TITLE OF THE INVENTION

EPOXY BASED REINFORCING PATCHES HAVING IMPROVED DAMPING LOSS FACTOR

CROSS-REFERENCE TO RELATED APPLICATIONS

[0000] This application claims the benefit of United States Provisional

Application Serial Number 62/588,620, entitled "EPOXY BASED REINFORCING PATCHES HAVING IMPROVED DAMPING LOSS FACTOR," filed November 20, 2017 - which is hereby incorporated herein by reference in its entirety, including all references cited therein.

STATEMENT REGARDING FEDERALLY SPONSORED RESEARCH OR DEVELOPMENT

[0001] Not applicable.

REFERENCE TO A SEQUENCE LISTING

[0002] Not applicable.

BACKGROUND OF THE INVENTION

1. Field of the Invention

[0003] The present invention relates in general to reinforcing patches or sheets having improved damping loss factor, such as, but not limited to, those adapted for applying localized reinforcement to sheet metal, sheet plastic structures, and/or other substrates. More particularly, the present invention is directed to epoxy fiberglass reinforcing patches or sheets that utilize epoxy-modified dimerized fatty acids combined with an epoxy terminated polyurethane interpenetrating network (IPN). The patches of the present invention are suitable for use in both expandable and non-expandable heat curable applications.

2. Background Art

[0004] Reinforcing sheets for localized, lightweight reinforcement have been known in the art for years and are the subject of a plurality of patents and/or publications, including: United States Patent No. 4,444,818 entitled "Reinforcing Adhesive Sheets," United States Patent No. 4,766,183 entitled "Thermosetting Composition for an Interpenetrating Polymer Network System," United States Patent No. 4,842,938 entitled "Metal Reinforcing Patch and Method for Reinforcing Metal," United States Patent No. 4,803,105 entitled "Reinforcing Sheet for the Reinforcement of Panel and Method of Reinforcing Panel," United States Patent No. 4,803,108 entitled "Honeycomb Reinforcing Sheet for the Reinforcement of Panels and Method of Reinforcing Panels," United States Patent No. 4,900,601 entitled "Multi-Layer Body Structure for the Reinforcement of a Panel and a Method of Reinforcing a Panel," United States Patent No. 4,929,483 entitled "Method of Reinforcing Sheet Metal Panels, Shaped Plastic Panels or the Like and a Stiffening Member Usable for Performing the Method," United States Patent No. 5,092,947 entitled "Method of Reinforcing Panels," and United States Patent No. 6,586,089 entitled "Epoxy Based Reinforcing Patches with Improved Adhesion to Oily Metal Surfaces," - all of which are hereby incorporated herein by reference in their entirety including the references cited therein.

[0005] Generally, these reinforcing sheets include one or more layers of a stiffening material and one or more layers of a polymeric material that acts as a binder for the stiffening material, as well as an adhesive for securing the reinforcing sheet to a substrate.

[0006] United States Patent No. 4,444,818 appears to disclose a thermosetting adhesive sheet that is comprised of a thermosetting resin sheet-shaped prepreg with a reinforcing material embedded therein, and a flattened tubular material provided on one side of the prepeg. The flattened tubular material being capable of nearly recovering the original tubular form on heating and being narrower in width than the prepreg. The prepreg may be of the two-layer structure comprising a first thermosetting resin composition layer and a second thermosetting resin composition layer.

[0007] United States Patent Nos. 4,766,183 and 4,842,938 appear to disclose a method for making a one package heat curable (i.e., thermosetting) composition which, on heating, forms a urethane/epoxy/silicone interpenetrating polymer network (IPN) system; one package heat curable compositions made by such a method; metal reinforcing patches, directly adherent to an oily metal surface such as an oily steel surface, comprising a sheet-like carrier having thereon such a one package heat curable composition in combination with a filler admixed therewith, said filler possibly including magnetic particles; a method for reinforcing metal which comprises applying thereto such a metal reinforcing patch and curing said heat curable composition at an elevated temperature to form a urethane/epoxy/silicone interpenetrating polymer network.

