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WO2025240130A1 - Agent de liaison de caoutchouc au métal à base d'eau présentant une résistance améliorée pré-cuisson - Google Patents

Agent de liaison de caoutchouc au métal à base d'eau présentant une résistance améliorée pré-cuisson

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Publication number
WO2025240130A1
WO2025240130A1 PCT/US2025/027279 US2025027279W WO2025240130A1 WO 2025240130 A1 WO2025240130 A1 WO 2025240130A1 US 2025027279 W US2025027279 W US 2025027279W WO 2025240130 A1 WO2025240130 A1 WO 2025240130A1
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WO
WIPO (PCT)
Prior art keywords
bonding agent
agent formulation
tellurium
sulfur
mixture
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
PCT/US2025/027279
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English (en)
Inventor
Stefan Dehnicke
Philipp ZUTAVERN
Kai Ziegler
Annika Katrin HARLOFF
Nico FUNKEN
Roger CASSELL
Dean Edward Hoy
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DDP Specialty Electronic Materials US LLC
Original Assignee
DDP Specialty Electronic Materials US LLC
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Publication date
Application filed by DDP Specialty Electronic Materials US LLC filed Critical DDP Specialty Electronic Materials US LLC
Publication of WO2025240130A1 publication Critical patent/WO2025240130A1/fr
Pending legal-status Critical Current
Anticipated expiration legal-status Critical

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/26—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers modified by chemical after-treatment
    • C08L23/32—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers modified by chemical after-treatment by reaction with compounds containing phosphorus or sulfur
    • C08L23/34—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers modified by chemical after-treatment by reaction with compounds containing phosphorus or sulfur by chlorosulfonation
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/04—Non-macromolecular additives inorganic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/06—Non-macromolecular additives organic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J123/00—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers
    • C09J123/26—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers modified by chemical after-treatment
    • C09J123/32—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers modified by chemical after-treatment by reaction with compounds containing phosphorus or sulfur
    • C09J123/34—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers modified by chemical after-treatment by reaction with compounds containing phosphorus or sulfur by chlorosulfonation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2296—Oxides; Hydroxides of metals of zinc
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/32—Phosphorus-containing compounds
    • C08K2003/321—Phosphates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/08—Metals

