Adhesive suitable for spray coating

Abstract

Disclosed is a two part system comprising a first component comprising one or more epoxy resins and an epoxy functional material, the epoxy functional material having a functionality of greater than 4 and a viscosity of 500 cps or less at 23 DEG C according to ASTM D2556-14; and a second component comprising one or more phosphate esters, the one or more phosphate esters having a viscosity of 500 cps or less at 23 DEG C according to ASTM D2556-14 during deposition.

Description

Technical Field

[0001] The present teachings are generally directed to a room temperature activated thermosetting composition comprising a first component including an epoxy functional ingredient and optionally, in the case of a foamable composition, a blowing agent decomposition initiator, and a second component including an acidic ingredient that functions as a curing agent. Background Art

[0002] Sprayable formulations for adhesion and / or sealing are useful due to their simplified deposition capabilities. However, materials with sufficiently low viscosities for spraying often lack physical characteristics or present manufacturing challenges.

[0003] It may be desirable for the sprayable material to have a viscosity of 500 cPs as measured according to ASTM D2556-14. This limits the presence or percentage of certain resins and curing agents in the formulation. High molecular weight to very high molecular weight polymers or resins with high viscosity will be limited to the percentage allowed. Controlling reactivity, thixotropic properties and maintaining an accurate ratio of resin to curing agent are some challenges for these sprayable thermosetting compositions.

[0004] The disadvantage of spraying very low viscosity materials is that the material may flow freely on the substrate. Adjusting the ratio of bifunctional to multifunctional materials in the resin side and curing agent side can help control reactivity and provide rapid crosslinking, thereby forming the three-dimensional structure of the material.

[0005] In order to achieve the viscosity requirements for impact mixing (usually 500 cPs for the liquid portion), the liquid component of the material should be low viscosity at the deposition temperature, preferably highly shear thinning, or both. High molecular weight to very high molecular weight polymers may have concentration limitations. Also, the concentration of very high viscosity liquids or semisolids may be limited. Limiting the choice of ingredients to smaller molecules and monomers in the formulation may cause difficulties.

[0006] PCT Publication Nos. WO 2020 / 101732, WO 2020 / 205355, WO 2020 / 206346, and WO 2020 / 198139 describe the use of phosphoric acid and phosphate esters for curing-in-place compositions. These compositions are commonly used in various room temperature activated systems, such as rigid structural foams, cavity fillings, gaskets, and sealants. The benefits of such compositions may include the ability to adhere to various substrates, including low volatile organic compounds (VOCs), insensitivity to dispensing temperature, insensitivity to the precise mixing ratio of the two-part system, the ability to adjust physical and mechanical properties, or any combination thereof.

[0007] The present teachings address one or more of the above-mentioned problems by providing a two-component composition that maintains a sufficiently low viscosity to be suitable for spraying while rapidly cross-linking to avoid running and maintain desired physical properties. Summary of the invention

[0008] The present teachings provide a two-part system comprising: a first component comprising one or more epoxy resins and an epoxy-functional material having an epoxy functionality greater than 4 and a viscosity of 500 cps or less at 23°C according to ASTM D2556-14; and a second component comprising one or more phosphate esters having a viscosity of 500 cps or less at 23°C according to ASTM D2556-14 during deposition.

[0009] The teachings herein further relate to a two-part system (two-component system) comprising: a first component comprising one or more epoxy resins and an epoxy-functional compound having an epoxy functionality greater than 4 and a viscosity of 500 mPa.s or less in its pure state; and a second component comprising one or more phosphate esters, each of the one or more phosphate esters having a viscosity of 500 mPa.s or less in its pure state. In each case, the viscosity is determined as described in the specification.

[0010] The teachings herein also relate to a two-part system (two-component system) comprising a first component consisting essentially of one or more epoxy resins, an epoxy-functional compound having an epoxy functionality greater than 4, and optionally one or more non-liquid components. The total viscosity of the one or more epoxy resins and epoxy-functional compounds is 500 mPa·s (mixed with each other but without the one or more non-liquid components). The system comprises a second component consisting essentially of one or more phosphate esters and optionally one or more non-liquid components. The one or more phosphate esters have a total viscosity of 500 mPa.s or less (mixed with each other but without the one or more non-liquid components). In each case, the viscosity is determined as described in the specification.

[0011] After mixing the first component and the second component, the resulting composition may be cured at a temperature of about 0°C to about 50°C.

[0012] The first component may include epoxidized diphenylamine. The one or more phosphates may include phosphates derived from cashew nut shell liquid (CNSL). The one or more phosphates may include phosphates derived from 2-ethylhexyl glycidyl ether. The one or more phosphates may include phosphates derived from phenyl glycidyl ether. The one or more phosphates may include phosphates derived from epoxidized p-tert-butylphenol.

[0013] The two-part system can include one or more additives selected from core-shell polymers, calcium carbonate, minerals, reinforcing fibers, hydrophobic silica, monomers, plate-like aluminum oxides or any combination thereof. Relative to the gross weight of the two-part system, calcium carbonate can exist with an amount of about 0.01 % by weight to about 10 % by weight. Ultrafine calcium carbonate (about 1 micron average particle size), fine calcium carbonate (about 4 micron average particle sizes), medium fine calcium carbonate (about 22 micron average particle sizes) or any combination thereof can be included in the two-part system.

[0014] One or both of the first component and the second component may include wollastonite.One or both of the first component and the second component may include fumed silica.

[0015] The one or more epoxy resins or epoxy functional materials may include one or more liquid epoxy resins, one or more epoxy phenol novolac resins, one or more aliphatic multifunctional epoxy resins, one or more phenoxy resins, one or more silane-modified epoxy resins, or any combination thereof.

[0016] The two-part system may include one or more epoxy phenol novolac resins having an epoxy functionality of about 2 to about 3; epoxy phenol novolac resins having an epoxy functionality of about 3 to about 4; or both. The two-part system may include one or more epoxy phenol novolac resins present in an amount of about 15 wt % to about 70 wt % relative to the total weight of the first component.

[0017] The two-part system may be substantially free of curing agents, latent curing accelerators, or both, other than the one or more phosphate esters.

[0018] The first component, the second component, or both may include a dicarboxylic acid-based component. The first component is substantially free of any epoxy resin that is solid in its pure state at a temperature of 20° C. to 25° C. The second component may be substantially free of any epoxy resin that is solid in its pure state at a temperature of 20° C. to 25° C.

[0019] The first component and the second component may be present in a ratio of about 5 parts by volume first component: 1 part by volume second component to about 1 part by volume first component: 1 part by volume second component.

[0020] The second component may include less than 5% by weight of an epoxy resin that is solid in its pure state at a temperature of 20°C to 25°C, relative to the total weight of the second component.

[0021] In each case, the viscosity was measured at a shear rate of 0.004 (1 / sec) for 120 seconds, the rate was then increased logarithmically from 0.004 to 400 (1 / sec) over a period of 120 seconds and maintained at 400 (1 / sec) for an additional 120 seconds; wherein the test was terminated by immediately reducing the shear rate from 400 to 0.004 (1 / sec) and then measuring the viscosity recovery over the next 480 seconds.

[0022] The two-part system may include one or more epoxy phenol novolac resins present in an amount of at least 40 wt. %, preferably at least 50 wt. %, relative to the total weight of the first component.

[0023] The two-part system may include one or more aliphatic multifunctional epoxy resins in an amount of at least 10% by weight relative to the total weight of the first component. BRIEF DESCRIPTION OF THE DRAWINGS

[0024] Figure 1 Shown is how the viscosity of Kane Ace MX-267 changes at different temperatures and shear rates.

[0025] Figure 2 The viscosities of the liquid portions of Side A (first component) and Side B (second component) of the example formulations are shown.

[0026] Figure 3A and Figure 3B The viscosities of Side A (first component) and Side B (second component) of two different formulations were compared.

[0027] Figure 4 The viscosity of the B side (second component) of formulation 248 (including non-liquid ingredients) at different RPM rates is shown.

[0028] Figure 5A and Figure 5B Shown are 3-stage thixotropy test results showing viscosity at different shear rates and 2 different temperatures. DETAILED DESCRIPTION

[0029] This teaching satisfies one or more of the above-mentioned needs through the improved compositions and methods described herein. The explanations and descriptions presented herein are intended to make other technical personnel in the art familiar with this teaching, its principles and its practical application. Those skilled in the art can modify and apply this teaching in its various forms, such as being able to make it most suitable for the needs of a particular purpose. Therefore, the specific embodiments of this teaching set forth are not intended to be exhaustive or limit this teaching. Therefore, the scope of this teaching should not be determined with reference to the above description, but should be determined with reference to the full scope of the equivalents given by the attached claims and such claims. The disclosures of all articles and references (including patent applications and publications) are incorporated by reference for all purposes. As will be understood from the following claims, other combinations are also possible, which are also incorporated by reference in this written specification.

