US20050020703A1 - Two component (epoxy/amine) structural foam-in-place material - Google Patents
Two component (epoxy/amine) structural foam-in-place material Download PDFInfo
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- US20050020703A1 US20050020703A1 US10/916,103 US91610304A US2005020703A1 US 20050020703 A1 US20050020703 A1 US 20050020703A1 US 91610304 A US91610304 A US 91610304A US 2005020703 A1 US2005020703 A1 US 2005020703A1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/32—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof from compositions containing microballoons, e.g. syntactic foams
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2363/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
- Y10T428/24355—Continuous and nonuniform or irregular surface on layer or component [e.g., roofing, etc.]
- Y10T428/24372—Particulate matter
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
- Y10T428/24479—Structurally defined web or sheet [e.g., overall dimension, etc.] including variation in thickness
- Y10T428/24612—Composite web or sheet
Definitions
- the present invention relates generally to foam-in-place structural materials used for reinforcement of structural members. More particularly, the present invention relates to a two-component epoxy/amine foamed material exhibiting improved mechanical properties (good balance of high compressive strength, compressive modulus, glass transition temperature and cured ductility) as well as enhanced shear-thinning characteristics.
- these structural reinforcement characteristics in many applications, including automotive, may also benefit from a shear-thinning structural material which exhibits an increased viscosity at zero shear rate and a decreased viscosity at higher shear rates prior to curing. This enables the material to flow more easily while being dispensed but then have flow minimally following dispensing. This shear thinning behavior can also assist with the development of a uniform, consistent foamed cell structure by allowing more effective foaming gas entrapment.
- a number of prior art techniques are available to control the rate of foam expansion and the cure rate. For example, a wide-range of reactivities are available in commercial resins and curing agents.
- resins are available in a range of viscosities, which is another parameter and can be used to control the foam expansion rate. That is, it is known that a low viscosity resin can generally be expanded to a greater volume with a given volume of gas than a higher viscosity material; however, the resin must have sufficient viscosity to contain the gas at the pressures at which it is generated in order for the foam to be properly formed.
- foamed products must have good environmental resistance and, most significantly, in many applications they must protect metal from corrosion while maintaining adhesion to the substrate.
- foamed parts were made using polyurethane, which provides a number of desirable attributes. It is known, however, that alternatives to urethane-based foams or more precisely materials based on the reaction of the isocyanate chemical functional group are frequently more environmentally desirable, in part due to the potential for unreacted functional groups in the finished products and difficulty in handling isocyanate functional chemicals in manufacturing processes.
- the polyurethane materials found in the prior art fail to provide optimum mechanical properties, generally possessing lower elastic modulus strength and lower glass transition temperature than what is capable with epoxy-based materials. In comparison with polyurethane materials, however, the epoxy-based materials found in the prior art often exhibit both poor cured ductility and higher viscosity during dispensing.
- a structural material which exhibits improved mechanical properties, such as higher compressive strength, compressive modulus, and glass transition temperature, as well as better-cured ductility.
- the improved mechanical properties allow the structural material of the present invention to be capable of plastically deforming when loaded beyond its yield stress.
- modulus or glass transition temperature there is no significant reduction in modulus or glass transition temperature.
- an improved material which can be used in a variety of applications wherein one or both components utilize a thixotropic filler, which produces pronounced shear-thinning characteristics.
- the present invention relates to methods, materials, and products for foam-in-place structural reinforcement of hollow structures such as automobile cavities.
- the present invention comprises a two-component foam-in-place structural material for producing a foamed product.
- the first component of the system includes an epoxy-based resin.
- the first component is formulated with a physical blowing agent, and more preferably one having a shell or skin that will change state to provide volumetric increase to create expansion.
- the shell is a thermoplastic that, upon heating, will melt or soften to enable a solvent core to expand the shell.
- the second component includes an amine, and is formulated with an agent for allowing the resulting material to exhibit ductility with little reduction in modulus, glass transition temperature, or both.
- the amine of the present invention could be a primary or secondary amine.
- the amine is an epoxy curing agent or modifier, and preferably, a high solids epoxy curing agent, though it could be a water-borne epoxy-curing agent.
- Other examples of an amine suitable for use in the present invention include polyamides, aliphatic amines, and cycloaliphatic amines as well as other agents that can function as accelerators or catalysts.
- An optional thixotropic filler is included in either or both of the first or second components, and possibly as a stand-alone component. In one embodiment, this additive preferably causes the material to have high viscosity at a near zero shear rate and low viscosity at a higher shear rate, which is more commonly known in the art as shear-thinning.
- the present invention provides a method of forming a foamed product, which comprises the steps of combining the first component (with a blowing agent) with the second component (with a curing agent).
- the first component preferably an epoxy
- the second component of the formulation e.g. an amine
- an exothermic reaction or reactive mixture is created between the epoxy component and the amine component when combined.
- the heat generated by the exothermic reaction softens the thermoplastic shell of the blowing agent formulated within the epoxy component thereby enables the solvent core within the thermoplastic shell to expand the thermoplastic shell and thereby create expansion.
- the mixture of materials is in liquid form. However, it is contemplated that the mixture of materials could also comprise a paste or solids of varying viscosities and textures.
- the present invention relates generally to a two component structural foam-in-place material and method for making the same formed by cross-linking reactions between an epoxy resin and a curing agent that creates a three-dimensional covalent bond network. It is contemplated that the addition of a curing agent to the epoxy resin causes the resin to cure or harden into a rigidified cross-linked polymer. When an epoxy resin is mixed with a curing agent containing labile hydrogen atoms, the epoxy ring opens and reacts with the curative. Generally speaking, cured epoxy foams are produced using one of three types of curing agents, such as amines, polyphenols, and anhydrides.
- Cure of the foam is achieved by polyaddition whereby the cure reaction between the epoxy resin and a curing agent is typically exothermic and can generate a considerable amount of heat.
- the control of such heat and the exothermic reaction is an important consideration of the foam-in-place material of the present invention. Since the foam-in-place material of the present invention is particularly useful in the production of automobiles and other vehicles to maintain and/or increase the strength of structural members such as frame members, rails, rockers, pillars, radiator support beams, doors, hatches, reinforcing beams and the like, exothermic control prevents the charring or burning of the interior of the foam.
- the method and composition of the present invention has two main components: (1) an epoxy resin component formulated with a physical blowing agent having a thermoplastic shell with a solvent core, and (2) an amine curing agent component which, when cured, produces a material capable of plastically deforming when mechanically loaded with an insignificant reduction in modulus or glass transition temperature reduction when compared with traditional epoxy/amine systems.
- a thixotropic additive is formulated into one or both the first and second components, which produces shear-thinning characteristics useful for processing and generation of a foamed product.
- the exothermic reaction generated by the combination or mixture of the first and second components serves to soften the physical blowing agent, which consists of a thermoplastic shell with a solvent core.
- the solvent expands the shell to create an expanded particle.
- the preferred solvent and shell is selected for its expansion properties when exposed to the heat of the exothermic reaction, which occurs during polymerization.
- GVI 4040 by using the preferred fillers, and less reactive amine functional materials such as an amine sold under the commercial name GVI 4040, excessive exotherm, which would otherwise be produced by the curing reaction (and which could produce charring), is prevented.
- the components or formulation of the present invention include the following:
- the first or resin component of the present invention is selected for its structurally adhering characteristics and for imparting rigidity.
- Suitable resins may include a cross-linkable polymer and, more preferably an epoxy.
- the properties of advantageous epoxy resins are described, for example, in the chapter entitled “Epoxy Resins” in the Second Edition of the Encyclopedia of Polymer Science and Engineering, Volume 6, pp. 322-382 (1986).
- the preferred epoxy resin has a number average molecular weight of from about 350 to about 600 and, on average, each molecule of epoxy has from about 1.8 to about 2.5 epoxide functional groups.
- the preferred epoxy resin has a viscosity of from about 5,000 to 100,000 cps (Brookfield viscosity) at 70° F.
- the preferred form of the resin is a liquid and may further comprise a high viscosity resin with relatively low reactivity.
- Exemplary epoxy resins which could be utilized in the present invention include polyglycidyl ethers obtained by reacting polyhydric phenols such as bisphenol A, bisphenol F, bisphenol AD, catechol, resorcinol, or polyhydric alcohols such as glycerin and polyethylene glycol with haloepoxides such as epichlorohydrin; glycidylether esters obtained by reacting hydroxycarboxylic acids such as p-hydroxybenzoic acid or beta-hydroxy naphthoic acid with epichlorohydrin or the like; polyglycidyl esters obtained by reacting polycarboxylic acids such as phthalic acid, tetrahydrophthalic acid or terephthalic acid with epichlorohydrin or the like; epoxidated phenolic-novolac
- epoxy resins may also be used in the present invention.
- mixtures of liquid (at room temperature), semi-solid, and/or solid epoxy resins can be employed.
- a preferable epoxy resin for use in the present invention includes DER 331.
- the preferred form of the resin is a liquid.
- Other commercially available epoxy resins, which may be suitable in the present invention include, but are not limited to DER 317, DER 337 and DER 324.
- a resin forms from about 35% to about 99% by weight of the first or resin component and more preferably from about 65% to about 98% by weight of the composition of the present invention.
- the resin component of the present invention may also be formulated with a blowing agent and, more particularly, a blowing agent having a thermoplastic shell with a solvent core.
- a blowing agent may be a chemical agent, (i.e. one that thermally decomposes and evolves gas due to the heat of the exothermic epoxy reaction), or a physical agent, which simply vaporizes at its boiling temperature to liberate gas.
- particle size of the blowing agent may be adjusted so as to provide the desired foaming characteristics in the cured foam.
- Suitable chemical blowing agent activators include, but are not limited to, ureas (such as the surface-coated, oil-treated urea sold by Uniroyal Chemicals under the trademark BIKOT) polyols, organic acids, amines, and lead, zinc, tin, calcium and cadmium oxides and salts (including carboxylic acid salts).
- blowing agent based on the weight of the foamable composition
- a blowing agent based on the weight of the foamable composition
- the optimum amount will of course vary depending upon the activator/accelerator selected, the amount of blowing agent, cure temperature and other variables.
- the solvent core of the blowing agent of the present invention is a liquid.
- the amine component of the present invention may be formulated with a curing agent, which enables the material to achieve modulus or glass transition temperature compared to materials found in the prior art but is still capable of significant plastic deformation following curing.
- the preferred amine component facilitates a cured structural material having improved mechanical properties such as higher compressive strain to failure when compared with materials produced using traditional curing agents.
- the presence of the enhanced mechanical properties is particularly useful in structural reinforcement applications found in the automotive industry but whose utility is not limited to such applications.
- the cross-linking of the first or resin component utilized in the present invention may be accomplished by the addition of any of the chemical materials known in the art for curing such resins.
- curing agents Such materials are referred to herein as “curing agents”, but also include the substances known to workers in the field as curatives, hardeners, activators, catalysts or accelerators. While certain curing agents promote curing by catalytic action, others participate directly in the reaction of the resin and are incorporated into the thermoset polymeric network formed by condensation, chain-extension and/or cross-linking of the synthetic resin.
