Two-component phosphate ester cavity-filled semi-rigid foam

Abstract

To provide a method and composition related to two component epoxy phosphate ester based foam materials.SOLUTION: There is provided a method comprising: providing a two-component system, the two-component system including an A side and a B side, the A side including epoxy material and the B side including phosphate ester and phosphoric acid; mixing the A side and the B side to form a resulting reaction product; wherein the resulting reaction product of the A side and the B side cures at a temperature of less than 50°C. There is also provided a composition comprising: a) a first component including epoxy; b) a second component including phosphate ester and phosphoric acid; wherein a resulting reaction product of the first component and second component cures at a temperature of less than 50°C.SELECTED DRAWING: None

Description

Technical Field

[0001] The present teachings generally relate to foam materials based on a two-component epoxy phosphate ester.

Background Art

[0002] In the transportation and construction industries, foam materials are frequently employed for various applications. For example, a foam material can provide one or more of structural support, sealing, and sound attenuation. When room temperature activation (e.g., expansion) is desired, polyurethane-based foams are most commonly used. Polyurethane foams have many drawbacks, some of which include containing isocyanates, limited adhesion ability to certain substrates, poor hydrolysis resistance in wet or humid environments, being unsuitable for use in low-speed reaction systems, high sensitivity to temperature changes during dispensing and foaming, and the requirement of a high specificity of mixing ratio during formulation.

[0003] As an alternative to polyurethane-based foams, phosphoric acid has been used for in-situ foaming reactions in polymer materials. However, phosphoric acid presents additional concerns. For example, the reaction time with phosphoric acid is very fast, making it unsuitable for assembly processes that require time to place the polymer material on the surface prior to the foaming process. Therefore, a somewhat slower reaction time is preferable. In some situations, the properties of phosphoric acid can pose negative health and safety risks due to its low pH and splash hazard. Therefore, alternative materials with reduced health and safety risks would be preferable. Also, there is a significant difference in viscosity between phosphoric acid and the oligomeric or polymer material with which it reacts. This poses challenges in both the production (e.g., mixing) and storage of the materials. Phosphoric acid also has a much lower molecular weight than many oligomeric and polymer materials, and consequently a much lower molecular weight per functional reactant group, which leads to undesirable mixing ratios. Relatively equal mixing ratios of 1:1 or 2:1 would be preferable. Finally, the reactive properties of phosphoric acid make it difficult to formulate adhesive and sealant materials, as many chemical components can become unstable when used with phosphoric acid. It would be desirable to have the ability to include various different parts (moieties) that may be advantageous for adhesion, physical or chemical compatibility, or other reasons.

[0004] International Publication No. 2016 / 149700, incorporated herein by reference for all purposes, discloses the use of phosphate esters as a substitute for phosphate. Furthermore, the addition of some amount of phosphate in addition to the ester may provide a significant benefit to one or more of the following: the rate of reactivity and / or additional functionality. For example, if reactivity at low temperatures is desired, adding a certain amount of phosphate in combination with the phosphate ester may increase the reaction rate compared to the use of the phosphate ester alone. In another example, the addition of phosphate may impart polyfunctionality to the foam material, preventing foam collapse. Such collapse can occur due to the reaction between the phosphate ester and the metal carbonate (which lowers the average functionality of the material). The addition of phosphate effectively compensates for the reaction between the metal carbonate and the phosphate ester, thereby minimizing foam collapse.

[0005] Despite the above teachings, there is still a need for improved foam materials. There is a need for foam materials that offer room-temperature curing. There is a need for foam materials that offer expansion and crosslinking at lower temperatures compared to known foam materials. There is a need for foam materials that offer adhesion to a wide variety of substrates. There is a need for foam materials that utilize components that enable both curing and foaming without the need for additional components. There is a need for foam materials that provide desired properties regarding flammability, fumigation, and toxicity (FST), while eliminating the use of undesirable agents in imparting these properties. [Prior art documents] [Patent Documents]

[0006] [Patent Document 1] International Publication No. 2016 / 149700 [Overview of the Initiative] [Problems that the invention aims to solve]

[0007] This instruction provides one or more of the above-mentioned benefits. The foam material of this instruction can be used for one or more of the following: cavity filling, sealing, reinforcement, or buffering. [Means for solving the problem]

[0008] This instruction provides a method comprising the steps of: providing a two-component system, wherein the two-component system comprises side A and side B, side A comprising an epoxy material and side B comprising a phosphate ester and phosphate; and mixing side A and side B to form a reaction product obtained as a result, wherein the reaction product obtained from side A and side B hardens at a temperature of less than 50 degrees.

[0009] Side B may contain one or more phosphate esters. Side A, Side B, or both may contain one or more fillers and / or one or more reinforcing materials. Side A may contain one or more metal carbonates.

[0010] The foaming and curing reactions can occur at temperatures ranging from approximately 10°C to approximately 35°C. The formation and curing reactions can occur at higher or lower temperatures. The degree of foaming can vary depending on the temperature at which foaming and curing occur. The foaming and curing reactions can occur at temperatures ranging from approximately 15°C to approximately 25°C.

