the amount of hydrophobic fumed silica ranges from 0 to 10 wt% of the curable composition. In some embodiments, the amount of hydrophobic fumed silica ranges from 1 to 5 wt% of the curable composition. In some embodiments, the amount of hydrophobic fumed silica is 5 wt% of the curable composition.

[0048] In some embodiments, the amount of adhesion promoter (e.g., γ-glycidyloxypropyltrimethoxysilane) ranges from 0 to 10 wt % of the curable composition. In some embodiments, the amount of adhesion promoter ranges from 0.1 to 1 wt % of the curable composition. In some embodiments, the amount of adhesion promoter is 0.5 wt % of the curable composition.

[0049] In some embodiments, the amount of nonionic silane dispersant (e.g., carbon black) ranges from 0 to 10 wt.% of the curable composition. In some embodiments, the amount of nonionic silane dispersant ranges from 0.1 to 1 wt.% of the curable composition. In some embodiments, the amount of nonionic silane dispersant is 0.5 wt.% of the curable composition.

[0050] In one embodiment, the curable composition is a thermosetting composition.

[0051] In one embodiment, the curable composition is an adhesive composition.

[0052] In one embodiment, the curable composition is a sealant composition.

[0053] In one embodiment, the curable composition includes 14 wt. % epoxidized cashew nut shell diluent, 23 wt. % epoxidized cashew nut shell resin, 55 wt. % acrylonitrile-butadiene copolymer-epoxy adduct, 3 wt. % hydrophobic fumed silica, 0.5 wt. % γ-glycidyloxypropyltrimethoxysilane, 0.5 wt. % silane dispersant, and 4 wt. % adipic dihydrazide, and exhibits the physical properties of a flexible sealant that can adhere to oily metals and has high temperature resistance.

[0054] In one embodiment, the curable composition includes 16 wt % epoxidized cashew nut shell diluent, 25 wt % epoxidized cashew nut shell resin, 50 wt % acrylonitrile-butadiene copolymer-epoxy adduct, 3 wt % hydrophobic fumed silica, 0.5 wt % γ-glycidyloxypropyltrimethoxysilane, 0.5 wt % silane dispersant, and 5 wt % adipic acid dihydrazide, and exhibits the physical properties of a flexible sealant that can adhere to oily metals and has high temperature resistance.

[0055] In one embodiment, the curable composition includes 16 wt % epoxidized cashew nut shell diluent, 26 wt % epoxidized cashew nut shell resin, 47 wt % acrylonitrile-butadiene copolymer-epoxy adduct, 5 wt % hydrophobic fumed silica, 1 wt % γ-glycidyloxypropyltrimethoxysilane, and 5 wt % adipic acid dihydrazide, and exhibits the physical properties of a flexible sealant that can adhere to oily metals and has high temperature resistance. [Example]

[0056] The following examples are provided to more fully illustrate the objects, features, and advantages of the present disclosure, but are not intended to be limiting. Additionally, units such as parts, %, and given amounts are by weight in the examples unless otherwise specified.

[0057] Curable compositions were prepared by mixing the components to homogeneity according to the ratios set forth in Table 1 and are represented by sample numbers as indicated.

[0058] [Table 2]

[0059] Each of the samples shown in Table 1 was prepared similarly, except for varying amounts of the components.

[0060] The weight ratios of the cashew nut shell oil epoxy and epoxy-rubber copolymer adducts in Examples 1 to 6 in Table 1 are shown in Table 2.

[0061] [Table 3]

[0062] The samples in Table 1 were each evaluated by the knife / peel test and the high-temperature resistance test. The tests were the same as those described above. Additionally, samples designated PV1297 and AL6302R were evaluated by these three tests, and the results are shown in Table 3. The sample designated PV1297 is a stretchable, wash-resistant, weld-through semi-structural sealer known as Terson® PV1297 and Terostat® 1297. The sample designated AL6302R is a pumpable, high-temperature sealant-based, thermosetting polyvinyl chloride (PVC)-polyacrylate plastisol known as Teroson® AL6302R and Terosol® 6302R.

[0063] Knife / peel testing encompasses the determination of the relative adhesion of flexible adhesives and sealants to rigid and semi-rigid substrates. The knife / peel test involves dispensing a bead of curable composition onto an oily rolled steel surface, hardening the bead to form a cured composition, cooling the cured composition to room temperature, cutting a piece of the cured composition from the oily rolled steel, and verifying that the cured composition has adhered to the oily rolled steel.