- the thermosettable synthetic resin is an epoxy resin
- Such curatives (along with other curatives useful for hardening epoxy resins) are described in the chapter in the Encyclopedia of Polymer Science and Engineering referenced above.
- Suitable compounds useful as curing agents include amines, amino compounds, amine salts, and quaternary ammonium compounds. While any type of amine could be used, it is contemplated that suitable amine components for formulation in the present invention include cycloaliphatic amine curing agents which have a long cure time, relative to other commercially available curing agents, with epoxy resins and serves to increase the glass transition temperature of the cured epoxy, thereby increasing mechanical stability at higher temperatures.
- a particularly preferred amine utilized in the present invention is sold by Air Products under the trade name Ancamine 2556.
- the present invention comprises the formulation of additional additive component(s), which will cause either or both of the components described above to enable shear thinning to enhance processing attributes of the material.
- One such additive component of the present invention includes a filler.
- fillers are added to epoxy foam formulations to lower cost, alter color, reduce reaction exotherm, and control shrinkage rates.
- Fillers in the form of fine particles may also serve as nucleating agents. Small particles provide sites for heterogeneous nucleation, which allow for initiation and subsequent growth of foam cells when certain blowing agent types are used. In heterogeneous nucleation, gas molecules driven by supersaturation preferentially form nucleation sites on the solid/fluid interfaces of the nucleating agent.
- the ultimate cell size is determined by other factors including the exotherm, the rate of cure, the amount of blowing agent, and interactions between the epoxy and other formulation components.
- suitable fillers are known in the art and discussed in commonly-assigned U.S. Pat. No. 5,648,401, incorporated by reference
- a particular preferred additive of the present invention is a thixotropic additive formulated within either or potentially both of the first and second components which causes both components to be shear-thinning.
- An example of such a thixotropic filler is an aramid pulp and is sold under the trade name Kevlar 1F543.
- the thixoptropic filler is formulated in at least one, and potentially both the first or epoxy component and the second or amine component. This additive effectuates shear thinning or an increased viscosity at a zero shear rate and a decreased viscosity at a higher shear rate.
- hollow glass microspheres may be added to reduce the density of the foam while maintaining good strength and stiffness.
- Commercially available hollow glass microspheres include materials sold by Minnesota Mining & Manufacturing under the trademark SCOTCHLITE, with suitable grades including those available under the designations B38, C15, K20, and VS 5500.
- the glass microspheres preferably have diameters in the range of from about 5 to 200 micrometers.
- the crush strength of the hollow glass microspheres may be selected in accordance with the desired characteristics of the cured thermoset foam or chosen reinforced structural member containing such foam. Suitable reinforcements may be included as well. For instance, glass fiber is one type of reinforcement since it helps increase the strength and stiffness of the standard reinforcement foam. The glass fiber may be chopped, milled, or in other suitable physical form.
- fillers or reinforcements may also optionally be present in the foamable composition.
- Any of the conventional organic or inorganic fillers known in the thermosettable resin art may be used including, for example, silica (including fumed or pyrogenic silica, which may also function as a thixotropic or rheological control agent), calcium carbonate (including coated and/or precipitated calcium carbonate, which may also act as a thixotropic or rheological control agent, especially when it is in the form of fine particles), fibers other than glass fibers (e.g., wollastinite fibers, carbon fibers, ceramic fibers, aramid fibers), alumina, clays, sand, metals (e.g. aluminum powder), microspheres other than glass microspheres such as ceramic microspheres, thermoplastic resin microspheres, thermoset rein microspheres, and carbon microspheres (all of which may be solid or hollow, expanded or expandable) and the like.
- silica including fumed or pyrogenic silica, which
- diluents reactive or non-reactive
- glycidyl ethers such as glycidyl ethers, glycidyl esters, acrylics, solvents and plasticizers, toughening or flexibilizing agents (e.g., aliphatic diepoxides, polyaminoamides, liquid polysulfide polymers, rubbers including liquid nitrile rubbers such as butadiene-acrylonitile copolymers, which may be functionalized with carboxyl groups, amine groups or the like), coupling agents/wetting agents/adhesion promoters (e.g., silanes), colorants (e.g., dyes and pigments such as carbon black), stabilizers (e.g., antioxidants, UV stabilizers) and the like.
- the preferred formulation set forth below may utilize these additional components such as an optional coloring agent, reinforcements and fillers.
- the first or resin component and the second or amine component are combined, preferably in liquid form.
- the materials can be mixed either statically or dynamically with the mixture then being placed in a mold cavity of chosen shape and dimension, the mold cavity can be an automotive body cavity or any cavity that could be structurally reinforced by the foam-in-place structural material.
- atomized streams of the separate components or materials can be impinged into a mold cavity.
- the thixotropic filler and the resin are preferably premixed. Once mixed, the composition cures at room temperature (that is, without adding external heat).
- the method, apparatus, and formulation comprising the present invention is suitable for application, and may be used in conjunction with, a variety of substrates and members used for reinforcement of automotive and aerospace vehicles.
- the present invention may be applied, coated, or otherwise disposed upon substrates found within portions of an automotive vehicle such as surfaces or members encompassing on automotive rockers, rail members, frame members, cross-members, chassis engine cradles, roof systems, vehicle window frames, vehicle deck lids, lift gates, roof bows, lift gates, roof headers, roof rails, fender assemblies, pillar assemblies, door assemblies, radiator/rad supports, bumpers, a rail member, a frame member, a door assembly, a rocker, a frame cross member, a vehicle window frame, a vehicle deck lid, a lift gate, a vehicle pillar assembly, a vehicle hatch, a vehicle roof system, a roof bow, a roof rail, a roof header, a fender assembly, a bumper, and a front end structure, body panels such as hood
- the present invention may be utilized in conjunction with a structural reinforcement system such as those disclosed in U.S. Pat. Nos. 4,922,596, 4,978,562, 5,124,186, and 5,884,960 and commonly owned, co-pending U.S. application Ser. Nos. 09/502,686 filed Feb. 11, 2000, 09/524,961 filed Mar. 14, 2000, 60/223,667 filed Aug. 7, 2000, 60/225,126 filed Aug. 14, 2000, 09/676,443 filed Sep. 29, 2000, 09/676,335 filed Sep. 29, 2000, 09/676,725 filed Sep. 29, 2000, and particularly, 09/459,756 filed Dec. 10, 1999, all of which are expressly incorporated by reference.
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Abstract
The present invention relates to methods, materials, and products for forming a foamed product, comprising the steps of combining an epoxy-based component with an amine-based component. The epoxy component is cross-linked through a polymerization reaction catalyzed by the amine formulation. In this regard, a reactive mixture or exothermic reaction is created between the epoxy component and the amine component when combined. The heat generated by the exothermic reaction softens a thermoplastic shell of a blowing agent formulated within the epoxy component thereby enabling a solvent core within the thermoplastic shell of the blowing agent to expand from the heat generated by the exothermic reaction.
Description
- The present invention relates generally to foam-in-place structural materials used for reinforcement of structural members. More particularly, the present invention relates to a two-component epoxy/amine foamed material exhibiting improved mechanical properties (good balance of high compressive strength, compressive modulus, glass transition temperature and cured ductility) as well as enhanced shear-thinning characteristics.
- Traditional foam-in-place structural materials known in the art generally disclose polyurethane materials, polyurea, or epoxy-based materials. These materials incorporate a method to create volumetric expansion and a curing mechanism as well to effectuate curing at room temperature and achieve a degree of control of expansion and cure rate characteristics. Although these prior art materials are both useful and successful in a number of applications, certain structural reinforcement applications in the automotive industry, for example, would benefit from a material having an improved balance of mechanical properties, such as a higher compressive strength, little change in modulus over a broad temperature range and a glass transition temperature that exceeds 200° F. In addition, improved cured ductility that enables the material to deform plastically when stresses exceeding the material yield strength are applied would provide definite benefit. Further, these structural reinforcement characteristics in many applications, including automotive, may also benefit from a shear-thinning structural material which exhibits an increased viscosity at zero shear rate and a decreased viscosity at higher shear rates prior to curing. This enables the material to flow more easily while being dispensed but then have flow minimally following dispensing. This shear thinning behavior can also assist with the development of a uniform, consistent foamed cell structure by allowing more effective foaming gas entrapment.
- As known by those skilled in the art, a number of factors determine the suitability of a process for forming a foamed product of the type in which a blowing agent forms cells in a synthetic resin as the resin is cured. Most significantly, the interaction of the rate of cure and the rate at which the blowing gas is generated must be matched to create the proper cured product. If the resin cures too rapidly there is inadequate time for the gas to form the proper size and number of gas voids in the finished product. Over expansion of the forming foam product must also be avoided. Rapid expansion due to a slow cure rate relative to gas evolution may cause the expanding foam to simply collapse as a result of inadequate wall strength surrounding the individual gas cells.
- A number of prior art techniques are available to control the rate of foam expansion and the cure rate. For example, a wide-range of reactivities are available in commercial resins and curing agents. In addition, resins are available in a range of viscosities, which is another parameter and can be used to control the foam expansion rate. That is, it is known that a low viscosity resin can generally be expanded to a greater volume with a given volume of gas than a higher viscosity material; however, the resin must have sufficient viscosity to contain the gas at the pressures at which it is generated in order for the foam to be properly formed.
- With respect to automotive applications, foamed products must have good environmental resistance and, most significantly, in many applications they must protect metal from corrosion while maintaining adhesion to the substrate. In the past many foamed parts were made using polyurethane, which provides a number of desirable attributes. It is known, however, that alternatives to urethane-based foams or more precisely materials based on the reaction of the isocyanate chemical functional group are frequently more environmentally desirable, in part due to the potential for unreacted functional groups in the finished products and difficulty in handling isocyanate functional chemicals in manufacturing processes. In addition, the polyurethane materials found in the prior art fail to provide optimum mechanical properties, generally possessing lower elastic modulus strength and lower glass transition temperature than what is capable with epoxy-based materials. In comparison with polyurethane materials, however, the epoxy-based materials found in the prior art often exhibit both poor cured ductility and higher viscosity during dispensing.
- Accordingly, there is a need in industry and manufacturing operations for a structural material, which exhibits improved mechanical properties, such as higher compressive strength, compressive modulus, and glass transition temperature, as well as better-cured ductility. The improved mechanical properties allow the structural material of the present invention to be capable of plastically deforming when loaded beyond its yield stress. However, unlike prior art materials, there is no significant reduction in modulus or glass transition temperature. In addition, there is a need for an improved material, which can be used in a variety of applications wherein one or both components utilize a thixotropic filler, which produces pronounced shear-thinning characteristics. By providing a material with excellent cured physical properties and desirable processing attributes, the present invention addresses and overcomes the shortcomings found in the prior art.