[0030] For the purposes of this specification, the terms "two-part system" and "two-component system" are used interchangeably. The same applies herein to the individual terms "part," "component," and "side," such as "A-side," "Side A," "B-side," and "Side B." Unless expressly stated otherwise, the "first component" corresponds to the "first part," "Side A," and "A-side," respectively. Unless expressly stated otherwise, the "second component" corresponds to the "second part," "Side B," and "B-side," respectively.

[0031] A low viscosity two-component material suitable for spray application is described herein, which can be dispensed and mixed using an impact mixing application system. The present teaching relates to applying a low viscosity two-component composition (preferably having two sides (components) formulated with a viscosity of 500 cPs or less at 23 ° C according to ASTM D2556-14), wherein the two components collide at high speed to produce impact mixing. The two components can also be mixed in a static or dynamic mixer. After mixing, the resulting formulation can then be sprayed onto a substrate, or sprayed into a mold or cavity.

[0032] The present teachings relate to a two-component room temperature activated composition comprising an epoxy functional system (side A (first component)) cured with an acid or acid derivative (side B (second component)), wherein both sides are preferably formulated to have a viscosity of 500 cPs or less at 23°C according to ASTM D2556-14.

[0033] The present teachings present an impact-mixable system comprising an epoxy-functional material or mixture cured with an acid, acid derivative, or combination thereof. The impact-mixed material can then be forced into a mold or cavity or dispensed onto a substrate.

[0034] The present teachings relate to a system suitable for spraying (air assisted or airless). After being impinged, the mixed material is extruded through a nozzle before being applied to a substrate.

[0035] The present teachings relate to two-component compositions that do not contain any volatile or flammable components. Some key components in other two-component polymer systems are volatile or flammable at elevated temperatures. Unlike many acrylate and polyurethane based formulations and formulations containing solvents, the lack of volatile components in the current two-component thermosetting compositions reduces the risk of inhalation of toxic materials during any spraying process.

[0036] The lack of any volatile and / or flammable components allows the user to increase the dispensing temperature when it is necessary to adjust the applied viscosity or curing dynamics. Both Side A (first component) and Side B (second component) of the current two-component composition are stable at elevated temperatures. Both Side A (first component) and Side B (second component) can be maintained at elevated temperatures (up to 80°C or even higher) for extended periods of time without causing decomposition or reactive instability.

[0037] Both Side A (first component) and Side B (second component) may be insensitive to moisture, including at elevated temperatures. Sprayed materials are typically low viscosity and are finely divided to be exposed to large amounts of air immediately after leaving the nozzle before contacting the substrate.

[0038] The viscosity of the liquid portion of both sides of the formulation is usually 500 cPs or less. This limits the presence or percentage of certain resins and curing agents in the formulation. High molecular weight to very high molecular weight polymers or resins with high viscosity will be limited to the allowed percentage. Controlling reactivity, thixotropic properties and maintaining an accurate ratio of resin to curing agent are some challenges for these sprayable thermosetting compositions.

[0039] One disadvantage of spraying very low viscosity materials is that the material may flow freely on the substrate. Adjusting the ratio of bifunctional materials to multifunctional materials in the resin side and the curing agent side can help control reactivity and provide rapid crosslinking to form the 3D structure of the material. Although the use of monofunctional resins and bifunctional resins is conducive to reducing viscosity, it may also be desirable to use multifunctional materials in side A (first component), side B (second component), or both sides.

[0040] The important component in the side A (first component) of the sprayable thermosetting composition is polymer microparticles, which can be core-shell materials. As an example, Kane Ace MX-267 can be utilized, which includes a core-shell additive dispersed in an epoxy resin based on bisphenol F. The polymer microparticles dispersed in the epoxy resin are liquid impact modifier components composed of liquid and solid. Although the viscosity of the core-shell is high, it is important for spraying that the liquid viscosity (viscosity of the bisphenol F resin) is preferably low viscosity.

[0041] The present teachings relate to a two-component thermosetting composition that is not very sensitive to the mixing ratio. For example, if the target ratio of side A (first component) to side B (second component) is 4:1 (v / v), then a deviation of up to 15% in the ratio will not significantly affect the final properties.

[0042] The composition herein is preferably a low viscosity composition containing at least an epoxy functional component in side A (first component) and an acid or acid derivative liquid having a pH of less than 7 in side B (second component). Both side A (first component) and side B (second component) can be a formulated combination of multiple materials including liquid-dissolved solid and particulate components. The viscosity of both components is typically 500 cPs or less at 23°C according to ASTM D2556-14.

[0043] The final product is the result of mixing Side A (first component) (resin side) and Side B (second component) (curing agent side) and using a mixing device, which may be an impingement mixer. Impingement mixing is one of the most effective mixing methods, especially at low viscosities. Two-component static and dynamic mixing devices or cartridges or other types of mixing methods may be used to deposit these materials.

[0044] The current composition is a system that can be deposited and mixed using an impingement mixing system, which contains an epoxy functional material or mixture (Side A (first component)) cured with an acid, acid derivative, or mixture thereof (Side B (second component)). In the impingement mixing system, Side A (first component) and Side B (second component) collide at very high speeds (under high pressure, in the range of 1200 to 3000 psi) in a mixing chamber or mixing head. Then, depending on the type of application, the mixed material can be pushed out of a nozzle or injected directly into a mold or cavity.

[0045] Impact mixing is the preferred type of mixing / dispensing machine for making materials such as polyurethanes and polyureas react quickly. The impact mixing process is a very fast process that can be used for large-volume deposition, is fully automatic and importantly, self-cleaning. In this process, two or more systems collide at high speed, instantly randomize and mix, and immediately leave the chamber while the materials are still in liquid form. After mixing and pushing the materials out of the chamber, the plunger closes and empties the mixing head. This mixing method can be used for other two-component systems if the viscosity of the liquid portion of the mixture at the deposition temperature is below the viscosity threshold of the specific impact mixing equipment (usually below 500cPs); the key element is the ability to produce a fine liquid particle stream (commonly called an atomized stream).

[0046] In order to achieve the viscosity requirements for impact mixing (typically 500 cPs for the liquid portion), the liquid component of the material should be low viscosity at the deposition temperature, preferably highly shear thinning, or both. High molecular weight to very high molecular weight polymers may have concentration limitations. Moreover, the concentration of very high viscosity liquids or semisolids may be limited. Limiting the selection of ingredients to smaller molecules and monomers in the formulation may cause difficulties. These difficulties and methods to overcome them are explained in the current teachings.

[0047] Systems with very low viscosities containing many monomers and low molecular weight resins typically mean more reactive groups (functionality) per unit volume and greater molecular mobility, particularly during the early stages of the reaction. The typical result of using smaller molecules is faster curing and shorter open times and higher reaction exotherms. A potential disadvantage of very fast curing materials is that the processing time is limited, or similarly, there is not enough time to complete the assembly process. On the other hand, depending on the process, the open time and the fixing time may be limited. Having a longer processing time typically means a longer fixing time, which is generally undesirable. In order to overcome this problem, each component has been used in the side A (first component) and the side B (second component) of the current invention to control and balance the processing time and fixing time of the final product.

[0048] Adjusting the ratio of monofunctional and difunctional ingredients to higher functionality multifunctional ingredients in the resin side and curing agent side helps control reactivity and provide early crosslinking, which begins to create a three-dimensional structure of the material (and stops the material from flowing freely) shortly after the material is sprayed or dispensed. Although the use of monofunctional and difunctional resins is beneficial for controlling viscosity, the use of multifunctional materials in side A (first component), side B (second component) or both sides will improve the properties of the cured composition. If most of one or both sides of the sprayed material are monofunctional, the curing time may be too long or the material may not be fully cured. Monofunctional resins and curing agents usually do not constitute the majority of side A (first component) or side B (second component); however, they can be used to control the reaction kinetics and the properties of the final product. Maintaining a balance between monofunctional resins and difunctional resins to multifunctional resins and curing agents is necessary to prevent the material form from flowing on the surface or curing too quickly. In order to control this balance, the formulation may require a higher viscosity material (usually a material with a higher reactive functional group), which may create additional difficulties. In the following sections, the ingredients used to control viscosity are explained, as well as the effects of high shear rates and temperature on sprayability and final properties.

[0049] The sprayable thermosetting composition described herein can contain a bifunctional component with extremely low viscosity. Bisphenol-A epoxy resin can be used. DER 732 from Olin Company is an example. DER 732 is a product of epichlorohydrin and polypropylene glycol with a viscosity of 60 to 70 cPs at 25°C. Although it is a low viscosity material, it cures slowly. Epoxidized diphenylamine resins such as Epotec YDM 441 are another component that reacts slowly with phosphoric acid and phosphate esters, which affects the processing time. The viscosity of this tetrafunctional epoxide is 3000 to 6000 cPs at 50°C. The viscosity is significantly reduced (shear thinning) at elevated temperatures or high shear rates. Despite having a higher viscosity, the benefit of including epoxidized diphenylamine is that the percentage required to affect the processing, fixation and curing time of the formulation is extremely low (0.2% to 2% of the formulation). The chemical structures of DER 732 and Epotec YDM 441 are shown below, respectively.