[0011] The curing time of the resulting reaction product may be less than 15 minutes. The curing time of the resulting reaction product may be approximately 5 to 10 minutes. The curing time may be 30 minutes or less. The curing time may be 60 minutes or less. The foaming time may be 10 minutes or less, 5 minutes or less, or even 1 minute or less. The foaming time will be shorter than the time required to complete curing. The method may be free of any additional curing agents. The resulting reaction product may have a volume expansion of at least 200%.

[0012] Phosphoric acid may be added after the preparation of the phosphate ester. Sides A and B may be mixed in a volume ratio of approximately 1:4 to approximately 4:1 (Side A:Side B). Sides A and B may be mixed in a volume ratio of approximately 2:1 (Side A:Side B). The reaction product may expand completely in less than 10 minutes, less than 5 minutes, or even less than 2 minutes. The method may include a step of adding a second amount of phosphoric acid. The viscosity of side A at 23°C may be approximately 20,000 cP to approximately 50,000 cP. The viscosity of side A at 23°C may be approximately 35,000 cP to approximately 45,000 cP. Side A can be formulated with increasing functionality to create an infinite network by using functionalities higher than 2.

[0013] The disclosure further provides a composition comprising: a) a first component comprising an epoxy material; and b) a second component comprising a phosphate ester and phosphoric acid. The reaction product resulting from the first and second components cures at a temperature of less than 50°C.

[0014] The second component may contain at least one phosphate ester. The second component may contain at least two different phosphate esters. The first component, the second component, or both may contain one or more fillers and / or one or more reinforcing materials. The first component may contain calcium carbonate.

[0015] The curing temperature (for example, the temperature at which the material begins to harden or the temperature at which the material completes its hardening) may be approximately 10°C to approximately 35°C. The curing temperature may also be approximately 15°C to approximately 25°C.

[0016] The resulting reaction product may have a curing time of less than 15 minutes. The resulting reaction product may have a curing time of approximately 5 to 10 minutes. The resulting reaction product may have a volume expansion of at least 200%.

[0017] The volume mixing ratio of side A to side B may be approximately 1:4 to approximately 4:1 (side A:side B). The volume mixing ratio of side A to side B may be approximately 2:1 (side A:side B). The reaction product may expand completely in less than 10 minutes, less than 5 minutes, or even less than 2 minutes. The composition may contain a second amount of phosphoric acid. The viscosity of side A at 23°C may be approximately 20,000 cP to approximately 50,000 cP. The viscosity of side A at 23°C may be approximately 35,000 cP to approximately 45,000 cP. Side A can be formulated with increasing functionalities to create an infinite network by using functionalities higher than 2.

[0018] This instruction further provides a composition comprising: a) a first component comprising one or more of i) a liquid epoxy resin; ii) a flexible epoxy resin; iii) an epoxyphenol novolac resin; iv) an aliphatic polyfunctional epoxy resin; v) calcium carbonate; vi) wollastonite; and vii) hydrophobic silica; and b) a second component comprising one or more of i) a first phosphate ester; ii) a second phosphate ester; iii) hydrophobic silica; and iv) phosphoric acid, wherein the reaction product resulting from the first and second components cures at a temperature of less than 50°C. [Modes for carrying out the invention]

[0019] This instruction satisfies one or more of the above needs through the improved devices and methods described herein. The explanations and examples presented herein are intended to familiarize those skilled in the art with this instruction, its principles, and its practical applications. Those skilled in the art can adapt and apply this instruction to numerous forms that may be most appropriate to the specific requirements of use. Accordingly, the specific embodiments of this instruction shown are neither exhaustive nor intended to limit this instruction. Thus, the scope of this instruction should not be determined by reference to the above description, but rather by reference to the accompanying claims and the full scope of the equivalents to which such claims are entitled. All disclosures of papers and references, including patent applications and patent publications, are incorporated by reference for all purposes. Furthermore, other combinations that can be gathered from the accompanying claims are implementable, and such combinations are also incorporated by reference into this written description.

[0020] This application asserts the filing date benefit of U.S. Provisional Patent Application No. 62 / 767543, filed November 15, 2018, and the contents of said Provisional Application are incorporated herein by reference for all purposes.

[0021] This instruction provides a method comprising the step of providing a two-component system comprising side A and side B. Side A comprises epoxy, and side B comprises a phosphate ester and optionally phosphate. Sides A and B can be mixed to form a resulting reaction product. The resulting reaction product of sides A and B hardens at a temperature below 50°C.

[0022] At least one component of the two-component system may contain a phosphate ester. The phosphate ester can be produced by the reaction of phosphoric acid with various epoxide-functional monomers, although other preparation methods are also possible. The phosphate ester may also be produced by the reaction of an epoxidized cashew nut liquid (CNSL) polymer to produce epichlorohydrin phosphate. The phosphate ester can be used to produce 1,2-propanediol,3-[(2-ethylhexyl)oxyl]phosphate.