[0064] More specifically, beads of curable composition are dispensed to have final bead dimensions of 8±1 mm at the base and 5±1 mm in height. Typically, a minimum length of 50 mm is required for each test.

[0065] After hardening and cooling, the cutting process was performed by cutting off the tip of the bead to form a peeled tab approximately 25 ± 5 mm long and securing it in a gripping device such as a gripping vise. The peeled tab was then held in a gripping device and the bead was pulled. While pulling, a knife notch was made in the bead every 6 ± 2 mm at a 45-degree angle to an oiled rolled steel test plate. The amount of cohesive failure was assessed and recorded as a percentage. Generally, cohesive failure was classified into four groups:

[0066] Cohesion scale: 1.>95% 2.75~95% 3.25~75% 4.<25%

[0067] Compositions were deemed to pass the knife / peel test if cohesive failure was significant (ie, cohesive failure of 75% or greater and fell into the top two groups listed above).

[0068] In other words, evidence of adhesion to oily cold rolled steel resulted in a pass in the knife / peel test, whereas evidence of cohesion resulted in a fail in the knife / peel test.

[0069] The mandrel bend test is described as SAE J243 ADS-2 Method B. This test was used to determine the adhesive properties of a sealant composition when bent around a mandrel. The mandrel bend test involves dispensing a bead of curable composition onto an oiled rolled steel surface, curing the composition under elevated temperature conditions, cooling the cured composition to room temperature and then to -40°C for 30 minutes, wrapping a 1-100 mm diameter mandrel around the mandrel, and evaluating the cured composition for cracking or loss of adhesion.

[0070] In some cases, the curable composition may be applied to an aluminum foil, cured for a specific time and temperature by dry air or baking, and then cooled after curing. The aluminum foil with the cured beads is then wrapped around a mandrel and evaluated for cracking or reduced adhesion. During the wrapping process, either the aluminum foil or the cured beads may be in contact with the mandrel.

[0071] Suitable times and temperatures for curing the composition include, for example, about 130°C to about 180°C for 30 minutes.

[0072] A curable composition passed the mandrel bend test if it showed no cracks or loss of adhesion after wrapping around the mandrel.

[0073] The high temperature resistance test involves dispensing a bead of the curable composition onto an oiled rolled steel surface, allowing the bead to cure into a cured composition, placing the cured composition in an oven at 200°C for at least 1 hour, and evaluating the cured composition for cracking, expansion, shrinkage, bubbling, or decomposition. If there is no cracking, expansion, shrinkage, bubbling, or decomposition, the composition passed the high temperature resistance test.

[0074] These tests showed that Example 4, which uses an epoxidized cashew nut shell diluent and resin with an acrylonitrile-butadiene copolymer-epoxy adduct, exhibited good adhesion to oily metal, flexibility, and high temperature resistance. Therefore, additional tests, described below, were conducted by varying the weight ratios of the components of the curable composition.

[0075] [Table 4]

[0076] Referring to Tables 2 and 3, it is readily apparent that Samples 4-6 (ratios of epoxidized cashew nut shell diluent and resin to butadiene-acrylonitrile copolymer-epoxy adduct of 0.7-0.9) provide good adhesion to oily metal, flexibility, and high-temperature resistance. In comparison, two commercial seam sealants (i.e., Teroson® PV1297, a polyvinyl chloride-based seam sealant, and Teroson® AL6302R, a PVC / polyacrylate plastisol-based seam sealant) did not provide acceptable adhesion to oily metal, flexibility, or high-temperature resistance.

[0077] In some embodiments, the method of the present invention includes a step of sealing seams on uncoated oily metal prior to pre-treating the metal. Cleaning steps, such as metal pre-treatment, typically include: This is done before any metallization process such as powder coating or electrodeposition.

[0078] During application, the curable compositions are used over metal seams between welded or bonded joints, overlap joints, butt joints, and other visible seams where a seal would be beneficial. Seams include round and square seams in thin metal films and tubing. The curable compositions may also be applied directly to bare, oil-filled, primed, or electro-deposited metal prior to application of a curable top or overcoat or powder coating that can be cured or set by exposure to elevated temperatures.

[0079] While the principles of the present invention have been described herein, it is to be understood by those skilled in the art that this description is made by way of example only and is not intended to be limiting as to the scope of the invention. Other embodiments in addition to the exemplary embodiments shown and described herein are contemplated within the scope of the present invention. Modifications and substitutions made by those skilled in the art are deemed to be within the scope of the present invention.