[0008] United States Patent No. 4,803,105 appears to disclose a reinforcing sheet adaptable to the reinforcement of a panel formed of metal, plastic or sheet molding compound, which reinforcing sheet contains a moisture impermeable barrier embedded in a thermosetting adhesive layer and a reinforcement adhered to the surface of the adhesive layer opposite the surface to be applied to the panel to be reinforced. The reinforcing sheet with improved resistance to the adverse effects of moisture is advantageously used to reinforce cold rolled steel, such as an automobile panel.

[0009] United States Patent No. 4,803,108 appears to disclose a reinforcing sheet adaptable to the reinforcement of a panel formed of metal, plastic or sheet molding compound, which reinforcing sheet contains a perforated honeycomb member with a thermosetting adhesive layer on each side of the honeycomb member and a reinforcement backing adhered to one of the adhesive layers, the other adhesive layer being applied to the panel to be reinforced. The reinforcing sheet provides excellent flexural reinforcement and impact absorbing properties and is advantageously used to reinforce cold rolled steel, such as an automobile panel.

[0010] United States Patent No. 4,900,601 appears to disclose a multi-layer body member that consists of a support member ( e.g ., a glass fiber tissue impregnated with a thermosetting resin), which is covered by a layer of thermosetting adhesive resin. In order to protect the sticky surface of the adhesive resin, a protection foil made of a material shrinking under the influence of heat is provided. The foil comprises slits which open to apertures after a preliminary heat treatment such that an essential portion of the sticky resin surface is freely exposed. Thus, the need to remove the protection foil prior to applying the multi-layer body member to the surface to be reinforced is removed.

[001 1] United States Patent Nos. 4,929,483 and 5,092,947 appear to disclose the method of reinforcing a panel of sheet metal, a shaped plastic body or the like by means of a one- or multi-layer stiffening member of essentially flat shape which comprises a layer at least partially consisting of a thermosetting resin. The stiffening member is subjected to a first heat treatment until at least one of the surfaces of the stiffening member is sticky. Thereafter, the stiffening member is applied to the surface of an element to be reinforced. Finally, the stiffening member is subjected to a second, final heat treatment until all layers comprising a thermosetting resin material are cured. Thus, it is not necessary to manually prepare the stiffening member by removing a protection foil from its sticky surface prior to applying it to the element to be reinforced and a fully automated handling is possible.

[0012] United States Patent No. 6,586,089 appears to disclose reinforcing sheets that exhibit improved adhesion to cold and/or oily substrates that have an adhesive layer which contains an epoxy-terminated adduct of an epoxy resin and a rubber that contains a low amount of a nitrile monomer.

[0013] While the above-identified references, appear to disclose a plurality of reinforcing patches, none of the above-identified references disclose reinforcing patches having improved damping loss factor as disclosed herein.

[0014] It is therefore an object of the present invention to provide new, useful, and nonobvious reinforcing patches having improved damping loss factor for both expandable and non-expandable heat curable applications.

[0015] These and other objects of the present invention will become apparent in light of the present specification, claims, and drawings.

SUMMARY OF THE INVENTION

[0016] In one embodiment, the present invention is directed to a reinforcing sheet comprising: (a) one or more layers of a reinforcing material; and (b) a thermosetting adhesive associated with at least a portion of the reinforcing material, wherein the thermosetting adhesive includes: (1 ) a curing agent, and (2) an epoxy- modified dimerized fatty acid combined with an epoxy terminated polyurethane interpenetrating network.

[0017] In a preferred embodiment of the present invention, the reinforcing material comprises a woven fabric, such as woven fiberglass. In this embodiment, the woven fiberglass preferably ranges in thickness from approximately 0.25 mm to approximately 5.00 mm, and more preferably ranges in thickness from approximately 0.75 mm to approximately 2.50 mm.

[0018] In another preferred embodiment of the present invention, the thermosetting adhesive further comprises microspheres and/or a blowing agent.