[0023] At least one of the components in the two-component system may contain one or more phosphate esters. At least one of the components in the two-component system may contain exactly two different phosphate esters. For example, the second component or the B side may contain the first phosphate ester and the second phosphate ester. The first phosphate ester may be a reaction product of an epoxidized cashew nut liquid (CNSL) polymer for producing a phosphate ester. The second phosphate ester may be a reaction product of 2-propanediol, 3-[(2-ethylhexyl)oxyl]-phosphate.

[0024] The first phosphate ester may be present in an amount of about 55% to about 75% by weight of the second component or the B side. The first phosphate ester may be present in an amount of about 60% to about 70% by weight of the second component or the B side. The first phosphate ester may be present in an amount of about 60% by weight of the second component or the B side. The first phosphate ester may be present in an amount of about 65% by weight of the second component or the B side. The second phosphate ester may be present in an amount of about 15% to about 35% by weight of the second component or the B side. The second phosphate ester may be present in an amount of about 20% to about 30% by weight of the second component or the B side. The second phosphate ester may be present in an amount of about 25% by weight of the second component or the B side. The second phosphate ester may be present in an amount of about 28% by weight of the second component or the B side.

[0025] At least one of the components in the two-component system may contain phosphoric acid. Preferably, the component containing one or more phosphate esters further contains phosphoric acid. For example, the second component or the B side may contain one or more phosphate esters and phosphoric acid. The addition of phosphoric acid to the B side could result in an increase in the expansion (e.g., foaming) of the resulting reaction product and / or a reduction in the reaction time. The reaction time can be adjusted by the use of various concentrations of phosphoric acid. The addition of phosphoric acid to the B side can increase the reactivity of the system to help maintain the desired levels of expansion and curing when the temperature is below 23°C.

[0026] The phosphoric acid may be orthophosphoric acid. The phosphoric acid may be polyphosphoric acid. The phosphoric acid may be an 85% aqueous solution. The phosphoric acid may be present in an amount of about 1 wt% to about 10 wt% of the second component or the B side. The phosphoric acid may be present in an amount of about 5 wt% to about 8 wt% of the second component or the B side.

[0027] Curing and / or foaming can occur at a temperature below 40°C. Curing and / or foaming can occur at a temperature below 30°C. Curing and / or foaming can occur at a temperature below 20°C. Curing and / or foaming can occur at a temperature of about 10°C to about 35°C. Curing and / or foaming can occur at room temperature (e.g., a temperature of about 15°C to about 25°C). Curing and / or foaming can occur at a temperature of about 23°C. Curing and / or foaming can occur at a temperature of about 10°C.

[0028] The present disclosure achieves a relatively fast curing and / or foaming time that occurs without stimulation (e.g., at ambient temperature or room temperature) compared to other curing agents / curing systems. For example, the curing time of the resulting reaction product can be less than 75 minutes. The curing time of the resulting reaction product can be less than 50 minutes. The curing time of the resulting reaction product can be less than 30 minutes, and further less than about 20 minutes. The curing time of the resulting reaction product can be about 5 minutes to about 20 minutes. The curing time of the resulting reaction product can be about 10 minutes. The curing time of the resulting reaction product can be about 7 minutes. The curing time of the resulting reaction product can be about 5 minutes.

[0029] Foaming will begin before the resulting reaction product is fully cured. The foaming time of the resulting reaction product can be less than 30 minutes, and further less than about 20 minutes. The foaming time of the resulting reaction product can be about 30 seconds to about 10 minutes. The foaming time of the resulting reaction product can be about 5 minutes. The foaming time of the resulting reaction product can be about 7 minutes.

[0030] The foam materials described herein may further include epoxy-based materials containing one or more epoxy resins. Epoxy resin is used herein to mean any conventional dimer, oligomer, or polymer epoxy material containing at least one epoxy functional group. The term epoxy resin may also be used to refer to a single epoxy resin or to a combination of multiple epoxy resins. Epoxy may be aliphatic, alicyclic, aromatic, etc. Epoxy may be supplied as a solid (e.g., pellets, lumps, fragments, etc.) or as a liquid (e.g., liquid epoxy resin). In use herein, unless otherwise specified, a resin is a solid resin if it is solid at 23°C, and a liquid resin if it is liquid at 23°C. At least a portion of the epoxy resin may be a liquid epoxy resin. For solid epoxy to be used, it will typically be necessary to dissolve it in a liquid resin.

[0031] The foam materials described herein may include a liquid epoxy resin. The liquid epoxy resin may be present as the first component or part of the A-side of the two-component system of this teaching. The liquid epoxy resin may be the liquid reaction product of epichlorohydrin and bisphenol A. The liquid epoxy resin may have an epoxide equivalent (g / eq) of about 82 to about 192 as measured according to ASTM D-1652. The liquid epoxy resin may have an epoxide percentage of about 20 to about 25. The liquid epoxy resin may have a viscosity of 11,000 to 14,000 mPa·s at 25°C as measured according to ASTM D-445. One suitable liquid epoxy resin is sold under the trademark name DER(trademark) 331.