[0050]

[0051] These are examples of liquid materials in side A (first component) that help delay the rapid reaction of the material at the deposition temperature. The use of metal carbonates in side A (first component) can also slow down the reaction by reacting with the acid and / or acidic derivatives in side B (second component) to produce salts. These metal carbonates can be used when it is desired to foam the resulting material by releasing carbon dioxide as a decomposition product.

[0052] Additional components may be selected to optimize the reactivity of the system. When certain components are added to Side B (the second component), they may affect processing and cure times. Epoxonic 328 (a dicarboxylic acid), many commercially available phosphate esters, and cashew nut shell liquid based phosphate esters are some examples. These acids and esters react much slower than phenyl glycidyl ether based phosphate esters, 2-ethylhexyl glycidyl ether based phosphate esters, and phosphoric acid. Using a higher ratio of ester to phosphoric acid can also slow the reaction and increase processing time if desired. These are materials and formulation techniques for optimizing reactivity if desired. As mentioned above, the gel time or fixation time may need to be adjusted depending on the manufacturing process of the part.

[0053] Another component that can be used in a sprayable thermosetting composition is a bisphenol F epoxy resin with dispersed core-shell particles. This component is a liquid ingredient containing an impact modifier that provides fracture toughness and consistent morphology and provides low viscosity compared to other existing compositions with similar percentages of core / shell particles. Although the material has a relatively high viscosity at room temperature (compared to other liquids in the sprayable composition), the viscosity decreases rapidly at elevated temperatures and shear rates. There are many benefits to using this material in a formulation. An example of this component is available under the trade name KaneAce MX-267. This component does not significantly increase the "liquid viscosity" because it contains 63% low-viscosity bisphenol F diepoxide. An important criterion for verifying that a formulation can be impact mixed is the liquid viscosity (i.e., the viscosity of all liquid ingredients in the absence of particulate matter). The viscosity of the liquid bisphenol F resin at 25°C is 2000 to 3000 cPs. The other 37% of the core-shell product is butadiene-acrylic copolymer particles and is therefore part of the particulate matter group.

[0054] Unless otherwise specifically stated, the viscosity of the above-mentioned liquid bisphenol F resin is measured at 23° C. according to ASTM D2556-14.

[0055] The polymer microparticle component (or core-shell material) can be a thixotropic shear-thinning material that has unique behaviors at different temperatures and shear rates, with extreme shear-thinning behavior at deposition temperature. Figure 1 How the viscosity of Kane Ace MX-267 changes at different temperatures and shear rates is shown. The core-shell containing composition has very low viscosity at high shear and higher temperatures, which are the deposition conditions for these thermosetting sprayable compositions. Therefore, the formulation can benefit from the properties of this core-shell particle combination and is not significantly affected by high viscosity.

[0056] The systems described herein may also include epoxy phenol novolac resins. Examples of such components may be found under the trade names Epalloy 8250 or DEN 426 from Olin Corporation. This component may be a 2.6 functional resin. This material is a fast curing resin with a relatively high viscosity. This is useful for obtaining the final properties as well as some initial reaction and crosslinking that helps maintain the three-dimensional structure of the sprayed material after deposition.

[0057] Figure 2The viscosity of the liquid portion of side A (first component) and side B (second component) of the example formulations is shown. The viscosity of both side A (first component) and side B (second component) is significantly reduced at higher temperatures. This facilitates impact mixing and spraying of the material. The measurements shown are made at a shear rate lower than the shear rate that occurs during impact mixing. When measured at a higher shear rate, the measured apparent viscosity will be lower. Therefore, the viscosity under deposition conditions is expected to be lower than Figure 2 Viscosities shown.

[0058] Figure 2 The Brookfield viscosity according to ASTM D2556-14 of the liquid portion of side A (first component) and side B (second component) of formulation 248B is shown. The Brookfield viscosity is measured at a speed between 20 RPM and 100 RPM using a LV3 spindle. 20 RPM equals 6.8 S -1 Shear rate, and 100RPM equals 34S -1 .

[0059] Side A (first component, first part) can include a difunctional or multifunctional silicone prepolymer with epoxy terminal groups. A non-limiting example can be a product with the trade name Silmer EPC Di-50, which is a siloxane prepolymer with alicyclic epoxy groups. Silmer EPC Di-50 is a difunctional reactive polymer that can reduce the elastic modulus in the cured composition. The material has a low viscosity (50 to 150 cps at 25°C), which can significantly reduce the viscosity of the mixed liquid part of side A. Another example is Silmer EPC Di-100, which is another linear difunctional epoxide-terminated siloxane prepolymer with a viscosity of 150 to 300 cPs at 25°C.

[0060] Unless otherwise specifically stated, the viscosity of the above silicone prepolymers is measured at 23° C. according to ASTM D2556-14.

[0061] The A side (first component) may also include one or a combination of a bifunctional reactive diluent or a multifunctional reactive diluent. Examples of suitable reactive diluents include, but are not limited to, those sold under the trade names GE-31, GE-24 and Those sold as GE-21 are commercially available from the Huntsman Company. GE-31 is a trifunctional diluent (trimethylolethane triglycidyl ether) with a viscosity of 200 to 300 cps, which can be used to reduce viscosity, increase crosslink density and enhance chemical resistance. GE-21 is an aliphatic difunctional diluent (1,4-butanediol diglycidyl ether) having a viscosity of 120 to 130 cps at 25°C and can be used to reduce viscosity and improve flexibility. GE-25 is another aliphatic difunctional diluent (1,6-hexanediol diglycidyl ether) having a viscosity of 143 to 156 cps at 25°C and can be used to reduce viscosity.

[0062] The A side (first component) may include any combination of monofunctional reactive diluents. Monofunctional reactive diluents may be used to reduce the viscosity and crosslink density of the final product, thereby potentially affecting the reaction exotherm and physical properties. Some examples of monofunctional reactive diluents may include, but are not limited to GE-6, GE-7, GE-8, GE-11, GE-12 and GE-13. GE-6 is 2-ethylhexyl glycidyl ether having a viscosity of 1 to 4 cps at 25°C. GE-7 is C8-C 10 Aliphatic glycidyl ether, viscosity at 25°C 1 to 6 cps. GE-8 is C 12 -C 14 Aliphatic glycidyl ether with a viscosity of 5 to 10 cps at 25°C. GE-11 is p-tert-butylphenyl glycidyl ether and has a viscosity of 20 to 30 cps at 25°C. GE-12 is nonylphenyl glycidyl ether with a viscosity of 100 to 140 cps at 25°C. GE-13 is phenyl glycidyl ether having a viscosity of 4 to 7 cps at 25°C (all measured at 23°C according to ASTM D2556-14).

[0063] Unless otherwise specifically stated, the viscosity of the above reactive diluents is measured at 23° C. according to ASTM D2556-14.

[0064] The B side (second component, second part) may include one or more commercially available phosphate esters. Some non-limiting examples of commercially available phosphate esters include Butyl Acid Phosphate from Isle Chem Company, with an acid value of 430 mg KOH / g and a viscosity of 343 cps at 25°C; Phenyl Acid Phosphate from Isle Chemical Company, with an acid value of 273 to 325 mg KOH / g; Ilco Phos 202 from ILCO Chemikaline Company, with an acid value of 440 to 490 mg KOH / g; Miramer SC 1400 from MIWON, with an acid value of 220 to 350 mg KOH / g and a viscosity of 1100 cps at 25°C.

[0065] The B side (second component) may also include a carboxyl terminated butadiene-acrylonitrile (CTBN) copolymer or any other CTBN copolymer. In the B side (second component), CTBN can improve toughness and reduce acidity. Hypro 1300x31 has a high viscosity (65000 cPs at 27°C), but only a small amount is used. An example of a suitable CTBN copolymer can be obtained from Huntsman Corporation under the trade name Hypro1300x31.

[0066] The B side (second component) can also include difunctional dimer acid and / or trimer acid. These dimer acid and trimer acid reduce acidity, improve compatibility, and are stable in the formulated composition of the B side (second component). They can also improve the flexibility of the final product. The example of suitable dimer acid and trimer acid can obtain (acid number is 196mg KOH / g) from Croda Company (Croda Company) with trade name Prypol 1013 and obtain (acid number is 189mg KOH / g) from Croda Company with trade name Pripol 1040.

[0067] Table 1 shows the formulation details for two different sprayable formulations (248 and LV5). Figure 3A and Figure 3B The viscosity of side A (first component) and side B (second component) of two different formulations was compared (shear rate 34S -1). The viscosity of side A (first component) and side B (second component) of formulation LV5 (at the same temperature and shear rate) is much lower than the viscosity of formulation 248. The viscosities of both formulations are low enough to be sprayed. However, the viscosity of formulation LV5 is about 50% lower than the viscosity of formulation 248. This example shows that the viscosity of the formulation can be reduced by as much as 50% with comparable or improved properties.

[0068] As shown in Table 2, the processing time, density and lap shear properties of the two formulations remained unchanged. The tensile strength and elastic modulus of the LV5 material with lower viscosity increased. In other words, using the above formulation technology, physical and mechanical properties can be adjusted without changing the specific gravity or open time / processing time of the final product. When the viscosity of the formulation is reduced, it may be difficult to achieve sufficient failure strain. However, as shown in Table 2, using these compositions, materials with high elongation and high modulus can be prepared (Sample 248).

