2-Component Phosphate Ester-Based Elastomer Epoxy Composition and Uses thereof

Abstract

The present invention provides a two-component system comprising: a first component comprising one or more epoxy resins; a second component comprising one or more phosphate esters; and an elastomer composition that is cured at a temperature of about 0°C to about 50°C when the first component and the second component are mixed, and a method for using the two-component system.

Description

Technology Field

[0001] The present invention generally relates to a composition having a first component and a second component and a method of using said composition. More specifically, the present invention relates to a two-component epoxy and phosphate ester-based cured elastomer material capable of adhering to various substrates, which can be used as a gasket and sealant material that foams in place. Background Technology

[0002] Gasket and sealant materials are frequently used in the transportation and construction industries for various purposes. For example, gasket materials can provide one or more of the following: sealing, water and wind separation, contamination and dust blockage, and rattle prevention.

[0003] Die-cut gasket and sealant materials have been used in industry, particularly in the transportation and construction sectors. Typically, die-cut peel-off and adhesive gasket / seal materials include a foam formed prior to application to the workpiece, and adhesion to the workpiece is achieved via an adhesive, such as a pressure-sensitive adhesive. Some disadvantages of die-cut gasket / seal materials include the additional labor and process resources inherent in the die-cut process, waste generated by the die-cut, and the need for a separate adhesive.

[0004] In-situ foaming reactions allow gaskets and sealing materials to be dispensed directly onto the workpiece. When room-temperature activation (e.g., expansion and curing) is required, polyurethane foams are the most common. Polyurethane foams have numerous drawbacks, some of which include the inclusion of isocyanate-functional monomers or oligomers, high VOCs, limited adhesion to certain substrates, poor hydrolytic resistance in wet or humid environments, unsuitability for use in slow-reaction systems, high sensitivity to temperature changes during dispensing and foaming, and the need for high specificity in mixing ratios during formulation, where each formulation is sensitive to the mixing ratio. Another type of in-situ curing gasket / seal material is silicone-based. These have their own disadvantages, including poor tear resistance on various substrates, high cost, and a lack of control over expansion and stiffness.

[0005] As an alternative to polyurethane foams, phosphoric acid has been used for in-situ foaming reactions in polymeric materials. However, because the reaction time with phosphoric acid is very fast, it is not suitable for assembly processes that require time to position the polymeric material on a surface before foaming. Therefore, a somewhat delayed reaction time may be desirable. In some situations, there may be concerns regarding the low pH and splash risk of phosphoric acid. Thus, alternative materials with a high pH and reduced splash risk may be desirable. The difficulty in manufacturing elastomer materials due to the plefunctionality of phosphoric acid is another drawback of using it. There is a significant difference in viscosity between phosphoric acid and polymeric materials. This causes problems in both the manufacturing (e.g., mixing) and storage of the material. Additionally, since phosphoric acid has a much lower molecular weight than many polymeric materials, it results in undesirable mixing ratios. Mixing ratios of relatively similar 1:1, 2:1, or 4:1 (typically monomer or oligomeric material to phosphoric acid) are preferred. Finally, the high reactivity of phosphoric acid makes it difficult to formulate adhesive and sealant materials, as many chemical components can become unstable when used with it. It would be desirable to include various different moietyes that may be advantageous for adhesion, physical or chemical compatibility, mechanical properties, or other reasons.

[0006] International Publication No. WO 2016 / 149700 A1 (incorporated herein by reference for all purposes) discloses the use of phosphate esters as substitutes for phosphoric acid.

[0007] Notwithstanding the foregoing teachings, there is a need for improved elastomer materials that can be used as gaskets and sealing materials. There is a need for gaskets and sealing materials that are in-situ forming foams that cure at room temperature (e.g., ambient temperature). There is a need for gaskets and sealing materials that provide expansion and crosslinking over a wide range of ambient temperatures compared to known gaskets and sealing materials. There is a need for gaskets and sealing materials that provide adhesion to a wide range of substrates, including untreated and uncleaned substrates. There is a need for gaskets and sealing materials that use components capable of curing and foaming without the need for additional components. There is a need for gaskets and sealing materials that provide desirable fire, smoke, and toxicity (FST) properties while eliminating or reducing the use of undesirable agents. The problem to be solved

[0008] These teachings provide one or more of the advantages mentioned above. The gasket and sealing materials of the present invention may be used for one or more of cavity filling, sealing, or damping. means of solving the problem

[0009] The present invention provides a two-component system comprising: a first component comprising one or more epoxy resins; and a second component comprising one or more phosphate esters. When the first component and the second component are mixed, the composition can react to produce an acceptable finished product over a temperature range of about 0°C to about 50°C. Optionally, a heat source may be used to reduce the time to reach a dry touch (e.g., non-stick) state.

[0010] The present invention provides a two-component system comprising: a first component comprising one or more epoxy resins which may be liquid or solid epoxy, flexible epoxy resin, or aliphatic polyfunctional epoxy resin, one or more reactive diluents, and one or more first component additives; and a second component comprising a first phosphate ester, optionally a second phosphate ester, optionally a third phosphate ester, and one or more second component additives; wherein, when the first component and the second component are mixed to form a curable composition, the curable composition is cured at a temperature of about 0°C to about 50°C.

[0011] The second component may include a third phosphate ester. The second component may include at least one phosphate ester that is a product of the reaction between phosphoric acid and a mono-functional epoxy. One or more phosphate esters may include phosphate esters derived from cashew nut shell liquid (CNSL). The second component may include partially added phosphoric acid.

[0012] The first component may include one or more first component additives. One or more first component additives may include a metal carbonate which may be calcium carbonate, one or more minerals, reinforcing fibers, hydrophobic silica, or any combination thereof. Calcium carbonate may be present in an amount of about 2% to about 40% by weight of side A of the composition (e.g., the first component). Calcium carbonate may include ultrafine calcium carbonate, fine calcium carbonate, intermediate fine calcium carbonate, or any combination thereof. The first component may include fine calcium carbonate in an amount of about 4% to about 8% by weight. The first component may include intermediate fine calcium carbonate in an amount of about 13% to about 18% by weight.

[0013] The second component may include one or more second component additives. One or more second component additives may include minerals, reinforcing fibers, hydrophobic silica, or any combination thereof.

[0014] One or more epoxy resins may comprise one or more liquid epoxy resins, one or more flexible epoxy resins, one or more aliphatic polyfunctional epoxy resins, one or more reactive diluents, or any combination thereof. One or more epoxy resins may comprise a reaction product of epichlorohydrin and bisphenol A. One or more epoxy resins may be present in an amount of about 5% by weight to about 30% by weight. One or more epoxy resins (which may be flexible epoxy resins) may comprise difunctional glycidyl ether epoxy resins, unmodified BPA-based epoxy resins, polyfunctional epoxidized polybutadiene resins, or any combination thereof. To produce a final composition that is an elastomer, one or more of the formulated product components are expected to be flexible or elastomers. One or more epoxy resins may be present in an amount of about 10% by weight to about 45% by weight. One or more aliphatic polyfunctional epoxy resins may include epoxidized sorbitol. One or more aliphatic polyfunctional epoxy resins may be present in an amount of about 1% by weight to about 30% by weight. One or more reactive diluents may include polyglycol diglycidyl ether, trimethylolethane triglycidyl, or both. One or more reactive diluents may be present in an amount of about 4% by weight to about 25% by weight.

[0015] The reaction temperature may be about 0°C to about 50°C. The reaction temperature may be about 15°C to about 25°C. The curing time of the curable composition may be about 5 minutes to about 25 minutes, which can be accelerated using a heating source. The curing time of the curable composition may be about 7 minutes to about 10 minutes. The resulting reaction product may have a volume expansion of about 100% to about 800%. The resulting reaction product may have a volume expansion of about 400% to about 500%.

[0016] The curable composition may be dispensed onto any surface that can benefit from the foamed elastomer material. This may include a workpiece made of an automotive component. The reaction product of the curable composition may be a gasket or a sealant. The two-component system may not contain a latent curing agent, a curing accelerator, or both.

[0017] The teachings of this specification also relate to a method comprising: providing a two-component system comprising a first component and a second component, wherein the first component comprises one or more epoxy resins and the second component comprises one or more phosphate esters; and mixing the first component and the second component to form a reaction product, wherein when the first component and the second component are mixed to produce a curable composition, the curable composition is cured at a temperature of about 0°C to about 50°C.

[0018] The second component may include two or three different phosphate esters. The first component may include one or more first component additives. The second component may include one or more second component additives. One or more first component additives may include calcium carbonate.