[0032] The liquid epoxy resin may be present in an amount of about 10% to about 30% by weight of the first component or side A. The liquid epoxy resin may be present in an amount of about 15% to about 25% by weight of the first component or side A. The liquid epoxy resin may be present in an amount of about 20% by weight of the first component or side A.

[0033] The foam materials described herein may include a flexible epoxy resin. The inclusion of a flexible component may reduce the modulus or increase the strain to failure. The flexible epoxy resin can improve the gas containment capacity of the foam by acting as a viscosity modifier. The flexible epoxy resin may be the first component or A side of the two-component system of this teaching. The flexible epoxy resin may be a bifunctional glycidyl ether epoxy resin. The flexible epoxy resin may be a bifunctional epoxy derived from cardanol obtained from cashew nut shell liquid (CNSL). The flexible epoxy resin may have an epoxide equivalent weight (EEW) of about 350 to about 500 according to ASTM D-1652-97. The flexible epoxy resin may have a viscosity of 10,000 to 35,000 cP at 25°C as measured according to ASTM D2196. One example of such a flexible epoxy resin is commercially available from Cardolite Corporation in Monmouth Junction, New Jersey, under the trademark name Cardolite NC-514.

[0034] The flexible epoxy resin, if present, may be present in an amount of about 5% to about 25% by weight of the first component or side A. The flexible epoxy resin may be present in an amount of about 10% to about 20% by weight of the first component or side A. The flexible epoxy resin may be present in an amount of about 15% by weight of the first component or side A. The flexible epoxy resin may be present in an amount of at least about 5% by weight, at least about 10% by weight, and even at least about 15% by weight of the first component or side A. The flexible epoxy resin may be present in an amount of less than about 50% by weight, less than about 30% by weight, and even less than about 25% by weight of the first component or side A.

[0035] The foam material described herein may further include an epoxyphenol novolac resin. The epoxyphenol novolac resin may be present as the first component or A-side portion of the two-component system of this teaching. The first component or A-side may include a first epoxyphenol novolac resin and a second epoxyphenol novolac resin. The epoxyphenol novolac resin may have an epoxide equivalent (g / eq) of about 165 to about 178 as measured according to ASTM D-1652. The epoxyphenol novolac resin may have an epoxide equivalent (g / eq) of about 171 to about 183 as measured according to ASTM D-1652. The epoxyphenol novolac resin may have an average epoxy functionality of about 2.6 to about 3.6. For example, the first epoxyphenol novolac resin may have an epoxy functionality of about 2.6 and the second epoxyphenol novolac resin may have an epoxy functionality of about 3.6. The epoxyphenol novolac resin may have a viscosity of 18,000 to 28,000 cP at 25°C. The epoxyphenol novolac resin may have a viscosity of 20,000 to 30,000 cP at 52°C. Suitable flexible epoxy resins are commercially available from CVC Thermoset Specialties in Morestown, New Jersey, under the trademark names Epalloy 8250 and Epalloy 8330.

[0036] The epoxyphenol novolac resin may be present in an amount of about 1% to about 45% by weight of the first component or side A. The epoxyphenol novolac resin may be present in an amount of about 5% to about 35% by weight of the first component or side A. The epoxyphenol novolac resin may be present in an amount of about 10% to about 20% by weight of the first component or side A. The epoxyphenol novolac resin may be present in an amount of about 15% by weight of the first component or side A. The epoxyphenol novolac resin may be present in an amount of about 35% to about 40% by weight of the first component or side A. The epoxyphenol novolac resin may be present in an amount of at least about 5% by weight, at least about 10% by weight, and even at least about 30% by weight of the first component or side A. The epoxyphenol novolac resin may be present in an amount of less than about 70% by weight, less than about 50% by weight, and even less than about 30% by weight of the first component or side A.

[0037] The foam material may contain an aliphatic polyfunctional epoxy resin. The aliphatic polyfunctional epoxy resin may be present as the first component or part of the A-side of the two-component system of this teaching. The aliphatic polyfunctional epoxy resin may be epoxidized sorbitol. The aliphatic polyfunctional epoxy resin may have an epoxide equivalent (g / eq) of about 160 to about 195 as measured according to ASTM D-1652. The aliphatic polyfunctional epoxy resin may have a viscosity of 8000 to 18000 cP at 25°C. One suitable aliphatic polyfunctional epoxy resin is commercially available from CVC Thermoset Specialties, Inc. in Morestown, New Jersey, under the trademark name Erisys GE-60.

[0038] Aliphatic polyfunctional epoxy resin may be present in an amount of about 15% to about 35% by weight of the first component or side A. Aliphatic polyfunctional epoxy resin may be present in an amount of about 20% to about 30% by weight of the first component or side A. Aliphatic polyfunctional epoxy resin may be present in an amount of about 20% to about 25% by weight of the first component or side A.

[0039] It is possible that one or more of the A-side components described herein impart additional functionality to the A-side. The B-side may be formed, at least in part, as a salt utilizing at least some of the phosphoric acid and acid esters of the B-side. This essentially reduces the reactive functionality of the B-side. In an effort to compensate for this reduced functionality, the A-side may be formulated to increase its functionality by using a functionality higher than 2, thereby creating an infinite network.

