WO2003033613A1 - Adhesifs sans danger pour l'environnement destines au collage de caoutchouc vulcanise - Google Patents

Adhesifs sans danger pour l'environnement destines au collage de caoutchouc vulcanise Download PDF

Info

Publication number
WO2003033613A1
WO2003033613A1 PCT/US2002/033362 US0233362W WO03033613A1 WO 2003033613 A1 WO2003033613 A1 WO 2003033613A1 US 0233362 W US0233362 W US 0233362W WO 03033613 A1 WO03033613 A1 WO 03033613A1
Authority
WO
WIPO (PCT)
Prior art keywords
phr
parts
adhesive composition
halogen
compound
Prior art date
Application number
PCT/US2002/033362
Other languages
English (en)
Inventor
Christian C. Green
Douglas H. Mowrey
Original Assignee
Lord Corporation
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Priority claimed from US10/222,545 external-priority patent/US20040033374A1/en
Application filed by Lord Corporation filed Critical Lord Corporation
Priority to CA2462612A priority Critical patent/CA2462612C/fr
Priority to MXPA04003502A priority patent/MXPA04003502A/es
Publication of WO2003033613A1 publication Critical patent/WO2003033613A1/fr

Links

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
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/10—Homopolymers or copolymers of propene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L15/00—Compositions of rubber derivatives
    • C08L15/02—Rubber derivatives containing halogen
    • 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
    • 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
    • C09J123/28—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 halogens or compounds containing halogen
    • 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
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/08—Copolymers of ethene
    • C08L23/0846—Copolymers of ethene with unsaturated hydrocarbons containing other atoms than carbon or hydrogen atoms
    • C08L23/0892—Copolymers of ethene with unsaturated hydrocarbons containing other atoms than carbon or hydrogen atoms containing monomers with other atoms than carbon, hydrogen or oxygen atoms
    • 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
    • C08L23/28—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 halogens or compounds containing halogen
    • 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
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2312/00—Crosslinking
    • C08L2312/08—Crosslinking by silane
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
    • C08L2666/02—Organic macromolecular compounds, natural resins, waxes or and bituminous materials
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L51/06—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L61/00—Compositions of condensation polymers of aldehydes or ketones; Compositions of derivatives of such polymers
    • C08L61/04—Condensation polymers of aldehydes or ketones with phenols only
    • C08L61/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons

Definitions

  • the invention relates to formulated adhesives applied to bond rubber to substrates like metal, during the vulcanization process which generally contain a crosslinking agent and one or more halogenated polymers/film formers, characterized by low levels of lead compounds.
  • Bonding of rubber vulcanizates to substrates, especially metal is conventionally obtained by two-coat primer-overcoat adhesive systems or one-coat primerless systems.
  • adhesive compositions must exhibit excellent bonding as retention of rubber on the substrate after bond destruction, adequate sweep resistance i.e., ability of the uncured adhesive coating on the substrate to remain undisturbed against the force of injected green rubber into the mold cavity, good storage stability of the wet adliesive and durable adhesion under extreme environmental conditions, typically measured by the hot tear test (ASTM D-429) boiling water and salt spray tests (ASTM B-l 17-97, for example).
  • U.S. Pat. No. 3,640,941 describes a one-coat rubber-to -metal adhesive containing four essential ingredients: (a) a graft polymer of a polybutadiene and a substituted cyclopentadiene monomer, (b) dibasic lead phosphite, (c) resorcinol and (d) a volatile solvent.
  • a graft polymer of a polybutadiene and a substituted cyclopentadiene monomer (b) dibasic lead phosphite, (c) resorcinol and (d) a volatile solvent.
  • this adhesive system between 25-150 parts by weight of dibasic lead phosphate per 100 parts of polymer is described as necessary to achieve the desired performance.
  • U.S. Pat. No. 4,119,587 discloses a one-coat adliesive composition comprised of the three essential constituents: (a) halogenated polyolefinic, (b) aromatic nitroso compound, and (c) lead salts.
  • U.S. Pat. No 5, 268,404 discloses adhesives comprising a halogenated polyolefm, an aromatic nitroso compound, metal oxide such as zinc oxide or magnesium oxide, and optionally a vulcanizing agent such as sulfur or selenium, a phenolic epoxy resin, or carbon black.
  • Lead compounds useful as additive in RTM adhesives provide either an acid scavenging feature and/or corrosion resistance in conjunction with halogenated polymers. Due to the increasing demand from both government and industry to use adhesive materials that do not contain bio-accumulative ingredients. Conventional rubber-to-metal adhesives have required effective amounts of lead compounds and selenium to provide essential resistance to heat and corrosion. It would be desirable to provide adhesives for bonding of rubber to metal during the vulcanization processes that contain less than 1000 ppm of undesirable ingredients such as lead and selenium-containing compounds while at the same time providing comparable heat and corrosion resistance.
  • a general object of the invention is to provide adhesive compositions containing no more than about 1000 ppm of lead that can bond vulcanized elastomers to rigid substrates, especially metal that provide durable, rubber tearing primary adhesive bonds after exposure to harsh conditions.
  • the adhesives exhibit excellent bond versatility, sweep resistance, and in-can storage stability.
  • the adhesive compositions of the present invention consist essentially of less than 1000 ppm of lead, at least one solvent, a halogenated polyolefm, a nitroso compound or brominated dichlorobutadiene, zinc phosphate and optional maleimide compound.
  • rubber-to-metal adhesive system containing less than about 1000 ppm of lead and consisting essentially of chlorosulfonated polyethylene and/or chlorinated natural rubber, a poly-C-nitroso compound or brominated dichlorobutadiene polymer, carbon black, silica, zinc phosphate, and at least one component selected from the group consisting of a polyisocyanate, epoxy resin, and a maleimide compound.
  • rubber-to-metal adhesive system containing less than about 1000 ppm of lead and consisting essentially of chlorosulfonated polyethylene and chlorinated natural rubber, a poly-C-nitroso compound, carbon black, silica, zinc phosphate, and at least one component selected from the group consisting of a polyisocyanate, epoxy resin and a maleimide compound.
  • rubber-to-metal adhesive system containing less than about 1000 ppm of lead and consisting essentially of chlorosulfonated polyethylene and chlorinated natural rubber, brominated dichlorobutadiene polymer, carbon black, silica, zinc phosphate and at least one component selected from the group consisting of a polyisocyanate, epoxy resin and/or a maleimide compound.
  • the adliesive comprises
  • At least one halogen-containing polyolefm preferably selected from the group consisting of chlorinated natural rubber and chlorosulfonated polyethylene;
  • an inert water or organic solvent diluent said diluent being present in an amount to provide a liquid composition suitable for use as an adhesive, said liquid adhesive having a total solids content in the range from about 5 to about 80 percent.
  • the adhesive compositions of the invention are characterized by the unexpected ability to provide strong vulcanized rubber-to-substrate bonds with durability and environmental resistance without the need for priming the substrate surface, However, they can be used with convention substrate primer compositions if one so desires.
  • the compositions provide excellent adhesion for both unvulcanized and vulcanized elastomer compositions, without the need to chlorinate the rubber surface.
  • the compositions of the invention exhibit excellent shelf-life stability, resistance to in-mold sweep, provide ample pre-bake resistance, good layover characteristics, and are effective over a broad spectrum of bonding temperatures, e.g., from about 90° C. to over 180° C.
  • the vulcanizable rubber substrates bonded by the invention are comprised of vulcanizable rubbers. These rubbers are formulated in numerous recipes, widely available and beyond the scope of this disclosure. Examples of the synthetic rubber used as vulcanizable rubber herein include the following.
  • Homopolymers of conjugated diene compound such as isoprene, butadiene, and chloroprene.
  • Examples include polyisoprene rubber (LR), polybutadiene rubber (BR), and polychloroprene rubber.
  • Copolymers of said conjugated diene compound with a vinyl compound such as styrene, acrylonitrile, vinylpyridine, acrylic acid, methacrylic acid, alkyl acrylate, and alkyl methacrylate.
  • a vinyl compound such as styrene, acrylonitrile, vinylpyridine, acrylic acid, methacrylic acid, alkyl acrylate, and alkyl methacrylate.
  • SBR styrene-butadiene copolymer rubber
  • vinylpyridine butadiene styrene copolymer rubber acrylonitrile butadiene copolymer rubber, acrylic acid butadiene copolymer rubber, methacrylic acid butadiene copolymer rubber, methyl acrylate butadiene copolymer rubber, and methyl methacrylate butadiene copolymer rubber.
  • olefin such as ethylene, propylene, and isobutylene
  • HR isobuty
  • EPDM Copolymers of olefin with non-conjugated diene.
  • examples include ethylene- propylene-cyclopentadiene terpolymer, ethylene-propylene-5-ethylidene-2-norbornene terpolymer, and ethyl ene-propylene-l,4-hexadiene terpolymer,
  • Polyalkenamer obtained by ring opening polymerization of cycloolefin examples include polypentenamer.
  • Rubber obtained by ring opening polymerization of oxirane examples include polyepichlorohydrin rubber vulcanizable with sulfur.