[0019] The above method may include a step of curing the composition at a temperature of about 10°C to about 35°C, said curing may occur at a temperature of about 15°C to about 25°C, and the curing time of the curable composition may be about 5 minutes to about 15 minutes. The curing time of the curable composition may be about 7 minutes to about 10 minutes. The reaction product may have a volume expansion of about 100% to about 800%. The reaction product may have a volume expansion of about 400% to about 500%.

[0020] The above method may include the step of dispensing a curable composition onto a workpiece made of an automobile component. The reaction product of the curable composition may be a gasket or a sealant. The two-component system may not include a latent curing agent, a curing accelerator, or both. Specific details for implementing the invention

[0021] The teachings herein satisfy one or more of the above needs by the improved compositions and methods described herein. The descriptions and examples provided herein are intended to inform those skilled in the art of the teachings, their principles, and their practical applications. Those skilled in the art may adapt and apply the teachings in various forms as best suited to the requirements of a particular use. Accordingly, specific embodiments of the teachings as presented are not intended to exclude or limit the teachings. Therefore, the scope of the teachings should not be determined by reference to the descriptions above, but rather by reference to the appended claims, along with the full scope of equivalents for which such claims are qualified. The disclosures of all papers and references, including patent applications and publications, are referred to by reference for all purposes. Other combinations are also possible, such as those derived from the claims below, which are also referred to by reference in the descriptions provided herein.

[0022] This application claims the benefit of the filing date of U.S. Provisional Application No. 62 / 828,693 filed on April 3, 2019, the contents of which are incorporated herein by reference for all purposes.

[0023] The present teaching provides a composition that may be a two-part composition comprising an A-side (i.e., "first component") and a B-side (i.e., "second component"). When mixed, the two-part composition may form a curable composition, and the reaction product may be an elastomer material that can be used as a gasket or sealing material when fully cured.

[0024] The A-side may comprise one or more epoxy resins, one or more additives, one or more monomers, or both. The one or more epoxy resins may comprise one or more liquid epoxy resins, one or more flexible epoxy resins, one or more epoxyphenol novolak resins, one or more aliphatic polyfunctional epoxy resins, one or more reactive diluents, one or more silane-modified epoxy resins, one or more monomers, or any combination thereof. The one or more additives may comprise one or more toughening agents (e.g., core-shell polymer particles), metal carbonates, minerals, reinforcing fibers, hydrophobic silica, tabula alumina, or any combination thereof.

[0025] The B-side may comprise one or more phosphate esters, phosphoric acid, one or more additives, one or more monomers, or any combination thereof. One or more phosphate esters may comprise a first phosphate ester, a second phosphate ester, a third phosphate ester, or any combination thereof. One or more additives may comprise a mineral, a reinforcing fiber, hydrophobic silica, or any combination thereof.

[0026] One or more phosphate esters may be one or more custom phosphate esters. One or more custom phosphate esters may be produced by the reaction of phosphoric acid with various alcohols. One or more custom phosphate esters may be produced by the reaction of phosphoric acid with the epoxide group of a phosphate ester precursor (i.e., the component that has not yet reacted with the phosphoric acid). One or more custom phosphate esters may be prepared by the reaction of phosphoric acid with the glycidyl ether of cashew nut shell liquid (CNSL), as sold commercially under the trade name Cardolite® LITE 2513HP from Cardolite Corporation (Monmouth, Yungtion, New Jersey). One or more custom phosphate esters may be prepared by the reaction of phosphoric acid with the phenyl glycidyl ether, as sold commercially under the trade name ERISYS® GE-13 from CVC Thermoset Specialties (Moorestown, New Jersey). One or more custom phosphate esters can be prepared by the reaction of phosphoric acid with 2-ethylhexyl glycidyl ether, as sold under the trade name ERISYS® GE-6, which is commercially available from CVC Thermoset Specialties (Moorestown, New Jersey). One or more custom phosphate esters can be prepared by the reaction of phosphoric acid with epoxidized para-tertylphenol, as sold under the trade name ERISYS® GE-11, which is commercially available from CVC Thermoset Specialties (Moorestown, New Jersey). One or more custom phosphate esters may generally be reaction products of phosphoric acid and mono-epoxide functional molecules.

[0027] One or more phosphate esters may be one or more commercially pre-reacted phosphate esters. One or more commercially pre-reacted phosphate esters, when replaced on the B-side instead of the customized phosphate ester, may produce a curable composition that reacts more slowly and foams, presumably due to a lower amount of free phosphate. The reaction and foaming of one or more commercially pre-reacted phosphate esters may be improved (i.e., enhanced) by the addition of phosphate on the B-side. One or more commercially pre-reacted phosphate esters may have a pH of about 1 to 3 in an aqueous solution. One or more commercially pre-reacted phosphate esters may have a viscosity of about 32,500 cP to about 42,500 cP at 25°C as measured according to ASTM D445. One or more commercially pre-reacted phosphate esters may be nonylphenol ethoxylated phosphate esters. Examples of suitable commercially pre-reacted phosphate esters may be those commercially available from Ashland, Inc. (Covington, Kentucky) under the trade names Dextrol™ OC-110, Dextrol OC-40, and Strodex MO-100.

[0028] Commercially pre-reacted phosphate esters may be present on the B-side. One or more commercially pre-reacted phosphate esters may be present in an amount of about 5% to about 50% by weight of the B-side. One or more commercially pre-reacted phosphate esters may be present in an amount of about 0.1% to about 30% by weight of the B-side. One or more commercially pre-reacted phosphate esters may be present in an amount of about 10% to about 14% by weight of the B-side. One or more commercially pre-reacted phosphate esters may be present in an amount of about 12% by weight of the B-side.

[0029] One or more phosphate esters can be produced by a reaction of a stoichiometric ratio of a phosphate ester precursor to phosphoric acid. One or more phosphate esters can be prepared by a reaction of about 0.7:1 of a phosphate ester precursor to phosphoric acid to about 1:0.7 of a phosphate ester precursor to phosphoric acid. One or more phosphate esters can be prepared by a reaction of about 0.8:1 of a phosphate ester precursor to phosphoric acid to about 1:0.8 of a phosphate ester precursor to phosphoric acid. One or more phosphate esters can be prepared by a reaction of about 0.9:1 of a phosphate ester precursor to phosphoric acid to about 1:0.9 of a phosphate ester precursor to phosphoric acid. One or more phosphate esters can be prepared by a reaction of about 1:1 of a phosphate ester precursor to phosphoric acid. One or more phosphate esters can be prepared by a reaction of about 0.8:1 of a phosphate ester precursor to phosphoric acid.

[0030] Cashew nut shell liquid (CNSL) may comprise a chemical substance typically extracted from cashew nut shell liquid (CNSL) comprising anacardic acid, cardol, cardanol, or any combination thereof. Preferably, the glycidyl ether of the cashew nut shell liquid (CNSL) is a glycidyl ether of cardanol.

[0031] One or more phosphate esters may be selected from mono-esters, di-esters, or triesters as shown below.

[0032]

[0033] mono-ester di-ester tri-ester

[0034] One or more phosphate esters can be obtained by reacting an epoxide group with a phosphoric acid as shown below:

[0035]

[0036] The B-side may comprise one or more phosphate esters, one or more phosphate ester precursors, or both. The B-side may comprise one or more phosphate ester precursors that can be combined with phosphoric acid before combination with the A-side. The B-side may comprise one or more phosphate esters that undergo a pre-reaction (i.e., epoxide and phosphate reaction) before addition to the B-side.

[0037] The first phosphate ester may be the reaction product of glycidyl ether and phosphoric acid in cashew nut shell liquid (CNSL) (e.g., Cardolite® LITE 2513HP). The second phosphate ester may be the reaction product of stoichiometric amounts of approximately 1:1 2-ethylhexyl glycidyl to phosphoric acid (e.g., ERISYS® GE-6). The third phosphate ester may be the reaction product of stoichiometric amounts of 0.8:1 phosphoric acid and 2-ethylhexyl glycidyl ether (e.g., ERISYS® GE-6). However, many possibilities exist for the first, second, or third phosphate esters.