[0040] The foam material may contain metal carbonates. The foam material may contain calcium carbonate. The calcium carbonate may be present as one or more calcium carbonate fillers and may be introduced from mineral fillers having a low metal carbonate concentration. One or more calcium carbonate fillers may have a median particle size of about 3 microns to about 25 microns. The calcium carbonate may be medium fine ground. For example, the median particle size of the calcium carbonate may be about 22 microns. An example of a suitable medium fine ground calcium carbonate is Hubercarb® Q200, commercially available from Huber Engineered Material, Atlanta, Georgia. The calcium carbonate may be fine particle size. For example, the median particle size of the calcium carbonate may be 4 microns. An example of a suitable fine particle size calcium carbonate is Hubercarb® Q4, commercially available from Huber Engineered Material, Atlanta, Georgia.

[0041] Calcium carbonate may be present as the first component or part of side A of the two-component system of this instruction. Calcium carbonate may be present in amounts less than 40% by weight of the first component or side A, between about 10% by weight and about 30% by weight of the first component or side A, and between about 15% by weight and about 25% by weight of the first component or side A. Calcium carbonate may be present in amounts of about 20% by weight of the first component or side A. Calcium carbonate may be present in amounts of at least about 5% by weight of the first component or side A, at least about 10% by weight of the first component or side A, and at least about 15% by weight of the first component or side A. Calcium carbonate may be present in amounts less than about 60% by weight of the first component or side A, less than about 45% by weight of the first component or side A, and less than about 30% by weight of the first component or side A.

[0042] The first component or side A may contain about 10% to about 20% by weight of finely ground calcium carbonate. The first component or side A may contain about 15% by weight of finely ground calcium carbonate. The first component or side A may contain about 2% to about 9% by weight of finely ground calcium carbonate. The first component or side A may contain about 5% to about 7% by weight of finely ground calcium carbonate. The first component or side A may contain about 15% by weight of finely ground calcium carbonate and about 5% by weight of finely ground calcium carbonate. For example, the ratio of finely ground calcium carbonate to finely ground calcium carbonate in the first component or side A may be about 3:1.

[0043] Calcium carbonate may be included in a coating or selected in a specific size (e.g., a larger size) in an effort to slow down or reduce the expansion of the material. The coating may be any material that decomposes during the activation / expansion process. The coating may be a wax, a fatty acid, or a combination thereof.

[0044] The foam material may contain one or more minerals. The characteristic external shape of individual crystals or groups of crystals of the minerals may be needle-like or needle-shaped. The median grain size of the minerals may be approximately 10 μm to approximately 20 μm.

[0045] The foam material may contain reinforcing materials such as wollastonite or calcium silicate. The wollastonite may be relatively pure CaSiO3. The wollastonite may contain one or more of iron, magnesium, manganese, aluminum, potassium, sodium, or strontium that substitute for calcium in the mineral structure. The median particle size of the wollastonite may be approximately 18 μm. The median particle size of the wollastonite may be approximately 12 μm. Suitable wollastonite is commercially available from NYCO Minerals Inc. in Willsboro, New York, under the trademark names NYGLOS® 12 and NYGLOS® 8.

[0046] Wollastonite may be present as the first component or part of side A of the two-component system of this instruction. Wollastonite may be present in an amount of about 1% to about 10% by weight of the first component or side A. Wollastonite may be present in an amount of about 3% to about 7% by weight of the first component or side A. Wollastonite may be present in an amount of about 5% by weight of the first component or side A.

[0047] As yet another means of slowing down or delaying the expansion process, an inorganic complex containing a metal carbonate concentration, but not comprising a metal carbonate alone, may be included.

[0048] The foam material may contain hydrophobic silica. The hydrophobic silica may be fumed. The fumed silica may be surface-treated with polydimethylsiloxane. The hydrophobic silica may be present as the first component or part of side A in the two-component system of this teaching. The hydrophobic silica may be present as the second component or part of side B in the two-component system of this teaching. The hydrophobic silica may be present as part of both the first component or side A and the second component or side B in the two-component system of this teaching. A suitable hydrophobic silica is commercially available from Evonik Corporation in Palsipani, New Jersey, under the trademark name AEROSIL® R202.

[0049] Hydrophobic silica may be present in an amount of about 0.25% to about 2% by weight of the first component or side A. Hydrophobic silica may be present in an amount of about 0.5% to about 1.5% by weight of the first component or side A. Hydrophobic silica may be present in an amount of about 1% by weight of the first component or side A. Hydrophobic silica may be present in an amount of about 1% to about 10% by weight of the second component or side B. Hydrophobic silica may be present in an amount of about 1% to about 8% by weight of the second component or side B. Hydrophobic silica may be present in an amount of about 6% by weight of the second component or side B. For example, the ratio of hydrophobic silica in the first component or side A to the second component or side B may be about 1:10 to about 10:1. The ratio of hydrophobic silica in the first component or side A to the second component or side B may be 1:6.