  • Additional examples include their halides, such as chlorinated isobutylene-isoprene copolymer rubber (Cl-IIR) and brominated isobutylene-isoprene copolymer rubber (Br-LTR).
  • Cl-IIR chlorinated isobutylene-isoprene copolymer rubber
  • Br-LTR brominated isobutylene-isoprene copolymer rubber
  • Other examples include polymers obtained by ring opening polymerization of norbornene, The above-mentioned rubber may be blended with a saturated elastomer such as epichlorohydrin rubber, polypropylene oxide rubber, and chlorosulfonated polyethylene.
  • halogenated film former such as halogen-containing polyolefm film formers.
  • halogen-containing polyolefm film formers include natural or synthetic elastomers.
  • the halogens employed in the halogenated polyolefinic elastomers will usually be chlorine or bromine, although fluorine can also be used.
  • a combination of halogen atoms can also be employed in which case the halogen-containing polyolefinic elastomer will have more than one halogen substituted thereon.
  • the amount of halogen does not appear critical and can range from as low as about 3 weight percent to more than 70 weight percent, depending on the nature of the base polymer.
  • Halogen-containing polyolefinic elastomers and their preparation are well known in the art and no need is seen to elucidate in any detail on these materials or their manufacture.
  • Representative halogen-containing polyolefinic elastomers include, without being limited thereto, chlorinated natural rubber, chlorine- and bromine-containing synthetic rubbers including polychloroprene, chlorinated polychloroprene, chlorinated polybutadiene, chlorinated butadiene styrene copolymers, chlorinated ethylene propylene copolymers and ethylene/propylene/non-conjugated diene terpolymers, chlorinated polyethylene, chlorosulfonated polyethylene, copolymers of ⁇ -chloroacrylonitrile and 2,3-dichloro-l,3- butadiene, chlorinated poly( vinyl chloride), and the like, including mixtures of such halogen- containing elastomers.
  • substantially any of the known halogen-containing derivatives of natural and synthetic elastomers can be employed in the practice of this invention, including mixtures of such elastomers.
  • Chlorosulfonated polyethylene elastomers alone or in combination with chlorinated rubber are the most preferred halogen-containing film former, Chlorosulfonated polyethylene containing 35%, and 43% (wt.) of chlorine are commercially available from E. I. DuPont de Nemours & Co. under the HYPALON ® mark.
  • Chlorinated natural rubber is commercially available from Bayer Aktiengesellschaft, under the PERGUT® mark, and LFE, Inc. under the Aquaprene® mark.
  • chlorinated natural rubber and chlorosulfonated polyethylene is a particularly beneficial film former.
  • chlorinated polyolefm CPE
  • the chlorine content should be greater than about 60 percent and the CPE molecular weight greater than about 500, Such chlorine contents can be obtained by a process involving the dispersion and chlorination of high surface area polyolefinic particles in an aqueous medium taught in U.S. Patent No, 5,534,991.
  • a supplemental film former is used in some of the embodiments according to the invention. These are based on a brominated polymer of 2,3-dichloro-l,3-butadiene; 1,3- butadiene; 2,3 -dibromo- 1,3 -butadiene; isoprene; 2,3-dimethylbutadiene; chloroprene; bromoprene; 2,3-dibromo-l,3-butadiene; 1,1,2-trichlorobutadiene; cyanoprene; hexachlorobutadiene and combinations thereof.
  • Copolymerizable monomers herein refers to monomers which are capable of undergoing copolymerization with the butadiene monomers described above.
  • Typical copolymerizable monomers useful in the supplemental film former include ⁇ -haloacrylonitriles such as ⁇ - bromoacrylonitrile and ⁇ -chloroacrylonitrile; ⁇ , ⁇ -unsaturated carboxylic acids such as acrylic, methacrylic, 2-ethylacrylic, 2-propylacrylic, 2-butylacrylic and itaconic acids; alkyl- 2-haloac ⁇ ylates such as ethyl-2-chloroacrylate and ethyl-2-bromo acrylate; styrene; styrene sulfonic acid; ⁇ -halostyrenes; chloro styrene; ⁇ -methylstyrene; ⁇ -bromovinylketone; vinylidene chloride; vinyl toluenes; vinylnaphthalenes; vinyl ethers, esters, and ketones such as methyl vinyl ether, vinyl acetate, and methyl vinyl
  • the brominated polydichlorobutadiene polymers are incorporated either as a solvent solution in organic diluent embodiments, or for water-based diluents, incorporated by forming a latex according to methods known in the art.
  • the brominated polymer can be dissolved in a solvent, a surfactant can be added with water to the solution, and a phase-inversion under high shear is carried out, followed by removal of the organic solvent to obtain a latex having a total solids content of from about 10 to 60, preferably 25 to 50 percent by weight. Solutions of copolymers of brominated dichlorobutadiene in chlorinated aliphatic or aromatic solvents are readily prepared.
  • a latex polymer can also be prepared by emulsion polymerization of chlorinated ethylenically unsaturated monomers via conventional emulsion polymerization process and brominated in the aqueous phase without the disperse particles coagulating or precipitating, according to U.S. Patent No. 5, 306,740.
  • a preferred protective colloid for the latex is polyvinyl alcohol as described in more detail in U.S. Patent No. 6,268,422, incorporated herein by reference.
  • a 2,3-dichlorobutadiene : ⁇ -bromoacrylonitrile copolymer (55-80 wt.% : 45-20%, respectively) with polyvinyl alcohol protective colloid is a preferred aqueous dispersion for supplemental film formers in aqueous adhesive embodiments.
  • an aromatic nitroso compound is included with halogen- containing polyolefm film former, zinc phosphte or Zn/Al/phos.
  • Another adhesive embodiment comprises halogen-containing polyolefm film former, zinc phosphte or Zn/Al/phos, a nitroso compound and one or more than one adhesion promoter specified below.
  • the nitroso compound can be any aromatic hydrocarbon, such as benzenes, naphthalenes, anthracenes, biphenyls, and the like, containing at least two nitroso groups attached directly to non-adjacent ring carbon atoms.
  • nitroso compounds are described as poly-C-nitroso aromatic compounds having from 1 to 3 aromatic nuclei, including fused aromatic nuclei, having from 2 to 6 nitroso groups attached directly to non-adjacent nuclear carbon atoms.
  • the nuclear hydrogen atoms of the aromatic nucleus can be replaced by alkyl, alkoxy, cycloalkyl, aryl, aralkyl, alkaryl, arylamine, arylnitroso, amino, halogen, and like groups.
  • the presence of such substituents on the aromatic nuclei has little effect on the activity of the poly-C-nitroso compounds in the present invention.
  • the preferred poly-C-nitroso materials are the di-nitroso aromatic compounds, especially the dinitrosobenzenes and dinitrosonaphthalenes, such as the meta- or para- dinitrosobenzenes and the meta- or para-dinitrosonaphthalenes.
  • Particularly preferred poly- C-nitroso compounds are characterized by the formula (R) m -Ar-(NO) 2 wherein Ar is selected from the group consisting of phenylene and naphthalene; R is a monovalent organic radical selected from the group consisting of alkyl, cycloalkyl, aryl, aralkyl, alkaryl, arylamine and alkoxy radicals having from 1 to 20 carbon atoms, amino, or halogen, and is preferably an alkyl group having from 1 to 8 carbon atoms; and m is zero, 1, 2, 3, or 4. Preferably m is zero, DNB is incorporated into the adhesive composition by addition as a solvent dispersion.