[0038] The first phosphate ester may be present in an amount of about 10% to about 60% by weight of the B-side. The first phosphate ester may be present in an amount of about 25% to about 35% by weight of the B-side. The first phosphate ester may be present in an amount of about 28% to about 32% by weight of the B-side. The first phosphate ester may be present in an amount of about 32% by weight of the B-side. The second phosphate ester may be present in an amount of about 5% to about 40% by weight of the B-side. The second phosphate ester may be present in an amount of about 15% to about 25% by weight of the B-side. The second phosphate ester may be present in an amount of about 18% to about 22% by weight of the B-side. The second phosphate ester may be present in an amount of about 21% by weight of the B-side. The tertian phosphate ester may be present in an amount of about 10% to about 65% by weight of the B-side. The tertian phosphate ester may be present in an amount of about 35% to about 45% by weight of the B-side. The tertian phosphate ester may be present in an amount of about 42% by weight of the B-side. The tertian phosphate ester may be present in an amount of about 58% by weight of the B-side. The tertian phosphate ester may be present in an amount of about 60% by weight of the B-side.

[0039] The B-side may contain phosphoric acid. The phosphoric acid may be ortho-phosphoric acid, polyphosphoric acid, or both. The phosphoric acid may be polyphosphoric acid. The phosphoric acid may be a free acid that is added independently of or both of the one or more phosphoric acid esters. Adding phosphoric acid to the B-side may result in increased expansion (e.g., foaming) of the resulting reaction product. Adding phosphoric acid to the B-side may increase the reactivity of the two-part system, helping to maintain the desired level of expansion, curing, or both when the temperature is below 23°C.

[0040] Independently added phosphoric acid may be present in an aqueous solution of 85% or more (i.e., reagent grade). Independently added phosphoric acid may be present in an amount of about 1% to about 20% by weight of the B-side. Independently added phosphoric acid may be present in an amount of about 2% to about 6% by weight of the B-side. Independently added phosphoric acid may be present in an amount of about 4% by weight of the B-side.

[0041] One or more phosphate esters prepared from the reaction of phosphoric acid and a phosphate ester precursor may contain free acid. One or more phosphate esters may have about 1% or more free acid, about 3% or more free acid, about 5% or more free acid, about 15% or less free acid, about 13% or less free acid, or even about 11% or less free acid.

[0042] A two-component system can foam as a result of the reaction between an acid and a metal carbonate or metal bicarbonate upon the addition of the A-side and the B-side, thereby causing the release of a gas (e.g., carbon dioxide) that acts as a chemical blowing agent. Such reaction mechanism is described in U.S. Patent No. 5,648,401 (incorporated herein by reference for all purposes).

[0043] The reaction, foaming, or both may occur at a temperature of about 50°C or lower, about 30°C or lower, about 20°C or lower, or even about 0°C or lower. The curing, foaming, or both may occur at a temperature of about 0°C or higher, about 10°C or higher, or even about 20°C or higher. The curing, foaming, or both may occur at a temperature of about 10°C to about 35°C, and the curing, foaming, or both may occur at a temperature of about 10°C. The curing, foaming, or both may occur at room temperature (e.g., a temperature of about 15°C to about 25°C). The curing, foaming, or both may occur at a temperature of about 23°C.

[0044] The content of this instruction assumes a relatively rapid curing time, foaming time, or both compared to other curing agents or curing systems that occur without the addition of stimulation (e.g., at room temperature). The curing time of the reaction product may be 75 minutes or less, 50 minutes or less, 30 minutes or less, 20 minutes or less, 2 minutes or more, 8 minutes or more, or even 16 minutes or more. The curing time of the resulting reaction product may be about 5 minutes to about 20 minutes. The curing time of the resulting reaction product may be about 10 minutes. The curing time of the resulting reaction product may be about 7 minutes. The curing time of the resulting reaction product may be about 5 minutes.

[0045] Foaming may begin before the complete reaction of the generated reaction product. The foaming time of the reaction product (i.e., the time frame in which the 2-component system actively foams) may be 30 minutes or less, or even 20 minutes or less. The foaming time of the reaction product may be about 1 minute to about 10 minutes. The foaming time of the reaction product may be about 5 minutes. The foaming time of the reaction product may be about 7 minutes.

[0046] The A-side may comprise one or more epoxide-functional materials (i.e., one or more epoxy resins). The one or more epoxy resins may be any conventional dimer, oligomer, or polymeric epoxy resin. The one or more epoxy resins may contain at least one epoxide functional group (i.e., monofunctional) or more than one epoxide functional group (i.e., polyfunctional). The one or more epoxy resins may contain one or more epoxide functional groups, two or more epoxide functional groups, three or more epoxide functional groups, or even four or more epoxide functional groups. The one or more epoxy resins may be modified epoxy resins (e.g., silane modified, modified elastomer, etc.). The one or more epoxy resins may be aliphatic, alicyclic, aromatic, etc., or any combination thereof. One or more epoxy resins may be supplied as a solid (e.g., pellets, chunks, pieces, etc., or any combination thereof) or a liquid (e.g., liquid epoxy resin). However, if solid resins are used, they may first be dissolved in a liquid resin or another suitable solvent. As used herein, unless otherwise described, an epoxy resin is a solid when it is solid at a temperature of 23°C and a liquid resin when it is liquid at a temperature of 23°C. One or more epoxy resins may include one or more liquid epoxy resins, one or more flexible epoxy resins, one or more epoxyphenol novolak resins, one or more aliphatic polyfunctional epoxy resins, one or more reactive diluents, one or more silane-modified epoxy resins, or any combination thereof.

[0047] A two-component system may comprise one or more liquid epoxy resins. A two-part system may comprise one or more liquid epoxy resins. The liquid epoxy resin may function as a base for the epoxy resin component. The liquid epoxy resin may be a reaction product of epichlorohydrin (hereinafter "EPH") and any ordinary bisphenol. The liquid epoxy resin may be a reaction product of EPH and bisphenol A (hereinafter "BPA"), bisphenol F (hereinafter "BPF"), or both. One or more liquid epoxy resins (which may be standard or commercial liquid epoxy resins) may have an epoxide equivalent (hereinafter "EEW") of about 100 g / equivalent to about 1000 g / equivalent as measured according to ASTM D 1652-9775. The liquid epoxy resin may have an epoxide percentage of about 20 to about 25. One or more liquid epoxy resins may have a viscosity of about 10 cP to about 100,000 cP at 25°C as measured according to ASTM D445. An example of a suitable BPA-based liquid epoxy resin may be DER™ 331, which is commercially available from The Olin Corporation (Clayton, Missouri). Additionally, an example of a BP-based liquid epoxy resin may be YDF-170, which is commercially available from Kookdo Chemical (Seoul, South Korea).

[0048] One or more liquid epoxy resins may be present as part of the A-side. One or more liquid epoxy resins may be present in an amount of about 4% to about 50% by weight of the A-side. One or more liquid epoxy resins may be present in an amount of about 10% to about 30% by weight of the A-side. One or more liquid epoxy resins may be present in an amount of about 8% by weight of the A-side.

[0049] The two-component system may comprise one or more flexible epoxy resins. One or more flexible epoxy resins may have functions such as reducing elastic modulus, increasing deformation to failure, reducing recovery time, reducing degree of crosslinking density, increasing impact resistance, improving adhesion, improving peel resistance, or any combination thereof. One or more flexible epoxy resins may improve the gas trapping ability of the two-part system by acting as viscosity modifiers. One or more flexible epoxy resins may be difunctional glycidyl ether epoxy resins, unmodified BPA-based epoxy resins, multifunctional epoxide-containing polybutadiene resins, or any combination thereof. One or more flexible epoxy resins may have an EEW of about 260 to about 500 as measured according to ASTM D1652-97. One or more flexible epoxy resins may have a viscosity of about 700 cP to about 500,000 cP at 25°C when measured according to ASTM D445. Examples of suitable flexible epoxy resins may include NC-514 (commercially available from Cardolite Corporation, Monmouth, Yungtion, New Jersey), Araldite® PY 4122 (commercially available from Huntsman Advanced Materials, Inc., Salt Lake City, Utah), Poly bd® 605E (commercially available from Cray Valley, Exton, Pennsylvania), or any combination thereof.