[0019] In yet another preferred embodiment, the curing agent comprises a boron trifluoride-amine complex, an organic-acid hydrazide, and/or dicyandiamide.

[0020] In a preferred embodiment of the present invention, the curing agent is represented by at least one of the following tautomeric chemical structures:

[0021] In another preferred embodiment of the present invention, the curing agent is represented by the following chemical structure:

[0022] In a preferred embodiment of the present invention, the epoxy-modified dimerized fatty acid is represented by the following chemical structure:

wherein Ri comprises an alkyl, cycloalkyl, polycycloalkyl, heterocycloalkyl, aryl, alkaryl, aralkyl, alkoxy, alkanoyl, aroyl, alkenyl, alkynyl and/or cyano group containing approximately 1 to approximately 40 carbon atoms.

[0023] In another preferred embodiment of the present invention, the epoxy- modified dimerized fatty acid is represented by the following chemical structure:

wherein Ri comprises an alkyl, cycloalkyl, polycycloalkyl, heterocycloalkyl, aryl, alkaryl, aralkyl, alkoxy, alkanoyl, aroyl, alkenyl, alkynyl and/or cyano group containing approximately 35 to approximately 40 carbon atoms.

[0024] In yet another preferred embodiment of the present invention, the epoxy- modified dimerized fatty acid is represented by the following chemical structure:

wherein Ri is tall oil based. [0025] In another aspect of the present invention, the epoxy terminated polyurethane interpenetrating network is represented by the following chemical structure:

wherein A ₁ is represented by the following chemical structure:

wherein R ₁ comprises an alkyl, cycloalkyl, polycycloalkyl, heterocycloalkyl, aryl, alkaryl, aralkyl, alkoxy, alkanoyl, aroyl, alkenyl, alkynyl and/or cyano group containing approximately 1 to approximately 75 carbon atoms, an oligomer, and/or a polymer; and wherein A ₂ = A ₁ or comprises an alkyl, cycloalkyl, polycycloalkyl, heterocycloalkyl, aryl, alkaryl, aralkyl, alkoxy, alkanoyl, aroyl, alkenyl, alkynyl and/or cyano group containing approximately 1 to approximately 35 carbon atoms, an oligomer, and/or a polymer.

[0026] In a preferred embodiment of the present invention, the epoxy terminated polyurethane interpenetrating network is represented by the following chemical structure:

wherein A ₁ is represented by the following chemical structure:

wherein Ri comprises an alkyl, alkenyl, and/or alkynyl group containing approximately 1 to approximately 35 carbon atoms, an oligomer, and/or a urethane polymer; and wherein A ₂ = Ai.

DETAILED DESCRIPTION OF THE INVENTION

[0027] While this invention is susceptible of embodiment in many different forms, there is shown in the drawings and/or described herein in detail several specific embodiments with the understanding that the present disclosure is to be considered as an exemplification of the principles of the invention and is not intended to limit the invention to the embodiments illustrated.

[0028] In accordance with the present invention, surprisingly effective epoxy fiberglass reinforcing patches or sheets that utilize epoxy-modified dimerized fatty acids combined with an epoxy terminated polyurethane interpenetrating network (IPN) are provided herein. The patches of the present invention are suitable for use in both expandable and non-expandable heat curable applications - just to name a few.

[0029] The present invention is directed to a reinforcing sheet or patch that includes: (a) one or more layers of a reinforcing material ( e.g ., woven fabric, woven fiberglass, etcetera) that preferably ranges in thickness from approximately 0.25 mm to approximately 5.00 mm, and more preferably ranges in thickness from approximately 0.75 mm to approximately 1.50 mm; and (b) a thermosetting adhesive associated {e.g., impregnated, etch coated, dip coated, spin coated, brush coated and/or spray coated) with at least a portion of the reinforcing material. Preferably, the thermosetting adhesive includes a curing agent (e.g., aliphatic curing agents, cycloaliphatic curing agents, polyamide curing agents, amidoamine curing agents, waterborne polyamides, latent curatives, tertiary amines, boron trifluoride-amine complexes, hydrazides, organic-acid hydrazides, dicyandiamide, etcetera), and an epoxy-modified dimerized fatty acid combined with an epoxy terminated polyurethane interpenetrating network.