[0050] The foam material may include calcined kaolin clay. Impuring the clay with a metal carbonate may also stimulate the foaming (e.g., expansion) process. The calcined kaolin clay may be present as the first component or part of side A in the two-component system of this teaching. The calcined kaolin clay may be present in an amount of about 0.25% to about 5% by weight of the first component or side A. The calcined kaolin clay may be present in an amount of about 1% by weight of the first component or side A. The calcined kaolin clay may have an average particle size (average Stokes equivalent diameter) of 1.3 μm. The calcined kaolin clay may have an average particle size (median Malvern laser) of 3.2 μm. A suitable calcined kaolin clay is commercially available from KaMin® LLC in Macon, Georgia, under the trademark name KaMin® 70C.

[0051] Side B may contain one or more phosphate esters. Side B may contain phosphoric acid. Side B may contain a material for modifying viscosity. The material for modifying viscosity may be a silica-based material. One or more phosphate esters can be selected from mono-esters, di-esters, or tri-esters, as shown below. [ka]

[0052] One or more esters may be combined alone with component A or mixed with phosphoric acid before being combined with additional components. The resulting reactions of one or more epoxide-functional materials with phosphoric acid are described below. [ka] [ka] [ka]

[0053] The viscosity of side A at 23°C may be approximately 20,000 cP to approximately 50,000 cP, and even approximately 35,000 cP to 45,000 cP. The viscosity of side A at 10°C may be approximately 280,000 cP to 350,000 cP, and even approximately 300,000 cP to approximately 325,000 cP. The viscosity of side B at 23°C may be approximately 20,000 cP to approximately 50,000 cP, and even approximately 35,000 cP to approximately 45,000 cP. The viscosity of side B at 10°C may be approximately 130,000 cP to approximately 220,000 cP, and even approximately 175,000 cP to 195,000 cP.

[0054] In one non-limiting embodiment of this teaching, the foam material may contain in the first component or side A one or more of the following: liquid epoxy resin, flexible epoxy resin, epoxyphenol novolac resin, aliphatic polyfunctional epoxy resin, calcium carbonate, wollastonite, and hydrophobic silica. The foam material may contain in the second component or side B one or more of the following: phosphate ester, hydrophobic silica, and phosphoric acid. In one non-limiting embodiment, the teaching provides a composition comprising: a) a first component comprising i) a liquid epoxy resin; ii) a flexible epoxy resin; iii) an epoxyphenol novolac resin; iv) an aliphatic polyfunctional epoxy resin; v) calcium carbonate; vi) wollastonite; and vii) hydrophobic silica; and b) a second component comprising i) a first phosphate ester; ii) a second phosphate ester; iii) hydrophobic silica; and iv) phosphoric acid, wherein the reaction product resulting from the first and second components cures at a temperature below 50°C.

[0055] The foam material may contain one or more additives (e.g., functional additives) to improve one or more of the properties of the composition. Examples of additives include antioxidants, ozone degradation inhibitors, ultraviolet absorbers, antistatic agents, colorants, coupling agents, curing agents, flame retardants, foaming agents, heat stabilizers, impact resistance modifiers, lubricants, plasticizers, preservatives, processing aids, and stabilizers, as well as combinations thereof.

[0056] Table 1 below provides some non-exclusive examples of formulations based on these instructions.

[0057] [Table 1]

[0058] Table 2 provides technical data for the formulations described in this instruction at curing temperatures of 23°C and 10°C.

[0059] [Table 2]

[0060] Additional examples of formulations according to this instruction are provided in Table 3 below.

[0061] [Table 3]

[0062] As shown in Table 3, the addition of 85% phosphoric acid to side B results in increased expansion and helps maintain the desired expansion level when the temperature is below 23°C.

[0063] The two-component system of this instruction may be provided as a parallel-type cartridge, pail, and drum. The reaction product resulting from the two components cures at temperatures below 50°C, resulting in excellent adhesion to many substrates and a fast curing time.

[0064] The use of the teachings herein may result in a material exhibiting sufficient flame retardancy to meet one or more of the requirements for demonstrating flame retardancy set out in 14 C. FR 25.853 and 14 C. FR 25.856 (the U.S. Department of Transportation Federal Regulations for Interior Cabin Interiors, including, but not limited to, 14 C. FR 25.853(a) and Reference Addendum F and the procedures referenced therein), any of the aforementioned Regulations provisions are incorporated herein by reference for any purpose.

[0065] In use herein, unless otherwise stated, the teachings assume that any member of a genus (list) may be removed from the genus and / or any member of a Markush grouping may be removed from the grouping.