[0050] One or more flexible epoxy resins may be present on the A-side. One or more flexible epoxy resins may be present in an amount of about 10% to about 50% by weight of the A-side. One or more flexible epoxy resins may be present in an amount of about 35% to about 45% by weight of the A-side. One or more flexible epoxy resins may be present in an amount of about 39% by weight of the A-side. One or more flexible epoxy resins may include a difunctional glycidyl ether epoxy resin in an amount of about 10% to about 18% by weight of the A-side, an unmodified BPA-based epoxy resin in an amount of about 8% to about 16% by weight of the A-side, and a multifunctional epoxide-modified polybutadiene resin in an amount of about 8% to about 16% by weight of the A-side. One or more flexible epoxy resins may comprise about 14% by weight of a difunctional glycidyl ether epoxy resin on the A-side, about 12% by weight of an unmodified BPA-based epoxy resin on the A-side, and 12% by weight of a polyfunctional epoxidized polybutadiene resin on the A-side. The two-component system may comprise a two-functional glycidyl ether epoxy resin, a difunctional epoxy derived from cardanol, and a polyfunctional epoxidized polybutadiene resin in a ratio of about 1:1:1. The two-component system may comprise a two-functional glycidyl ether epoxy resin, a difunctional epoxy derived from cardanol, and a polyfunctional epoxidized polybutadiene resin in a ratio of about 1:0.8:0.8. The two-component system may comprise a difunctional glycidyl ether epoxy resin, a difunctional epoxy derived from cardanol, and a multifunctional epoxidized polybutadiene resin, and is included in a ratio of about 1:0.9:0.9.

[0051] The two-component system described herein may also comprise one or more epoxyphenol novolak resins. One or more epoxyphenol novolak resins may function to impart chemical resistance, solvent resistance, temperature resistance, or any combination thereof to the reaction product. One or more epoxyphenol novolak resins may be present as a portion of the A-side. One or more epoxyphenol novolak resins may have an EEW of about 165 g / equivalent to about 183 g / equivalent when measured according to ASTM D 1652-9775. One or more epoxyphenol novolak resins may have an average epoxy functional group of about 2.1 to about 6.5. It is also important to control the reaction rate and the ability to prevent foam collapse during and / or after the reaction process. One or more epoxy phenol novolak resins may have a viscosity of about 18,000 cP to about 30,000 cP at 25°C when measured according to ASTM D445. Examples of suitable epoxy phenol novolak resins may be those commercially available from CVC Thermoset Specialties (Moorestown, New Jersey) and sold under the trade names Epalloy® 8250 and Epalloy® 8330.

[0052] One or more epoxyphenol novolak resins may be present in an amount of about 30% to about 50% by weight of the A-side. One or more epoxyphenol novolak resins may be present in an amount of about 35% to about 45% by weight of the first component or the A-side. One or more epoxyphenol novolak resins may be present in an amount of about 38% to about 42% by weight of the A-side. One or more epoxyphenol novolak resins may be present in an amount of about 42% by weight of the A-side. One or more epoxyphenol novolak resins may include an about 3.6 functional epoxyphenol novolak resin present in an amount of about 2% to about 18% by weight of the A-side and an about 6.5 functional epoxy novolak resin present in an amount of about 22% to about 32% by weight of the A-side. One or more epoxyphenol novolak resins may include an approximately 3.6 functional epoxyphenol novolak resin present in an amount of approximately 15% by weight of the A-side and an approximately 6.5 functional epoxyphenol novolak resin present in an amount of approximately 28% by weight of the A-side. The two-component system may include an approximately 3.6 functional epoxyphenol novolak resin and an approximately 6.5 functional epoxyphenol novolak resin in a ratio of approximately 1:2 to approximately 1:3.

[0053] The two-component system may comprise one or more aliphatic polyfunctional epoxy resins. One or more aliphatic polyfunctional epoxy resins may increase the degree of crosslinking of the reaction product and increase the chemical resistance of the reaction product, or increase both. These resins have the ability to increase the crosslinking density of the resulting reaction product while preserving or enhancing the elastomeric properties of the reaction product. Generally, polyfunctional materials will make the reaction product less elastic. One or more aliphatic polyfunctional epoxy resins may comprise epoxidized sorbitol. One or more aliphatic polyfunctional epoxy resins may have an EEW of about 160 g / equivalent to about 195 g / equivalent when measured according to ASTM D 1652-97. One or more aliphatic polyfunctional epoxy resins may have a viscosity of about 4,000 cP to about 18,000 cP at 25°C when measured according to ASTM D445. Examples of suitable aliphatic multifunctional epoxy resins may be those commercially available from CVC Thermoset Specialties (Moorestown, New Jersey), sold under the trade names ERISYS® GE-60 and ERISYS® GE-61.

[0054] One or more aliphatic multifunctional epoxy resins may be present as part of the A-side. One or more aliphatic multifunctional epoxy resins may be present in an amount of about 5% to about 20% by weight of the A-side. One or more aliphatic multifunctional epoxy resins may be present in an amount of about 8% to about 16% by weight of the A-side. One or more aliphatic multifunctional epoxy resins may be present in an amount of about 10% to about 14% by weight of the A-side. One or more aliphatic multifunctional epoxy resins may be present in an amount of about 12% by weight of the A-side.

[0055] The two-component system may include one or more reactive diluents. One or more reactive diluents may reduce the overall viscosity of the two-part system, alter the flow of the two-part system during the dispensing process or on the processed part after dispensing, or reduce the degree of crosslinking of the reaction product in single functional groups. In cases where the diluent is statistically more functional than the difunctional, the diluent may increase the crosslinking density. One or more reactive diluents may be polymers, thereby increasing the flexibility of the reaction product; one or more reactive diluents may be polyfunctional, thereby promoting increased crosslinking and imparting chemical resistance to the reaction product; or both. One or more reactive diluents may include polyglycol diglycidyl ether, trimethylolethane triglycidyl, or both. One or more reactive diluents may have an EEW of about 100 g / equivalent to about 300 g / equivalent when measured according to ASTM D1652-97. One or more reactive diluents may have a viscosity of about 10 cP to about 1000 cP at 25°C when measured according to ASTM D445. Examples of suitable reactive diluents may be those sold under the trade names ERISYS® GE-31 and ERISYS® GE-24, which are commercially available from CVC Thermoset Specialties (Moorestown, New Jersey).

[0056] One or more reactive diluents may be present in an amount of about 5% to about 20% by weight of the A-side. One or more reactive diluents may be present in an amount of about 8% to about 16% by weight of the A-side. One or more reactive diluents may be present in an amount of about 10% to about 14% by weight of the A-side. One or more reactive diluents may be present in an amount of about 13% by weight of the A-side. One or more reactive diluents may include polyglycol diglycidyl ether present in an amount of about 2% to about 6% by weight of the A-side, and trimethylolethane triglycidyl ether present in an amount of about 6% to about 14% of the A-side. One or more reactive diluents may include polyglycol diglycidyl ether present in an amount of about 4% by weight of the A-side, and trimethylolethane triglycidyl ether present in an amount of about 9% of the A-side. The two-component system may each include polyglycol diglycidyl ether and trimethylolethane triglycidyl ether in a ratio of about 1:2 to about 1:3.

[0057] The 2-component system may comprise one or more silane-modified epoxy resins. One or more silane-modified epoxy resins may function to impart improved adhesion to reaction products, particularly glass, metal, or both. An example of a suitable silane-modified epoxy resin may be one commercially available from Kookdo Chemical (located in South Korea) under the trade name EPOKUKDO® KSR-177. Another suitable material is a silicone prepolymer having a cycloaliphatic epoxide group. An example of such a material is available from Siltech Corporation, located in Ontario, Canada, under the trade name Silmer EPC Di-50.

[0058] One or more silane-modified epoxy resins may be present on the A-side. One or more silane-modified epoxy resins may be present in an amount of about 1% to about 15% by weight of the A-side. One or more silane-modified epoxy resins may be present in an amount of about 2% to about 6% by weight of the A-side. One or more silane-modified epoxy resins may be present in an amount of about 4% by weight of the A-side.

[0059] A two-component system may comprise one or more monomers. One or more monomers may function to impart adhesion properties of the reaction product to a metal substrate, increase the flexibility of the reaction product, increase the impact resistance of the reaction product, or any combination thereof. One or more monomers may be monofunctional, difunctional, or even polyfunctional. One or more monomers may be esterification reaction products of an alcohol and acrylic acid or methacrylic acid. One or more monomers may be monofunctional acrylic monomers. Preferably, one or more monomers may be a mixture of a methacrylate acid ester and 2-(2-ethoxyethoxy)ethyl acrylate. An example of a suitable monomer may be one sold under the trade name SR 9050, which is commercially available from Sartomer (Exton, Pennsylvania).

[0060] A two-component system may include one or more monomers on the A-side, the B-side, or both. One or more monomers may be present in an amount of about 0.1% to about 26% by weight of the A-side, the B-side, or both the A-side and the B-side. One or more monomers may be present in an amount of about 12% to about 24% by weight of the A-side, the B-side, or both the A-side and the B-side. One or more monomers may be present in an amount of about 14% to about 22% by weight of the A-side, the B-side, or both the A-side and the B-side. One or more monomers may be present in an amount of about 18% by weight of the A-side, the B-side, or both the A-side and the B-side.