Definitions

  • a key feature of a bonding agent in this type of application is its ability to withstand high temperature treatment without losing significant bonding capability towards the iirbber. This feature is commonly referred to as the “prebake resistance.”
  • the prebake resistance at a given temperature is measured in minutes and evaluated by storing bonding agent coated metal parts in a vulcanization mold or an oven, followed by the covulcanization with the selected rubber stock.
  • Current commercially available standard bonding agents of the Cover 1-type typically show a prebake resistance at 150°C of about 8-12 minutes and 5-8 minutes at 160°C.
  • a further increase of the vulcanization temperature to 170°C results in 1-4 minutes prebake resistance when subsequently co-vulcanized with conventional sulfur cured natural rubber (NR) formulations.
  • NR sulfur cured natural rubber
  • This mill base is then mixed with latex systems based on chloro-sulfonated- poly-ethylene polymers (CSM) and brominated di-chloro-butadiene polymer (Br-DCB) to form a stable waler based bonding agent formulation.
  • CSM chloro-sulfonated- poly-ethylene polymers
  • Br-DCB brominated di-chloro-butadiene polymer
  • the best results were obtained with each of sulfur and tellurium in approximately equal weight amount and each present in a range of 1 to 7 wt.% of the total weight of the bonding agent formulation.
  • Formulations containing sulfur or tellurium alone are also rubber to metal bonding agents, but do not show a significant impact on the pre-bake resistance of the formulation.
  • the present invention relates to a novel bonding agent formulation containing A) at least one film forming polymer; B) at least one of polynitroso based cross linker and a bismaleimid based cross linker; C) a carrier liquid; D) at least one surfactant; E) a filler and an anti-corrosion pigment; and F) a vulcanizing additive comprising a mixture of sulfur and tellurium or a mixture of selenium and tellurium.
  • the present invention provides a water based aqueous bonding agent formulation that typically includes A) at least one film forming polymer such as latex; B) at least one or both of polynitroso based cross linker and a bismaleimid based cross linker; C) carrier liquid; D) at least one surfactant; E) fillers and anti-corrosion pigments; and F) a vulcanizing additive comprising a mixture of sulfur and tellurium, or a mixture of sulfur, selenium and tellurium.
  • A. The film forming polymer
  • the bonding agent formulation of the present invention comprises a film forming polymer.
  • the film-forming polymer is a polymer tha t forms a film when a layer of that polymer is applied to a substrate dispersed or dissolved within the carrier fluid.
  • a layer of either a polymer solution in organic solvent or a waterborne composition containing a dispersed polymer is applied to a substrate, and the carrier fluid is removed, for example, by drying either at room temperature (25°C) or at elevated temperature (i.e., above 25°C, usually 100°C or lower).
  • the film forming polymer also generally has at least one group that may react with the niiroso group such as a carbon-carbon double bond.
  • suitable polymers which may be used alone or in combination, include an olefin polymer which may be substituted or unsubstituted or a mixture thereof.
  • Olefin polymers also called polyolefins, include polymers based on monomer molecules that are unsaturated aliphatic hydrocarbons containing one double bond per molecule. Examples of such olefin polymers are polyethylene, polypropylene, polyisobutene, polybut- 1 -ene, poly- 4-methylpent-l-ene, and the various copolymers thereof.
  • polymers based on natural rubber and polymers based on synthetic rubber such as for example polyisoprene: polybutadiene; polymers of adducts of butadiene and cyclic conjugated dienes; copolymers of butadiene and styrene; copolymers of ethylene, propylene, and dienes; copolymers of acrylonitrile and butadiene; and the various copolymers thereof.
  • polymers described above that also include one or more multi-functional monomers to provide crosslinking.
  • the polyolefin may be halogenated.
  • Halogenated polyolefins may have structures that are the same as those of unsubstituted polyolefins except that halogen atoms replace one or more of the hydrogen atoms.
  • the halogens may be chlorine, bromine, fluorine, or a mixture thereof.
  • the preferred halogens are chlorine, bromine, and mixtures thereof.
  • the amount of halogen ranges from 3 to 70 percent by weight of the polymer.
  • the halogenated polyolefin desirably may be a substituted polydiene polymer (i.e., a polymer that has the structure of a polydiene polymer in halogen atoms are substituted for some hydrogen atoms).