[0066] Unless otherwise stated, any numerical value described herein includes all values ​​from the lowest to the highest value in increments of one unit, provided that there is at least a two-unit gap between any lower and higher value. For example, if the values ​​of a component quantity, property, or process variable, such as temperature, pressure, or time, are stated to be, for example, 1 to 90, preferably 20 to 80, and more preferably 30 to 70, then intermediate range values ​​(e.g., 15 to 85, 22 to 68, 43 to 51, 30 to 32, etc.) are considered to be within the scope of the teachings herein. Similarly, individual intermediate values ​​are also within the scope of the teachings herein. For values ​​less than 1, one unit is considered to be correspondingly 0.0001, 0.001, 0.01, or 0.1. These are merely examples of what is specifically intended, and all feasible combinations of numerical values ​​between the lowest and highest values ​​listed are considered to be expressly stated in this application in a similar manner. As can be seen, the instruction of quantities expressed as “parts by weight” in this specification is also intended to be expressed in terms of weight percent for the same range. Therefore, the range expression in terms of “at least “x” parts by weight” of the resulting composition is also intended to be a instruction of the range in weight percent of the resulting composition for the same stated quantity “x”.

[0067] Unless otherwise stated, all ranges include all numbers at both endpoints and between them. The use of “approximately” or “approximately” in relation to a range applies to both ends of the range. Thus, “approximately 20–30” is intended to cover “approximately 20–approximately 30” including at least the specified endpoint. Unless otherwise stated, instructions using the terms “approximately” or “approximately” in combination with a numerical quantity cover not only the stated quantity but also instructions for its approximation. For example, the instruction “approximately 100” covers the instruction “100”.

[0068] All disclosures in papers and references, including patent applications and patent publications, are incorporated by reference for any purpose. The term “essentially consisting of ○○” used to describe a combination includes the identified element, raw material, component, or process, as well as other such elements, raw materials, components, or processes that do not substantially affect the basic and novel characteristics of the combination. The use of the terms “comprising ○○” or “containing ○○” used herein to describe a combination of elements, raw materials, components, or processes also assumes embodiments consisting of or essentially comprising such elements, raw materials, components, or processes.

[0069] Multiple elements, raw materials, components, or processes may be provided by a single, integrated element, raw material, component, or process. Alternatively, a single, integrated element, raw material, component, or process may be divided into multiple separate elements, raw materials, components, or processes. The disclosure of "a" or "one" as a translation of the original "a" or "one" used to describe an element, raw material, component, or process is not intended to exclude additional elements, raw materials, components, or processes.

[0070] Embodiments of the present invention are, for example, as follows: [Embodiment 1] A step of providing a two-component system, wherein the two-component system comprises side A and side B, side A comprises epoxy, and side B comprises a phosphate ester and phosphate, A step of mixing side A and side B to form the resulting reaction product, In a method that provides, A method wherein the reaction products obtained as a result from side A and side B harden at a temperature of less than 50°C.

[0071] [Embodiment 2] The method according to Embodiment 1, wherein side B contains two different phosphate esters. [Embodiment 3] The method according to Embodiment 1 or Embodiment 2, wherein side A, side B, or both thereof contain a filler. [Embodiment 4] The method according to any one of Embodiments 1 to 3, wherein side A contains calcium carbonate. [Embodiment 5] The method according to any one of Embodiments 1 to 4, wherein curing occurs at a temperature of approximately 10°C to approximately 35°C.

[0072] [Embodiment 6] The method according to any one of Embodiments 1 to 5, wherein curing occurs at a temperature of approximately 15°C to approximately 25°C. [Embodiment 7] The method according to any one of Embodiments 1 to 6, wherein the curing time of the reaction product obtained as a result is less than 15 minutes. [Embodiment 8] The method according to any one of Embodiments 1 to 7, wherein the curing time of the reaction product obtained as a result is about 5 minutes to about 10 minutes.

[0073] [Embodiment 9] The method described above is the method according to any one of Embodiments 1 to 8, wherein no curing agent is included. [Embodiment 10] The method according to any one of Embodiments 1 to 9, wherein the reaction product obtained as a result has a volume expansion of at least 200%. [Embodiment 11] The method according to any one of Embodiments 1 to 10, wherein the phosphoric acid is added after the preparation of the phosphoric acid ester.

[0074] [Embodiment 12] The method according to any one of Embodiments 1 to 11, wherein side A and side B are mixed in a volume mixing ratio of approximately 1:4 to approximately 4:1 (side A:side B). [Embodiment 13] The method according to any one of Embodiments 1 to 12, wherein side A and side B are mixed in a volume mixing ratio of approximately 2:1 (side A:side B). [Embodiment 14] The method according to any one of Embodiments 1 to 13, wherein the reaction product expands completely in less than 10 minutes, less than 5 minutes, or even less than 2 minutes.

[0075] [Embodiment 15] The method according to any one of Embodiments 1 to 14, comprising the step of adding a second amount of phosphoric acid. [Embodiment 16] The method according to any one of Embodiments 1 to 15, wherein the viscosity of side A at 23°C is approximately 20,000 cP to approximately 50,000 cP. [Embodiment 17] The method according to any one of Embodiments 1 to 16, wherein the viscosity of side A at 23°C is approximately 35,000 cP to approximately 45,000 cP.

[0076] [Embodiment 18] The method according to any one of Embodiments 1 to 17, wherein side A is formulated to increase its sensory content to create an infinite network by using a sensory content higher than 2. [Embodiment 19] A composition, a) A first component containing epoxy, b) comprising a second component containing a phosphate ester and phosphoric acid, A composition in which the reaction product resulting from the first component and the second component hardens at a temperature of less than 50°C.