[0069] Table 1. Formulation details of two different sprayable formulations (248 and LV5)

[0070]

[0071]

[0072] Table 2. Properties of two different sprayable formulations (248 and LV5)

[0073]

[0074] In addition to some of the ingredients currently taught to be shear thinning, the entire formulation may also be highly shear thinning. This means that the apparent viscosity of the material is significantly reduced during the impact and spraying process (deposition) and facilitates deposition. Shortly after deposition, when the shear rate is reduced or becomes zero, the material immediately returns to a higher viscosity, close to the initial viscosity at the low shear rate. This allows the user to take advantage of low viscosity when needed (during mixing and spraying); and enables the user to apply thick materials without worrying about sagging or material flow.

[0075] Figure 3A and Figure 3B The viscosity of side B (second component) (including non-liquid ingredients) of formulation 248 at two different temperatures and different shear rates (all of which are considered to be very low compared to those at deposition conditions) is shown. The viscosity of side A (first component) and side B (second component) decreases significantly at higher temperatures and higher shear rates.

[0076] Figure 4 The viscosity of the B side (second component) of formulation 248 (including non-liquid ingredients) at different RPM rates is shown. Figure 5A and Figure 5B 3ITT (3-stage Thixotropy Test) results are shown, which show viscosity at different shear rates and two different temperatures (57°C and 64°C). 3ITT is a rheological technique that explores the structural recovery of viscoelastic materials over time. The procedure is typically a shear rate controlled test, measuring the viscosity at a very low shear rate, followed by a much higher rate, and then returning to the original shear rate. The time spent at each shear rate depends on the material, the only criterion being that a constant shear viscosity value (or plateau value) can be achieved at each shear rate. The reported results typically compare the initial plateau value to the final value, or the time required for the viscosity to recover to its original value.

[0077] In our specific example, the viscosity is measured at a shear rate of 0.004 (1 / sec) for 120 seconds, then the rate is increased logarithmically from 0.004 to 400 (1 / sec) over a period of 120 seconds and maintained at 400 (1 / sec) for an additional 120 seconds. The test is concluded by immediately reducing the shear rate from 400 to 0.004 (1 / sec) and then measuring the viscosity recovery over the next 480 seconds.

[0078] Side A (first component) and Side B (second component) are both at high viscosity at very low shear rates of 0.004 (1 / sec). When the shear rate increases to 400 (1 / sec), the viscosity of both components drops very quickly, and then once the shear rate returns to 0.004 (1 / sec), they return to close to their initial viscosity. The occurrence of shear thinning and thixotropy at different temperatures is beneficial, especially in reducing viscosity when needed (only during mixing and deposition), and then returning to a higher viscosity to maintain thickness or shape and reduce the fluidity of the material (immediately after deposition). These shear rates are generally lower than the shear rates to which the material is exposed during impact and spraying.

[0079] Another advantage of current thermosetting compositions is that the formulations do not utilize organic volatiles or other flammable ingredients to reduce viscosity. Some key ingredients in other two-component technologies contain organic volatiles or are flammable at elevated temperatures. For example, in spray polyurethane foam applications, due to the inhalation hazard caused by spraying polyurethane (usually isocyanate monomers), the application area should be limited to personnel wearing appropriate personal protective equipment. The lack of organic volatile ingredients reduces the risk and severity of inhaling materials while spraying. It does not contain toxic substances that hinder spraying. The lack of any organic volatiles and flammable ingredients allows the user to increase the temperature as needed to adjust the application viscosity or curing dynamics.

[0080] The two-component thermosetting compositions described herein may be relatively insensitive to the mixing ratio. For example, a target ratio of side A (first component) to side B (second component) is 4: 1 (v / v). However, small deviations from this ratio may not significantly affect the final properties. Table 3 shows embodiments in which the ratio varies within the range of 3.4: 1 to 4.6: 1, and illustrates that significant deviations from the target ratio do not affect the physical properties of the sprayed material. This is considered to be another advantage of the thermosetting compositions described herein. In the event that the mixing ratio deviates from this ratio due to pressure fluctuations from the pumping system in the impact device or other types of failures from the static / dynamic mixing device, the final properties of the composition may not be significantly affected.

[0081] Table 3. Examples of ratio variations in the range 3.4:1 to 4.6:1 and the effect on properties.

[0082]

[0083] This teaching illustrates the feasibility of spraying for a variety of room temperature activated systems (including rigid structural foams, cavity filling materials, gaskets and sealants), wherein phosphoric acid, phosphate esters and acidic components can be used as curing agents for epoxy resins and can be used as foaming agents. Table 4A shows several different sprayable formulations, and Table 4B illustrates their characteristics. The goal of this study is to spray, high strength bonding with aluminum and electroplated (E-coated) aluminum at low density. As shown in the table, all compositions maintain good lap shear results and show a range of mechanical properties, from extremely rigid structural materials to more compliant higher failure strain compositions.

[0084] Table 4A

[0085]

[0086]

[0087] Table 4B

[0088]

[0089] As can be understood from the above, sample 232W shows improved elongation compared to the other samples, but the tensile modulus and compression modulus are reduced. Sample 248B has a higher tensile modulus than the remaining samples, but has a lower elongation. Sample P-100 has relatively high compression modulus and tensile modulus and tensile strength, but fails in the lap shear test in the presence of the plating solution. Therefore, the composition can be formulated to meet the needs of a specific application.

[0090] Both Side A (first component) and Side B (second component) of the two-component composition described herein can be stable at elevated temperatures, which allows the user to incorporate higher viscosity materials into the formulated composition and utilize heat for mixing and spraying processes (where the viscosity needs to remain below a threshold at the deposition temperature). Both Side A (first component) and Side B (second component) can be maintained at elevated temperatures (up to 80° C. or even higher) for extended periods of time (e.g., hours or days) without risk of decomposition or reaction instability.

[0091] Both Side A (first component) and Side B (second component) may be insensitive to moisture. The sprayed material is extremely thin and is exposed to large amounts of air immediately after leaving the nozzle and before contacting the substrate. Therefore, current two-component sprayable compositions may not require any special processing adaptations due to their relative moisture insensitivity.

[0092] Depending on the type of chemical utilized, the amount of material per injection, and / or the viscosity and quantity of the chemical streams, a variety of mixing head types are possible. For example, in cases where the volumetric mixing ratio is close to or at 1:1, a straight mixing head may be sufficient. However, when the ratio is far from 1:1 and / or higher mixing energy is required due to higher viscosity, an L-shaped mixing head may be preferred. In other words, the viscosity at the application temperature and the ratio of the two components affect the exact type of equipment required to deliver the two components to the mixing head at high pressure. Although impact mixing works best for compositions with very low viscosities, any two-component static or dynamic mixing equipment can also be used to apply the current materials.

[0093] There are impingement systems with appropriate pumping units that are able to provide sufficient pressure to impinge a sufficiently highly filled system (due to the high viscosity material used in solid fillers). Those systems can also maintain precise ratios, temperatures, and uniform flow. However, in order to maintain a high quality mix and provide uniform flow, the viscosity of the liquid portion of the material cannot exceed a certain range.

[0094] The A side (first component) may include one or more additional epoxy functional materials, which may include epoxy resins. The additional epoxy resins may include multifunctional aromatic epoxy resins, multifunctional aliphatic epoxy resins, silane-modified epoxy resins, epoxy / elastomer adducts, epoxidized natural products such as soybean oil, or any combination thereof.

[0095] Side A (first component) can include one or more epoxy-based materials (i.e., one or more epoxy resins). The one or more epoxy resins can be any conventional dimerization, oligomerization or polymerization epoxy resin. The one or more epoxy resins can contain at least one epoxy functional group (i.e., monofunctional) or can contain more than one epoxy functional group (i.e., multifunctional). The one or more epoxy resins can contain one or more epoxy functional groups, two or more epoxy functional groups, three or more epoxy functional groups or even four or more epoxy functional groups. The one or more epoxy resins can be modified epoxy resins (e.g., silane-modified, elastomer-modified, etc.). The one or more epoxy resins can be aliphatic, alicyclic, aromatic, etc. or any combination thereof. The one or more epoxy resins can be supplied as solid (e.g., as pellets, blocks, sheets, etc. or any combination thereof) or liquid (e.g., liquid epoxy resin). As used herein, unless otherwise specified, an epoxy resin is a solid if it is solid at a temperature of 23° C., and is a liquid resin if it is liquid at a temperature of 23° C. The one or more epoxy resins may include one or more liquid epoxy resins, one or more flexible epoxy resins, one or more epoxy phenol novolac resins, one or more aliphatic multifunctional epoxy resins, one or more reactive diluents, one or more phenoxy resins, one or more silane-modified epoxy resins, or any combination thereof.