  • Suitable poly diene polymers include, for example, polybutadiene, polyisoprene, and mixtures thereof. Some suitable polydiene polymers have no monomer units that are not residues of diene molecules.
  • every' halogenated olefin polymer in the bonding agent formulation is a substituted polydiene polymer in which no monomer units are other than resi dues of diene molecules.
  • the halogenated polyolefin may be substituted with bromine, which is a halogenated olefin polymer in which at least one halogen is bromine.
  • a bromine substituted olefin polymer may or may not contain atoms of halogens other than bromine.
  • Another halogenated polyolefin may be substituted with chlorine, which is a halogenated olefin polymer in which at least one halogen is chlorine.
  • a chlorine substituted polyolefin may or may not contain atoms of halogens other than chlorine.
  • One specific type of chlorine substituted olefin polymer is chlorinated polyolefin, which is an olefin polymer in which all the substituents are chlorine.
  • One useful chlorinated polyolefin is chlorinated polyethylene (CPE).
  • a usefid halogenated polyolefin is a mixed-halogen polyolefin, which is a halogenated polyolefin that has two or more different types of halogen atoms.
  • a mixed-halogen substituted olefin polymer is used that has chlorine and bromine.
  • One suitable mixed-halogen substituted olefin polymer for example, is brominated polydichlorobutadiene ("BPDCD").
  • At least one halogenated polyolefin is used that has no substituent on the olefin polymer selected from nitrile, carboxyl, carboxylate ester, ether, peroxyester, or combination thereof. In some embodiments, every halogenated olefin polymer has no substituent on the olefin polymer selected from nitrile, carboxyl, carboxylate ester, ether, peroxyester, or combination thereof. In some embodiments, at least one halogenated olefin polymer is used that has no substituent on the olefin polymer other than halogen. In some embodiments, every halogenated olefin polymer in the bonding agent formulation has no substituent on the olefin polymer other than halogen.
  • halosulfonated polyolefin which is a polymer that has the structure of unsubstituted olefin polymer in which some hydrogen atoms are replaced by halogen atoms and in which some other hydrogen atoms are replaced by sulfonyl halide groups, which have the chemical formula SOX.
  • X is a halogen atom.
  • the halogens in the sulfonyl halide groups may be chlorine, bromine, fluorine, or a mixture thereof. In some embodiments, the halogens in the sulfonyl halide groups are chlorine, bromine, or a mixture thereof.
  • the halogen in the sulfonyl halide groups is chlorine. In some embodiments, every halogen in every sulfonyl halide group of every halosulfonated olefin polymer is either chlorine or bromine. In some embodiments, every halogen in every sulfonyl halide group of every halosulfonated olefin polymer in the bonding agent formulation is chlorine.
  • the film forming polymer is one selected from a chlorosulfonated polyolefin, a brominated polydichlorobutadiene, or a chlorinated polyisoprene.
  • two different film forming polymers selected from a chlorosulfonated polyolefin, a brominated polydichlorobutadiene, or a chlorinated polyisoprene are used.
  • one latex polymer may be a chlorosulfonated polyolefin latex and the other may be abrominated 2,3 dichorlobutadiene.
  • the amounts of film-forming polymer(s) used in the present bonding agent formulation can be from 2 wt.% to 75 wt.%, preferably from 5 wt.% to 60 wt.%, and most preferably from 10 wt.% to 40 wt.%, based on the total weight of the aqueous bonding agent formulation.
  • cross-linkers play a major role in bonding rubber to metals. Typically, these cross-linkers combine various film forming polymers with other components such as pigments, such as carbon black and or metal oxides that are dispersed in organic solvents or in water with surfactants.
  • a substrate e.g., metal
  • rubber is then applied and covulcanized with the bonding agent formulation. During vulcanization, one substrate is bonded to another substrate through the co-vu!canized bonding agent formulation. Because the bonding agent formulation acts to adhere the rubber and the metal substrate, it is also sometime referred to as adhesive composition.
  • poly-( 1 ,4-phenyleneazine N,N-dioxide) referred to herein as “p-PDNB” or
  • paradinitrosobenzene is used as one of cross-linkers for rubber.
  • Paradinitrosobenzene or its nuclearly substituted derivatives such as those described in US Pat. No. 3,258,388 when describing poly-c-nitroso aromatic compounds have been used in many commercially available bonding agent formulations for bonding natural rubbers to metal.
  • a polynitroso compound is an aromatic hydrocarbon containing at least two nitroso groups attached directly to non-adjacent. nuclear carbon atoms.