[0030] In a preferred embodiment of the present invention, the curing agent is represented by at least one of the following tautomeric chemical structures:

[0031] In this embodiment the first tautomer of the curing agent generally comprises the following ¹ H-NMR spectrogram:

PPM

Solvent = DMSO 300 MHz

and/or the following ¹³ C-NMR spectrogram:

PPM and the second tautomer of the curing agent generally comprises the following ¹ H-NMR spectrogram:

Solvent = DMSO 300 MHz

and/or the following ¹³ C-NMR spectrogram:

160 140 120 100 80 60 40 20 0

PPM

[0032] In another preferred embodiment of the present invention, the curing agent is represented by the following chemical structure:

[0033] In this embodiment the curing agent generally comprises the following ¹ H-

NMR spectrogram:

PPM

Solvent = DMSO 300 MHz

and/or the following ¹³ C-NMR spectrogram:

160 140 120 100 80 60 40 20 0

PPM

[0034] The above-identified curing agents and/or their precursors, are available from common commercial chemical vendors, such as Sigma-Aldrich Chemical Co., of St. Louis, Missouri.

[0035] Suitable examples of epoxy-modified dimerized fatty acids include those represented by the following chemical structure:

wherein Ri comprises an alkyl, cycloalkyl, polycycloalkyl, heterocycloalkyl, aryl, alkaryl, aralkyl, alkoxy, alkanoyl, aroyl, alkenyl, alkynyl and/or cyano group containing approximately 1 to approximately 40 carbon atoms. In one embodiment, Ri is tall oil based.

[0036] In another preferred embodiment of the present invention, the epoxy- modified dimerized fatty acid is represented by the following chemical structure:

wherein Ri comprises an alkyl, cycloalkyl, polycycloalkyl, heterocycloalkyl, aryl, alkaryl, aralkyl, alkoxy, alkanoyl, aroyl, alkenyl, alkynyl and/or cyano group containing approximately 35 to approximately 40 carbon atoms. [0037] In yet another preferred embodiment of the present invention, the epoxy- modified dimerized fatty acid is represented by the following chemical structure:

wherein Ri is tall oil based ( e.g C36, C ₃₆ H _72, etcetera).

[0038] In this embodiment the epoxy-modified dimerized fatty acid curing agent generally comprises the following ¹ H-NMR spectrogram:

Solvent = DMSO 300 MHz

and/or the following ¹³ C-NMR spectrogram:

PPM [0039] The above-identified epoxy-modified dimerized fatty acid and/or its precursors, are available from common commercial chemical vendors, such as Sigma- Aldrich Chemical Co., of St. Louis, Missouri.

[0040] In accordance with the present invention, suitable examples of epoxy terminated polyurethane interpenetrating networks include those represented by the following chemical structure:

wherein A ₁ is represented by the following chemical structure:

wherein Ri comprises an alkyl, cycloalkyl, polycycloalkyl, heterocycloalkyl, aryl, alkaryl, aralkyl, alkoxy, alkanoyl, aroyl, alkenyl, alkynyl and/or cyano group containing approximately 1 to approximately 75 carbon atoms, an oligomer, and/or a polymer; and wherein A ₂ = Ai and/or comprises an alkyl, cycloalkyl, polycycloalkyl, heterocycloalkyl, aryl, alkaryl, aralkyl, alkoxy, alkanoyl, aroyl, alkenyl, alkynyl and/or cyano group containing approximately 1 to approximately 35 carbon atoms, an oligomer, and/or a polymer.

