WO1999002583A1 - Adhesif aqueux - Google Patents

Adhesif aqueux Download PDF

Info

Publication number
WO1999002583A1
WO1999002583A1 PCT/US1998/013762 US9813762W WO9902583A1 WO 1999002583 A1 WO1999002583 A1 WO 1999002583A1 US 9813762 W US9813762 W US 9813762W WO 9902583 A1 WO9902583 A1 WO 9902583A1
Authority
WO
WIPO (PCT)
Prior art keywords
chlorinated
butadiene
adhesive composition
nitroso compound
phenolic resole
Prior art date
Application number
PCT/US1998/013762
Other languages
English (en)
Inventor
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
Application filed by Lord Corporation filed Critical Lord Corporation
Publication of WO1999002583A1 publication Critical patent/WO1999002583A1/fr

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/12—Bonding of a preformed macromolecular material to the same or other solid material such as metal, glass, leather, e.g. using adhesives
    • C08J5/124—Bonding of a preformed macromolecular material to the same or other solid material such as metal, glass, leather, e.g. using adhesives using adhesives based on a macromolecular component
    • C08J5/127—Aqueous adhesives
    • 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
    • C09J111/00—Adhesives based on homopolymers or copolymers of chloroprene
    • C09J111/02—Latex
    • 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
    • C09J115/00—Adhesives based on rubber derivatives
    • C09J115/02—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
    • 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
    • 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
    • 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
    • C09J161/00—Adhesives based on condensation polymers of aldehydes or ketones; Adhesives based on derivatives of such polymers
    • C09J161/04—Condensation polymers of aldehydes or ketones with phenols only
    • C09J161/06—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
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2321/00—Characterised by the use of unspecified rubbers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L11/00—Compositions of homopolymers or copolymers of chloroprene
    • 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
    • C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
    • C08L25/02—Homopolymers or copolymers of hydrocarbons
    • C08L25/04—Homopolymers or copolymers of styrene
    • C08L25/08—Copolymers of styrene
    • C08L25/10—Copolymers of styrene with conjugated dienes
    • 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
    • C08L2666/04—Macromolecular compounds according to groups C08L7/00 - C08L49/00, or C08L55/00 - C08L57/00; Derivatives thereof
    • 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
    • C08L2666/14—Macromolecular compounds according to C08L59/00 - C08L87/00; Derivatives thereof
    • C08L2666/16—Addition or condensation polymers of aldehydes or ketones according to C08L59/00 - C08L61/00; Derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
    • C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L27/04—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
    • C08L27/06—Homopolymers or copolymers of vinyl chloride
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L29/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical; Compositions of hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Compositions of derivatives of such polymers
    • C08L29/02—Homopolymers or copolymers of unsaturated alcohols
    • C08L29/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L7/00—Compositions of natural rubber
    • 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 present invention relates to an aqueous adhesive for bonding a rubber or elastomeric substrate to a metal substrate, particularly a metal substrate that requires an unusually flexible, but robust adhesive.
  • elastomer-to-metal adhesives require an unusual degree of flexibility. For example, it is often desirable to apply the adhesive to an article in its preformed condition. In such a situation, the adhesive must be sufficiently flexible and robust to withstand the stresses of subsequent article-forming operations. Applying an adhesive to preformed stock is particularly important to those industries engaged in fabricating parts from metal sheet stock or coil metal such as appliance cabinets, automobile parts and metal siding, to name just a few.
  • the adhesive is applied to a coil metal and the adhesive-treated coil metal then is dried in a continuous operation known as coil coating.
  • the adhesive-treated coil metal then is shaped and bonded with an elastomeric substrate to produce a final article.
  • the adhesive is subjected to considerable flexing before it is used to adhere to the elastomeric substrate.
  • the shaping and bonding usually occurs a certain time period after the adhesive is applied, sometimes ranging up to a week or more.
  • Organic solvent-based adhesive systems for coil metal bonding are known such as Chemlok® 208A adhesive primer/Chemlok® 237 adhesive overcoat system commercially available from Lord Corporation.
  • Chemlok® 208A adhesive primer/Chemlok® 237 adhesive overcoat system commercially available from Lord Corporation.