  • "Nuclear" carbon atom is a carbon atom that is part of an aromatic ring. Suitable aromatic compounds may have 1 to 3 aromatic nuclei, including fused aromatic nuclei.
  • Suitable polynitroso compounds may have 2 to 6 nitroso groups attached directly to non-adjacent nuclear carbon atoms. Also included in the class of polynitroso compounds are the substituted polynitroso compounds, in which one or more hydrogen atoms attached to nuclear carbon atoms are replaced by organic or inorganic substituent groups, such as for example alkyl, alkoxy, cycloalkyd, aryl, aralkyl, alkaryl, arylamine, arylnitroso, amino, and halogen.
  • a composition of the present invention contains one or more polynitroso compounds with 2 nitroso groups.
  • some suitable polynitroso compounds have the chemical formula R m -Ar-(NO)2, where Ar is phenylene or naphthalene; R is a monovalent organic radical having 1 to 20 carbon atoms, an amino group, or a halogen; and m is 0, 1, 2, 3, or 4. If m is greater than 1, the R groups may be the same or different from each other.
  • R is, in some embodiments, an alkyl, cycloalkyl, aryl, aralkyl, alkaryl, arylamine, or alkoxy radical w ith 1 to 20 carbon atoms; or R can be, in some embodiments, an alkyl group with 1 to 8 carbon atoms. In some embodiments, however, the value of m is zero.
  • Suitable pol vnilroso compounds are m-dinitrosobenzene; p- dinitrosobenzene; m-dinitrosonaphthalene; p-dinitrosonaphthalene; 2,5-dinitroso-p- cymene; 2 -methyl- 1 ,4-dinitrosobenzene; 2 -methyl-5-chloro- 1,4-dinitrosobenzene; 2- fluoro- 1,4-dinitrosobenzene; 2-methoxy-l,3-dinitrosobenzene; 2-benzyl-l,4- dinitrosobenzene; 2-cycfehexyl-l,4,-dinitrosobenzene; and mixtures thereof.
  • the one or more polynitroso compound used is selected from dinitrosobenzenes, substituted dinitrosobenzenes, dinitrosonaphthalenes, substituted dinitrosonaphthalenes, the polymeric form of p-dinitroso-benzene, the polymeric form of 1,4-dinitrosonaphthalene, polymeric form of 1,4-dinitrosobenzene, and mixtures thereof.
  • the polynitroso cross-linker can be present in the bonding agent formulation in an amount of 1 wt.% to 15 wt.%, preferably 3 wt.% to 12 wt.%, and more preferably 5 wt.% to 10 wt.%, and most preferably 6 wt.% to 9 wt.%, all based on the total weight of the bonding agent formulation.
  • the preferred embodiments of the present invention also include a second or a co cross-linker that is bismaleimide-containing monomers or polymers.
  • a bismaleimide-containing monomer or polymer can be a bismaleimide-containing monomer having the following chemical Formula (I): Formula (I) wherein R, in tire above Formula (II), can be alkyl, aryl, mixed alkyl-aryl hydrocarbons, or one or more maleimide units.
  • Suitable one or more bismaleimide-containing monomers include, for example, N,N’-ethylene-bismaleimide, N,N'-hexamethyiene-bismaleimide, N,N'-meta-phenylene-bismaleimide, N,N'-para-phenylene-bismaleimide, N,N'-4,4'- biphenylene-bismaleimide, N,hT-4,4'-diphenylmethane-bisnialeimide, N,N'-4,4’-(diphenyl ether)-bismaleimide, N,N' -4, 4' -(diphenyl sulfide)-bismaieimide, N,N'-m- phenylenebismaleimide, 4,4'-diphenylmethanebismaleimide, N,N'-(4-methyl-m-phenylene)- bismaleimide, polyphenylmethane bisnialeimide, N,N'-4,4'-dipheny
  • the bismaleimide-containing monomers or polymers can be present in the aqueous bonding agent formulation in an amount of 0 wt.% to 15 wt.%, preferably 0.5 wt.% to 5 wt.%, and more preferably 0.75 wt.% to 3 wt.%, and most preferably 1 wt.% to 2 wt.%, all based on the total weight of the aqueous bonding agent formulation.
  • the carrier liquid facilitates the formation of a coating of the bonding agent formulation on the unvulcanizable rubber, or other substrate.
  • the carrier liquid may be an organic solvent or water.
  • the carrier liquid may solubilize one or more of the components in the bonding agent formulation, for example, it is generally desirable for the film forming polymer to be dissolved whereas the p-PDNB may be particulates dispersed therein.
  • suitable organic solvents include aromatic hydrocarbons, such as benzene, toluene, xylene and the like, and the chlorinated aromatic hydrocarbons such as monochlorobenzene, dichlorobenzene and the like.
  • Aliphatic hydrocarbons, chlorinated aliphatic hydrocarbons, ethers and/or alcohols may be used in small amounts (less than 10% by volume) of the carrier liquid such as those organic solvents or water.
  • the carrier liquid such as those organic solvents or water.
  • water or Di-water is used as the earner liquid.
  • the bonding agent formulation of the present invention typically contains 10 wt.% to 70 wt.%, preferably 20 w.% to 60 wt.%, more preferably 30 wt.% to 55 wt.%, and most preferably 40 to 50 wt.% of the carrier liquid based on the total weight of the bonding agent formulation.