- The present invention relates to methods, materials, and products for foam-in-place structural reinforcement of hollow structures such as automobile cavities. In one embodiment, the present invention comprises a two-component foam-in-place structural material for producing a foamed product. Though other resin systems are possible, the first component of the system includes an epoxy-based resin. Preferably, the first component is formulated with a physical blowing agent, and more preferably one having a shell or skin that will change state to provide volumetric increase to create expansion. For example, the shell is a thermoplastic that, upon heating, will melt or soften to enable a solvent core to expand the shell. The second component includes an amine, and is formulated with an agent for allowing the resulting material to exhibit ductility with little reduction in modulus, glass transition temperature, or both. It is contemplated that the amine of the present invention could be a primary or secondary amine. Generally speaking, the amine is an epoxy curing agent or modifier, and preferably, a high solids epoxy curing agent, though it could be a water-borne epoxy-curing agent. Other examples of an amine suitable for use in the present invention include polyamides, aliphatic amines, and cycloaliphatic amines as well as other agents that can function as accelerators or catalysts. An optional thixotropic filler is included in either or both of the first or second components, and possibly as a stand-alone component. In one embodiment, this additive preferably causes the material to have high viscosity at a near zero shear rate and low viscosity at a higher shear rate, which is more commonly known in the art as shear-thinning.
- The present invention provides a method of forming a foamed product, which comprises the steps of combining the first component (with a blowing agent) with the second component (with a curing agent). The first component, preferably an epoxy, is cross-linked through a polymerization reaction with the second component of the formulation (e.g. an amine). In this regard, an exothermic reaction or reactive mixture is created between the epoxy component and the amine component when combined. The heat generated by the exothermic reaction softens the thermoplastic shell of the blowing agent formulated within the epoxy component thereby enables the solvent core within the thermoplastic shell to expand the thermoplastic shell and thereby create expansion. In a preferred embodiment the mixture of materials is in liquid form. However, it is contemplated that the mixture of materials could also comprise a paste or solids of varying viscosities and textures.
- As used herein, all concentrations shall be expressed as percentages by weight unless otherwise specified.
- The present invention relates generally to a two component structural foam-in-place material and method for making the same formed by cross-linking reactions between an epoxy resin and a curing agent that creates a three-dimensional covalent bond network. It is contemplated that the addition of a curing agent to the epoxy resin causes the resin to cure or harden into a rigidified cross-linked polymer. When an epoxy resin is mixed with a curing agent containing labile hydrogen atoms, the epoxy ring opens and reacts with the curative. Generally speaking, cured epoxy foams are produced using one of three types of curing agents, such as amines, polyphenols, and anhydrides. Cure of the foam is achieved by polyaddition whereby the cure reaction between the epoxy resin and a curing agent is typically exothermic and can generate a considerable amount of heat. The control of such heat and the exothermic reaction is an important consideration of the foam-in-place material of the present invention. Since the foam-in-place material of the present invention is particularly useful in the production of automobiles and other vehicles to maintain and/or increase the strength of structural members such as frame members, rails, rockers, pillars, radiator support beams, doors, hatches, reinforcing beams and the like, exothermic control prevents the charring or burning of the interior of the foam.
- More particularly, the method and composition of the present invention has two main components: (1) an epoxy resin component formulated with a physical blowing agent having a thermoplastic shell with a solvent core, and (2) an amine curing agent component which, when cured, produces a material capable of plastically deforming when mechanically loaded with an insignificant reduction in modulus or glass transition temperature reduction when compared with traditional epoxy/amine systems. In addition, a thixotropic additive is formulated into one or both the first and second components, which produces shear-thinning characteristics useful for processing and generation of a foamed product. Moreover, the exothermic reaction generated by the combination or mixture of the first and second components serves to soften the physical blowing agent, which consists of a thermoplastic shell with a solvent core. As the thermoplastic shell softens, the solvent expands the shell to create an expanded particle. The preferred solvent and shell is selected for its expansion properties when exposed to the heat of the exothermic reaction, which occurs during polymerization. However, by using the preferred fillers, and less reactive amine functional materials such as an amine sold under the commercial name GVI 4040, excessive exotherm, which would otherwise be produced by the curing reaction (and which could produce charring), is prevented.
- In a particularly preferred embodiment, the components or formulation of the present invention include the following:
- Resin Component
- The first or resin component of the present invention is selected for its structurally adhering characteristics and for imparting rigidity. Suitable resins may include a cross-linkable polymer and, more preferably an epoxy. The properties of advantageous epoxy resins are described, for example, in the chapter entitled “Epoxy Resins” in the Second Edition of the Encyclopedia of Polymer Science and Engineering, Volume 6, pp. 322-382 (1986). The preferred epoxy resin has a number average molecular weight of from about 350 to about 600 and, on average, each molecule of epoxy has from about 1.8 to about 2.5 epoxide functional groups. The preferred epoxy resin has a viscosity of from about 5,000 to 100,000 cps (Brookfield viscosity) at 70° F. and a specific gravity of from about 1.0 to about 1.4. As stated, the preferred form of the resin is a liquid and may further comprise a high viscosity resin with relatively low reactivity. Exemplary epoxy resins which could be utilized in the present invention include polyglycidyl ethers obtained by reacting polyhydric phenols such as bisphenol A, bisphenol F, bisphenol AD, catechol, resorcinol, or polyhydric alcohols such as glycerin and polyethylene glycol with haloepoxides such as epichlorohydrin; glycidylether esters obtained by reacting hydroxycarboxylic acids such as p-hydroxybenzoic acid or beta-hydroxy naphthoic acid with epichlorohydrin or the like; polyglycidyl esters obtained by reacting polycarboxylic acids such as phthalic acid, tetrahydrophthalic acid or terephthalic acid with epichlorohydrin or the like; epoxidated phenolic-novolac resins (sometimes also referred to as polyglycidyl ethers of phenolic novolac compounds); epoxidated polyolefins; glycidylated aminoalcohol compounds and aminophenol compounds, hydantoin diepoxides and urethane-modified epoxy resins. Mixtures of epoxy resins may also be used in the present invention. For example, mixtures of liquid (at room temperature), semi-solid, and/or solid epoxy resins can be employed. A preferable epoxy resin for use in the present invention includes DER 331. As stated, the preferred form of the resin is a liquid. Other commercially available epoxy resins, which may be suitable in the present invention include, but are not limited to DER 317, DER 337 and DER 324. A resin forms from about 35% to about 99% by weight of the first or resin component and more preferably from about 65% to about 98% by weight of the composition of the present invention.
- It is contemplated that the resin component of the present invention may also be formulated with a blowing agent and, more particularly, a blowing agent having a thermoplastic shell with a solvent core. Because epoxies normally react with a curing agent without evolving volatiles, the addition of a blowing agent is typically required to create a foamed product. The blowing agent may be a chemical agent, (i.e. one that thermally decomposes and evolves gas due to the heat of the exothermic epoxy reaction), or a physical agent, which simply vaporizes at its boiling temperature to liberate gas. In the event that a chemical blowing agent is used, particle size of the blowing agent may be adjusted so as to provide the desired foaming characteristics in the cured foam. For example, smaller particle sizes tend to provide foams having more uniform cell structure. In some alternative formulations of the present invention, it may be desirable to also use a blowing agent activator or accelerator so as to lower the temperature at which release of gas from the blowing agent takes place. Suitable chemical blowing agent activators include, but are not limited to, ureas (such as the surface-coated, oil-treated urea sold by Uniroyal Chemicals under the trademark BIKOT) polyols, organic acids, amines, and lead, zinc, tin, calcium and cadmium oxides and salts (including carboxylic acid salts).
- Typically, from about 0.1% to about 2% of a blowing agent based on the weight of the foamable composition is employed, although the optimum amount will of course vary depending upon the activator/accelerator selected, the amount of blowing agent, cure temperature and other variables. An example of a preferred physical blowing agent, which according to the present invention is formulated with the first or resin component, is sold under the trade name Expancel 820-DU. Most preferably, the solvent core of the blowing agent of the present invention is a liquid.
- Amine Component.
- The amine component of the present invention may be formulated with a curing agent, which enables the material to achieve modulus or glass transition temperature compared to materials found in the prior art but is still capable of significant plastic deformation following curing. In addition, the preferred amine component facilitates a cured structural material having improved mechanical properties such as higher compressive strain to failure when compared with materials produced using traditional curing agents. The presence of the enhanced mechanical properties is particularly useful in structural reinforcement applications found in the automotive industry but whose utility is not limited to such applications. Accordingly, the cross-linking of the first or resin component utilized in the present invention may be accomplished by the addition of any of the chemical materials known in the art for curing such resins. Such materials are referred to herein as “curing agents”, but also include the substances known to workers in the field as curatives, hardeners, activators, catalysts or accelerators. While certain curing agents promote curing by catalytic action, others participate directly in the reaction of the resin and are incorporated into the thermoset polymeric network formed by condensation, chain-extension and/or cross-linking of the synthetic resin. When the thermosettable synthetic resin is an epoxy resin, it may be particularly desirable to employ at least one curing agent, which is a nitrogen-containing compound. Such curatives (along with other curatives useful for hardening epoxy resins) are described in the chapter in the Encyclopedia of Polymer Science and Engineering referenced above. Suitable compounds useful as curing agents include amines, amino compounds, amine salts, and quaternary ammonium compounds. While any type of amine could be used, it is contemplated that suitable amine components for formulation in the present invention include cycloaliphatic amine curing agents which have a long cure time, relative to other commercially available curing agents, with epoxy resins and serves to increase the glass transition temperature of the cured epoxy, thereby increasing mechanical stability at higher temperatures. A particularly preferred amine utilized in the present invention is sold by Air Products under the trade name Ancamine 2556.
- Additive(s)
- Further, the present invention comprises the formulation of additional additive component(s), which will cause either or both of the components described above to enable shear thinning to enhance processing attributes of the material. One such additive component of the present invention includes a filler. Typically, fillers are added to epoxy foam formulations to lower cost, alter color, reduce reaction exotherm, and control shrinkage rates. Fillers in the form of fine particles (for example, carbon black or fumed silica) may also serve as nucleating agents. Small particles provide sites for heterogeneous nucleation, which allow for initiation and subsequent growth of foam cells when certain blowing agent types are used. In heterogeneous nucleation, gas molecules driven by supersaturation preferentially form nucleation sites on the solid/fluid interfaces of the nucleating agent. The ultimate cell size is determined by other factors including the exotherm, the rate of cure, the amount of blowing agent, and interactions between the epoxy and other formulation components. Although a number of suitable fillers are known in the art and discussed in commonly-assigned U.S. Pat. No. 5,648,401, incorporated by reference, a particular preferred additive of the present invention is a thixotropic additive formulated within either or potentially both of the first and second components which causes both components to be shear-thinning. An example of such a thixotropic filler is an aramid pulp and is sold under the trade name Kevlar 1F543. In a particularly preferred embodiment, the thixoptropic filler is formulated in at least one, and potentially both the first or epoxy component and the second or amine component. This additive effectuates shear thinning or an increased viscosity at a zero shear rate and a decreased viscosity at a higher shear rate.