[0061] Curing rate, degree of crosslinking, or both may be a function of the functionality of the two-component system (A-side and B-side). Higher-order functionality (i.e., the number of functional groups for one or more polymerizable components) may be required for a two-part system having a prepolymerized component with a shorter polymer length (i.e., lower viscosity); consequently, the lack of a structural backbone due to the shorter polymer is compensated by a higher degree of crosslinking. Lower-order functionality may be required for a two-part system having a prepolymerized component with a longer length (i.e., higher viscosity); consequently, the presence of more structural backbones due to the longer polymer excludes the need for higher functionality.

[0062] The activity of the B-side can be at least partially reduced by the reaction of the metal carbonate in the A-side with the phosphoric acid and phosphoric acid ester, and as a result, the activity of the B-side can be reduced in the in situ reaction mixture. The A-side may include a component with increased activity to compensate for the reduced function of the B-side. The A-side may be formulated to have increased activity by using a reactive component having a functional group higher than 2.

[0063] The 2-component system may include one or more additives. The one or more additives may include one or more toughening agents, calcium carbonate, minerals, reinforcing fibers, hydrophobic silica, tabular alumina, or any combination thereof.

[0064] A two-component system may include one or more toughening agents. One or more toughening agents may function to distribute energy within the reaction product (i.e., increase impact resistance). One or more toughening agents may contribute to increased T-peel strength. One or more toughening agents may include thermoplastic resins, thermosetting resins or thermosetting resins, elastomers, or any combination thereof. One or more toughening agents may include elastomers (including elastomer-containing materials), core-shell polymers (which may include, but are not limited to, elastomers), or both.

[0065] The core-shell polymer may comprise a first polymer material (i.e., core material) and a second polymer material (i.e., shell material). The first polymer material may be entirely encapsulated by the second polymer material. The core-shell polymer may comprise the first polymer material in an amount of about 30% or more, 50% or more, or even 70% or more. The first polymer material, the second polymer material, or both may comprise one, two, three, or even more than three polymers combined together, react together (e.g., polymerized sequentially, or both), or be part of a separate or identical core-shell polymer system. Examples of suitable core-shell polymers may be those commercially available from Kaneka North America LLC (Pasadena, Texas) under the trade names Kane Ace® MX-267 and MX-257.

[0066] The core-shell polymer may be present in an amount of about 1% to about 25% by weight of the A-side, B-side, or a combination of both A-side and B-side (e.g., if present in an amount of 10% by weight, it may be present in an amount of 5% of the A-side and 5% of the B-side). The core-shell polymer may be present in an amount of about 5% to about 20% by weight of the A-side, B-side, or a combination of both A-side and B-side. The core-shell polymer may be present in an amount of about 5% by weight of the A-side, B-side, or a combination of both A-side and B-side. The core-shell polymer may be present in an amount of about 17% by weight of the A-side, B-side, or a combination of both A-side and B-side.

[0067] The two-part system may comprise one or more metal carbonates. One or more metal carbonates may generate gas in the presence of acid, act as fillers, delay curing activity, and function to control the initiation or full extent or both of the foaming (e.g., expansion) process. One or more metal carbonates may be metal carbonates or metal bicarbonates. Examples of suitable metal carbonates include calcium carbonate, nickel carbonate, barium carbonate, sodium bicarbonate, and potassium bicarbonate. Preferably, one or more metal carbonates may comprise calcium carbonate. The total surface area of ​​the metal carbonate, metal bicarbonate, or both, which can control the expansion and curing of the two-part system and is thereby available to react with acid, is a function of both the particle size of the metal carbonate, metal bicarbonate, or both and the amount present in the two-part system.

[0068] Calcium carbonate (CaCO3) may be present as one or more calcium bicarbonate fillers. One or more calcium bicarbonate fillers may have a median particle size of about 1 to about 50 microns. Calcium carbonate may have a medium-fine particle size. For example, the median particle size of medium-fine calcium carbonate may be about 22 microns. An example of suitable medium-fine calcium carbonate may be Hubercarb® Q200, which is commercially available from Huber Engineered Materials, Atlanta, Georgia. Calcium carbonate may have a fine particle size. For example, the median particle size of fine calcium carbonate may be about 4 microns. An example of suitable fine calcium carbonate may be Hubercarb® Q4, which is commercially available from Huber Engineered Materials, Atlanta, Georgia. Calcium carbonate may have an ultrafine particle size. For example, the median particle size of the ultrafine calcium carbonate may be about 1 micron. An example of a suitable ultrafine calcium carbonate may be Hubercarb® Q2, which is commercially available from Huber Engineered Materials, Atlanta, Georgia. The two-part system may comprise medium-fine calcium carbonate, fine calcium carbonate, ultrafine calcium carbonate, or any combination thereof.

[0069] Calcium carbonate may be present in an amount of about 1% to about 25% by weight of the A-side. Calcium carbonate may be present in an amount of about 4% to about 18% by weight of the A-side. Calcium carbonate may be present in an amount of about 8% to about 12% by weight of the A-side. Calcium carbonate may be present in an amount of about 20% by weight of the A-side. Calcium carbonate may include fine calcium carbonate present in an amount of about 4% to about 8% by weight of the A-side and intermediate fine calcium carbonate present in an amount of about 13% to about 18% by weight of the A-side. The calcium carbonate may include fine calcium carbonate present in an amount of about 6% by weight of the A-side and intermediate fine calcium carbonate present in an amount of about 15% by weight of the A-side. Calcium carbonate may include fine calcium carbonate present in an amount of about 5% by weight of the A-side and intermediate fine calcium carbonate present in an amount of about 5% by weight of the A-side. The ratio of intermediate fine calcium carbonate to fine calcium carbonate may be about 3:1 to about 1:3. The ratio of intermediate fine calcium carbonate to fine calcium carbonate may be about 1:1.

[0070] Calcium carbonate may contain a coating agent. The coating agent may be any material that is destroyed during the activation process, the expansion process, or both, so that expansion is delayed, slowed, or both. The coating agent may be a wax, a fatty acid, or a combination thereof.

[0071] The two-component system may include one or more minerals. One or more minerals (i.e., mineral reinforcing agents) may function to structurally reinforce the reaction product. One or more minerals may improve the tensile strength, flexural strength, or both of the reaction product. One or more minerals may be any suitable silicate mineral, including but not limited to inosilicates (e.g., wollastonite) and phylosilicates (e.g., kaolinite, vermiculite, talc, muscovite, etc.). The characteristic appearance of individual crystals or crystal groups of one or more minerals may be acicular or needle-like. The median grain size of one or more minerals may be about 10 microns to about 20 microns. The median grain size may be about 12 microns to about 18 microns.

[0072] One or more minerals may include wollastonite (CaSiO3). The wollastonite may be relatively pure (i.e., less than 2 weight percent of impurities such as other metal oxides). The wollastonite may contain impurities including one or more oxides of iron, magnesium, manganese, aluminum, potassium, sodium, or strontium that substitute for calcium in the mineral structure. Examples of suitable wollastonite may be those commercially available from NYCO Minerals Inc. (Willsboro, New York) under the trade names NYGLOS® 12 and NYGLOS® 8.

[0073] One or more minerals may be present as part of the A-side, the B-side, or both. Wollastonite may be present in an amount of about 0.1% to about 10% by weight of the A-side, the B-side, or both the A-side and the B-side. Wollastonite may be present in an amount of about 3% to about 7% by weight of the A-side, the B-side, or both the A-side and the B-side. Wollastonite may be present in an amount of about 4% by weight of the A-side, the B-side, or both the A-side and the B-side.

[0074] Calcined kaolin clay may be present as part of the A-side. Calcined kaolin clay may be present in an amount of about 0.1% to about 5% by weight of the A-side. Calcined kaolin clay may be present in an amount of about 1% to about 4% by weight of the A-side, the B-side, or both the A-side and the B-side. Calcined kaolin clay may be present in an amount of about 2% by weight.