[0096] The two-part system may include one or more liquid epoxy resins. The liquid epoxy resin may serve as a base for the epoxy resin component. The liquid epoxy resin may be a reaction product of epichlorohydrin (hereinafter referred to as "EPH") and any conventional bisphenol. The liquid epoxy resin may be a reaction product of EPH and bisphenol A (hereinafter referred to as "BPA"), bisphenol F (hereinafter referred to as "BPF"), or both. The liquid epoxy resin may have an epoxy equivalent weight (hereinafter referred to as "EEW") of about 160 g / equivalent to about 192 g / equivalent as measured in accordance with ASTM D1652-97. The liquid epoxy resin may have an epoxy percentage of about 20 to about 25. The liquid epoxy resin may have a viscosity of about 2,000 cP to about 14,000 cP at 25°C as measured in accordance with ASTM D445. An example of a suitable BPA-based liquid epoxy resin may be DER TM 331, commercially available from The Olin Corporation, Clayton, MO. An example of a suitable BPF-based liquid epoxy resin may be YDF-170, commercially available from Kukdo Chemical (Korea).

[0097] The liquid epoxy resin may be present as part of the A side (first component). The liquid epoxy resin may be present in an amount of about 4% to about 70% by weight of the A side (first component). The liquid epoxy resin may be present in an amount of about 6% to about 10% by weight of the A side (first component). The liquid epoxy resin may be present in an amount of about 8% by weight of the A side (first component).

[0098] The two-part system can include one or more flexible epoxy resins. The one or more flexible epoxy resins can play a role in reducing the compression modulus of the reaction product, increasing failure strain, reducing recovery time, reducing crosslink density, increasing impact resistance, improving adhesion, improving peel resistance or any combination thereof. The one or more flexible epoxy resins can improve the gas interception capacity of the two-part system by acting as a viscosity modifier. The one or more flexible epoxy resins can be difunctional glycidyl ether epoxy resins, unmodified BPA-based epoxy resins, multifunctional epoxidized polybutadiene resins or any combination thereof. The one or more flexible epoxy resins can have an EEW of about 260 to about 500 as measured according to ASTM D1652-97. The one or more flexible epoxy resins can have a viscosity of about 700 cP to about 25,000 cP at 25 ° C as measured according to ASTM D445. Examples of suitable flexible epoxies may include NC-514 (commercially available from Cardolite Corporation, Monmouth Junction NJ), PY 4122 (commercially available from Huntsman Advanced Materials, Inc., Salt Lake City, UT), Poly 605E (commercially available from Cray Valley, Exton, PA), or any combination thereof.

[0099] The one or more flexible epoxy resins may be present on the A side (first component). The one or more flexible epoxy resins may be present in an amount of about 0.5% by weight to about 40% by weight of the A side (first component). The one or more flexible epoxy resins may be present in an amount of about 35% by weight to about 45% by weight of the A side (first component). The one or more flexible epoxy resins may be present in an amount of about 39% by weight of the A side (first component). The one or more flexible epoxy resins may include a difunctional glycidyl ether epoxy resin in an amount of about 10% by weight to about 18% by weight of the A side (first component), an unmodified BPA-based epoxy resin in an amount of about 8% by weight to about 16% by weight of the A side (first component), and a multifunctional epoxidized polybutadiene resin in an amount of about 8% by weight to about 16% by weight of the A side (first component). The one or more flexible epoxy resins may include a difunctional glycidyl ether epoxy resin in an amount of about 5% to 20% by weight of the A side (first component), an unmodified BPA-based epoxy resin in an amount of about 5% to about 20% by weight of the A side (first component), and a multifunctional epoxidized polybutadiene resin in an amount of about 5% to about 20% by weight of the A side (first component). The two-component system may include a difunctional glycidyl ether epoxy resin, a difunctional epoxy resin derived from cardanol, and a multifunctional epoxidized polybutadiene resin in a ratio of about 1:1:1, respectively. The two-component system may include a difunctional glycidyl ether epoxy resin, a difunctional epoxy resin derived from cardanol, and a multifunctional epoxidized polybutadiene resin. The above resins may be present in a ratio of about 1:0.8:0.8, respectively. The two-component system may include a difunctional glycidyl ether epoxy resin, a difunctional epoxy resin derived from cardanol, and a multifunctional epoxidized polybutadiene resin. The above resins may be present in a ratio of about 1:0.9:0.9, respectively.

[0100] The two-part system described herein may also include one or more epoxy phenol novolac resins. The one or more epoxy phenol novolac resins may serve to impart chemical resistance, solvent resistance, temperature resistance, or any combination thereof to the reaction product. The one or more epoxy phenol novolac resins may be present as part of the A side (first component). The one or more epoxy phenol novolac resins may have an EEW of about 165 g / equivalent to about 183 g / equivalent as measured according to ASTM D1652-97. The one or more epoxy phenol novolac resins may have an average epoxy functionality of about 2.1 to about 6.5. The one or more epoxy phenol novolac resins may have a viscosity of about 18,000 cP to about 30,000 cP at 25 ° C as measured according to ASTM D445. Examples of suitable epoxy phenol novolac resins may be those sold under the following trade names: 8250 (oligomeric reaction products of formaldehyde with 1-chloro-2,3-propylene oxide and phenol; functionality 2.6) and 8330 (poly[(phenyl glycidyl ether)-co-formaldehyde]; 3.6 functionality), commercially available from CVC Thermoset Specialties, Moorestown, NJ.

[0101] The one or more epoxy phenol novolac resins may be present in an amount of about 10% by weight to about 60% by weight of the A side (first component). The one or more epoxy phenol novolac resins may be present in an amount of about 35% by weight to about 45% by weight of the first component or the A side (first component). The one or more epoxy phenol novolac resins may be present in an amount of about 38% by weight to about 42% by weight of the A side (first component). The one or more epoxy phenol novolac resins may be present in an amount of about 42% by weight of the A side (first component). The one or more epoxy phenol novolac resins may include about 3.6 functional epoxy phenol novolac resins present in an amount of about 0.1% by weight to about 50% by weight of the A side (first component) and about 6.5 functional epoxy novolac resins present in an amount of about 22% by weight to about 32% by weight of the A side (first component). The one or more epoxy phenol novolac resins may include an about 3.6 functional epoxy phenol novolac resin present in an amount of about 15 wt % of the A side (first component) and an about 6.5 functional epoxy novolac resin present in an amount of about 28 wt % of the A side (first component). The two-part system may include an about 3.6 functional epoxy phenol novolac resin and an about 6.5 functional epoxy phenol novolac resin in a ratio of about 1:2 to about 1:3.

[0102] The two-part system may include one or more aliphatic multifunctional epoxy resins. The one or more aliphatic multifunctional epoxy resins may serve to increase the degree of crosslinking of the reaction product, increase the chemical resistance of the reaction product, or both. The one or more aliphatic multifunctional epoxy resins may include epoxidized sorbitol. The one or more aliphatic multifunctional epoxy resins may have an EEW of about 160 g / equivalent to about 195 g / equivalent as measured according to ASTM D1652-97. The one or more aliphatic multifunctional epoxy resins may have a viscosity of about 4,000 cP to about 18,000 cP at 25° C. as measured according to ASTM D445. Examples of suitable aliphatic multifunctional epoxy resins may be those sold under the trade name GE-60 and Those sold as GE-61 are commercially available from CVC Thermoset Specialties, Inc. of Moorestown, New Jersey.

[0103] The one or more aliphatic multifunctional epoxy resins may be present as a part of the A side (first component). The one or more aliphatic multifunctional epoxy resins may be present in an amount of about 4 wt % to about 60 wt % of the A side (first component). The one or more aliphatic multifunctional epoxy resins may be present in an amount of about 10 wt % to about 22 wt % of the A side. The one or more aliphatic multifunctional epoxy resins may be present in an amount of about 20 wt % of the A side (first component). The one or more aliphatic multifunctional epoxy resins may be present in an amount of about 13 wt % of the A side (first component).

[0104] The two-part system may include one or more reactive diluents. For multifunctional diluents, the one or more reactive diluents may act to reduce the overall viscosity of the two-part system so as to modify the dispensing process or the flow of the two-part system on the workpiece after dispensing, increase the degree of crosslinking of the reaction product, or both. The one or more reactive diluents may be polymeric, whereby the reactive diluent may increase the flexibility of the reaction product; the one or more reactive diluents may be multifunctional, whereby the reactive diluent may promote increased crosslinking and impart chemical resistance to the reaction product; or both. The one or more reactive diluents may include polyethylene glycol diglycidyl ether, trimethylolethane triglycidyl, or both. The one or more reactive diluents may have an EEW of about 150 g / equivalent to about 170 g / equivalent as measured according to ASTM D 1652-97. The one or more reactive diluents may have a viscosity of about 200 cP to about 300 cP at 25°C as measured according to ASTM D445. Examples of suitable reactive diluents may be those sold under the trade name GE-31 and Those sold as GE-24 are commercially available from CVC Thermoset Specialties, Inc. of Moorestown, New Jersey.