- Still further, a number of other additives can be utilized in the present invention such as carbon black, solid rubber particles, hollow microspheres, and inert polymer particles, if desired in a particular application. For example, hollow glass microspheres may be added to reduce the density of the foam while maintaining good strength and stiffness. Commercially available hollow glass microspheres (sometimes also referred to as glass microballoons or microbubbles) include materials sold by Minnesota Mining & Manufacturing under the trademark SCOTCHLITE, with suitable grades including those available under the designations B38, C15, K20, and VS 5500. The glass microspheres preferably have diameters in the range of from about 5 to 200 micrometers. The crush strength of the hollow glass microspheres may be selected in accordance with the desired characteristics of the cured thermoset foam or chosen reinforced structural member containing such foam. Suitable reinforcements may be included as well. For instance, glass fiber is one type of reinforcement since it helps increase the strength and stiffness of the standard reinforcement foam. The glass fiber may be chopped, milled, or in other suitable physical form.
- Other types of fillers or reinforcements may also optionally be present in the foamable composition. Any of the conventional organic or inorganic fillers known in the thermosettable resin art may be used including, for example, silica (including fumed or pyrogenic silica, which may also function as a thixotropic or rheological control agent), calcium carbonate (including coated and/or precipitated calcium carbonate, which may also act as a thixotropic or rheological control agent, especially when it is in the form of fine particles), fibers other than glass fibers (e.g., wollastinite fibers, carbon fibers, ceramic fibers, aramid fibers), alumina, clays, sand, metals (e.g. aluminum powder), microspheres other than glass microspheres such as ceramic microspheres, thermoplastic resin microspheres, thermoset rein microspheres, and carbon microspheres (all of which may be solid or hollow, expanded or expandable) and the like.
- Other optional additives or components which could be utilized in alternative embodiments or formulations of the present invention include diluents (reactive or non-reactive) such as glycidyl ethers, glycidyl esters, acrylics, solvents and plasticizers, toughening or flexibilizing agents (e.g., aliphatic diepoxides, polyaminoamides, liquid polysulfide polymers, rubbers including liquid nitrile rubbers such as butadiene-acrylonitile copolymers, which may be functionalized with carboxyl groups, amine groups or the like), coupling agents/wetting agents/adhesion promoters (e.g., silanes), colorants (e.g., dyes and pigments such as carbon black), stabilizers (e.g., antioxidants, UV stabilizers) and the like. In this regard, the preferred formulation set forth below may utilize these additional components such as an optional coloring agent, reinforcements and fillers.
- Although the components of the present invention may be formulated in a variety of ranges as disclosed herein, the following table sets forth a preferred formulation in percent by weight for the components of the composition of the present invention:
First Component Second Component (Epoxy) (weight %) (Amine) (weight %) DER 331 97.943 Ancamine 2556 60.714 Kevlar 1F543 0.748 GVI 4040 12.500 Expancel 820-DU 0.935 Kevlar 1F543 1.786 Phtalo Green 0.374 Polyfil 90 12.500 Nanomer I.30.E 12.500 - In the method of the present invention, the first or resin component and the second or amine component are combined, preferably in liquid form. For example, the materials can be mixed either statically or dynamically with the mixture then being placed in a mold cavity of chosen shape and dimension, the mold cavity can be an automotive body cavity or any cavity that could be structurally reinforced by the foam-in-place structural material. In an alternative embodiment or methodology, atomized streams of the separate components or materials can be impinged into a mold cavity. The thixotropic filler and the resin are preferably premixed. Once mixed, the composition cures at room temperature (that is, without adding external heat).
- It is contemplated that the method, apparatus, and formulation comprising the present invention is suitable for application, and may be used in conjunction with, a variety of substrates and members used for reinforcement of automotive and aerospace vehicles. Most notably, the present invention may be applied, coated, or otherwise disposed upon substrates found within portions of an automotive vehicle such as surfaces or members encompassing on automotive rockers, rail members, frame members, cross-members, chassis engine cradles, roof systems, vehicle window frames, vehicle deck lids, lift gates, roof bows, lift gates, roof headers, roof rails, fender assemblies, pillar assemblies, door assemblies, radiator/rad supports, bumpers, a rail member, a frame member, a door assembly, a rocker, a frame cross member, a vehicle window frame, a vehicle deck lid, a lift gate, a vehicle pillar assembly, a vehicle hatch, a vehicle roof system, a roof bow, a roof rail, a roof header, a fender assembly, a bumper, and a front end structure, body panels such as hoods, trunks, hatches, cargo doors, front end structures, and door impact bars in automotive vehicles as well as other portions of an automotive vehicle which may be adjacent to the exterior of the vehicle. The targeted placement of the present invention within an automotive vehicle will be dictated by performance requirements and economics of the specific application and requirements. In addition, the present invention may be utilized in conjunction with a structural reinforcement system such as those disclosed in U.S. Pat. Nos. 4,922,596, 4,978,562, 5,124,186, and 5,884,960 and commonly owned, co-pending U.S. application Ser. Nos. 09/502,686 filed Feb. 11, 2000, 09/524,961 filed Mar. 14, 2000, 60/223,667 filed Aug. 7, 2000, 60/225,126 filed Aug. 14, 2000, 09/676,443 filed Sep. 29, 2000, 09/676,335 filed Sep. 29, 2000, 09/676,725 filed Sep. 29, 2000, and particularly, 09/459,756 filed Dec. 10, 1999, all of which are expressly incorporated by reference.
- Thus, it is apparent that there has been provided in accordance with the invention a method and apparatus that fully satisfy the objects, aims and advantages set forth above. While the invention has been described in connection with specific embodiments thereof it is evident that many alternatives, modifications, and variations will be apparent to those skilled in the art in light of the foregoing description. Accordingly, it is intended to embrace all such alternatives, modifications and variations that fall within the spirit and broad scope of the appended claims.
Claims (21)
1-19. (canceled)
20. A method for producing a foamed article, comprising the steps of:
providing an epoxy component that includes:
i) an epoxy resin;
ii) a thixotropic additive;
iii) a reactive diluent;
iv) hollow glass microspheres; and
v) a blowing agent, the blowing agent being expandable microspheres;
providing a substantially liquid amine component that includes:
i) an aliphatic amine curing agent; and
ii) thixotropic additive;
combining and dispensing said epoxy component and said amine component to form a reactive mixture wherein:
i) the epoxy component and the amine component are formed as prior to forming the reactive mixture;
ii) the epoxy component and the amine component react together exothermically to produce heat;
iii) the admixture exhibits higher viscosity a zero shear rate and decreased viscosity at higher shear rate; and
iv) the heat causes the expandable microspheres to soften and expand;
providing the reactive mixture within an automotive body cavity contemporaneously with the formation of the mixture or shortly thereafter.
21. The method for producing a foamed article recited in claim 20 , wherein said epoxy resin comprises from about 35% to about 95% by weight of said reactive mixture.
22. The method for producing a foamed article recited in claim 20 , further including the step of combining said blowing agent of said epoxy component with an inert filler followed by combining said blowing agent of said epoxy component with said epoxy resin of said epoxy component.
23. The method for producing a foamed article recited in claim 20 , wherein said reactive mixture further includes an additive selected form the group consisting of carbon black, ceramic microspheres, polymer particles, rubber particles, ceramic particles, inert mineral particles and combinations thereof.
24. The method for producing a foamed article recited in claim 20 , wherein the thixotropic additive of the epoxy component is fumed silica.
25. The method of producing a foamed article recited in claim 21 , wherein said cavity is at least partially provided by a component of an automotive vehicle selected from a rail member, a frame member, a door assembly, a rocker, a frame cross member, a vehicle window frame, a vehicle deck lid, a lift gate, a vehicle pillar assembly or a vehicle latch.
26. The method for producing a foamed article recited in claim 20 , wherein the epoxy resin includes an ingredient selected from an epoxidated polyolefin, an epoxidated phenolic-novolac resin, a polyglycidyl ester, a glycidylether ester or a polyglycidyl ether.
27. The method for producing a foamed article recited in claim 26 , wherein the epoxy component includes an ingredient selected from a liquid nitrile rubber, a clay or a pigment.
28. The method for producing a foamed article recited in claim 26 , wherein amine component includes an ingredient selected from a liquid nitrile rubber or hollow glass microspheres.
29. A method for producing a foamed article, comprising the steps of:
providing an epoxy component that includes:
i) a bisphenol epoxy resin, the epoxy resin being from 35% to 99% by weight of the epoxy component;
ii) a thixotropic additive, the thixotropic additive being a fumed silica;
iii) an oxide;
iv) a reactive diluent;
v) liquid nitrile rubber;
vi) hollow glass microspheres;
vii) clay;
viii) a pigment; and
ix) a blowing agent, the blowing agent being expandable microspheres;
providing a substantially liquid amine component that includes:
i) an aliphatic amine curing agent;
ii) thixotropic additive including fumed silica or wollastonite; and
iii) rubber, the rubber being a liquid nitrile rubber;
combining and dispensing said epoxy component and said amine component at around room temperature to form a reactive mixture wherein:
i) the epoxy component and the amine component are formed prior to forming the reactive mixture;
ii) the epoxy component and the amine component react together exothermically to produce heat;
iii) the admixture exhibits higher viscosity a zero shear rate and decrease viscosity at higher shear rate; and
iv) the heat causes the expandable microspheres to soften and expand without addition of external heat;
providing the reactive mixture within an automotive body cavity contemporaneously with the formation of the mixture or shortly thereafter; and
allowing the reactive mixture to cure to form said foamed article.
30. The method for producing a foamed article recited in claim 29 , wherein said epoxy resin comprises from about 35% to about 95% by weight of said reactive mixture.
31. The method for producing a foamed article recited in claim 29 , wherein said epoxy resin and said thixotropic additive of said epoxy component are combined prior to adding said blowing agent to the epoxy component.
32. The method for producing a foamed article recited in claim 31 , further including the step of combining said blowing agent of said epoxy component with an inert filler prior to combining said blowing agent of said epoxy component with said epoxy resin of said epoxy component and said thixotropic additive.
33. The method for producing a foamed article recited in claim 29 , wherein the oxide is a calcium oxide and the reactive diluent is a glycidyl ether.
34. The method for producing a foamed article recited in claim 29 , wherein the epoxy resin includes a chemical selected from an epoxidated polyolefin, an epoxidated phenolic-novolac resin, a polyglycidyl ester, a glycidylether ester or a polyglycidyl ether.
35. The method for producing a foamed article recited in claim 29 , wherein the foamed article has a glass transition temperature greater than 200° F.