  • the nitroso compound may be replaced by the corresponding oxime or the corresponding nitro compound with the appropriate oxidation/reduction agent.
  • Exemplary non-limiting embodiments of poly-C-nitroso compounds which are suitable for use in the practice of the invention include m-dinitrosobenzene, p- dinitrosobenzene, m-dinitrosonaphthalene, p-dinitrosonaphthalene, 2,5-dinitroso-p-cymeme, 2-methyl-l ,4-dinitrosobenzene, 2-methyl-5-chloro- 1 ,4-dinitrosobenzene, 2-fluoro- 1 ,4- dinitrosobenzene, 2-methoxy-l-3-dinitrosobenzene, 5-chloro-l,3-dinitrosobenzene, 2-benzyl- 1,4-dinitrobenzene, and 2-cyclohexyl-l,4-dinitrosobenzene.
  • Amount of aiOmatic dinitroso compound used in the adhesive may be from 1 to 200 parts by weight per 100 parts of halogenated polyolefin and preferably from 50 to 150 parts.
  • Nitroso compounds are typically provided as 20-45wt.% dispsersion in aromatic or chlorinated aromatic solvent.
  • Adhesives according to the preferred embodiments further comprise at least one adhesion promoter, such as phenolic resin solutions, or dispersions, diisocyanates, polyisocyanates, epoxy resins, and/or epoxy-phenolic resins which are known and commercially available. Generally from 1 - 200 wt. parts of adhesion promoter is preferably present, per 100 wt. parts of halogen-containing film former (PHR).
  • PHR halogen-containing film former
  • Polyisocyanates include blocked polyisocyanate and an unblocked polyisocyanates as aliphatic or cycloaliphatic polyisocyanates or adducts thereof.
  • a water-dispersible isocyanate as an isocyanurate group containing-polyisocyanate based on 1,6-hexamethylene diisocyanate is selected, IN non-aqueous embodiments, polymethylene phenylisocyanate is preffered.
  • the polyisocyanate in the adhesive composition of the invention can be used in an amount of about 5% to about 55%, preferably 20 to 40%, more preferably about 25 to about 35 percent by weight, based on the total weight of the solid components of the composition.
  • Adhesive in a total solids content of from 20-50 wt.% can contain of di-, or poly-isocyanate from 1% to 25%, preferably from 4% - 20% by wt, On a PHR basis, the amount can range from 1 to 200 PHR on 100 wt. parts halogen-containing film former.
  • polyisocyanates should be rendered more hydrophilic by chemically modifying the polyisocyanate structure to add a hydrophilic group thereto, or by mixing the polyisocyanate with an external emulsifier, or both.
  • the polyisocyanate is rendered hydrophilic by the addition of the polyisocyanate with a non-ionic ethylene oxide unit-containing polyether alcohol.
  • the emulsifier also preferably is the reaction product of the polyisocyanate with a non-ionic ethylene oxide unit-containing polyether alcohol as taught in U.S. Pat. No.
  • Exemplary polyisocyanates are 1,4-diisocyanatobutane, l,5-diisocyanato-2,2-dimethylpentane, 2,2,4- and 2,4,4-trimethyl- 1 ,6-diisocyanatohexane, 1 , 10-diisocyanatodecane, 4,4'-diisocyanato-dicyclohexylmethane, 1,6-hexamethylene diisocyanate, 1,12-dodecane diisocyanate, cyclobutane-l,3-diisocyanate, cyclohexane-1,3- and/or 1,4-diisocyanate, l-isocyanato-3,3,5-trimethyl-5-isocyanatomethyl cyclohexane (isophorone or LPDI).
  • 1,4-diisocyanatobutane 1,4-diisocyanatobutane, l,5
  • hydrophilically modified polyisocyanate compound is available from Bayer Inc. of Pittsburgh, Pa., under the trade designation Desmodur® and from Mobay Chemical Corporation under the designation Mondur®.
  • Desmodur® compounds are described as a water-dispersible, solvent free polyisocyanate based on hexamethylene diisocyanate (HDI) having a NCO content of 18.5 to 20,5%.
  • HDI hexamethylene diisocyanate
  • Phenolic resins are well known compositions, and include water insoluble, or water-dispersible resoles or novolaks.
  • the resoles employed are normally base catalyzed resins having a formaldehyde factor (i.e., parts, by weight, of 40 weight percent aqueous formaldehyde per 100 patts by weight of unsubstituted phenol) of the order of about 90 to about 180.
  • a novolak is used in conjunction with formaldehye or a formaldehyde source, such as those known, and described in U.S. Pat. No. 5,268,404.
  • Phenolic resins are condensates of phenol, substituted phenols, or mixtures thereof and aldehyde.
  • Example starting materials include cresol, bisphenol-A, para-substituted phenols such as para-t-butylphenol, para-phenylphenol, and the like.
  • formaldehyde or a material that generates formaldehyde in situ is the aldehyde that is employed to make the phenolic resin.
  • Phenolics are dissolved in organic carrier in solvent- based adhesive embodiments herein, or dispersed in water with aqueous adhesive embodiments herein.
  • a suitable phenolic resin for use in the invention is a resole produced by reacting formaldehyde with bisphenol-A in a mol ratio of from about 2 to about 3.75 moles of formaldehyde per mole of bisphenol-A, in the presence of a catalytic amount of an alkali metal or barium oxide or hydroxide condensation catalyst, the reaction being carried out at elevated temperatures. The condensation reaction product is then neutralized to apH of from about 3 to about 8.
  • An exemplary novolak resin is para-substituted phenol such as para-t- butylphenol or para-phenyl-phenol condensate with formaldehyde.
  • Another exemplary phenolic is a novalak of a mixture of 20 percent by weight of phenol and 80 percent by weight of t-butylphenol condensed with formaldehyde at a formaldehyde factor of 50, in the presence of an acid catalyst.
  • Another suitable phenolic resin for use in the invention is a resole produced by reacting formaldehyde with bisphenol-A in a mol ratio of from about 2 to about 3.75 moles of formaldehyde per mole of bisphenol-A, in the presence of a catalytic amount of an alkali metal or barium oxide or hydroxide condensation catalyst, the reaction being carried out at elevated temperatures. The condensation reaction product is then neutralized to a pH of from about 3 to about 8,
  • the phenolic resin that is employed need not be pulverized or ground to a very fine particle size, and it need not be dissolved in an organic solvent, prior to utilization in the process of the invention in the preparation of the aqueous dispersion.
  • a coupling solvent is preferably used, as taught in U.S Pat. No. 5,268,404, incorporated by reference.
  • An exemplary coupling solvent such as alcohols having a boiling point above 100 C, glycol ethers, ethers, and esters.
  • useful coupling solvents include ethanol, n- propanol, isopropyl alcohol, ethylene glycol monobutyl ether, ethylene glycol monoisobutyl ether, ethylene glycol monomethyl ether acetate, diethylene glycol monobutyl ether, diethylene glycol monoethyl ether acetate, propylene glycol monopropyl ether, methoxy acetone, and the like.
  • Phenolic resins are conventionally dispersed in water using a conventional colloidal protective material.
  • a preferred colloidal protective material is hydrolysed polyvinyl acetate, having a hydrolysis level of 85 to 95 percent and viscosity at 4% solids in water of 4 to 25 rnPa at 25 °C.