  • U.S. Patent No. 4,167,500 discloses an aqueous adhesive composition that includes a water dispersible phenolic novolak resin, a methylene donor such as a high molecular weight aldehyde homopolymer or copolymer and water.
  • U.S. Patent No. 5,030,515 discloses a bonding method that includes employing as a primer a mixture of epoxidized diene polymer and a resole type phenolic resin. A separate overcoat that includes dinitrosobenzene is used with this primer.
  • Patent No. 5,093,203 discloses a two part adhesive system that includes a primer and an overcoat.
  • the primer includes polychloroprene, phenolic resin and a metal oxide.
  • the separate overcoat includes dinitrosobenzene, a halogenated polyolefin and a metal oxide.
  • U.S. Patent No. 5,162,156 discloses a two part adhesive system that includes a primer and an overcoat.
  • the primer includes a phenolic novolak and a halogenated polyolefin.
  • the separate overcoat includes dinitrosobenzene and a halogenated polyolefin.
  • U.S. Patent No. 5,200,455 discloses a two part adhesive system that includes a primer and an overcoat.
  • the aqueous primer includes a polyvinyl alcohol- stabilized phenolic resin dispersion, halogenated polyolefin latex, metal oxide and, optionally, a formaldehyde donor.
  • the separate overcoat includes dinitrosobenzene, a halogenated polyolefin latex and polymaleimide.
  • aqueous adhesives for applying to flexible metal substrates that have extended shelf-life stability (in other words, they can be stored for substantial periods of time without undue gelation or loss of adhesive capability); have good layover stability (in other words, metal substrates can be coated with wet adhesive, dried and stored for a substantial period of time prior to bonding without substantial loss of adhesion properties); the adhesive is heat-reactive or activated; and the adhesive is easily applied via a coil coating operation.
  • an aqueous adhesive composition that includes an aqueous dispersible or soluble phenolic resole, at least one aromatic nitroso compound or aromatic nitroso compound precursor and at least one halogenated polyolefin.
  • This adhesive exhibits superior flexibility combined with sufficient stability and adhesive performance. In addition, it avoids the environmental and workplace problems associated with conventional volatile organic solvent-based adhesives since it is aqueous-based.
  • the adhesive composition includes an aqueous dispersible or soluble phenolic resole, at least one aromatic nitroso compound or aromatic nitroso compound precursor and at least one halogenated polyolefin. As used herein, these components constitute the "primary components" of the invention.
  • aqueous adhesive composition exhibits shelf-life stability despite the fact that it includes a combination of the aromatic nitroso compound or aromatic nitroso compound precursor and the phenolic resole.
  • Previous attempts to commercialize adhesive compositions that include both an aromatic nitroso compound and a phenolic compound or resin have been unsuccessful.
  • the previous compositions were unstable in that they formed a gel or paste either immediately or a brief time after formulation.
  • the use of an aqueous-based system, the addition of an aqueous dispersible or soluble phenolic resole and a lower amount of the aromatic nitroso compound have unexpectedly resulted in a stable adhesive.
  • the phenolic resole is an aqueous dispersible or soluble heat-reactive condensation product of an aldehyde having from 1 to 8 carbon atoms, such as formaldehyde, acetaldehyde, isobutyraldehyde, ethylhexaldehyde, and the like, with phenolic compounds such as unsubstituted phenol, or substituted phenol such as o-cresol, m-cresol, p-cresol, mixed cresols (for example, cresylic acid and m-cresol and/or p- cresol), xylenol, diphenylolpropane, p-butylphenol, p-tert-amylphenol, p-octylphenol, p,p'-dihydroxydiphenylether and the like.
  • an aldehyde having from 1 to 8 carbon atoms such as formaldehyde, acetaldehyde, iso
  • the resoles are well-known and are typically base catalyzed resins having a formaldehyde factor (in other words, parts by weight of 40 weight percent aqueous formaldehyde per 100 parts by weight of unsubstituted phenol) of the order of 90 to 180.
  • the phenolic resole is formulated or mixed into the adhesive as an aqueous dispersion or solution.