  • the bonding agent formulation of the present invention contains surfactants to disperse one or more components of the formulation and are particularly useful when w'ater is the carrier liquid.
  • the surfactant may be an amphoteric, anionic, cationic, anionic or nonionic surfactant.
  • the surfactan t is anionic, nonionic or mixture of these.
  • nonionic surfactants are alkoxylates, copolymers of ethylene oxide and propylene oxide, and mixtures thereof.
  • suitable alkoxylates are ethoxylates.
  • One suitable nonionic surfactant is nonylphenol ethoxylate.
  • the nonionic surfactant is an ethoylated fatty alcohol.
  • a fatty alcohol polyalkylene glycol ether is used together with ethoylated fatty alcohol.
  • nonionic surfactant some suitable amounts of nonionic surfactant are, for example, 3 PHR or more: or 5 PHR or more; or 8 PHR or more. Independently, among embodiments in which nonionic surfactant is used, some suitable amounts of nonionic surfactant are, for example, 30 PHR or less; or 20 PHR or less; or 15 PHR or less.
  • PHR means 100 times the ratio of the weight of that ingredient to the sum of the weights of all film-forming polymers in the bonding agent formulation. The weights are dry weights not including any weight of the carrier liquid.
  • the bonding agent formulation contains one or more anionic surfactants.
  • anionic surfactant some suitable amounts of anionic surfactant are, for example, 3 PHR or more; or 5 PHR or more; or 8 PHR or more.
  • some suitable amounts of anionic surfactant are, for example, 30 PHR or less; or 20 PHR or less; or 15 PHR or less.
  • the amount of anionic sur factant in the formulation of the present invention is 0.1 PHR or less; or 0.01 PHR or less. In some embodiments, no anionic surfactant is present.
  • the bonding agent formulation of the presen t invention may contain other components such as fillers known in the rubber art including, for example, carbon black, fumed silica, clay and other inorganic particulates.
  • the formulation may also contain an anti-corrosion pigment such as lead oxide, zinc phosphate, zinc oxide, molybdate modified zinc oxide.
  • the amounts of fillers and anti-corrosion pigments, when present, may be present in an amount of 1 wt.% to 10 wt.%, preferably 2 wt. % to 9 wt.%, more preferably 3 wt.% to 8 wt.%, and most preferably 5 wt.% to 7 wt.%, all based on the total weight of the bonding agent formulation.
  • the bonding agent formulation of the present invention comprises at least one vulcanizing additive to aid the process of vulcanization of rubbers.
  • vulcanizing additive include, for example, sulfur, a thiuram polysulfide compound such as tetramethyl-thiuram disulfide and dipentamethylenethiuram tetrasulfide; 4,4-dithiomorpholine; p-quinonedioxime; p,p '-dibenzoquinone dioxime; cyclic sulfur imide; a peroxide, and mixtures thereof.
  • bonding agent formulations that include one or more of these commonly used vulcanizing additives would not achieve the desired prebake resistance characteristics of a minimum of 20 minutes at 170°C. It was surprising to discover that adding tellurium, or a combination of selenium and tellurium, in addition to a common vulcanizing additive enables the desired prebake resistance property of the bonding agent formulation.
  • the combination use of sulfur and tellurium, or the mixture of selenium and tellurium should be present in the bonding agent formulation in the amounts between 1 wt.% to 7 wt.%, preferably between 1 .5 wt.% to 5 wt.%, more preferably between 2 wt.% to 4 wt.%, and most preferably between 2.5 wt.% to 3.5 wt.%, all based on the total weight of the bonding agent formulation.
  • weight ratio of sulfur to tellurium to kept in the bonding agent formulation at 2: 1 to 1:2, preferably at 1.5:1 to 1 :1.5 and more preferably around 1: 1.
  • the use of tellurium can be replaced with equal weight amount of a mixture of selenium and tellurium.
  • the weight ratio between selenium and tellurium is typically 2: 1 to 1 :2, preferably at 1.5:1 to 1:1.5 and more preferably around 1 :1.
  • the present bonding agent formulation is used to bonding any substrate desired to be bonded to rubber.
  • the substrate may be a synthetic or natural fabric; organic plastics such as polyolefins, polycarbonates, polyamides, polyimides and polyesters ceramics including inorganic glass; wood; and metal.
  • organic plastics such as polyolefins, polycarbonates, polyamides, polyimides and polyesters ceramics including inorganic glass; wood; and metal.
  • the metal or ceramic may be any typically used in the production of automobiles, trains, busses, trucks and airplanes.
  • ferrous based metals and alloys including steels, aluminum and alloys of aluminum, and magnesium and alloys of magnesium.
  • the rubber to be bonded to the substrate may be any rubber such as those known in the art.
  • the rubber may be any of the natural rubbers and olefinic synthetic rubbers including, for example, polychloroprene, polybutadiene, neoprene, butyl rubber, and halogenated butyl rubber.