36. A method for producing a foamed article, comprising the steps of:
providing a substantially liquid epoxy component that includes:
i) an epoxy resin, the epoxy resin being a glycidyl ether of bisphenol A, the epoxy resin being from 65% to 98% by weight of the epoxy component;
ii) a thixotropic additive, the thixotropic additive being a fumed silica;
iii) calcium oxide;
iv) a reactive diluent, the diluent being a glycidyl ether;
v) liquid nitrile rubber;
vi) hollow glass microspheres;
vii) clay;
viii) a pigment; and
ix) a blowing agent, the blowing agent being expandable microspheres formed of thermoplastic shells filled with a solvent core;
providing a substantially liquid amine component that includes:
i) an aliphatic amine curing agent;
ii) thixotropic additive including fumed silica and wollastonite;
iii) hollow glass microspheres; and
iv) rubber, the rubber being a liquid nitrile rubber;
combining and dispensing said epoxy component and said amine component at around room temperature to form a reactive mixture wherein:
i) the epoxy component and the amine component are formed as separate liquids prior to forming the reactive mixture;
ii) the epoxy component and the amine component react together exothermically to produce heat;
iii) the admixture exhibits higher viscosity a zero shear rate and decrease viscosity at higher shear rate; and
iv) the heat causes the thermoplastic shell filled with a solvent core to soften and expand due to gas pressure from said solvent core without addition of external heat;
providing the reactive mixture within an automotive body cavity contemporaneously with the formation of the mixture or shortly thereafter; and
allowing the reactive mixture to cure to form said foamed article wherein said foamed article is capable of substantial plastic deformation after curing without substantial loss of strength modulus and wherein said foamed article has a glass transition temperature greater than 200° F. after such plastic deformation.
37. The method of producing a foamed article recited in claim 36 , wherein said cavity is at least partially provided by a component of an automotive vehicle selected from a rail member, a frame member, a door assembly, a rocker or a frame cross member.
38. The method of producing a foamed article recited in claim 36 , wherein said cavity is at least partially provided by a component of an automotive vehicle selected from a vehicle window frame, a vehicle deck lid, a lift gate, a vehicle pillar assembly or a vehicle latch.
39. The method of producing a foamed article recited in claim 36 , wherein said epoxy resin and said thixotropic additive of the epoxy component are combined prior to adding said blowing agent to the epoxy component.
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Publication number | Priority date | Publication date | Assignee | Title |
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US20040221953A1 (en) * | 2003-05-07 | 2004-11-11 | L&L Products, Inc. | Activatable material for sealing, baffling or reinforcing and method of forming same |
US20040266898A1 (en) * | 2003-06-26 | 2004-12-30 | L&L Products, Inc. | Expandable material |
US20050119372A1 (en) * | 2001-05-02 | 2005-06-02 | L&L Products, Inc. | Two component (epoxy/amine) structural foam-in-place material |
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US20070088138A1 (en) * | 2003-03-04 | 2007-04-19 | L&L Products, Inc. | Epoxy/elastomer adduct, method of forming same and materials and articles formed therewith |
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Publication number | Priority date | Publication date | Assignee | Title |
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US7300616B2 (en) * | 2004-04-02 | 2007-11-27 | Wycech Joseph S | Method and apparatus for forming an article of manufacture and an article of manufacture made by a new and novel process |
US7838589B2 (en) | 2004-07-21 | 2010-11-23 | Zephyros, Inc. | Sealant material |
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US20070032575A1 (en) * | 2005-08-08 | 2007-02-08 | Texas Research International, Inc. | Syntactic foam |
US7484946B2 (en) | 2005-08-19 | 2009-02-03 | Zephyros, Inc. | Method and assembly for locating material within a structure |
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US20070293603A1 (en) * | 2006-06-19 | 2007-12-20 | Ashland Licensing And Intellectual Property Llc | Epoxy adhesive composition and use thereof |
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US20100189908A1 (en) * | 2006-12-29 | 2010-07-29 | Olang Fatemeh N | Formulation method for plural component latex- foam |
US8875472B2 (en) * | 2006-12-29 | 2014-11-04 | Owens Corning Intellectual Capital, Llc | Room temperature crosslinked foam |
US8779016B2 (en) * | 2006-12-29 | 2014-07-15 | Owens Corning Intellectual Capital, Llc | Spray-in latex foam for sealing and insulating |
US20110123717A1 (en) * | 2006-12-29 | 2011-05-26 | O'leary Robert J | Two part spray foam using a blowing agent as a plasticizer and a room temperature crosslinking agent |
US20080161432A1 (en) | 2006-12-29 | 2008-07-03 | Korwin-Edson Michelle L | Room temperature crosslinked foam |
US9868836B2 (en) * | 2006-12-29 | 2018-01-16 | Owens Corning Intellectual Capital, Llc | Room temperature crosslinked foam |
WO2008088815A1 (en) * | 2007-01-16 | 2008-07-24 | Advanced Building Composites Llc | Composites for use as building materials, other molded items, and methods of and systems for making them |
US20080226866A1 (en) * | 2007-03-15 | 2008-09-18 | Zephyros, Inc. | Sealant material |
KR101378852B1 (en) * | 2007-09-12 | 2014-03-27 | 엘지디스플레이 주식회사 | Display Device |
US9802369B2 (en) | 2008-03-14 | 2017-10-31 | Bauer Hockey, Llc | Epoxy core with expandable microspheres |
US20100116179A1 (en) * | 2008-10-15 | 2010-05-13 | Baker Charles H | Polyurethane composite matrix material and composite thereof |
US20110224317A1 (en) * | 2009-01-19 | 2011-09-15 | Owens Corning Intellectual Capital, Llc | Spray foams with fine particulate blowing agent |
GB201016530D0 (en) | 2010-09-30 | 2010-11-17 | Zephyros Inc | Improvements in or relating to adhesives |
CN103379986B (en) | 2010-12-08 | 2016-10-19 | 泽菲罗斯公司 | Black box |
WO2013142145A1 (en) | 2012-03-20 | 2013-09-26 | Zephyros, Inc. | Baffle assembly |
EP3483046A1 (en) | 2012-06-08 | 2019-05-15 | Zephyros Inc. | Baffle with expanding material |
WO2014066693A1 (en) | 2012-10-25 | 2014-05-01 | Kohler Co. | Engineered composite material and products produced therefrom |
US20150024138A1 (en) * | 2013-02-19 | 2015-01-22 | Nanotech Industries, Inc. | Method for forming a sprayable nonisocyanate polymer foam composition |
MX2016015003A (en) | 2014-05-16 | 2017-09-28 | Aarbakke Innovation A S | Multifunction wellbore tubular penetration tool. |
US11286335B2 (en) | 2018-05-17 | 2022-03-29 | Evonik Operations Gmbh | Fast-curing epoxy systems |
EP3569629B1 (en) | 2018-05-17 | 2022-07-06 | Evonik Operations GmbH | Fast curing epoxy systems |
EP3569630B1 (en) | 2018-05-17 | 2022-08-03 | Evonik Operations GmbH | Fast curing epoxy systems |
US11359048B2 (en) | 2018-05-17 | 2022-06-14 | Evonik Operations Gmbh | Fast-curing epoxy systems |
USD938887S1 (en) | 2018-06-21 | 2021-12-21 | Zephyros, Inc. | Sealing device |
AU2018437759A1 (en) * | 2018-08-21 | 2021-03-11 | Evonik Operations Gmbh | Fast curing epoxy system for producing rigid foam and use of the foam in composites or as insulation material |
US11285643B2 (en) | 2018-11-02 | 2022-03-29 | UNIVERSITé LAVAL | Thermoset porous composites and methods thereof |
WO2023086039A1 (en) | 2021-11-12 | 2023-05-19 | Sabanci Üniversitesi | Polyoxazoline based thermal latent curing agents for thermoset resins |
CN115368727A (en) * | 2022-09-16 | 2022-11-22 | 上海嘉均瑞科技有限公司 | High-resilience polyurethane foam material and preparation method thereof |
Citations (91)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4427481A (en) * | 1978-02-27 | 1984-01-24 | R & D Chemical Company | Magnetized hot melt adhesive and method of preparing same |
US4538380A (en) * | 1983-11-16 | 1985-09-03 | Profile Extrusions Company | Low friction weather seal |
US4601769A (en) * | 1985-09-27 | 1986-07-22 | Dehoff Ronald L | Process for stabilizing the viscosity of an epoxy resin-acid anhydride system during reaction and cure |
US4693775A (en) * | 1986-03-06 | 1987-09-15 | United Technologies Automotive, Inc. | Hot melt, synthetic, magnetic sealant |
US4724243A (en) * | 1986-12-29 | 1988-02-09 | United Technologies Automotive, Inc. | Hot melt magnetic sealant, method of making and method of using same |
US4749434A (en) * | 1986-12-29 | 1988-06-07 | United Technologies Automotive, Inc. | Hot melt magnetic sealant, method of making and method of using same |
US4769166A (en) * | 1987-06-01 | 1988-09-06 | United Technologies Automotive, Inc. | Expandable magnetic sealant |
US4898630A (en) * | 1987-11-18 | 1990-02-06 | Toyota Jidosha Kabushiki | Thermosetting highly foaming sealer and method of using it |
US4908273A (en) * | 1987-03-24 | 1990-03-13 | Ciba-Geigy Corporation | Multi-layer, heat-curable adhesive film |
US4923902A (en) * | 1988-03-10 | 1990-05-08 | Essex Composite Systems | Process and compositions for reinforcing structural members |
US4922596A (en) * | 1987-09-18 | 1990-05-08 | Essex Composite Systems | Method of manufacturing a lightweight composite automotive door beam |
US4995545A (en) * | 1988-03-10 | 1991-02-26 | Essex Composite Systems | Method of reinforcing a structure member |
US5124186A (en) * | 1990-02-05 | 1992-06-23 | Mpa Diversified Products Co. | Composite tubular door beam reinforced with a reacted core localized at the mid-span of the tube |
US5342873A (en) * | 1986-05-09 | 1994-08-30 | Sika Ag, Vorm. Kaspar Winkler & Co. | Reactive hot-melt adhesive |