  • Exemplary polyvinyl alcohol-stabilized phenolic resin dispersions are described in U.S. Pat. No. 4,124,554, incorporated herein by reference.
  • a particularly preferred aqueous dispersion of phenolic resin comprises a hydrophilic phenolic resole, etherified bis-phenol having a methylol functionality of from 1 to about 3.5, and low level of water- miscible cosolvent.
  • Water miscible co-solvents include diethylene glycol butyl ether, 2-butoxyethanol in an amount within the range from about 0.01 wt % to about 10 wt. % of theresin components.
  • the etherified bis-phenol can be suitably employed on a solids basis in an amount of from 10 wt. parts to 55 wt. parts with 90 to 45 wt.
  • a hydrophilic phenolic resole as is used in Example 2 below (phenolic dispersion). More preferably 20 wt. parts to 40 wt. parts of etherified bis-phenol is combined with 80 to 60 wt. parts of the hydrophilic phenolic resole, cosolvent, and colloidal protective additive.
  • chlorosulfonated polyethylene latex, phenol- formaldehyde resole, butylated Bis A- formaldehyde adduct PNOH, an Zn/Al phosphate are combined as a stable aqueous dispersion.
  • Methods for preparing preferred phenolic aqueous dispersions are disclosed in U.S. Pat. o. 5,548,015, incorporated herein by reference.
  • Another suitable adhesion promoter is a maleimide compound.
  • Maleimide can be used alone with halogenated film former and zinc phosphate, or Zn/Al phosphate, or preferably in combination with halogenated film former, a nitroso compound, and zinc phosphate, or Zn/Al phosphate metal scavenger.
  • Maleimide adhesion promoters include any of the maleimide, bis- or poly-maleimide and related compounds such as are described in U.S. Pat. Nos. 2,444,536 and 2,462,835, incorporated by reference.
  • the maleimide compound used herein may be an aliphatic or aromatic polymaleimide and must contain at least two maleimide groups.
  • Preferred maleimide compounds include the N,N'linked bismaleimides which are either joined directly at the nitrogen atoms without any intervening structure or in which the nitrogen atoms are joined to and separated by an intervening divalent radical such as alkylene, cycloalkylene, oxydimethylene, phenylene (all 3 isomers), 2,6-dimethylene-4-alkyphenol, or sulfonyl, m-phenylene-bis-maleimide is a presently preferred compound, and is available as "HVA-2" from E. I. du Pont de Nemours and Co., (Inc.).
  • a polymaleimide can be used, such as BMI-M-20 polymalei ide supplied by Mitsui Toatsu Fine Chemicals, Incorporated,
  • the amount of maleimide compound used in some embodiment adhesives may be from 1 to 100 parts by weight per 100 parts (PHR) of halogen-containing polyolefin, preferably 5 to 100 PHR, and more preferably 10 to 60 PHR.
  • PHR 100 parts by weight per 100 parts
  • Particularly preferred polymaleimide compounds have the formula:
  • x is from about 1 to 100
  • Such polymaleimides are common materials of commerce and are sold under different trade names by different companies. Amounts of maleimide typically range from 0 to 100 PHR, preferably 5 to 100 PHR, more preferably from 5 to 50 PHR of halogen-containing film former.
  • epoxy resins Another adhesion promoter, acting also as an acid acceptor is the class of epoxy resins.
  • Preferred epoxy resins are polyglycidyl polyethers of polyhydric phenols. These phenolic-epoxy resins are complex polymeric reaction products of polyhydric phenols with polyfunctional halohydrins and/or glycerol dichlorohydrin. The products thus obtained contain terminal epoxy groups.
  • a large number of epoxy resins of this type are disclosed in Greenlee U.S. Pat, Nos. 2,585,115 and 2,589,245. Several of these resins are available commercially.
  • Suitable polyhydric phenols useful in the preparation of the phenolic epoxy resins used herein include resorcinol and novolac resins resulting from condensation of phenol with formaldehyde.
  • Resorcinol is a very reactive dihydric phenol with formaldehyde, allowing for the preparation of resorcinol- formaldehyde novolacs.
  • Phenolic epoxy resins may be further characterized by reference of their epoxy weight of pure epoxy resins being the mean molecular weight of the resin divided by the mean number of epoxy radicals per molecule or in any case the number of grams of epoxy resin equivalent to one mole of the epoxy group or one gram equivalent of epoxide,
  • the phenolic epoxy resins that may be used in the present invention have an epoxy equivalent weight of about 400-1000.
  • Amount of epoxy resin, such as phenolic epoxy, used in the adliesive may be fromO to about 80 parts by weight per 100 parts by weight of said halogen- containing polyolefin, preferably from about 2 to about 80 PHR, more preferably from 2 to 50 PHR,
  • Optional vulcanizing agents that are suitable for use in one-coat embodiments not used in conjunction with metal primers, are sulfur and selenium.
  • the vulcanizing agents are well known and commercially available.
  • An amount of vulcanizing agent in the adliesive composition may be from 0 to about 40 parts by weight per 100 parts of halogen-containing polyolefm, preferably 2 to 30 PHR, and more preferably from 5 to 30 PHR.
  • the adliesive compositions of the invention can include conventional additives such as inert filer material, like barium sulfate, polymeric film- forming adjuncts, pigments, solvent and the like, with the amounts of such additions being within the range customarily employed.
  • a particularly preferred filler is carbon black and when utilized is incorporated in amounts ranging from 0 to 20% by weight on a dry solids basis.
  • Silicates, such as fumed silica, or hydrated silica are preferably used at levels of 0.2 to 2% to total weight of adhesive.
  • An amount of metal scavenger comprising zinc phosphate, effective as replacement for lead compounds is from 10 to 120 PHR, preferably 12 to 80 PHR.
  • the phosphates as phosphoric acid salts usable in the preparation of metal phosphate component are, for example, aluminum phosphate, zinc phosphate, and aluminum dihydrogentripolyphosphate.
  • Aluminum dihydrogentripolyphosphate is particularly preferably used in the present invention.
  • the aluminum phosphates can be treated with the Zn compounds in conventional methods such as follows. The treatment with a Zn compound can be effected after obtaining aluminum dihydrogentripolyphosphate.
  • particles of aluminum dihydrogentripolyphosphate are dispersed in a solution containing a Zn ion and the Zn ion is deposited as the hydroxide on the surface of the particles of aluminum dihydrogentripolyphosphate by changing the pH of the solution from a weak acidic side to an alkaline side by amines. Thereafter, the zinc hydroxide on the surface is converted to zinc oxide by filtering, washing with water, drying and heat-treating.
  • the substances capable of delivering a Zn ion for preparing a solution containing a Zn ion include zinc chloride, zinc hydroxide, zinc nitrate, zinc carbonate, zinc sulfate etc., phosphates treated with Zn compounds, particularly, aluminum dihydrogentripolyphosphate can provide excellent durability of adliesive properties.
  • Zn components are included in or coated on the particles of aluminum phosphate by, for example, adsorption or absorption.
  • the phosphates treated with Zn compounds can be used alone or preferably in mixtures with aluminum and/or zinc oxides.