  • the bonding agent formulation is particularly useful in bonding natural rubber or rubbers comprised of natural or synthetic natural rubber, which may have other additives usefill in vulcanizing the rubber described below.
  • the bonding agent formulation of the present invention may be applied to the substrate, unvulcanized rubber or both by any suitable means such as spraying, dipping or brushing.
  • Tire carrier liquid is then removed by any suitable method such as drying, which may be at ambient conditions or heated to a temperature below where the bonding agent formulation will react ( vulcanize). Typical temperatures may be from about 25°C to 100°C. Any suitable time may be used and maybe a few minutes to several days. To facilitate quicker drying, a vacuum or a flowing atmosphere may be used.
  • the interposing of the bonding agent between the substrate and unvulcanized rubber may occur any time after applying the coating of the bonding agent.
  • the method of interposing may be any suitable such that there is contact with both the substrate and rubber such that the coating interposed between them, which may be in direct contact or through one or more primer layers that may be optionally employed.
  • Any primer layer, if employed, may be any suitable one such as those known in the art.
  • the assemblage of the substrate, rubber and interposed bonding agent is then heated to a temperature for a time to vulcanize the rubber and bonding agent formulation thereby bonding the rubber to the substrate.
  • the temperature may' be any' suitable temperature depending on the rubber being used and desired properties.
  • the time may be any' suitable time depending on the rubber used and desired properties.
  • An applied pressure may also be employed as desired.
  • typical temperatures for vulcanization are from 120°C or 140°C to 200°C or 250 c C.
  • the time at temperature may be for 2 or 3 seconds or several days depending on any particular applications and tends to depend on the size of the particular assemblage.
  • All four bonding agent examples show, as presented m Table 6, good to excellent bonding performance in the initial vulcanization experiment at 170°C, without any prebaking.
  • the average tensile strength or Bond Force was in tire range from 10.5 to 12.0 MPa. These high forces correlate with superior fraction pattern of 100% rubber retention on the metal surface. Applying 10 minutes at 170°C heat in an oven prior to the vulcanization shows first impact on the bonding behavior.
  • the results are given with Table 7.
  • the observed bond strength was in the range from 7.3 to 12.3 MPa.
  • a first differentiation in bonding performance was observed in that Examples 1 and 4 dropped in bond strength and fraction pattern, whereas the Examples 2 and 3 withstand the heat treatment very well.
  • Example 2 The heat treatment at 170°C for 20 minutes underlines the superior prebake resistance of the bonding agent formulation with equal amounts tellurium and sulfur as shown with Example 2. The best performance with 12.5 MPa bond strength and still 100% rubber retention were achieved. Similar' results were observed with Example 3. The equal mixture of the two metals, selenium and tellurium, mixed with an equal amount of sulfur provided an excellent performance with 10.0 MPa bond strength. The fraction pattern showed significant spread of measured values from 5-100% break in the rubber stock. These results indicated a lower reactivity driven by the lower amount of the selected metals in combination with sulfur than what was observed with the Example 2.
  • Example 2 compared well with Example 3 with a 50% higher dosage of the performance driving metal sulfur mixture and underlined the synergetic interaction thereof.
  • Examples 1 and 4 showed low bond strength values from 4.4 to 5.2 MPa only, accompanied with 95% RC failure confirming that the tellurium alone does not impact the prebake resistance.
  • Examples 2 and 3 performed almost equally up to 20 minutes heat exposure at 170°C.
  • the bond strength values in the range of 10 to 12.5 MPa were observed in combination with excellent rubber retention.
  • the examples with equal amounts of both tellurium and sulfur in a range from 0.5 to 1.5% work well, the 1.5% dosage becomes more sustainable.
  • the bond agent formulations with the lowest equal concentration of tellurium and sulfur already performed well. Therefore, the present invention demonstrates the synergetic interaction of tellurium and sulfur. It also demonstrated that a mixture of tellurium, selenium and sulfur can strongly improve the prebake resistance when applied in equal amounts of the reactants.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Adhesives Or Adhesive Processes (AREA)