US5382606A (en) * | 1992-04-28 | 1995-01-17 | Sika Ag, Vorm. Kaspar Winkler & Co. | Curing agent for aqueous epoxy resin dispersions, process for its preparation and its use |
US5648401A (en) * | 1996-10-09 | 1997-07-15 | L & L Products, Inc. | Foamed articles and methods for making same |
US5712317A (en) * | 1994-03-31 | 1998-01-27 | Ppg Industries, Inc. | Curable, sprayable compositions for reinforcing thin rigid plates |
US5783272A (en) * | 1993-08-10 | 1998-07-21 | Dexter Corporation | Expandable films and molded products therefrom |
US5884960A (en) * | 1994-05-19 | 1999-03-23 | Henkel Corporation | Reinforced door beam |
US5894071A (en) * | 1994-04-15 | 1999-04-13 | Sika Ag, Vorm. Kaspar Winkler & Co. | Two-component adhesive-, sealing- or coating composition and it's use |
US6103784A (en) * | 1998-08-27 | 2000-08-15 | Henkel Corporation | Corrosion resistant structural foam |
US6174932B1 (en) * | 1998-05-20 | 2001-01-16 | Denovus Llc | Curable sealant composition |
US6228449B1 (en) * | 1994-01-31 | 2001-05-08 | 3M Innovative Properties Company | Sheet material |
US6232433B1 (en) * | 1996-10-02 | 2001-05-15 | Henkel Corporation | Radiation curable polyesters |
US6235842B1 (en) * | 1996-10-08 | 2001-05-22 | Hitachi Chemical Company, Ltd. | Phase-separated carboxyl group-containing elastomer modified phoenoxy resin optionally with epoxy resin |
US6263635B1 (en) * | 1999-12-10 | 2001-07-24 | L&L Products, Inc. | Tube reinforcement having displaceable modular components |
US6277898B1 (en) * | 1997-05-21 | 2001-08-21 | Denovus Llc | Curable sealant composition |
US6287669B1 (en) * | 1997-08-15 | 2001-09-11 | 3M Innovative Properties Company | Sealing method and article |
US20020009582A1 (en) * | 2000-06-06 | 2002-01-24 | Golden Michael R. | Epoxy based reinforcing patches with improved adhesion to oily metal surfaces |
US6348513B1 (en) * | 1998-08-27 | 2002-02-19 | Henkel Corporation | Reduced tack compositions useful for the production of reinforcing foams |
US6350791B1 (en) * | 1998-06-22 | 2002-02-26 | 3M Innovative Properties Company | Thermosettable adhesive |
US6376564B1 (en) * | 1998-08-27 | 2002-04-23 | Henkel Corporation | Storage-stable compositions useful for the production of structural foams |
US6403222B1 (en) * | 2000-09-22 | 2002-06-11 | Henkel Corporation | Wax-modified thermosettable compositions |
US6419305B1 (en) * | 2000-09-29 | 2002-07-16 | L&L Products, Inc. | Automotive pillar reinforcement system |
US6432475B1 (en) * | 1998-12-08 | 2002-08-13 | Nitto Denko Corporation | Pressure-sensitive adhesive composition, process for the preparation thereof and pressure-sensitive adhesive sheets |
US6437055B1 (en) * | 2000-04-07 | 2002-08-20 | Ppg Industries Ohio, Inc. | Electrodepositable coating from gelled epoxy-polyester and amine |
US6441081B1 (en) * | 1998-10-05 | 2002-08-27 | Sumitomo Chemical Company, Limited | Polypropylene-base resin composition and products of injection molding thereof |
US6441075B2 (en) * | 1996-04-26 | 2002-08-27 | Nissan Motor Co., Ltd. | Polyolefin-based resin composition and automotive molded plastic made from same |
US6440257B1 (en) * | 2000-05-18 | 2002-08-27 | Hexcel Corporation | Self-adhesive prepreg face sheets for sandwich panels |
US20020120064A1 (en) * | 2000-12-21 | 2002-08-29 | 3M Innovative Properties Company | Pressure-sensitive adhesive blends comprising ethylene/propylene-derived polymers and propylene-derived polymers and articles therefrom |
US6444149B1 (en) * | 1997-03-10 | 2002-09-03 | Perstorp Ab | Process for the manufacturing of an article of plastic material |
USH2047H1 (en) * | 1999-11-10 | 2002-09-03 | Henkel Corporation | Reinforcement laminate |
US6444713B1 (en) * | 1997-05-21 | 2002-09-03 | Denovus Llc | Foaming compositions and methods for making and using the compositions |
US20020123575A1 (en) * | 2000-12-28 | 2002-09-05 | Kabushiki Kaisha Toyota Chuo Kenkyusho | Resin composite material |
US6448338B1 (en) * | 1997-07-16 | 2002-09-10 | Henkel Teroson Gmbh | Hot-setting wash-fast sealant for shell structures |
US6451876B1 (en) * | 2000-10-10 | 2002-09-17 | Henkel Corporation | Two component thermosettable compositions useful for producing structural reinforcing adhesives |
US6455146B1 (en) * | 2000-10-31 | 2002-09-24 | Sika Corporation | Expansible synthetic resin baffle with magnetic attachment |
US6455476B1 (en) * | 1998-06-09 | 2002-09-24 | Henkel Corporation | Composition and process for lubricated plastic working of metals |
US20020137808A1 (en) * | 1999-04-28 | 2002-09-26 | 3M Innovative Properties Company | Uniform small cell foams and a continuous process for making same |
US20020136891A1 (en) * | 2000-12-29 | 2002-09-26 | 3M Innovative Properties Company | Pressure sensitive adhesive blends comprising (meth) acrylate polymers and articles therefrom |
US6506494B2 (en) * | 1999-12-20 | 2003-01-14 | 3M Innovative Properties Company | Ambient-temperature-stable, one-part curable epoxy adhesive |
US20030050352A1 (en) * | 2001-09-04 | 2003-03-13 | Symyx Technologies, Inc. | Foamed Polymer System employing blowing agent performance enhancer |
US20030060522A1 (en) * | 2001-09-24 | 2003-03-27 | L&L Products, Inc. | Homopolymerized epoxy-based foam-in-place material |
US20030069335A1 (en) * | 2001-09-07 | 2003-04-10 | L&L Products, Inc. | Structural hot melt material and methods |
US6548593B2 (en) * | 2000-05-02 | 2003-04-15 | Sika Schweiz Ag | Thixotropic agent |
US6561571B1 (en) * | 2000-09-29 | 2003-05-13 | L&L Products, Inc. | Structurally enhanced attachment of a reinforcing member |
US6607831B2 (en) * | 2000-12-28 | 2003-08-19 | 3M Innovative Properties Company | Multi-layer article |
US6617366B2 (en) * | 1998-10-30 | 2003-09-09 | Mitsui Chemicals, Inc. | Crosslinked olefin elastomer foam and elastomer composition therefor |
US6620501B1 (en) * | 2000-08-07 | 2003-09-16 | L&L Products, Inc. | Paintable seal system |
US6682818B2 (en) * | 2001-08-24 | 2004-01-27 | L&L Products, Inc. | Paintable material |
US6706772B2 (en) * | 2001-05-02 | 2004-03-16 | L&L Products, Inc. | Two component (epoxy/amine) structural foam-in-place material |
US20040063800A1 (en) * | 2002-09-16 | 2004-04-01 | Henkel Loctite Corporation | Foamable compositions |
US20040079478A1 (en) * | 2000-11-06 | 2004-04-29 | Sika Ag, Vorm. Kaspar Winkler & Co. | Adhesives for vehicle body manufacturing |
US6730713B2 (en) * | 2001-09-24 | 2004-05-04 | L&L Products, Inc. | Creation of epoxy-based foam-in-place material using encapsulated metal carbonate |
US6740379B1 (en) * | 1998-03-13 | 2004-05-25 | 3M Innovative Properties Company | Adhesive tape for adhering inserts to a page of a magazine |
US6740399B1 (en) * | 1999-03-31 | 2004-05-25 | 3M Innovative Properties Company | Multi-layered sealant |
US6753379B1 (en) * | 1999-11-05 | 2004-06-22 | 3M Innovative Properties Company | Heat activated adhesive |
US20040131840A1 (en) * | 2003-01-03 | 2004-07-08 | Ferguson Gregory A. | High expansion two-component structural foam |
US20040131839A1 (en) * | 2002-12-27 | 2004-07-08 | Eagle Glenn G. | Heat activated epoxy adhesive and use in a structural foam insert |
US6774171B2 (en) * | 2002-01-25 | 2004-08-10 | L&L Products, Inc. | Magnetic composition |
US6777079B2 (en) * | 2000-12-01 | 2004-08-17 | 3M Innovative Properties Company | Crosslinked pressure sensitive adhesive compositions, and adhesive articles based thereon, useful in high temperature applications |
US6776869B1 (en) * | 1998-12-19 | 2004-08-17 | Henkel-Teroson Gmbh | Impact-resistant epoxide resin compositions |
US6787605B2 (en) * | 1998-02-18 | 2004-09-07 | 3M Innovative Properties Company | Composition of polyphenylene ether, polystyrene and curable epoxy |
US6787065B1 (en) * | 1998-02-17 | 2004-09-07 | Henkel Kgaa | Use of a composition or premix based on volatile corrosion inhibitors, composition or premix, articles comprising said composition and preparation method |
US6787593B2 (en) * | 2002-03-27 | 2004-09-07 | Lear Corporation | Sound-deadening composites of metallocene copolymers for use in vehicle applications |
US6787606B1 (en) * | 2001-07-02 | 2004-09-07 | Henkel Corporation | Electrochromic device with composition of epoxy resin, toughener and latent curative |
US6790906B2 (en) * | 1996-02-14 | 2004-09-14 | Sika Schweiz Ag | Fire-retardant polyurethane systems |
US6790597B2 (en) * | 1994-09-02 | 2004-09-14 | Henkel Corporation | Thermosetting resin compositions containing maleimide and/or vinyl compounds |
US20040180193A1 (en) * | 2003-03-11 | 2004-09-16 | Nissan Motor Co., Ltd. | Resin composition, filler, and method of producing resin composition |
US20040181013A1 (en) * | 1998-10-06 | 2004-09-16 | Henkel Teroson Gmbh | Impact resistant epoxide resin compositions |
US6797371B1 (en) * | 1998-07-31 | 2004-09-28 | 3M Innovative Properties Company | Articles that include a polymer foam and method for preparing same |
US6838509B2 (en) * | 2001-01-19 | 2005-01-04 | Kabushiki Kaisha Toyota Jidoshokki | Phenolic resin composite material |
US20050003222A1 (en) * | 2003-07-03 | 2005-01-06 | 3M Innovative Properties Company | Heat-activatable adhesive |
US6846559B2 (en) * | 2002-04-01 | 2005-01-25 | L&L Products, Inc. | Activatable material |
US20050016677A1 (en) * | 2003-07-22 | 2005-01-27 | L&L Products, Inc. | Two-component adhesive material and method of use therefor |
US20050048276A1 (en) * | 2001-06-21 | 2005-03-03 | Magna International Of America, Inc. | Structural foam composite having nano-particle reinforcement and method of making the same |
US6884854B2 (en) * | 2000-04-10 | 2005-04-26 | Henkel Kommanditgesellschaft Auf Aktien | Composition of epoxy resin, low glass transition temperature copolymer, latent hardener and carboxy-terminated polyamide and/or polyamide |