  • a more preferred acid scavenger is a mixture of 25-35 wt.% zinc oxide, 25-35 wt.% zinc phosphate and 25-35 wt.% aluminum phosphate (Zn/Al phos.).
  • the most preferred acid scavenger comprises zinc phosphate in a 1: 1: 1 mixture of zinc oxide, zinc phosphate and aluminum phosphate. Such mixtures are sold by Heubach Company.
  • the prefe ⁇ 'ed embodiment includes a 20-50 parts of metal oxide such as zinc oxide in combination with 100 parts of zinc phosphate.
  • the amount of acid scavenger comprising zinc phosphate present in the adhesive composition ranges from about 5 to about 120 parts by weight per 100 parts of halogen-containing polyolefin (PHR), preferably from 10 to about 120 PHR, and more preferably from 12 to 80 PHR.
  • PHR halogen-containing polyolefin
  • the adhesive compositions of this invention are prepared by conventional means. For ease of application, as is conventional in this art, the components will be mixed and dispersed in an inert liquid diluents which, once the composition has been applied to the substrate, can be readily evaporated.
  • liquid diluents examples include water, aromatic and halogenated aromatic hydrocarbons such as benzene, toluene, xylene, chlorobenzene, dichlorobenzene, and the like; halogenated aliphatic hydrocarbons such as trichloroethylene, perchloroethylene, propylene dichloride and the like; ketones such as methyl ethyl ketone, methyl isobutyl ketone, and the like; ethers, naphthas, etc., including mixtures of such carriers.
  • Preferred diluents are xylene and toluene, ortho- and para-chlorotoluene, optionally in combination with tetrachloroethylene.
  • the amount of the diluent employed is that which provides a composition suitable for use as an adhesive.
  • Typical diluent amount, by weight to total adhesive weight ranges from 20 to 4000 parts per hundred weight parts of all halogen- containing film former (PHR). This amount will ordinarily be such as to provide a total solids content ranging from about 5% to 80%, preferably about 15% to about 40% percent by weight.
  • PHR halogen- containing film former
  • Parts of diluent per 100 wt, parts of halogen-containing polyolefm the diluent can be used in an amount ranging from 200 to 1000 PHR of halogenated film former.
  • the finely divided solid components should be predispersed using dispersing agent such as lignosulfonates including as a basic lignin monomer unit a substituted phenyl propane.
  • dispersing agent such as lignosulfonates including as a basic lignin monomer unit a substituted phenyl propane.
  • the adhesives herein may be coated on a primer or directly applied to the substrate.
  • the metal surface to which the elastomeric substrate is ultimately bonded to may optionally have a conventional water-based or solvent-based metal primer applied thereto.
  • Typical conventional water-based primers include phenolic resin-type primers such as CHEMLOK 802, CHEMLOK 805, CHEMLOK 8006, and CHEMLOK 8401 produced by Lord Corporation.
  • Typical solvent-based primers include phenolic resin-type primers such as CHEMLOK 205 or CHEMLOK 207 produced by Lord Corporation.
  • the adhesive composition is typically applied directly to a metal surface or directly to any primer which has been applied to the metal so as to ensure contact between the adhesive composition and the elastomeric substrate which is brought into contact with the coated metal surface.
  • the adhesive compositions of the present invention have been found to be particularly useful for bonding a wide variety of elastomeric materials, including both vulcanized and vulcanizable elastomeric materials, to themselves or to other substrates, particularly to metal substrates.
  • Elastomers which can be bonded include without limitation natural rubber, polychloroprene rubber, styrene-butadiene rubber, nitrile rubber, ethylene/propylene copolymer rubber (EPM); ethylene/propylene/diene terpolymer rubber (EPDM); butyl rubber, polyurethane rubber, PAREL type elastomers, and the like.
  • substrates which can be effectively bonded to themselves or to elastomers include fabrics such as fiberglass, polyamides, polyester, aramides, e.g., Kevlar, a trademark of E. I, du Pont de Nemours Co., (Inc.), of Wilmington, Del., glass, ceramics and the like.
  • Metals and their alloys to which the elastomers can be bonded include steel, stainless steel, lead, aluminum, copper, brass, bronze, Monel metals, nickel, zinc, and the like, including treated metals such as phosphatized steel, galvanized steel, and the like.
  • the adhesive compositions are applied to substrate surfaces in a conventional manner such as by dipping, spraying, brushing, and the like.
  • the substrate surfaces are allowed to dry after coating before being brought together.
  • the assembly is heated in accordance with conventional practices.
  • the exact conditions selected will depend upon the particular elastomer being bonded and whether or not it is cured. If the rubber is uncured, the curing is to be effected during bonding, the conditions will be dictated by the rubber composition and will generally be at a temperature of from about 140° C. to about 200° C. for from about 5 to about 60 minutes. If the rubber is already cured, the bonding temperature may range from about 90° C. to above 180° C. for from 15 to about 120 minutes. Alternatively, in situations where applicable, the adhesives can be interspersed between the surfaces to be joined as a solid film or tape (100% TSC adhesive system) with bonding being accomplished as before.
  • PA Primary Adhesion
  • Hot Tear (HT) testing is performed by placing part in an oven at 300°F for 15 minutes and immediately destroying the part on the 3 station United Tester at a speed of 20"/minute @ a 45 degree angle.
  • the boiling water (BW) test is performed by fastening the part in a fixture where the angle from the bond line to the rubber tail is 45 degrees. The tail is fastened to a cable where a 5-pound free weight is attached. The parts are immersed in this environment for a 2-hour duration. Parts are removed from the fixture and allowed to cool to ambient. The parts are destroyed manually by peeling the rubber from the substrate with needle nose pliers and the bond area is evaluated for rubber retention.
  • Salt spray (SS) testing is performed by applying a constant stress to the bond line by pulling the rubber tail and fastening the tail while the part is stressed. The part is then placed in a 5% salt fog at 95°F for a 1-week period. Parts are destroyed as in the above peeling and evaluated the same as the boiling water specimens.
  • the propylene glycol (PG) test is carried out by immersing stressed parts in a container of propylene glycol and the container is closed and placed in an oven at 250°F for 5 days. Bonded parts are evaluated the same manner as salt spray and boiling water.
  • PA Primary Adhesion, at 0', 3 ! time of pre-bake
  • BW Boiling Water, 0', 3' - time of pre-bake
  • Example 1 100 100 100 100 100 99 98
  • Example 1 100 84 100 80 100 74
  • Example 1 100 95 100 100 93.3 10.0
  • Example 1 100 100 100 100 44 29
  • Rubber Commercial peroxide cured EPDM, cured 7.5 minutes at 340° F (171°C).
  • Adhesives The adhesives were spray applied to provide approximately a 1.0 mils dry film thickness and the bonding area was 1" x 1" (2.54 cm. X 2.54 cm.)