Abstract

L'invention concerne une nouvelle formulation d'agent de liaison pour permettre d'améliorer les caractéristiques pré-cuisson d'une liaison de caoutchouc au métal et son procédé de fabrication et d'utilisation.
PCT/US2025/027279 2024-05-15 2025-05-01 Agent de liaison de caoutchouc au métal à base d'eau présentant une résistance améliorée pré-cuisson Pending WO2025240130A1 (fr)

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US202463647879P 2024-05-15 2024-05-15
US63/647,879 2024-05-15

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WO2025240130A1 true WO2025240130A1 (fr) 2025-11-20

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PCT/US2025/027279 Pending WO2025240130A1 (fr) 2024-05-15 2025-05-01 Agent de liaison de caoutchouc au métal à base d'eau présentant une résistance améliorée pré-cuisson

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5128403A (en) * 1991-04-10 1992-07-07 Lord Corporation High-temperature adhesive compositions
US20060105178A1 (en) * 2004-11-12 2006-05-18 Roitman Lipa L Materials for bonding elastomer
CN103627348A (zh) * 2013-11-07 2014-03-12 贾梦虹 硫化橡胶或热塑性橡胶与金属粘合剂
CN103074009B (zh) * 2013-01-24 2015-01-07 上海普力通新材料科技有限公司 弹性体与金属粘接用粘接促进剂及其粘合剂组合物
WO2019209418A1 (fr) * 2018-04-23 2019-10-31 Dow Global Technologies Llc Composition adhésive monocouche à base d'eau

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5128403A (en) * 1991-04-10 1992-07-07 Lord Corporation High-temperature adhesive compositions
US20060105178A1 (en) * 2004-11-12 2006-05-18 Roitman Lipa L Materials for bonding elastomer
CN103074009B (zh) * 2013-01-24 2015-01-07 上海普力通新材料科技有限公司 弹性体与金属粘接用粘接促进剂及其粘合剂组合物
CN103627348A (zh) * 2013-11-07 2014-03-12 贾梦虹 硫化橡胶或热塑性橡胶与金属粘合剂
WO2019209418A1 (fr) * 2018-04-23 2019-10-31 Dow Global Technologies Llc Composition adhésive monocouche à base d'eau

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