[0105] The one or more reactive diluents may be present in an amount of about 5% by weight to about 20% by weight of the A side (first component). The one or more reactive diluents may be present in an amount of about 8% by weight to about 16% by weight of the A side (first component). The one or more reactive diluents may be present in an amount of about 10% by weight to about 14% by weight of the A side (first component). The one or more reactive diluents may be present in an amount of about 13% by weight of the A side (first component). The one or more reactive diluents may include polyethylene glycol diglycidyl ether present in an amount of about 2% by weight to about 6% by weight of the A side (first component), and trimethylolethane triglycidyl ether present in an amount of about 6% by weight to about 14% by weight of the A side (first component). The one or more reactive diluents may include polyethylene glycol diglycidyl ether present in an amount of about 4% by weight of the A side (first component), and trimethylolethane triglycidyl ether present in an amount of about 9% by weight of the A side (first component). The two part system may include polyethylene glycol diglycidyl ether and trimethylolethane triglycidyl ether in a ratio of about 1:2 to about 1:3, respectively.

[0106] The two-part system may include one or more silane-modified epoxy resins. The one or more silane-modified epoxy resins may serve to impart improved adhesion to the reaction product, particularly to glass, metal, or both. Examples of suitable silane-modified epoxy resins may be those sold under the trade name Silane-modified epoxy resins sold as KSR-177 are commercially available from Kukdo Chemical (Korea). Silane-modified epoxy resins can be linear bifunctional silicone prepolymers (e.g., prepolymers having alicyclic epoxy groups) terminated with cyclic epoxides. Another suitable material is a silicone prepolymer having alicyclic epoxy groups. An example of such a material can be obtained from Siltech Corporation of Ontario, Canada under the trade name SilmerEPC Di-50.

[0107] The one or more silane-modified epoxy resins may be present in the A side (first component). The one or more silane-modified epoxy resins may be present in an amount of about 1 % by weight to about 7 % by weight of the A side (first component). The one or more silane-modified epoxy resins may be present in an amount of about 2 % by weight to about 6 % by weight of the A side (first component). The one or more silane-modified epoxy resins may be present in an amount of about 4 % by weight of the A side (first component).

[0108] The two-part system can include one or more tougheners. The one or more tougheners can play the role of distributing energy in the reaction product (that is, increasing impact resistance). The one or more tougheners can facilitate the T peel strength of increase. The one or more tougheners can include thermoplastics, thermosetting plastics or thermosetting plastics, elastomers, etc. or any combination thereof. The one or more tougheners can include elastomers (including elastomer-containing materials), core-shell polymers (which can include but are not limited to elastomers) or both.

[0109] Core-shell polymers (if present) can include a first polymer material (i.e., core material) and a second polymer material (i.e., shell material). The first polymer material can be completely encapsulated by the second polymer material. Core-shell polymers can include about 30% by weight or more, 50% by weight or more, or even 70% by weight or more of the first polymer material. The first polymer material, the second polymer material, or both can include one, two, three, or even more than three polymers combined together, reacted together (e.g., sequentially polymerized) or both, or can be a part of a separate or identical core-shell polymer system. Examples of suitable core-shell polymers can be those sold under the trade name Kane MX-267 and MX-257 are core-shell polymers sold commercially from Kaneka North America LLC in Pasadena, TX.

[0110] Core-shell polymer can be present in an amount of about 1 wt % to about 25 wt % of a combination of side A (first component), side B (second component) or side A (first component) and side B (second component) (for example, if present in an amount of 10 wt %, it can be present in an amount of 5 wt % in side A (first component) and 5 wt % in side B (second component)). Core-shell polymer can be present in an amount of about 5 wt % to about 20 wt % of a combination of side A (first component), side B (second component) or side A (first component) and side B (second component). Core-shell polymer can be present in an amount of about 5 wt % to about 50 wt % of a combination of side A (first component), side B (second component) or side A (first component) and side B (second component). Core-shell polymer can be present in an amount of about 17 wt % of a combination of side A (first component), side B (second component) or side A (first component) and side B (second component).

[0111] When a two-part system includes a metal carbonate in the A side (first component), the average functionality of the B side (second component) may be partially reduced when combined with the A side (first component) in the mixed composition. This may be due to the acid of the B side (second component) reacting with the metal carbonate of the A side (first component) to cause foaming. The A side (first component) may include components with increased functionality to compensate for the reduced functionality of the B side (second part). The A side (first component) can be formulated with increased functionality by using reactive ingredients with a functionality greater than 2, such as aliphatic multifunctional epoxy resins.

[0112] The B side (second component) may include one or more acids. The acid may be a liquid at room temperature. As described herein, room temperature may mean a temperature of about 20°C to 25°C. The acid may have a pH of less than 7. The acid may include a phosphate ester, phosphoric acid, citric acid, acetic acid, or any acid that is stable when mixed with phosphoric acid or a phosphate ester. The acid may include at least a phosphate ester and optionally phosphoric acid, citric acid, acetic acid, or any combination thereof.

[0113] The working time of the mixed composition can be adjusted by the choice of acid. Using a phosphate ester instead of phosphoric acid can delay the curing reaction due to its higher pH, lower functionality, higher viscosity or any combination thereof. The functionality and pH of the phosphate ester can be selected to adjust the working time.

[0114] The B side (second component) can include one or more phosphoric acid esters, phosphoric acid ester precursors or both. The one or more phosphoric acid esters can be pre-reacted. The B side (second component) can include one or more phosphoric acid ester precursors, which can be combined with phosphoric acid before being combined with the A side (first component).

[0115] The B side (second component) may include additional phosphoric acid. The additional phosphoric acid may include orthophosphoric acid, polyphosphoric acid, or both. The additional phosphoric acid may increase the crosslink density and shorten the reaction time. The reaction rate of the pre-reacted phosphate ester may be increased by adding additional phosphoric acid to the B side (second component). The additional phosphoric acid may increase the foaming of the mixed composition.

[0116] The one or more phosphates can be one or more customized phosphates. The one or more customized phosphates can be produced by the reaction of phosphoric acid and various alcohols. The one or more customized phosphates can be produced by the reaction of phosphoric acid and the epoxide group of a phosphate precursor (i.e., a component that has not yet reacted with phosphoric acid). The one or more customized phosphates can be produced by the reaction of phosphoric acid and the glycidyl ether of cashew nut shell liquid (CNSL) (such as under the trade name LITE 2513HP, commercially available from Cardolite Corporation, Monmouth Junction NJ). The one or more customized phosphate esters can be produced by reacting phosphoric acid with phenyl glycidyl ether (such as the one sold under the trade name The one or more customized phosphate esters can be produced by reacting phosphoric acid with 2-ethylhexyl glycidyl ether (such as that sold under the trade name GE-13, commercially available from CVC Thermoset Specialties, Inc., Moorestown, New Jersey). The one or more customized phosphate esters can be produced by reacting phosphoric acid with epoxidized p-tert-butylphenol (such as epoxidized tert-butylphenol sold under the trade name GE-6, commercially available from CVC Thermoset Specialties, Inc., Moorestown, New Jersey). GE-11 is commercially available from CVC Thermoset Specialties, Inc. of Moorestown, New Jersey).

[0117] The one or more phosphate esters may be one or more commercial pre-reacted phosphate esters. When one or more commercial pre-reacted phosphate esters are exchanged into the B side (second component) in place of a custom phosphate ester, they may produce a curable composition that reacts more slowly and foams, presumably due to a lower amount of free phosphoric acid. The reaction and foaming of the one or more commercial pre-reacted phosphate esters may be improved (i.e., accelerated) by adding phosphoric acid to the B side (second component). The pH of the one or more commercial pre-reacted phosphate esters in aqueous solution may be about 1 to 3. The one or more commercial 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. The one or more commercial pre-reacted phosphate esters may be nonylphenol ethoxylated phosphate esters. Examples of suitable commercial pre-reacted phosphate esters may be commercially available under the trade name Dextrol TM Those sold as OC-110, Dextrol OC-40, and Strodex MO-100 are commercially available from Ashland, Inc. of Covington, KY.

[0118] The commercially pre-reacted phosphate ester may be present in the B side (second component). The one or more commercially pre-reacted phosphate esters may be present in an amount of about 6 wt % to about 18 wt % of the B side (second component). The one or more commercially pre-reacted phosphate esters may be present in an amount of about 8 wt % to about 16 wt % of the B side (second component). The one or more commercially pre-reacted phosphate esters may be present in an amount of about 10 wt % to about 14 wt % of the B side (second component). The one or more commercially pre-reacted phosphate esters may be present in an amount of about 12 wt % of the B side (second component).

[0119] The one or more phosphates can be produced by the reaction of a series of stoichiometric ratios of a phosphate precursor and phosphoric acid. The one or more phosphates can be produced by the reaction of a phosphate precursor and phosphoric acid at about 0.7:1 to about 1:0.7. The one or more phosphates can be produced by the reaction of a phosphate precursor and phosphoric acid at about 0.8:1 to about 1:0.8. The one or more phosphates can be produced by the reaction of a phosphate precursor and phosphoric acid at about 0.9:1 to about 1:0.9. The one or more phosphates can be produced by the reaction of a phosphate precursor and phosphoric acid at about 1:1. The one or more phosphates can be produced by the reaction of a phosphate precursor and phosphoric acid at about 0.8:1.