US6911109B2 (en) * | 2000-12-11 | 2005-06-28 | Henkel Corporation | Two-part, room temperature curable epoxy resin/ (meth)acrylate compositions and process for using same to bond substrates |
US20050154089A1 (en) * | 2002-12-04 | 2005-07-14 | Denovus Llc | Metallic acrylate curing agents and usage thereof in intermediate compositions |
US20050159511A1 (en) * | 2002-05-03 | 2005-07-21 | Sika Schweiz Ag | Heat-curable eproxy resin composition |
US20050159531A1 (en) * | 2004-01-20 | 2005-07-21 | L&L Products, Inc. | Adhesive material and use therefor |
Family Cites Families (37)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4900771A (en) | 1989-01-26 | 1990-02-13 | Aster, Inc. | Hot applied plastisol compositions |
US4978562A (en) | 1990-02-05 | 1990-12-18 | Mpa Diversified Products, Inc. | Composite tubular door beam reinforced with a syntactic foam core localized at the mid-span of the tube |
JPH0459820A (en) | 1990-06-29 | 1992-02-26 | Mitsui Petrochem Ind Ltd | Injection-moldable epoxy resin composition |
US5266133A (en) * | 1993-02-17 | 1993-11-30 | Sika Corporation | Dry expansible sealant and baffle composition and product |
US7575653B2 (en) | 1993-04-15 | 2009-08-18 | 3M Innovative Properties Company | Melt-flowable materials and method of sealing surfaces |
US5932680A (en) | 1993-11-16 | 1999-08-03 | Henkel Kommanditgesellschaft Auf Aktien | Moisture-curing polyurethane hot-melt adhesive |
US6312668B2 (en) | 1993-12-06 | 2001-11-06 | 3M Innovative Properties Company | Optionally crosslinkable coatings, compositions and methods of use |
AU1403595A (en) * | 1993-12-27 | 1995-07-17 | Henkel Corporation | Self-dispersing curable epoxy resins and coatings |
DE19502381A1 (en) | 1995-01-26 | 1996-08-01 | Teroson Gmbh | Structural raw rubber-based adhesives |
DE19518673A1 (en) | 1995-05-20 | 1996-11-21 | Henkel Teroson Gmbh | Heat-curing foamed rubber compounds with high structural strength |
US6165588A (en) | 1998-09-02 | 2000-12-26 | Henkel Corporation | Reinforcement of hollow sections using extrusions and a polymer binding layer |
WO1997002967A1 (en) | 1995-07-12 | 1997-01-30 | L & L Products, Inc. | Hollow molded-to-shape expandable sealer |
KR19990063975A (en) | 1995-10-05 | 1999-07-26 | 웨인 씨. 제쉬크 | Thermosetting resin composition |
WO1997019124A1 (en) | 1995-11-18 | 1997-05-29 | Ciba Specialty Chemicals Holding Inc. | Powderable reactive resin compositions |
US5985435A (en) | 1996-01-23 | 1999-11-16 | L & L Products, Inc. | Magnetized hot melt adhesive articles |
DE19644855A1 (en) | 1996-10-29 | 1998-04-30 | Henkel Teroson Gmbh | Sulfur-free expanding, thermosetting rubber moldings |
JP2000504372A (en) | 1996-11-20 | 2000-04-11 | ジーカ ヒェミー ゲゼルシャフト ミット ベシュレンクテル ハフツング | Epoxy-amine adducts for use as emulsifiers for epoxy resins; aqueous-based epoxy resin dispersions and methods for their preparation |
WO1998052997A1 (en) | 1997-05-21 | 1998-11-26 | Denovus L.L.C. | Epoxy-containing foaming compositions and use thereof |
US6479560B2 (en) | 1997-05-21 | 2002-11-12 | Denovus Llc | Foaming compositions and methods for making and using the composition |
DE19729982A1 (en) | 1997-07-12 | 1999-01-14 | Sika Chemie Gmbh | Thixotropic two-component polyurethane systems |
US5948508A (en) | 1997-08-15 | 1999-09-07 | 3M Innovative Properties Company | On-line paintable insert |
US6451231B1 (en) | 1997-08-21 | 2002-09-17 | Henkel Corporation | Method of forming a high performance structural foam for stiffening parts |
JPH1160900A (en) | 1997-08-26 | 1999-03-05 | Nissan Motor Co Ltd | Car body-reinforcing epoxy resin composition and method for reinforcing car body |
US6162504A (en) | 1997-12-04 | 2000-12-19 | Henkel Corporation | Adhesives and sealants containing adhesion promoter comprising waste powder prime |
US6057382A (en) | 1998-05-01 | 2000-05-02 | 3M Innovative Properties Company | Epoxy/thermoplastic photocurable adhesive composition |
US6136398A (en) | 1998-05-01 | 2000-10-24 | 3M Innovative Properties Company | Energy cured sealant composition |
US6136944A (en) | 1998-09-21 | 2000-10-24 | Shell Oil Company | Adhesive of epoxy resin, amine-terminated polyamide and polyamine |
DE19845607A1 (en) | 1998-10-06 | 2000-04-20 | Henkel Teroson Gmbh | Impact-resistant epoxy resin compositions |
US6486256B1 (en) * | 1998-10-13 | 2002-11-26 | 3M Innovative Properties Company | Composition of epoxy resin, chain extender and polymeric toughener with separate base catalyst |
AU2365900A (en) | 1998-12-21 | 2000-07-12 | Magna International Of America, Inc. | Structural foam composite having nano-particle reinforcement and method of making the same |
DE19859728A1 (en) | 1998-12-23 | 2000-06-29 | Henkel Kgaa | Water-swellable hot melt adhesive |
DE19959916A1 (en) | 1998-12-30 | 2000-07-20 | Henkel Chile Sa | Aqueous polymer dispersion, useful for adhesives and coatings, contains organic and/or inorganic filler particles and organic polymer particles that are formed in presence of at least one filler |
US6133335A (en) | 1998-12-31 | 2000-10-17 | 3M Innovative Properties Company | Photo-polymerizable compositions and articles made therefrom |
DE19909270A1 (en) | 1999-03-03 | 2000-09-07 | Henkel Teroson Gmbh | Thermosetting, thermally expandable molded body |
WO2001057130A1 (en) | 2000-02-02 | 2001-08-09 | Denovus Llc | Polymeric blends and composites and laminates thereof |
CA2409750A1 (en) | 2000-05-16 | 2001-11-22 | Sika Corporation | Sound deadening and structural reinforcement compositions and methods of using the same |
US6319964B1 (en) * | 2000-06-30 | 2001-11-20 | Sika Corporation | Acoustic baffle with predetermined directional expansion characteristics |
-
2001
- 2001-05-02 US US09/847,252 patent/US6787579B2/en not_active Expired - Lifetime
-
2002
- 2002-02-04 JP JP2002587499A patent/JP4017986B2/en not_active Expired - Fee Related
- 2002-02-04 EP EP02718897A patent/EP1373383A1/en not_active Withdrawn
- 2002-02-04 CA CA002439611A patent/CA2439611A1/en not_active Abandoned
- 2002-02-04 WO PCT/US2002/003133 patent/WO2002090427A1/en active Application Filing
- 2002-11-22 US US10/301,948 patent/US6706772B2/en not_active Expired - Lifetime
-
2004
- 2004-08-11 US US10/916,103 patent/US20050020703A1/en not_active Abandoned
Patent Citations (98)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4427481A (en) * | 1978-02-27 | 1984-01-24 | R & D Chemical Company | Magnetized hot melt adhesive and method of preparing same |
US4538380A (en) * | 1983-11-16 | 1985-09-03 | Profile Extrusions Company | Low friction weather seal |
US4601769A (en) * | 1985-09-27 | 1986-07-22 | Dehoff Ronald L | Process for stabilizing the viscosity of an epoxy resin-acid anhydride system during reaction and cure |
US4693775A (en) * | 1986-03-06 | 1987-09-15 | United Technologies Automotive, Inc. | Hot melt, synthetic, magnetic sealant |
US5342873A (en) * | 1986-05-09 | 1994-08-30 | Sika Ag, Vorm. Kaspar Winkler & Co. | Reactive hot-melt adhesive |
US4749434A (en) * | 1986-12-29 | 1988-06-07 | United Technologies Automotive, Inc. | Hot melt magnetic sealant, method of making and method of using same |
US4724243A (en) * | 1986-12-29 | 1988-02-09 | United Technologies Automotive, Inc. | Hot melt magnetic sealant, method of making and method of using same |
US4908273A (en) * | 1987-03-24 | 1990-03-13 | Ciba-Geigy Corporation | Multi-layer, heat-curable adhesive film |
US4769166A (en) * | 1987-06-01 | 1988-09-06 | United Technologies Automotive, Inc. | Expandable magnetic sealant |
US4922596A (en) * | 1987-09-18 | 1990-05-08 | Essex Composite Systems | Method of manufacturing a lightweight composite automotive door beam |
US4898630A (en) * | 1987-11-18 | 1990-02-06 | Toyota Jidosha Kabushiki | Thermosetting highly foaming sealer and method of using it |
US4923902A (en) * | 1988-03-10 | 1990-05-08 | Essex Composite Systems | Process and compositions for reinforcing structural members |
US4995545A (en) * | 1988-03-10 | 1991-02-26 | Essex Composite Systems | Method of reinforcing a structure member |
US5124186A (en) * | 1990-02-05 | 1992-06-23 | Mpa Diversified Products Co. | Composite tubular door beam reinforced with a reacted core localized at the mid-span of the tube |
US5382606A (en) * | 1992-04-28 | 1995-01-17 | Sika Ag, Vorm. Kaspar Winkler & Co. | Curing agent for aqueous epoxy resin dispersions, process for its preparation and its use |
US5783272A (en) * | 1993-08-10 | 1998-07-21 | Dexter Corporation | Expandable films and molded products therefrom |
US6228449B1 (en) * | 1994-01-31 | 2001-05-08 | 3M Innovative Properties Company | Sheet material |
US5712317A (en) * | 1994-03-31 | 1998-01-27 | Ppg Industries, Inc. | Curable, sprayable compositions for reinforcing thin rigid plates |
US5894071A (en) * | 1994-04-15 | 1999-04-13 | Sika Ag, Vorm. Kaspar Winkler & Co. | Two-component adhesive-, sealing- or coating composition and it's use |
US5884960A (en) * | 1994-05-19 | 1999-03-23 | Henkel Corporation | Reinforced door beam |
US6790597B2 (en) * | 1994-09-02 | 2004-09-14 | Henkel Corporation | Thermosetting resin compositions containing maleimide and/or vinyl compounds |
US6790906B2 (en) * | 1996-02-14 | 2004-09-14 | Sika Schweiz Ag | Fire-retardant polyurethane systems |
US6441075B2 (en) * | 1996-04-26 | 2002-08-27 | Nissan Motor Co., Ltd. | Polyolefin-based resin composition and automotive molded plastic made from same |
US6232433B1 (en) * | 1996-10-02 | 2001-05-15 | Henkel Corporation | Radiation curable polyesters |
US6235842B1 (en) * | 1996-10-08 | 2001-05-22 | Hitachi Chemical Company, Ltd. | Phase-separated carboxyl group-containing elastomer modified phoenoxy resin optionally with epoxy resin |
US5648401A (en) * | 1996-10-09 | 1997-07-15 | L & L Products, Inc. | Foamed articles and methods for making same |