[0075] A two-component system may include one or more reinforcing fibers. The reinforcing fibers may function to structurally reinforce the reaction product. One or more reinforcing fibers may improve the tensile strength, flexural strength, or both of the reaction product. One or more reinforcing fibers may be present on the A-side, the B-side, or both. One or more reinforcing fibers may be homogeneously dispersed on the A-side, the B-side, or both. One or more reinforcing fibers may include polymer fibers, glass fibers (i.e., glass fibers), or both. Polymer fibers may include nylon, polyamide, polyester, polypropylene, polyethylene, polytetrafluoroethylene, aramid fibers (e.g., Kevlar®), or any combination thereof. Glass fibers may include alumino-borosilicate glass (“E-glass”), alkali-lime glass (“A-glass” or “C-glass”), electrical / chemical resistant glass (“E-CR-glass”), borosilicate glass (“D-glass”), alumino-silicate glass (“R-glass”) or “S-glass”), or any combination thereof. Reinforcing fibers may be chopped fibers. Reinforcing fibers may have a chopped length of about 0.1 cm or more, about 0.3 cm or more, or even about 0.6 cm or more. Reinforcing fibers may have a chopped length of about 2.0 cm or less, about 1.5 cm or less, or even about 1.0 cm or less. Examples of suitable glass fibers may be commercially available chopped strands from Jushi USA (Columbia, South Carolina).

[0076] Reinforcing fibers may be present in an amount of about 0.01 wt% to about 3 wt% in the A-side, B-side, or both the A-side and B-side. Reinforcing fibers may be present in an amount of about 0.1 wt% to about 1 wt% in the A-side, B-side, or both the A-side and B-side. Reinforcing fibers may be present in an amount of about 0.2 wt% in the A-side, B-side, or both the A-side and B-side. The two-component system may include one or more thixotropes for controlling viscosity.

[0077] The two-component system may include hydrophobic silica. The hydrophobic silica may function to control viscosity (e.g., thicken), control thixotropy, enhance hydrophobicity, or function in combination thereof. The hydrophobic silica may be fuming silica. The hydrophobic silica may be surface-treated. For example, the hydrophobic silica may be fuming silica surface-treated with polydimethylsiloxane (hereinafter "PDMS") or hexamethyldisilazane (hereinafter "HMDZ"). The hydrophobic silica may be present as a part of the A-side, the B-side, or both. An example of suitable hydrophobic silica is that which is commercially available from Evonik Corporation (Parshpany, New Jersey) under the trade name AEROSIL® R 202; and may be commercially available products sold under the trademarks CAB-O-SIL® TS-530 and TS-720 from Cabot Corporation (Boston, Massachusetts).

[0078] Hydrophobic silica may be present in an amount of about 0.25 wt% to about 6 wt% of the A-side, B-side, or both the A-side and B-side. Hydrophobic silica may be present in an amount of about 0.5 wt% to about 4 wt% of the A-side, B-side, or both the A-side and B-side. Hydrophobic silica may be present in an amount of about 1 wt% to about 2 wt% of the A-side, B-side, or both the A-side and B-side. Hydrophobic silica may be present in an amount of about 0.5 to about 2 wt% of the A-side. Hydrophobic silica may be present in an amount of about 3 wt% to about 5 wt% of the B-side. The ratio of hydrophobic silica to the A-side may be about 1:6 to about 6:1. The ratio of hydrophobic silica to the A-side may be about 1:4. The ratio of hydrophobic silica on the A-side to the B-side can be about 1:2 to about 2:1.

[0079] The two-part system may include tabula alumina. Tabula alumina may function to impart hardness, thermal shock resistance, mechanical shock resistance, high heat capacity, high electrical resistance, or any combination thereof to the reaction product. Tabula alumina may be alpha alumina converted into its corundum form (i.e., crystalline aluminum oxide) and calcined, and may be provided as granular or powder grades. Tabula alumina may be graded (i.e., size separated) from about 44 microns to about 4760 microns. Tabula alumina may be graded down to about 44 microns.

[0080] Tabula alumina may be present in an amount of about 0.1% to about 15% by weight of the A-side, B-side, or both the A-side and B-side. Tabula alumina may be present in an amount of about 4% to about 12% by weight of the A-side, B-side, or both the A-side and B-side. Tabula alumina may be present on the A-side in an amount of about 5% by weight. Tabula alumina may be present on the A-side in an amount of about 10% by weight.

[0081] A two-component system may include one or more functional additives to improve one or more various properties of the composition. Examples of suitable functional additives may include antioxidants, ozone inhibitors, UV absorbers, antistatic agents, colorants, coupling agents, curing agents, flame retardants, foaming agents, heat stabilizers, impact modifiers, lubricants, plasticizers, preservatives, processing aids, stabilizers, etc., and any combination thereof.

[0082] The viscosity of the A-side, B-side, or both may be sufficiently high at about 23°C to prevent the 2-part system from flowing undesirably into the area adjacent to the distributed bead when distributing the 2-part system on the workpiece, or to control the flow into the area adjacent to the distributed bead when distributing the 2-part system (i.e., to allow the desired amount of flow). The viscosity of the A-side, B-side, or both required to prevent undesirable flow or to control the flow may depend on the size of the distributed bead. For example, the thicker the bead of the distributed 2-part system, the higher the viscosity required to control unintended flow. The viscosity of the A-side at 23°C may be about 20,000 cp to about 50,000 cp, or even about 35,000 cp to about 45,000 cp at very low shear rates close to weakened conditions. At 23°C, the viscosity of the A-side and B-side may be about 250,000 cP to about 400,000 cP. At 10°C, the viscosity of the A-side may be about 280,000 cP to about 350,000 cP or even about 300,000 cP to about 325,000 cP. At 23°C, the viscosity of the B-side may be about 20,000 cP to about 50,000 cP or even about 35,000 cP to about 45,000 cP. At 10°C, the viscosity of the B-side may be about 130,000 cP to about 220,000 cP or even about 175,000 cP to about 195,000 cP.

[0083] When the A-side and B-side are mixed, the 2-component system can expand the original volume of the 2-component system by more than about 50%, more than about 100%, less than about 200%, less than about 800%, less than about 700%, or even less than about 600%. The 2-component system can expand the original volume of the 2-component system by about 400% to about 500%. The 2-component system can expand the original volume of the 2-component system by about 400%.

[0084] A two-component system may not contain a curing agent (i.e., a conventional curing agent), a curing accelerator, or both. Typical curing agents include Lewis bases (i.e., anionic catalysts), Lewis acids (i.e., cationic catalysts), UV catalysts, amines, anhydrides, phenols, thiols, or any combination thereof. Instead of the aforementioned curing agents, the two-component system may be cured by a polymerization reaction catalyzed by a phosphoric acid ester and an epoxide group, a hydroxyl group, or both. The two-component system may be cured and may also cause expansion through chemical interactions between the phosphoric acid ester and the metal carbonate. While utilizing the curing and expansion system of the present disclosure can reduce formulation complexity by reducing the total number of components (i.e., curing agent, curing accelerator, and foaming agent); however, it has been found that achieving the desired expansion and curing times becomes more challenging for optimization.

[0085] In one non-limiting embodiment of the present invention, the two-component system may comprise one or more of the following on the A-side (first component): liquid epoxy resin, flexible epoxy resin, aliphatic polyfunctional epoxy resin, reactive diluent, aramid pulp, medium fine calcium carbonate, fine calcium carbonate, hydrophobic silica, and wollastonite. The two-component system may comprise one or more of the following on the B-side (second component): a primary phosphate ester, a secondary phosphate ester, a tertiary phosphate ester, aramid fiber, and hydrophobic silica.

[0086] The two-component system can be mixed together in a ratio of 1:4 to 4:1, A-side to B-side. The two-component system can be mixed together in a ratio of 1:2 to 2:1, A-side to B-side. The two-component system can be mixed together in a ratio of 1:1, A-side to B-side. The two-component system can be mixed together in a ratio of 2:1, A-side to B-side.

[0087] A range of non-limiting exemplary formulations according to the present invention is provided in Table 1 below.

[0088] 1st component (A-side) weight% Liquid epoxy resin 6.0 - 10.0 Flexible epoxy resin 35.0 - 45.0 Aliphatic multifunctional epoxy resin 8.0 - 16.0 Reactive diluent 8.0 - 16.0 aramid fiber 0.1 - 1.0 Calcium carbonate (medium fine) 13.0 - 18.0 Calcium carbonate (fine) 4.0 - 8.0 fuming silica 0.5 - 2.0 wollastonite 3.0 - 7.0 2nd component (B-side) weight% monophosphate ester 25.0 - 35.0 disodium phosphate ester 15.0 - 25.0 3-phosphate ester 35.0 - 45.0 Aramid pulp 0.1 - 1.0 fuming silica 3.0 - 5.0

[0089] One important aspect of the gasket and sealing materials discussed herein is having an improved compression set (e.g., the resistance of the composition to permanent deformation after the applied force is removed according to ASTM D3571-17). Insufficient compression set leads to sealing failure of elastomer materials regarding water, dust, wind separation, and rattle prevention. Test samples were compressed to 50% of their cubic dimensions. Subsequently, the compressed cubes were placed in an oven at 70°C for 22 hours. They were removed and maintained at ambient temperature for a 30-minute recovery period. The resulting measured deformation was 10% lower. In addition to having high recovery from the compression set, low compressive stiffness is also desirable.