[0120] The one or more phosphate esters may be selected from monoesters, diesters or triesters as shown below:

[0121]

[0122] The one or more phosphate esters can be obtained from the reaction of epoxy groups with phosphoric acid as shown below:

[0123]

[0124] The B side (second component) may include one or more phosphate esters, one or more phosphate ester precursors, or both. The B side (second component) may include one or more phosphate ester precursors, which may be combined with phosphoric acid prior to being combined with the A side (first component). The B side (second component) may include one or more phosphate esters, which may be pre-reacted (i.e., epoxide and phosphate reacted) prior to being added to the B side (second component).

[0125] The first phosphate ester can be the reaction product of phosphoric acid and 2-ethylhexyl glycidyl ether. The second phosphate ester can be the reaction product of epoxidized p-tert-butylphenol, the reaction product of the glycidyl ether of cashew nut shell liquid (CNSL), nonylphenol ethoxylated phosphate or a combination thereof. The third phosphate ester can be the reaction product of phosphoric acid and phenyl glycidyl ether. Side B (second component) can include the first phosphate ester, the second phosphate ester, the third phosphate ester or a combination thereof.

[0126] The first phosphate ester may be present in an amount of about 1% to about 70% by weight of the B side (second component). The first phosphate ester may be present in an amount of about 5% to about 60% by weight of the B side (second component). The first phosphate ester may be present in an amount of about 10% to about 30% by weight of the B side (second component). The second phosphate ester (if present) may be present in an amount of about 1% to about 80% by weight of the B side (second component). The second phosphate ester may be present in an amount of about 3% to about 50% by weight of the B side (second component). The second phosphate ester may be present in an amount of about 5% to about 40% by weight of the B side (second component). The third phosphate ester (if present) may be present in an amount of about 0.5% to about 90% by weight of the B side (second component). The third phosphate ester may be present in an amount of about 10% to about 70% by weight of the B side (second component). The third phosphate ester may be present in an amount of about 20% to about 65% by weight of the B side (second component).

[0127] The B side (second component) may include phosphoric acid. The phosphoric acid may be orthophosphoric acid, polyphosphoric acid, or both. The phosphoric acid may be polyphosphoric acid. The phosphoric acid may be a free acid in one or more phosphate esters, an acid added independently of one or more phosphate esters, or both. Adding phosphoric acid to the B side (second component) may result in increased expansion (e.g., foaming) of the resulting reaction product. When the temperature is below 23° C., adding phosphoric acid to the B side (second component) may increase the reactivity of the two-part system to help maintain the desired expansion level, cure level, or both.

[0128] The independently added phosphoric acid, if present, may be in an aqueous solution (i.e., "reagent grade") in an amount of 85% or more or even 95% or more. The independently added phosphoric acid may be present in an amount of about 0.1% to about 30% by weight of the B side (second component). The independently added phosphoric acid may be present in an amount of about 2% to about 6% by weight of the B side (second component). The independently added phosphoric acid may be present in an amount of about 4% by weight of the B side (second component).

[0129] The one or more phosphates produced by the reaction of phosphoric acid with one or more epoxy group-containing components may include free acid. The one or more phosphates 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.

[0130] After adding the A side (first component) and the B side (second component), the two-component system may foam due to the reaction of the metal carbonate or metal bicarbonate with the acid, resulting in the release of a gas (e.g., carbon dioxide), thereby acting as a chemical blowing agent. This reaction mechanism is described in U.S. Pat. No. 5,648,401, which is incorporated herein by reference for all purposes.

[0131] Curing, foaming or both can occur at a temperature of about 50°C or less, 40°C or less, about 30°C or less, about 20°C or less, or about 0°C or less. Curing, foaming or both can occur at a temperature of about 0°C or more, about 10°C or more, or even about 20°C or more. Curing, foaming or both can occur at a temperature of about 10°C to about 50°C or even more. Curing, foaming or both can occur at a temperature of about 10°C. Curing, foaming or both can occur at room temperature (e.g., at a temperature of about 15°C to about 25°C). Curing, foaming or both can occur at a temperature of about 23°C. Curing and foaming can occur at different temperatures or at substantially the same temperature. As previously described, the system described herein may not contain any foaming. The system described herein may include only minimal foaming (e.g., 0.5% to about 2% volume expansion).

[0132] Foaming (if any) can start before the resulting reaction product is fully cured. The foaming time of the reaction product (i.e., the time range in which the two-part system actively foams) can be 30 minutes or less or even 20 minutes or less. The foaming time of the reaction product can be from about 1 minute to about 10 minutes. The foaming time of the reaction product can be about 5 minutes. The foaming time of the reaction product can be about 7 minutes.

[0133] The two-part system may include one or more additives. The one or more additives may include one or more toughening agents, calcium carbonate, minerals, reinforcing fibers or other reinforcing particles, hydrophobic silica, platy alumina, or any combination thereof.

[0134] The two-part system can include one or more minerals. The one or more minerals (i.e., "mineral reinforcement") can play a role in structurally strengthening the reaction product. The one or more minerals can improve the tensile strength, flexural strength, or both of the reaction product. The one or more minerals can be any suitable silicate minerals, including but not limited to chain silicates (e.g., wollastonite) and phyllosilicates (e.g., kaolinite, vermiculite, talc, muscovite, etc.). The characteristic external shape of a single crystal or a crystal group of the one or more minerals can be needle-like or needle-like. The median particle size of the one or more minerals can be about 10 microns to about 20 microns. The median particle size can be about 12 microns to about 18 microns.

[0135] The one or more minerals may include wollastonite (CaSiO3). The wollastonite may be relatively pure (i.e., less than 2% by weight 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, replacing calcium in the mineral structure. An example of a suitable wollastonite may be obtained under the trade name 12 and 8 Wollastonite is commercially available from NYCO Minerals Inc. of Willsboro, NY.

[0136] The one or more minerals may be present as part of the A side (first component), the B side (second component) or both. Wollastonite may be present in an amount of about 1% by weight to about 18% by weight of a combination of the A side (first component), the B side (second component) or the A side (first component) and the B side (second component). Wollastonite may be present in an amount of about 3% by weight to about 7% by weight of a combination of the A side (first component), the B side (second component) or the A side (first component) and the B side (second component). Wollastonite may be present in an amount of about 4% by weight of a combination of the A side (first component), the B side (second component) or the A side (first component) and the B side.

[0137] Reinforcing fiber can exist with the amount of about 0.01 % by weight to about 15 % by weight of the combination of A side (first component), B side (second component) or A side (first component) and B side (second component). Reinforcing fiber can exist with the amount of about 1 % by weight to about 10 % by weight of the combination of A side (first component), B side (second component) or A side (first component) and B side (second component). Reinforcing fiber can exist with the amount of about 3 % by weight of the combination of A side (first component), B side (second component) or A side (first component) and B side (second component).

[0138] The two-part system can include a hydrophobic silica. The hydrophobic silica can play a role in controlling viscosity (e.g., thickening), controlling thixotropy, enhancing hydrophobicity, or a combination thereof. The hydrophobic silica can be a fumed silica. The hydrophobic silica can be surface treated. For example, the hydrophobic silica can be a fumed silica surface treated with polydimethylsiloxane (hereinafter referred to as "PDMS") or hexamethyldisilazane (hereinafter referred to as "HMDZ"). The hydrophobic silica can be present as part of the A side (first component), the B side (second component), or both. Examples of suitable hydrophobic silicas can be those sold under the trade name Hydrophobic silica sold under the trade names R 202, commercially available from Evonik Corporation of Parsippany, New Jersey; and Those sold as TS-530 and TS-720 are commercially available from Cabot Corporation in Boston, MA.

[0139] Hydrophobic silica can be present in an amount of about 0.25% by weight to about 15% by weight of a combination of the A side (first component), the B side (second component), or the A side (first component) and the B side (second component). Hydrophobic silica can be present in an amount of about 0.1% by weight to about 4% by weight of a combination of the A side (first component), the B side (second component), or the A side (first component) and the B side (second component). Hydrophobic silica can be present in an amount of about 1% by weight to about 3% by weight of a combination of the A side (first component), the B side (second component), or the A side (first component) and the B side (second component). Hydrophobic silica can be present in an amount of about 1% by weight of the A side (first component). Hydrophobic silica can be present in an amount of about 1% by weight to about 3% by weight of the B side (second component). The ratio of the hydrophobic silica in the A side (first component) and the B side (second component) can be about 1:3 to about 3:1. The ratio of hydrophobic silica in the A side (first component) to the B side (second component) can be from about 1:2 to about 2:1.

[0140] The two-part system may be free of a curing agent (i.e., a typical 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 above-mentioned curing agents, the two-part system may be cured after a polymerization reaction between a phosphoric acid-catalyzed phosphate and an epoxy group, a hydroxyl group, or both. The two-part system may both cure and cause its expansion through the chemical interaction between the phosphate and calcium carbonate. It has been found that the complexity of the formulation may be reduced by reducing the number of total components (i.e., curing agent, curing accelerator, and blowing agent) using the curing and expansion system disclosed herein; however, achieving the desired expansion and curing time makes optimization more challenging.