Claims

1. Diluents, Epoxy-functionalized resins derived from nutshell oil, epoxy-rubber copolymer adducts, and hardener A curable composition comprising: the epoxy-functionalized resin is derived from a nut shell oil selected from the group consisting of almond oil, pine nut oil, walnut oil, Brazil nut oil, hazelnut oil, pistachio oil, peanut oil, cashew nut oil, coconut oil, chestnut oil, sunflower seed oil, macadamia nut oil, butternut oil, walnut oil, and combinations thereof, functionalized with at least one epoxy group; the diluent is derived from a nut shell oil, and the nut shell oil is selected from the group consisting of almond oil, pine nut oil, walnut oil, Brazil nut oil, hazelnut oil, pistachio oil, peanut oil, cashew nut oil, coconut oil, chestnut oil, sunflower seed oil, macadamia nut oil, butternut oil, walnut oil, and combinations thereof, functionalized with at least one epoxy group; a weight ratio of the sum of the diluent and the nutshell oil-derived epoxy-functionalized resin to the epoxy-rubber copolymer adduct is in the range of 0.5:1 to 0.9:1; A curable composition wherein the diluent and the nutshell oil-derived epoxy-functionalized resin are different components.

2. 10. The curable composition of claim 1, wherein the epoxy-functionalized resin is epoxidized cashew nut shell resin.

3. 3. The curable composition of claim 2, wherein the epoxidized cashew nut shell resin comprises a monofunctional epoxy resin, a difunctional epoxy resin, a multifunctional epoxy resin, or a blend thereof.

4. 2. The curable composition of claim 1, wherein the epoxy-functionalized resin comprises a monofunctional epoxy resin represented by the formula: 【Chemistry 1】

5. 2. The curable composition of claim 1, wherein the epoxy-functionalized resin comprises a difunctional epoxy resin represented by the formula: 【Chemistry 2】

6. 2. The curable composition of claim 1, wherein the epoxy-functionalized resin comprises a multifunctional epoxy resin represented by the formula: 【Transformation 3】

7. 10. The curable composition of claim 1, wherein the weight proportion of the epoxy-functionalized resin is greater than the weight proportion of the diluent.

8. The curable composition of claim 1, wherein the diluent is in the range of 10 to 20% by weight of the curable composition.

9. 10. The curable composition of claim 1, wherein the diluent is a liquid epoxidized cashew nut shell diluent.

10. 2. The curable composition of claim 1, wherein the epoxy-rubber copolymer adduct is an acrylonitrile-butadiene copolymer-epoxy adduct.

11. 11. The curable composition of claim 10, wherein the acrylonitrile-butadiene copolymer-epoxy adduct comprises 1 to 26 weight percent acrylonitrile and 74 to 99 weight percent butadiene.

12. 10. The curable composition of claim 1, further comprising 0 to 5 wt. % of a hydrophobic fumed silica additive, 0.1 to 2 wt. % of an adhesion promoter, and 0.1 to 2 wt. % of a nonionic silane dispersant.

13. 10. The curable composition of claim 1, wherein the curing agent is selected from the group consisting of hydrazides, aliphatic amines, Jeffamines, cycloaliphatic amines, aromatic amines, polyamides, amidoamines, secondary amines, Mannich bases, polymeric captans, anhydrides, latent hardeners, dicyandiamide, tertiary amines, imidazoles, substituted ureas, organic acids, photocuratives, or UV curatives.

14. The curable composition of claim 1 , wherein the curing agent is adipic acid dihydrazide.

15. 10. The curable composition of claim 1, further comprising at least one of a hydrophobic fumed silica additive and an adhesion promoter.

16. The curable composition of claim 16, wherein the adhesion promoter is gamma-glycidyloxypropyltrimethoxysilane.

17. The curable composition of claim 1 further comprising a nonionic silane dispersant.

18. 10 to 17 wt. % of an epoxidized cashew nut shell diluent; 20 to 26 wt. % epoxidized cashew nut shell resin; 47 to 60 wt. % of an acrylonitrile-butadiene copolymer-epoxy adduct; 3 to 5 wt. % hydrophobic fumed silica, 0.1 to 1 wt. % of gamma-glycidyloxypropyltrimethoxysilane, and Adipic dihydrazide in an amount appropriate to provide consistency in the curable composition Including, a weight ratio of the sum of the epoxidized cashew nut shell diluent and the epoxidized cashew nut shell resin to the epoxy-rubber copolymer adduct is in the range of 0.5:1 to 0.9:1; The curable composition, wherein the epoxidized cashew nut shell diluent and the epoxidized cashew nut shell resin are different components.

19. 19. The curable composition of claim 18, further comprising a nonionic silane dispersant in the range of 0.1 to 1 wt. % of the curable composition.