[0090] It may be desirable to achieve an appropriate compression set (e.g., less than 10% deformation and low compressive stiffness), a uniform cell structure, long elastomer chains, and a partially open cell composition while maintaining foam integrity. The ability to recover after deformation may be related to the retention of a high elastic portion of the composite loss modulus compared to the loss modulus. Storage and loss moduli are often expressed as G' (shear storage modulus) and G' (shear loss modulus), measured through means such as dynamic mechanical analysis (DMA). Therefore, structural aspects of the polymer structure that contribute to recovery compared to permanent deformation (e.g., creep) may be desirable. This involves methods that incorporate molecules with elastic elements to make the material less thermoplastic (i.e., higher crosslinking density) along with a more uniform cell structure. To achieve a uniform cell structure, a combination of fine metal carbonates, aliphatic polyfunctional epoxy resins, and epoxidized polybutadiene resins may be used. To maintain a higher crosslinking density, aliphatic polyfunctional epoxy resins may be used. Epoxidized polybutadiene resin, difunctional glycidyl ether epoxy resin, low-viscosity epoxy resin (reaction of epichlorohydrin and polypropylene glycol), and silicone prepolymers having alicyclic epoxy groups may be used on the A-side to improve elastomer properties. Diphosphate esters (glycidyl ether) The reaction product of cashew nut shell liquid and phosphoric acid can be used on the B-side to improve elastomer properties. Silicone prepolymers having alicyclic epoxy groups can also contribute to increased opening time.

[0091] Table 2 provides technical data of the formulation according to the present invention at a reaction temperature of 23°C, where the peak temperature may refer to the peak temperature reached during curing and may be a function of both the degree of crosslinking and the curing rate; a higher degree of crosslinking may provide a higher exothermic reaction; and since the reaction product absorbs heat faster than it dissipates from the exothermic reaction, a higher curing rate may generate a higher peak exothermic. Mechanical properties were measured according to ASTM D1621. Test samples were compressed to 50% of their cubic dimensions. The crosshead travel speed was maintained constant at 12.7 mm / min.

[0092] Physical properties Example of implementation appearance bright cream paste Mixing ratio based on volume ratio 2:1 Tested temperature 23℃ Time until expansion (seconds) 30 Expansion rate (%) 350 Curing time (minutes) 8 Hardened specific gravity (g / cm²) 3 ) 0.30 Peak fever 110 mechanical properties Peak stress (kPa) 36 Peak load (N) 22 Modulus (kPa) 100 Strain (%) at the peak 33 Yield stress (kPa) 23 Time (minutes) to recover to 100% after 1 week of 50% compression at 23℃ 2

[0093] Further examples of formulations according to the present invention are provided in Table 3 below. The stoichiometric amounts of phosphoric acid ester precursor versus phosphoric acid are shown in parentheses.

[0094] 1st component (A-side) Example 2 Liquid epoxy resin 9.0 Diglycidyl ether of bisphenol F 14.3 Epoxidized sorbitol 12.3 Unmodified epoxy resin 12.5 hydroxyl-terminated epoxidized polybutadiene 12.5 Aliphatic polyglycol diepoxide 4.0 Trimethylolethane triglycidyl ether 9.0 Aramid pulp 0.5 Calcium carbonate (medium fine particles) 15.0 Calcium carbonate (fine particle size) 6.0 fuming silica 1.0 wollastonite 4.0 gun 100.0 Component 2 (B-side) Monophosphate ester epoxy-reactive diluent / H3PO4(0.8:1) 31.8 Disodium phosphate ester epoxy-reactive diluent / H3PO4(1:1) 21.2 Disodium phosphate ester epoxy-reactive diluent / H3PO4(0.8:1) 42.5 Aramid pulp 0.2 fuming silica 4.2 gun 100.0

[0095] Table 4 provides technical data for the formulations according to Table 1 at a reaction temperature of 23°C. Compression modulus can be a function of the compressive stress (force per unit area) applied to the sample and the resulting compression (deformation). Therefore, elastomer materials generally require a lower compression modulus. Given two samples with uniform compression modulus, the sample with the lower density has a more reinforced matrix of the reaction product, which may result in a product of higher crosslinking. When observed as a ratio of density to compression modulus, a lower ratio may indicate that the matrix of the reaction product is stiffer overall. Comparative examples may include conventional die-cut, PSA-backed, and pre-foamed gaskets. Compression properties were measured according to ASTM D1621 using a 25.4 mm cube. The test sample was compressed to 50% of the cube's dimensions. The crosshead speed was maintained constant at 12.7 mm / min.

[0096] Comparison Example A Example 3 Example 4 Example 5 Example 6 A-side & B-side Density (g / cm³) 3 ) 0.46 0.34 0.34 0.40 0.30 Compression modulus (kPa) 170 247 164 216 236 ratio 0.0027 0.0014 0.0021 0.0019 0.0013 Example 7 Example 8 Example 9 Example 9 Example 10 A-side & B-side Density (g / cm³) 3 ) 0.27 0.30 0.28 0.28 0.32 Compression modulus (kPa) 305 173 103 96 328 ratio 0.0009 0.0017 0.0027 0.0029 0.0010

[0097] Further examples of formulations according to the present invention are provided in Table 5 below. The stoichiometric amounts of phosphoric acid ester precursor versus phosphoric acid are shown in parentheses.

[0098] 1st component (A-side) ) Example 11 Example 12 Bifunctional glycidyl ether epoxy resin 11.60 20.20 Epoxy phenolic novolak resin 4.83 Aliphatic multifunctional epoxy resin 29.95 24.04 Epoxidized polybutadiene resin 20.29 20.19 fabric softener 5.80 7.69 Liquid epoxy resin 6.76 4.81 silicone prepolymer 6.76 8.65 calcium carbonate 8.70 8.65 fuming silica 5.31 5.77 gun 100.0 100.0 2nd component (B-side) Monophosphate ester epoxy-reactive diluent / H3PO4(0.8:1) 50.99 87.21 Disodium phosphate ester epoxy-reactive diluent / H3PO4(1:1) 39.66 5.81 fuming silica 8.22 5.81 H3PO485% 1.13 1.17 gun 100.00 100.00

[0099] The two-component system may be provided as parallel cartridges, containers, or drums. The two-component system may be mixed before being applied to a workpiece. The two-component system may be applied to a workpiece through any suitable dispenser in which the two-component system is mixed before being applied to the workpiece. For example, the two-component system may be dispensed to a workpiece through a static mixer configured to deliver a mixed curable composition having an appropriate mixing ratio as described herein.

[0100] The resulting reaction product provides excellent adhesion to many substrates along with a fast curing time. The resulting reaction product can provide excellent adhesion to glass, metals, polymers (e.g., thermoplastics, thermosetting or thermosetting materials, or elastomers), or any combination thereof. In particular, the reaction product provides excellent adhesion to thermoplastics.

[0101] The two-component system may be cured and / or expanded before or after the complete assembly of the workpiece to which the two-component system is applied. For example, the two-component system may be distributed onto a first workpiece and may be cured and / or expanded, and then a second workpiece complementary to the first workpiece may be applied to the first workpiece. As another example, the two-component system may be distributed onto a first workpiece and a second workpiece complementary to the first workpiece may be applied to the first workpiece, and then the two-component system may be cured and / or expanded. A two-component system that is cured and / or expanded after the complete assembly of the workpiece may be expanded to fill the space between the first workpiece and the second workpiece. The first workpiece, the second workpiece, or both may include a groove in which the two-component system is distributed, expanded, or both. The two-component material may be distributed within the cavity.

[0102] Two-component systems can be used in transportation equipment. Two-component systems can be used in the automotive sector. Two-component systems can be used in fields including vehicle interiors, vehicle exteriors, HVAC ducts, side mirrors, electronic product packaging, tail lamps, headlamps, commercial vehicles, structures, etc.