[0077] [Embodiment 20] The composition according to embodiment 19, wherein the second component comprises at least two different phosphate esters. [Embodiment 21] The composition according to Embodiment 19 or Embodiment 20, wherein the first component, the second component, or both thereof, comprises a filler. [Embodiment 22] The composition according to any one of Embodiments 19 to 21, wherein the first component comprises calcium carbonate.

[0078] [Embodiment 23] The composition according to any one of Embodiments 19 to 22, wherein the curing temperature is approximately 10°C to approximately 35°C. [Embodiment 24] The composition according to any one of Embodiments 19 to 23, wherein the curing temperature is approximately 15°C to approximately 25°C. [Embodiment 25] The composition according to any one of Embodiments 19 to 24, wherein the curing time of the reaction product obtained as a result is less than 15 minutes.

[0079] [Embodiment 26] The composition according to any one of Embodiments 19 to 25, wherein the curing time of the reaction product obtained as a result is about 5 minutes to about 10 minutes. [Embodiment 27] The composition according to any one of Embodiments 19 to 26, wherein the reaction product obtained as a result has a volume expansion of at least 200%. [Embodiment 28] The composition according to any one of Embodiments 19 to 27, wherein the volume mixing ratio of side A to side B is approximately 1:4 to approximately 4:1 (side A:side B).

[0080] [Embodiment 29] The composition according to any one of Embodiments 19 to 28, wherein the volume mixing ratio of side A and side B is approximately 2:1 (side A:side B). [Embodiment 30] The composition according to any one of Embodiments 19 to 29, wherein the reaction product expands completely in less than 10 minutes, less than 5 minutes, or even less than 2 minutes. [Embodiment 31] A composition according to any one of Embodiments 19 to 30, comprising a second amount of phosphoric acid.

[0081] [Embodiment 32] The composition according to any one of Embodiments 19 to 31, wherein the viscosity of side A at 23°C is approximately 20,000 cP to approximately 50,000 cP. [Embodiment 33] The composition according to any one of Embodiments 19 to 32, wherein the viscosity of side A at 23°C is approximately 35,000 cP to approximately 45,000 cP. [Embodiment 34] The composition according to any one of Embodiments 19 to 33, wherein side A is formulated to increase its functionality to create an infinite network by using a functionality higher than 2.

[0082] [Embodiment 35] A composition, said composition, a) The first component, i) Liquid epoxy resin, ii) Flexible epoxy resin, iii) Epoxyphenol novolac resin, iv) Aliphatic polyfunctional epoxy resins v) Calcium carbonate, vi) Wollastnight vii) A first component containing hydrophobic silica, b) A second component, i) First phosphate ester, ii) Second phosphate ester, iii) Hydrophobic silica iv) comprising a second component containing phosphoric acid, A composition in which the reaction product resulting from the first component and the second component hardens at a temperature of less than 50°C.

[0083] It will be understood that the above description is for illustrative purposes only and not intended to impose any limitations. Those skilled in the art will see, upon reading the above description, that many other embodiments and applications are possible beyond those provided. Therefore, the scope of the invention should not be determined by reference to the above description, but rather by reference to the accompanying claims and the full scope of the equivalents to which such claims are entitled. All disclosures in papers and references, including patent applications and patent publications, are incorporated by reference for all purposes. The omission of any aspect of the subject matter disclosed herein in the accompanying claims shall not constitute an abandonment of such subject matter, nor should it be construed as a denial by which the inventors do not recognize such subject matter as part of the subject matter of the disclosed invention.

Claims

1. A step of providing a two-component system, wherein the two-component system comprises side A and side B, side A comprising epoxy and calcium carbonate, and side B comprising phosphate ester and phosphoric acid, A step of mixing side A and side B to form the resulting reaction product, It is equipped with, The reaction products obtained as a result from side A and side B harden at a temperature of less than 50°C and have a volume expansion of at least 200%, by a method, The aforementioned side B contains two different phosphate esters, consisting of a first phosphate ester and a second phosphate ester. The B side comprises 55% to 75% by weight of the first phosphate ester, 15% to 35% by weight of the second phosphate ester, and 1% to 10% by weight of the phosphoric acid. The A side and the B side are mixed in a volume mixing ratio of 1:4 to 4:1 (A side:B side). method.

2. The method according to claim 1, wherein side A, side B, or both thereof contain a filler.

3. The method according to claim 1 or 2, wherein side A and side B are mixed in a volume mixing ratio of 2:1 (side A:side B).

4. The method according to any one of claims 1 to 3, wherein the viscosity of side A at 23°C is 20,000 cP to 50,000 cP.

5. The method according to any one of claims 1 to 4, wherein the viscosity of side A at 23°C is 35,000 cP to 45,000 cP.

6. The method according to any one of claims 1 to 5, wherein side A is formulated to increase its sensory content in order to create an infinite network by using a sensory content higher than 2.

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