US6444149B1 (en) * | 1997-03-10 | 2002-09-03 | Perstorp Ab | Process for the manufacturing of an article of plastic material |
US6277898B1 (en) * | 1997-05-21 | 2001-08-21 | Denovus Llc | Curable sealant composition |
US6444713B1 (en) * | 1997-05-21 | 2002-09-03 | Denovus Llc | Foaming compositions and methods for making and using the compositions |
US6448338B1 (en) * | 1997-07-16 | 2002-09-10 | Henkel Teroson Gmbh | Hot-setting wash-fast sealant for shell structures |
US6287669B1 (en) * | 1997-08-15 | 2001-09-11 | 3M Innovative Properties Company | Sealing method and article |
US6787065B1 (en) * | 1998-02-17 | 2004-09-07 | Henkel Kgaa | Use of a composition or premix based on volatile corrosion inhibitors, composition or premix, articles comprising said composition and preparation method |
US6787605B2 (en) * | 1998-02-18 | 2004-09-07 | 3M Innovative Properties Company | Composition of polyphenylene ether, polystyrene and curable epoxy |
US6740379B1 (en) * | 1998-03-13 | 2004-05-25 | 3M Innovative Properties Company | Adhesive tape for adhering inserts to a page of a magazine |
US6174932B1 (en) * | 1998-05-20 | 2001-01-16 | Denovus Llc | Curable sealant composition |
US6455476B1 (en) * | 1998-06-09 | 2002-09-24 | Henkel Corporation | Composition and process for lubricated plastic working of metals |
US6350791B1 (en) * | 1998-06-22 | 2002-02-26 | 3M Innovative Properties Company | Thermosettable adhesive |
US6797371B1 (en) * | 1998-07-31 | 2004-09-28 | 3M Innovative Properties Company | Articles that include a polymer foam and method for preparing same |
US6348513B1 (en) * | 1998-08-27 | 2002-02-19 | Henkel Corporation | Reduced tack compositions useful for the production of reinforcing foams |
US6103784A (en) * | 1998-08-27 | 2000-08-15 | Henkel Corporation | Corrosion resistant structural foam |
US6218442B1 (en) * | 1998-08-27 | 2001-04-17 | Henkel Corporation | Corrosion resistant structural foam |
US6376564B1 (en) * | 1998-08-27 | 2002-04-23 | Henkel Corporation | Storage-stable compositions useful for the production of structural foams |
US6441081B1 (en) * | 1998-10-05 | 2002-08-27 | Sumitomo Chemical Company, Limited | Polypropylene-base resin composition and products of injection molding thereof |
US20040181013A1 (en) * | 1998-10-06 | 2004-09-16 | Henkel Teroson Gmbh | Impact resistant epoxide resin compositions |
US6617366B2 (en) * | 1998-10-30 | 2003-09-09 | Mitsui Chemicals, Inc. | Crosslinked olefin elastomer foam and elastomer composition therefor |
US6432475B1 (en) * | 1998-12-08 | 2002-08-13 | Nitto Denko Corporation | Pressure-sensitive adhesive composition, process for the preparation thereof and pressure-sensitive adhesive sheets |
US6776869B1 (en) * | 1998-12-19 | 2004-08-17 | Henkel-Teroson Gmbh | Impact-resistant epoxide resin compositions |
US6740399B1 (en) * | 1999-03-31 | 2004-05-25 | 3M Innovative Properties Company | Multi-layered sealant |
US20020137808A1 (en) * | 1999-04-28 | 2002-09-26 | 3M Innovative Properties Company | Uniform small cell foams and a continuous process for making same |
US6753379B1 (en) * | 1999-11-05 | 2004-06-22 | 3M Innovative Properties Company | Heat activated adhesive |
USH2047H1 (en) * | 1999-11-10 | 2002-09-03 | Henkel Corporation | Reinforcement laminate |
US6263635B1 (en) * | 1999-12-10 | 2001-07-24 | L&L Products, Inc. | Tube reinforcement having displaceable modular components |
US6506494B2 (en) * | 1999-12-20 | 2003-01-14 | 3M Innovative Properties Company | Ambient-temperature-stable, one-part curable epoxy adhesive |
US6437055B1 (en) * | 2000-04-07 | 2002-08-20 | Ppg Industries Ohio, Inc. | Electrodepositable coating from gelled epoxy-polyester and amine |
US6884854B2 (en) * | 2000-04-10 | 2005-04-26 | Henkel Kommanditgesellschaft Auf Aktien | Composition of epoxy resin, low glass transition temperature copolymer, latent hardener and carboxy-terminated polyamide and/or polyamide |
US6548593B2 (en) * | 2000-05-02 | 2003-04-15 | Sika Schweiz Ag | Thixotropic agent |
US6440257B1 (en) * | 2000-05-18 | 2002-08-27 | Hexcel Corporation | Self-adhesive prepreg face sheets for sandwich panels |
US20020009582A1 (en) * | 2000-06-06 | 2002-01-24 | Golden Michael R. | Epoxy based reinforcing patches with improved adhesion to oily metal surfaces |
US20040048060A1 (en) * | 2000-08-07 | 2004-03-11 | L&L Products, Inc. | Paintable seal system |
US6620501B1 (en) * | 2000-08-07 | 2003-09-16 | L&L Products, Inc. | Paintable seal system |
US6403222B1 (en) * | 2000-09-22 | 2002-06-11 | Henkel Corporation | Wax-modified thermosettable compositions |
US6419305B1 (en) * | 2000-09-29 | 2002-07-16 | L&L Products, Inc. | Automotive pillar reinforcement system |
US6561571B1 (en) * | 2000-09-29 | 2003-05-13 | L&L Products, Inc. | Structurally enhanced attachment of a reinforcing member |
US6451876B1 (en) * | 2000-10-10 | 2002-09-17 | Henkel Corporation | Two component thermosettable compositions useful for producing structural reinforcing adhesives |
US6455146B1 (en) * | 2000-10-31 | 2002-09-24 | Sika Corporation | Expansible synthetic resin baffle with magnetic attachment |
US20040079478A1 (en) * | 2000-11-06 | 2004-04-29 | Sika Ag, Vorm. Kaspar Winkler & Co. | Adhesives for vehicle body manufacturing |
US6777079B2 (en) * | 2000-12-01 | 2004-08-17 | 3M Innovative Properties Company | Crosslinked pressure sensitive adhesive compositions, and adhesive articles based thereon, useful in high temperature applications |
US6911109B2 (en) * | 2000-12-11 | 2005-06-28 | Henkel Corporation | Two-part, room temperature curable epoxy resin/ (meth)acrylate compositions and process for using same to bond substrates |
US20020120064A1 (en) * | 2000-12-21 | 2002-08-29 | 3M Innovative Properties Company | Pressure-sensitive adhesive blends comprising ethylene/propylene-derived polymers and propylene-derived polymers and articles therefrom |
US6607831B2 (en) * | 2000-12-28 | 2003-08-19 | 3M Innovative Properties Company | Multi-layer article |
US20020123575A1 (en) * | 2000-12-28 | 2002-09-05 | Kabushiki Kaisha Toyota Chuo Kenkyusho | Resin composite material |
US20020136891A1 (en) * | 2000-12-29 | 2002-09-26 | 3M Innovative Properties Company | Pressure sensitive adhesive blends comprising (meth) acrylate polymers and articles therefrom |
US6838509B2 (en) * | 2001-01-19 | 2005-01-04 | Kabushiki Kaisha Toyota Jidoshokki | Phenolic resin composite material |
US6787579B2 (en) * | 2001-05-02 | 2004-09-07 | L&L Products, Inc. | Two-component (epoxy/amine) structural foam-in-place material |
US6706772B2 (en) * | 2001-05-02 | 2004-03-16 | L&L Products, Inc. | Two component (epoxy/amine) structural foam-in-place material |
US20050048276A1 (en) * | 2001-06-21 | 2005-03-03 | Magna International Of America, Inc. | Structural foam composite having nano-particle reinforcement and method of making the same |
US6787606B1 (en) * | 2001-07-02 | 2004-09-07 | Henkel Corporation | Electrochromic device with composition of epoxy resin, toughener and latent curative |
US6682818B2 (en) * | 2001-08-24 | 2004-01-27 | L&L Products, Inc. | Paintable material |
US20040048078A1 (en) * | 2001-08-24 | 2004-03-11 | L&L Products, Inc. | Paintable material |
US20030050352A1 (en) * | 2001-09-04 | 2003-03-13 | Symyx Technologies, Inc. | Foamed Polymer System employing blowing agent performance enhancer |
US20030069335A1 (en) * | 2001-09-07 | 2003-04-10 | L&L Products, Inc. | Structural hot melt material and methods |
US6887914B2 (en) * | 2001-09-07 | 2005-05-03 | L&L Products, Inc. | Structural hot melt material and methods |
US6890964B2 (en) * | 2001-09-24 | 2005-05-10 | L&L Products, Inc. | Homopolymerized epoxy-based form-in-place material |
US20030060522A1 (en) * | 2001-09-24 | 2003-03-27 | L&L Products, Inc. | Homopolymerized epoxy-based foam-in-place material |
US6730713B2 (en) * | 2001-09-24 | 2004-05-04 | L&L Products, Inc. | Creation of epoxy-based foam-in-place material using encapsulated metal carbonate |
US6774171B2 (en) * | 2002-01-25 | 2004-08-10 | L&L Products, Inc. | Magnetic composition |
US6787593B2 (en) * | 2002-03-27 | 2004-09-07 | Lear Corporation | Sound-deadening composites of metallocene copolymers for use in vehicle applications |
US6846559B2 (en) * | 2002-04-01 | 2005-01-25 | L&L Products, Inc. | Activatable material |
US20050159511A1 (en) * | 2002-05-03 | 2005-07-21 | Sika Schweiz Ag | Heat-curable eproxy resin composition |
US6894082B2 (en) * | 2002-09-16 | 2005-05-17 | Henkel Corporation | Foamable compositions |
US20040063800A1 (en) * | 2002-09-16 | 2004-04-01 | Henkel Loctite Corporation | Foamable compositions |
US20050154089A1 (en) * | 2002-12-04 | 2005-07-14 | Denovus Llc | Metallic acrylate curing agents and usage thereof in intermediate compositions |
US20040131839A1 (en) * | 2002-12-27 | 2004-07-08 | Eagle Glenn G. | Heat activated epoxy adhesive and use in a structural foam insert |
US20040131840A1 (en) * | 2003-01-03 | 2004-07-08 | Ferguson Gregory A. | High expansion two-component structural foam |
US20040180193A1 (en) * | 2003-03-11 | 2004-09-16 | Nissan Motor Co., Ltd. | Resin composition, filler, and method of producing resin composition |
US20050003222A1 (en) * | 2003-07-03 | 2005-01-06 | 3M Innovative Properties Company | Heat-activatable adhesive |
US20050016677A1 (en) * | 2003-07-22 | 2005-01-27 | L&L Products, Inc. | Two-component adhesive material and method of use therefor |
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Also Published As
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US6787579B2 (en) | 2004-09-07 |
CA2439611A1 (en) | 2002-11-14 |
JP4017986B2 (en) | 2007-12-05 |
US6706772B2 (en) | 2004-03-16 |
WO2002090427A1 (en) | 2002-11-14 |
JP2004526044A (en) | 2004-08-26 |
US20030105175A1 (en) | 2003-06-05 |
EP1373383A1 (en) | 2004-01-02 |
US20020187305A1 (en) | 2002-12-12 |
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