Landscapes

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

Abstract

L'invention a trait à des compositions d'adhésifs permettant de coller efficacement du caoutchouc à un métal, ne contenant pas plus d'environ 1000 ppm de plomb, et convenant particulièrement au collage d'élastomères vulcanisés à des substrats rigides, tels que le métal. Lesdits adhésifs sont avantageusement utilisés en combinaison avec des couches primaires et en tant qu'adhésifs à couche unique, et permettent d'obtenir des liaisons durables entre le caoutchouc et le substrat, présentant une bonne adhérence primaire et une bonne résistance au déchirement après exposition à des conditions extrêmes. Lesdits adhésifs sont polyvalents et présentent une stabilité dans le moule et une stabilité de stockage en boîte excellentes. Dans un mode de réalisation, les compositions d'adhésifs de la présente invention sont essentiellement constituées de moins de 1000 ppm de plomb, d'au moins un diluant tel que l'eau ou un solvant organique, d'un filmogène contenant un halogène, éventuellement d'un composé nitreux, de dichlorobutadiène bromé, et/ou d'un promoteur d'adhérence, et d'un fixateur d'acide contenant du phosphate de zinc.
PCT/US2002/033362 2001-10-17 2002-10-17 Adhesifs sans danger pour l'environnement destines au collage de caoutchouc vulcanise WO2003033613A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
CA2462612A CA2462612C (fr) 2001-10-17 2002-10-17 Adhesifs sans danger pour l'environnement destines au collage de caoutchouc vulcanise
MXPA04003502A MXPA04003502A (es) 2001-10-17 2002-10-17 Adhesivos, favorables ambientalmente, para unir hule vulcanizado.

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
US33003301P 2001-10-17 2001-10-17
US60/330,033 2001-10-17
US10/222,545 US20040033374A1 (en) 2002-08-16 2002-08-16 Phenolic adhesives for bonding peroxide-cured elastomers
US10/222,545 2002-08-16

Publications (1)

Publication Number Publication Date
WO2003033613A1 true WO2003033613A1 (fr) 2003-04-24

Family

ID=26916919

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US2002/033362 WO2003033613A1 (fr) 2001-10-17 2002-10-17 Adhesifs sans danger pour l'environnement destines au collage de caoutchouc vulcanise

Country Status (3)

Country Link
CA (1) CA2462612C (fr)
MX (1) MXPA04003502A (fr)
WO (1) WO2003033613A1 (fr)

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2006007438A1 (fr) * 2004-06-16 2006-01-19 Lord Corporation Composition adhesive, procede de liaison a une surface metallique et adhesif caoutchouc-metal
US7144630B2 (en) 2002-01-30 2006-12-05 Rohm And Haas Company Aqueous adhesive compositions for bonding elastomers
EP2189507A1 (fr) * 2006-11-15 2010-05-26 Rohm and Haas Adhésifs à base d'eau pour élastomères
WO2017176625A1 (fr) * 2016-04-04 2017-10-12 Dow Global Technologies Llc Composition adhésive améliorée pour lier le caoutchouc à un métal
CN110437769A (zh) * 2019-09-18 2019-11-12 青岛科技大学 一种可硫化交联的卤化橡胶胶黏剂及其制备方法
CN110511300A (zh) * 2019-09-18 2019-11-29 青岛科技大学 一种卤化的反式丁二烯-异戊二烯共聚橡胶及其制备方法和用途
EP3950800A1 (fr) * 2020-08-03 2022-02-09 Henkel AG & Co. KGaA Amélioration de la résistance à la corrosion d'adhésifs et de produits d'étanchéité à base de caoutchouc