[0041] In a preferred embodiment of the present invention, the epoxy terminated polyurethane interpenetrating network is represented by the following chemical structure:

wherein A ₁ is represented by the following chemical structure:

wherein Ri comprises an alkyl, alkenyl, and/or alkynyl group containing approximately 1 to approximately 36 carbon atoms, an oligomer, and/or a urethane polymer; and wherein A ₂ = Ai.

[0042] In this embodiment Ai generally comprises the following ¹ H-NMR spectrogram:

5

PPM

Solvent = DMSO 300 MHz

and/or the following ¹³ C-NMR spectrogram:

PPM

[0043] The above-identified epoxy terminated polyurethane interpenetrating network and/or its precursors, are available from common commercial chemical vendors, such as Sigma-Aldrich Chemical Co., of St. Louis, Missouri.

[0044] Additional interpenetrating polymer networks are also contemplated for use in accordance with the present invention, including, for example, those disclosed in United States Patent No. 4,766,183 entitled "Thermosetting Composition for an Interpenetrating Polymer Network System," United States Patent No. 4,842,938 entitled "Metal Reinforcing Patch and Method for Reinforcing Metal," United States Patent No. 5,767,187 entitled "Interpenetrating Polymer Network Compositions," United States Patent No. 6,166,127 entitled "Interpenetrating Networks of Polymers," United States Patent No. 7,429,220 entitled "Golf Balls Containing Interpenetrating Polymer Networks," and United States Patent No. 7,790,288 entitled "Interpenetrating Polymer Network as Coating for Metal Substrate and Method Therefor" - which are hereby incorporated herein by reference in their entirety, including all references cited therein.

[0045] The invention is further described by the following examples.

Non-Expandable version (No Glass fiber)

Material Non-Expandable version (No Glass fiber)

Thickness 1.95 - 2.05 mm thickness patch.

Test Flexural Strength (N) at RT,

Acoustic efficiency, Oberst (SAE J 1637, 3.0 kg/m2, 200Hz, composite loss factor)

Substrate 60E(0.75mm), CRS(0.75mm) & AL 6022(0.9mm thickness) (l"x 6" size panel)

Oil Ferrocote 6130 oil

Bake cycle Low Bake - 171°C/10 min. (Metal temp.)

High Bake - 205°C/30 min. (Metal temp.)

Composite Loss Factor, 3.0kg/m2, 200Hz

Flexural Strength, (N)

Flexural Strength (N), min. 50N requirment.

Composite Loss Factor, min. 0.1 requirement

Non-Expandable version (with 7544 type Glass fiber)

Material Non-Expandable version (with 7544 type Glass fiber)

Thickness 1.95 - 2.05 mm patch material thickness alone.

Test Flexural Strength (N) at RT,

Acoustic efficiency, Oberst (SAE J 1637, 3.0 kg/m2, 200Hz, composite loss factor)

Substrate 60E(0.75mm), CRS(0.75mm) & AL 6022(0.9mm thickness) (l"x 6" size panel)

Oil Ferrocote 6130 oil

Bake cycle Low Bake - 171°C/10 min. (Metal temp.)

High Bake - 205°C/30 min. (Metal temp.)

Composite Loss Factor, 3.0kgm2, 200Hz

Flexural Strength, (N)

Flexural Strength (N), min. 150N requirment.

Composite Loss Factor, min. 0.1 requirement

EXAMPLE III

Low Expandable version (with 7628 type Glass fiber)

Material Low Expandable version (with 7628 type Glass fiber): 90-120 % Expansion range Thickness 1.95 - 2.05 mm patch material thickness alone.

Test Flexural Strength (N) at RT,

Acoustic efficiency, Oberst (SAE J 1637, 3.0 kg/m2, 200Hz, composite loss factor)

Substrate 60E(0.75mm), CRS(0.75mm) & AL 6022(0.9mm thickness) (l"x 6" size panel)

Oil Ferrocote 6130 oil

Bake cycle Low Bake - 171°C/10 min. (Metal temp.)

High Bake - 205°C/30 min. (Metal temp.)

Composite Loss Factor, 3.0kgm2, 200Hz Expansion, %

Flexural Strength, (N)

Flexural Strength (N), min. 150N requirment.