20. acrylonitrile-butadiene copolymer-epoxy adduct, hardener, a hydrophobic fumed silica additive, and providing a curable composition comprising an adhesion promoter; adding an epoxy-functionalized resin derived from nutshell oil; and Adding a diluent Including, the epoxy-functionalized resin is derived from a nut shell oil selected from the group consisting of almond oil, pine nut oil, walnut oil, Brazil nut oil, hazelnut oil, pistachio oil, peanut oil, cashew nut oil, coconut oil, chestnut oil, sunflower seed oil, macadamia nut oil, butternut oil, walnut oil, and combinations thereof, functionalized with at least one epoxy group; the diluent is derived from a nut shell oil, and the nut shell oil is selected from the group consisting of almond oil, pine nut oil, walnut oil, Brazil nut oil, hazelnut oil, pistachio oil, peanut oil, cashew nut oil, coconut oil, chestnut oil, sunflower seed oil, macadamia nut oil, butternut oil, walnut oil, and combinations thereof, functionalized with at least one epoxy group; a weight ratio of the sum of the diluent and the nutshell oil-derived epoxy-functionalized resin to the epoxy-rubber copolymer adduct is in the range of 0.5:1 to 0.9:1; A method of imparting flexibility to a curable composition, wherein the diluent and the nutshell oil-derived epoxy-functionalized resin are different components.

21. 21. The method of claim 20, further comprising sealing the seam with a curable composition.

22. 21. The method of claim 20, further comprising coating the outer periphery of the first tube with a curable composition to join the outer periphery of the first tube with the inner periphery of the second tube.

23. 21. The method of claim 20, further comprising sealing the seams of the electrodeposited metal with a curable composition.

24. 21. The method of claim 20, further comprising sealing the overcoated metal joint with a curable composition.

25. applying a curable composition to uncoated oily metal; pretreating the curable composition and the uncoated oiled metal; applying a layer of a heat-cured topcoat or powder coating to the pre-treated curable composition and uncoated oily metal; 23. The method of claim 22, further comprising:

26. mixing the epoxy-rubber copolymer adduct and the curing agent to obtain a mixture; and mixing an epoxy-functionalized resin derived from nutshell oil into the mixture to obtain a curable composition. Including, 2. The method for producing a curable composition according to claim 1, wherein the weight ratio of the sum of the diluent and the nutshell oil-derived epoxy-functionalized resin to the epoxy-rubber copolymer adduct is in the range of 0.5:1 to 0.9:

1.

27. 27. The method of claim 26, wherein a diluent derived from nut shell oil is added during at least one mixing step.

28. 27. The method of claim 26, further comprising mixing a nutshell oil-derived diluent into the mixture, wherein the diluent and the nutshell oil-derived epoxy-functionalized resin are different components.

29. acrylonitrile-butadiene copolymer-epoxy adduct, hardener, Hydrophobic fumed silica additive, adhesion promoters, and providing a curable composition comprising a nonionic silane dispersant; adding an epoxy-functionalized resin derived from nutshell oil; and Adding a diluent Including, the epoxy-functionalized resin is derived from a nut shell oil selected from the group consisting of almond oil, pine nut oil, walnut oil, Brazil nut oil, hazelnut oil, pistachio oil, peanut oil, cashew nut oil, coconut oil, chestnut oil, sunflower seed oil, macadamia nut oil, butternut oil, walnut oil, and combinations thereof, functionalized with at least one epoxy group; the diluent is derived from a nut shell oil, and the nut shell oil is selected from the group consisting of almond oil, pine nut oil, walnut oil, Brazil nut oil, hazelnut oil, pistachio oil, peanut oil, cashew nut oil, coconut oil, chestnut oil, sunflower seed oil, macadamia nut oil, butternut oil, walnut oil, and combinations thereof, functionalized with at least one epoxy group; a weight ratio of the sum of the diluent and the nutshell oil-derived epoxy-functionalized resin to the epoxy-rubber copolymer adduct is in the range of 0.5:1 to 0.9:1; A method for improving adhesion of a curable composition to oiled metal, wherein the diluent and the nutshell oil-derived epoxy-functionalized resin are different components.

30. 10. The composition of claim 1, wherein the epoxy-rubber copolymer adduct is an acrylonitrile-butadiene copolymer-epoxy adduct present in an amount of at least 47% of the total composition.

31. 10. The composition of claim 1, wherein the weight ratio of the sum of the diluent and the epoxy-functionalized resin to the epoxy-rubber copolymer adduct is 0.9 or less.

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