[0103] The present teachings provide a method that may include the step of providing a two-component system, said two-component system comprising an A-side (i.e., a first component) and a B-side (i.e., a second component). The A-side comprises one or more epoxy resins, and the B-side comprises one or more phosphate esters and optionally phosphoric acid. The A-side and the B-side may be mixed to form a curable composition. The method may include the step of forming a reaction product by curing the curable composition at a temperature of less than 50°C. The method may include the step of mixing the first component and the second component to form a reaction product. The method may include the step of curing the reaction product of the first component and the reaction product of the second component at a temperature of less than 50°C. The method may use an A-side comprising one or more epoxy resins, calcium carbonate, or both. The method may use a B-side comprising one or more phosphate esters, phosphoric acid, or both. The method may be utilized by an A-side, a B-side, or both having one or more additives.

[0104] By using the teachings in this specification, it is possible to produce a gasket that exhibits sufficient flame retardancy to satisfy one or more requirements for demonstrating flame retardancy (e.g., to satisfy vertical combustion and / or smoke density requirements (or some other requirements) as set forth in 14 CFR §25.853 and 14 CFR §25.856 (14 CFR §25.853(a), and the reference appendix F and procedures cited herein, but not limited to these) (all of which are referred to by reference for all purposes).

[0105] As used herein, unless otherwise described, the teaching assumes that any member of a genus (list) may be excluded from the genus and / or any member of a Markush group may be excluded from the group.

[0106] Unless otherwise stated, any numerical value cited herein includes all values ​​from a lower value to a higher value in increments of one unit, provided that there is at least two unit separations between any lower value and any higher value. For example, when the amount of a component, attribute, or value of a process variable, such as temperature, pressure, time, etc., is, for example, 1 to 90, preferably 20 to 80, more preferably 30 to 70, the intermediate range of such values ​​(e.g., 15 to 85, 22 to 68, 43 to 51, 30 to 32, etc.) is intended to be within the teachings of this specification. Likewise, individual intermediate values ​​are also within the teachings of this specification. For values ​​less than 1, one unit is appropriately considered to be 0.0001, 0.001, 0.01, or 0.1. These are merely examples of what is specifically intended, and all possible combinations of numerical values ​​between the listed lowest and highest values ​​should be deemed to be expressed in this application in the same manner. As can be seen, the teaching of a quantity expressed as "parts by weight" in this specification also implies the same range expressed in weight percentages. Accordingly, the expression within a certain range expressed as "at least 'x' parts by weight of the obtained composition" also implies the teaching of the same mentioned range of "x" in weight percentage of the obtained composition.

[0107] Unless otherwise stated, all ranges include two endpoints and all values ​​between these endpoints. The use of “about” or “approximately” in relation to a range applies to the two endpoints of the range. Thus, “about 20 to 30” is intended to cover “about 20 to about 30” by including at least a specified endpoint. Unless otherwise stated, instruction by the term “about” or “approximate” in combination with a quantity covers not only the instruction of the mentioned quantity but also an approximation of the mentioned quantity. For example, the instruction “about 100” covers the instruction of 100.

[0108] The disclosures of all papers and references, including patent applications and publications, are taken by reference for all purposes. The term “essentially composed of” describing a combination will include the identified elements, components, constituents, or steps, and any other elements, components, constituents, or steps that do not substantially affect the fundamental and novel features of such combination. The use of the terms “comprising” or “including” describing a combination of elements, components, constituents, or steps in this specification also presupposes an embodiment composed of or essentially composed of such elements, components, constituents, or steps.

[0109] Multiple elements, components, constituents, or steps may be provided by a single integrated element, component, constituent, or step. Alternatively, the single integrated element, component, constituent, or step may be divided into separate multiple elements, components, constituents, or steps. Disclosures of "one" or "one" describing an element, component, constituent, or step are not intended to exclude additional elements, components, constituents, or steps.

[0110] The foregoing description is understood to be illustrative rather than limiting. Reading the foregoing description will make it apparent to those skilled in the art that many embodiments and applications other than those provided are possible. Accordingly, the scope of the invention should not be determined by reference to the foregoing description, but by reference to the appended claims, together with the full scope of equivalents for which such claims are qualified. The disclosures of all papers and references, including patent applications and publications, are taken by reference for all purposes. Any omission of any aspect of the subject matter disclosed herein in the following claims is not a disclaimer of such subject matter, nor should it be construed that the inventors did not consider such subject matter as part of the disclosed inventive subject matter.

Claims

Claim 1 a) a first component comprising at least one flexible epoxy resin, wherein the flexible epoxy resin is present in an amount of 35% to 45% by weight of the first component; b) a second component comprising at least three phosphate esters obtained by reacting an epoxide group with a phosphoric acid; wherein the phosphate esters comprise: a first phosphate ester is a reaction product of phosphoric acid with a glycidyl ether of cashew nut shell liquid (CNSL); a second phosphate ester is a reaction product of stoichiometric amounts of 1:1 2-ethylhexyl glycidyl to phosphoric acid; and a third phosphate ester is a reaction product of stoichiometric amounts of 0.8:1 2-ethylhexyl glycidyl to phosphoric acid; and wherein an elastomer curable composition is formed at room temperature when the first component and the second component are mixed. Claim 2 A two-component system according to claim 1, wherein the first component comprises one or more first component additives. Claim 3 A two-component system according to paragraph 2, wherein one or more of the first component additives comprises one or more of calcium carbonate, minerals, reinforcing fibers, hydrophobic silica, or any combination thereof. Claim 4 A two-component system according to claim 1, comprising calcium carbonate present in an amount of 1% to 25% by weight of the first component. Claim 5 A two-component system according to claim 1, wherein the second component comprises one or more second component additives. Claim 6 A two-component system according to claim 5, wherein the one or more second component additives comprise one or more of minerals, reinforcing fibers, hydrophobic silica, or any combination thereof. Claim 7 A two-component system according to claim 1, wherein the first component further comprises one or more liquid epoxy resins, one or more aliphatic polyfunctional epoxy resins, one or more reactive diluents, or any combination thereof. Claim 8 A two-component system according to claim 1, comprising one or more liquid epoxy resins including the reaction product of epichlorohydrin and bisphenol A. Claim 9 A two-component system according to claim 1, comprising one or more liquid epoxy resins present in an amount of 10% to 30% by weight of the first component. Claim 10 A two-component system according to claim 1, comprising one or more flexible epoxy resins including a difunctional glycidyl ether epoxy resin, an unmodified BPA-based epoxy resin, a multifunctional epoxidized polybutadiene resin, or any combination thereof. Claim 11 A two-component system according to claim 1, comprising one or more flexible epoxy resins present in an amount of 39 weight percent of the first component. Claim 12 A two-component system according to claim 1, comprising one or more aliphatic multifunctional epoxy resins including epoxidized sorbitol. Claim 13 A two-component system according to claim 1, comprising one or more aliphatic multifunctional epoxy resins present in an amount of 5% to 20% by weight of the first component. Claim 14 A two-component system according to claim 1, comprising one or more reactive diluents including polyglycol diglycidyl ether, trimethylolethane triglycidyl ether, or both. Claim 15 A two-component system according to claim 1, comprising one or more reactive diluents present in an amount of 5% to 20% by weight of the first component. Claim 16 A two-component system according to claim 1, wherein the curing time of the curable composition is 5 to 15 minutes. Claim 17 A two-component system according to claim 1, wherein the curing time of the curable composition is 7 to 10 minutes. Claim 18 A two-component system according to claim 1, wherein the cured composition has a volume expansion of 100% to 800%. Claim 19 A two-component system according to claim 1, wherein the cured composition has a volume expansion of 400% to 500%. Claim 20 A two-component system according to claim 1, wherein the cured composition is distributed to a workpiece composed of an automobile part. Claim 21 A two-component system according to claim 1, wherein the cured composition forms a gasket. Claim 22 In claim 1, the two-component system is a two-component system that does not include a curing agent, a curing accelerator, or both. Claim 23 delete Claim 24 delete Claim 25 delete Claim 26 delete Claim 27 delete Claim 28 delete Claim 29 delete Claim 30 delete Claim 31 delete Claim 32 delete Claim 33 delete Claim 34 delete Claim 35 delete Claim 36 delete Claim 37 delete Claim 38 delete Claim 39 delete Claim 40 delete Claim 41 delete Claim 42 delete Claim 43 delete Claim 44 delete Claim 45 delete Claim 46 delete Claim 47 delete Claim 48 delete Claim 49 delete Claim 50 delete Claim 51 delete Claim 52 delete Claim 53 delete Claim 54 delete Claim 55 delete Claim 56 delete Claim 57 delete Claim 58 delete Claim 59 delete Claim 60 delete Claim 61 delete Claim 62 delete Claim 63 delete Claim 64 delete Claim 65 delete Claim 66 delete

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