[0141] As used herein, unless otherwise stated, the teachings contemplate that any member of a genus (list) may be excluded from that genus; and / or any member of a Markush group may be excluded from that group.

[0142] Unless otherwise stated, the numerical values ​​described herein include all numerical values ​​from lower values ​​to higher values, with an increment of 1 unit, provided that there is at least an interval of 2 units between any lower value and any higher value. As an example, if the amount of the value of a component, characteristic or process variable (such as temperature, pressure, time, etc.) is stated to be, for example, from 1 to 90, preferably from 20 to 80, more preferably from 30 to 70, it is intended that the intermediate range values ​​(for example, 15 to 85, 22 to 68, 43 to 51, 30 to 32, etc.) are within the teaching of this specification. Similarly, separate intermediate values ​​are also within this teaching. For values ​​less than 1, one unit is considered to be 0.0001, 0.001, 0.01 or 0.1 as appropriate. These are only examples of specific intent, and all possible combinations of numerical values ​​between the lowest and highest values ​​listed should be considered to be the content clearly stated in a similar manner in this application. It can be seen that the teaching of the amount represented as "parts by weight" herein also contemplates the same range represented by weight percentage. Thus, language within the range of "at least "x" parts by weight of the resulting composition" also contemplates teaching of the same recited amount range of "x" weight percent of the resulting composition.

[0143] Unless otherwise stated, all ranges include both endpoints and all numbers between the endpoints. The use of "about" or "approximately" in connection with a range applies to both ends of the range. Thus, "about 20 to 30" is intended to encompass "about 20 to about 30," including at least the specified endpoints. Unless otherwise stated, the term "about" or "approximately" with a numerical quantity encompasses the teaching of the cited quantity as well as the approximate value of the cited quantity. For example, a teaching of "about 100" encompasses a teaching of 100.

[0144] The disclosures of all articles and references, including patent applications and publications, are incorporated by reference for all purposes. The term "consisting essentially of" describing a combination shall include the identified elements, ingredients, components, or steps, as well as such other elements, ingredients, components, or steps that do not materially affect the basic and novel characteristics of the combination. The use of the terms "comprising" or "including" herein to describe a combination of elements, ingredients, components, or steps also contemplates embodiments consisting of or consisting essentially of the elements, ingredients, components, or steps.

[0145] Multiple elements, ingredients, components or steps can be provided by a single integrated element, ingredient, component or step. Alternatively, a single integrated element, ingredient, component or step can be divided into separate multiple elements, ingredients, components or steps. The disclosure of "a" or "one" describing an element, ingredient, component or step is not intended to exclude additional elements, ingredients, components or steps.

[0146] It should be understood that the above description is intended to be illustrative and not restrictive. Many embodiments and many applications other than the examples provided will be apparent to those skilled in the art after reading the above description. Therefore, the scope of the present invention should not be determined with reference to the above description, but with reference to the full scope of equivalents given by the appended claims and such claims. The disclosures of all articles and references (including patent applications and publications) are incorporated by reference for all purposes. The omission of any aspect of the subject matter disclosed herein in the following claims is not a disclaimer of this subject matter, nor should it be considered that the inventor considers this subject matter to be not part of the disclosed inventive subject matter.

Claims

1. A two-part system, comprising: a) a first component comprising one or more epoxy resins and an epoxy functional material having an epoxy functionality greater than 4 and a viscosity of 500 cps or less at 23° C. according to ASTM D2556-14; b) a second component comprising one or more phosphate esters having a viscosity at 23° C. according to ASTM D2556-14 of 500 cps or less during deposition.

2. A two-part system (two-component system), the two-part system comprising: a) a first component, the first component comprising - one or more epoxy resins; and - an epoxy-functional compound having an epoxy functionality greater than 4 and a viscosity in its pure state of 500 mPa·s or less; b) a second component comprising one or more phosphate esters, each of the one or more phosphate esters having a viscosity of 500 mPa·s or less in its pure state; In each case, the viscosity was determined as described in the description.

3. A two-part system (two-component system), the two-part system comprising: a) a first component, the first component consisting essentially of: - one or more epoxy resins; - epoxy-functional compounds having an epoxy functionality greater than 4; as well as -optionally one or more non-liquid ingredients; wherein the one or more epoxy resins and the epoxy-functional compound have a total viscosity (when mixed with each other but without the one or more non-liquid components) of 500 mPa-s; b) a second component, said second component consisting essentially of: - one or more phosphate esters, and -optionally one or more non-liquid ingredients; wherein the one or more phosphate esters have a total viscosity of 500 mPa·s or less (when mixed with each other but without the one or more non-liquid components); In each case, the viscosity was determined as described in the description.

4. The two-part system of any one of the preceding claims, wherein after mixing the first component and the second component, the resulting composition cures at a temperature of about 0°C to about 50°C.

5. A two-part system according to any one of the preceding claims, wherein the first component comprises epoxidized diphenylamine.

6. The two-part system of any one of the preceding claims, wherein the one or more phosphate esters comprises a phosphate ester derived from cashew nut shell liquid (CNSL).

7. The two-part system of any one of the preceding claims, wherein the one or more phosphate esters comprises a phosphate ester derived from 2-ethylhexyl glycidyl ether.

8. The two-part system of any one of the preceding claims, wherein the one or more phosphate esters comprises a phosphate ester derived from phenyl glycidyl ether.

9. The two-part system of any one of the preceding claims, wherein the one or more phosphate esters comprises a phosphate ester derived from epoxidized p-tert-butylphenol.

10. The two-part system according to any one of the preceding claims, wherein the first component and / or the second component comprises one or more additives selected from core-shell polymers, calcium carbonate, minerals, reinforcing fibers, hydrophobic silica, monomers, platy alumina or any combination thereof.

11. The two-part system of any one of the preceding claims, comprising calcium carbonate present in an amount of about 0.01 wt. % to about 10 wt. %, relative to the total weight of the two-part system.

12. The two-part system of any one of the preceding claims, comprising ultrafine calcium carbonate (about 1 micron average particle size), fine calcium carbonate (about 4 micron average particle size), medium fine calcium carbonate (about 22 micron average particle size), or any combination thereof.

13. A two-part system according to any one of the preceding claims, wherein one or both of the first component and the second component comprises wollastonite.

14. The two-part system of any one of the preceding claims, wherein one or both of the first component and the second component comprises fumed silica.

15. The two-part system of any of the preceding claims, wherein the one or more epoxy resins or epoxy-functional materials comprise one or more liquid epoxy resins, one or more epoxy phenol novolac resins, one or more aliphatic multifunctional epoxy resins, one or more phenoxy resins, one or more silane-modified epoxy resins, or any combination thereof.

16. The two-part system of any of the preceding claims, comprising one or more epoxy phenol novolac resins having an epoxy functionality of about 2 to about 3; epoxy phenol novolac resins having an epoxy functionality of about 3 to about 4; or both.

17. The two-part system of any of the preceding claims, comprising one or more epoxy phenol novolac resins present in an amount of about 15 wt% to about 70 wt% relative to the total weight of the first component.

18. The two-part system of any one of the preceding claims, wherein other than the one or more phosphate esters, the two-part system is substantially free of a curing agent, a latent curing accelerator, or both.

19. The two-part system of any one of the preceding claims, wherein the first component, the second component, or both, comprises a dicarboxylic acid based ingredient.

20. A two part system according to any one of the preceding claims, wherein the first component is substantially free of any epoxy resin which in its pure state is solid at a temperature of 20°C to 25°C.

21. The two-part system of any one of the preceding claims, wherein the first component and the second component are present in a ratio of about 5 parts by volume first component: 1 part by volume second component to about 1 part by volume first component: 1 part by volume second component.

22. A two part system according to any one of the preceding claims, wherein the second component is substantially free of any epoxy resin which in its pure state is solid at a temperature of 20°C to 25°C.

23. A two-part system according to any one of the preceding claims, wherein the second component comprises less than 5% by weight of an epoxy resin which in its pure state is solid at a temperature of 20°C to 25°C, relative to the total weight of the second component.

24. A two-part system according to any of the preceding claims, wherein the viscosity is measured at a shear rate of 0.004 (1 / sec) for 120 seconds, the rate is then increased logarithmically from 0.004 to 400 (1 / sec) over a period of 120 seconds and maintained at 400 (1 / sec) for an additional 120 seconds; wherein the test is terminated by immediately reducing the shear rate from 400 to 0.004 (1 / sec) and subsequently measuring the viscosity recovery over the next 480 seconds.

25. A two-part system according to any one of the preceding claims, comprising one or more epoxy phenol novolac resins present in an amount of at least 40 wt%, preferably at least 50 wt%, relative to the total weight of the first component.

26. The two-part system according to any one of the preceding claims, comprising one or more aliphatic multifunctional epoxy resins in an amount of at least 10% by weight relative to the total weight of the first component.

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