Composite Loss Factor, min. 0.1 requirement

Expansion range 90 - 120 %

EXAMPLE IV

High Expandable version (with 7628 type Glass fiber)

Material High Expandable version (with 7628 type Glass fiber): 130 - 2B0 % Expansion range Thickness 1.95 - 2.05 mm patch material thickness alone.

Test Flexural Strength (N) at RT,

Acoustic efficiency, Oberst (SAE J 1637, 3.0 kg/m2, 200Hz, composite loss factor)

Substrate 60E(0.75mm), CRS(0.75mm) & AL 6022(0.9mm thickness) (l"x 6" size panel)

Oil Ferrocote 6130 oil

Bake cycle Low Bake - 171°C/10 min. (Metal temp.)

High Bake - 205°C/30 min. (Metal temp.)

Composite Loss Factor, 3.0kgm2, 200Hz Expansion, %

Flexural Strength, (N)

Flexural Strength (N), min. 150N requirment.

Composite Loss Factor, min. 0.1 requirement

Expansion range 120 - 230 %

[0046] While certain embodiments have been illustrated and described, it should be understood that changes and modifications can be made therein in accordance with ordinary skill in the art without departing from the technology in its broader aspects as defined in the following claims.

[0047] The embodiments, illustratively described herein may suitably be practiced in the absence of any element or elements, limitation or limitations, not specifically disclosed herein. Thus, for example, the terms "comprising," "including," "containing," etcetera shall be read expansively and without limitation. Additionally, the terms and expressions employed herein have been used as terms of description and not of limitation, and there is no intention in the use of such terms and expressions of excluding any equivalents of the features shown and described or portions thereof, but it is recognized that various modifications are possible within the scope of the claimed technology. Additionally, the phrase "consisting essentially of" will be understood to include those elements specifically recited and those additional elements that do not materially affect the basic and novel characteristics of the claimed technology. The phrase "consisting of" excludes any element not specified.

[0048] The present disclosure is not to be limited in terms of the particular embodiments described in this application. Many modifications and variations can be made without departing from its spirit and scope, as will be apparent to those skilled in the art. Functionally equivalent methods and compositions within the scope of the disclosure, in addition to those enumerated herein, will be apparent to those skilled in the art from the foregoing descriptions. Such modifications and variations are intended to fall within the scope of the appended claims. The present disclosure is to be limited only by the terms of the appended claims, along with the full scope of equivalents to which such claims are entitled. It is to be understood that this disclosure is not limited to particular methods, reagents, compounds compositions or biological systems, which can of course vary. It is also to be understood that the terminology used herein is for the purpose of describing particular embodiments only, and is not intended to be limiting.

[0049] In addition, where features or aspects of the disclosure are described in terms of Markush groups, those skilled in the art will recognize that the disclosure is also thereby described in terms of any individual member or subgroup of members of the Markush group. [0050] As will be understood by one skilled in the art, for any and all purposes, particularly in terms of providing a written description, all ranges disclosed herein also encompass any and all possible subranges and combinations of subranges thereof. Any listed range can be easily recognized as sufficiently describing and enabling the same range being broken down into at least equal halves, thirds, quarters, fifths, tenths, etcetera. As a non-limiting example, each range discussed herein can be readily broken down into a lower third, middle third and upper third, etcetera. As will also be understood by one skilled in the art all language such as "up to," "at least," "greater than," "less than," and the like, include the number recited and refer to ranges which can be subsequently broken down into subranges as discussed above. Finally, as will be understood by one skilled in the art, a range includes each individual member.

[0051] All publications, patent applications, issued patents, and other documents referred to in this specification are herein incorporated by reference as if each individual publication, patent application, issued patent, or other document was specifically and individually indicated to be incorporated by reference in its entirety. Definitions that are contained in text incorporated by reference are excluded to the extent that they contradict definitions in this disclosure.

[0052] Other embodiments are set forth in the following claims.