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3830784A (en) * 1972-03-22 1974-08-20 Lord Corp Shelf-stable adhesive compositions for laminating elastomers to metal and textile substrates and such laminates
US4119587A (en) * 1977-02-25 1978-10-10 Lord Corporation Adhesive compositions comprising (a) halogenated polyolefin (b) aromatic nitroso compound and (c) lead salts
GB2155488A (en) * 1984-03-07 1985-09-25 Lord Corp Adhesive compositions comprising halodiene polymers
US5268404A (en) * 1989-12-04 1993-12-07 Lord Corporation One-coat rubber-to-metal bonding adhesive

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3830784A (en) * 1972-03-22 1974-08-20 Lord Corp Shelf-stable adhesive compositions for laminating elastomers to metal and textile substrates and such laminates
US4119587A (en) * 1977-02-25 1978-10-10 Lord Corporation Adhesive compositions comprising (a) halogenated polyolefin (b) aromatic nitroso compound and (c) lead salts
GB2155488A (en) * 1984-03-07 1985-09-25 Lord Corp Adhesive compositions comprising halodiene polymers
US5268404A (en) * 1989-12-04 1993-12-07 Lord Corporation One-coat rubber-to-metal bonding adhesive

Cited By (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7144630B2 (en) 2002-01-30 2006-12-05 Rohm And Haas Company Aqueous adhesive compositions for bonding elastomers
WO2006007438A1 (fr) * 2004-06-16 2006-01-19 Lord Corporation Composition adhesive, procede de liaison a une surface metallique et adhesif caoutchouc-metal
EA014015B1 (ru) * 2004-06-16 2010-08-30 Лорд Корпорейшн Композиция адгезива с измельченным пигментом, способ ее нанесения, способ и адгезив для связывания эластомера с металлической поверхностью
EP2189507A1 (fr) * 2006-11-15 2010-05-26 Rohm and Haas Adhésifs à base d'eau pour élastomères
US9328270B2 (en) 2006-11-15 2016-05-03 Rohm And Haas Company Waterborne adhesives for elastomers
US9441143B2 (en) 2006-11-15 2016-09-13 Rohm And Haas Company Waterborne adhesives for elastomers
WO2017176625A1 (fr) * 2016-04-04 2017-10-12 Dow Global Technologies Llc Composition adhésive améliorée pour lier le caoutchouc à un métal
CN109379894A (zh) * 2016-04-04 2019-02-22 陶氏环球技术有限责任公司 用于将橡胶粘结到金属上的改进的粘合剂组合物
US10975271B2 (en) 2016-04-04 2021-04-13 Ddp Specialty Electronic Materials Us, Llc Adhesive composition for bonding rubber to metal
CN109379894B (zh) * 2016-04-04 2021-05-28 陶氏环球技术有限责任公司 用于将橡胶粘结到金属上的改进的粘合剂组合物
CN110437769A (zh) * 2019-09-18 2019-11-12 青岛科技大学 一种可硫化交联的卤化橡胶胶黏剂及其制备方法
CN110511300A (zh) * 2019-09-18 2019-11-29 青岛科技大学 一种卤化的反式丁二烯-异戊二烯共聚橡胶及其制备方法和用途
CN110511300B (zh) * 2019-09-18 2021-09-14 青岛科技大学 一种卤化的反式丁二烯-异戊二烯共聚橡胶及其制备方法和用途
EP3950800A1 (fr) * 2020-08-03 2022-02-09 Henkel AG & Co. KGaA Amélioration de la résistance à la corrosion d'adhésifs et de produits d'étanchéité à base de caoutchouc
WO2022028865A1 (fr) * 2020-08-03 2022-02-10 Henkel Ag & Co. Kgaa Résistance à la corrosion améliorée d'adhésifs et d'agents d'étanchéité à base de caoutchouc

Also Published As

Publication number Publication date
CA2462612A1 (fr) 2003-04-24
CA2462612C (fr) 2011-08-02
MXPA04003502A (es) 2004-09-10

Similar Documents

Publication Publication Date Title
EP0624184B1 (fr) Compositions adhesives aqueuses contenant des resines phenoliques stabilisees
US5268404A (en) One-coat rubber-to-metal bonding adhesive
EP1797153B1 (fr) Composition adhesive, procede de liaison a une surface metallique et adhesif caoutchouc-metal
US6517663B1 (en) Bonding a thermoplastic elastomer to a magnesium based metal
US6841600B2 (en) Environmentally friendly adhesives for bonding vulcanized rubber
EP2189507B1 (fr) Adhésifs à base d'eau pour élastomères
EP1333057B1 (fr) Compositions adhésives pour liaison des élastomères
CA2462612C (fr) Adhesifs sans danger pour l'environnement destines au collage de caoutchouc vulcanise
EP0431762A2 (fr) Adhésif monocouche pour l'adhésion caoutchouc-métal
US20040033374A1 (en) Phenolic adhesives for bonding peroxide-cured elastomers
CN112262194B (zh) 水基单涂层粘合剂组合物
KR100866560B1 (ko) 접착제 조성물, 및 금속 표면에 결합하는 방법
WO2005047413A1 (fr) Adhesif thermoplastique etanche a faible teneur en formaldehyde
AU2005262499C1 (en) Adhesive composition, method for bonding to a metal surface and rubber to metal adhesive
US20220112409A1 (en) Bonding system

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A1

Designated state(s): CA

DFPE Request for preliminary examination filed prior to expiration of 19th month from priority date (pct application filed before 20040101)
WWE Wipo information: entry into national phase

Ref document number: 2462612

Country of ref document: CA

WWE Wipo information: entry into national phase

Ref document number: PA/a/2004/003502

Country of ref document: MX