  • One particularly desirable phenolic resole is a resole produced by reacting formaldehyde with bisphenol-A in a mol ratio of 2 to 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 wherein the reaction is carried out at elevated temperatures. The condensation product is then neutralized to a pH of 3 to 8.
  • a polyvinyl alcohol-stabilized aqueous dispersion of the above-described phenolic resoles is particularly preferred as the phenolic resole component of the invention.
  • This dispersion can be prepared by a process that includes mixing the preformed, solid, substantially water-insoluble, phenolic resole resin; water; an organic coupling solvent; and polyvinyl alcohol, at a temperature and for a period of time sufficient to form a dispersion of the phenolic resole resin in water.
  • Such polyvinyl alcohol-stabilized aqueous dispersions of a phenolic resole are described in more detail in U.S. Patent No. 4,124,554, incorporated herein by reference, and are available commercially from Georgia Pacific Corporation under the tradename UCAR® BKUA- 2370 and UCAR® BKUA-2392.
  • alcohols, glycol ethers, ethers, esters and ketones are the most useful coupling solvents.
  • 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.
  • the polyvinyl alcohol is typically prepared by hydrolysis of polyvinyl acetate.
  • the most useful polyvinyl alcohol polymers are hydrolyzed to an extent of 85 to 91 percent and have molecular weights such that a 4 percent solids solution of the polyvinyl alcohol in water has a viscosity of 4 to 25 centipoises at 25 °C.
  • the aqueous dispersible or soluble phenolic resole is present in the adhesive composition in an amount of 10 to 60, preferably 20 to 30, % dry weight (excluding water) based on the primary components of the adhesive composition.
  • the aromatic 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.
  • aromatic nitroso compounds are described, for example, in U.S. Patent No. 3,258,388; U.S. Patent No. 4,119,587 and U.S. Patent No. 5,496,884. More particularly, such nitroso compounds are described as 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 preferred nitroso compounds are the dinitroso aromatic compounds, especially the dinitrosobenzenes and dinitrosonaphthalenes, such as the meta- or para-dinitrosobenzenes and the meta- or para-dinitrosonaphthalenes.
  • the nuclear hydrogen atoms of the aromatic nucleus can be replaced by alkyl, alkoxy, cycloalkyl, aryl, aralkyl, alkaryl, arylamine, arylnitroso, amino, halogen and similar groups.
  • aromatic nitroso compound it will be understood to include both substituted and unsubstituted nitroso compounds.
  • 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
  • m is 0, 1, 2, 3, or 4, and preferably is 0.
  • Exemplary suitable aromatic nitroso compounds include m-dinitrosobenzene, p- dinitrosobenzene, m-dinitrosonaphthalene, p-dinitrosonaphthalene, 2,5-dinitroso-p- cymene, 2-methyl-l,4-dinitrosobenzene, 2-methyl-5-chloro-l,4- dinitrosobenzene, 2- fluoro-1,4- dinitrosobenzene, 2-methoxy-l-3-dinitrosobenzene, 5-chloro-l,3- dinitrosobenzene, 2-benzyl-l,4-dinitrosobenzene, 2-cyclohexyl-l,4-dinitrosobenzene and combinations thereof. Particularly preferred are m-dinitrosobenzene and p- dinitrosobenzene.
  • the aromatic nitroso compound precursor may be essentially any compound that is capable of being converted, typically by oxidation, to a nitroso compound at elevated temperatures, typically from about 140-200°C.
  • the most common aromatic nitroso compound precursors are derivatives of quinone compounds. Examples of such quinone compound derivatives include quinone dioxime, dibenzoquinone dioxime, 1,2,4,5-tetrachlorobenzoquinone, 2-methyl-l,4-benzoquinone dioxime, 1,4- naphthoquinone dioxime, 1 ,2-naphthoquinone dioxime and 2,6-naphthoquinone dioxime.
  • the adhesion promoting additive can be used in an amount of from 5 to 40, preferably 10 to 20, % dry weight (excluding water), based on the primary components of the inventive adhesive composition.
  • the halogenated polyolefin acts as a film-former and is formulated or mixed into the adhesive as an aqueous dispersion such as an emulsion or a latex.
  • the halogenated polyolefin can essentially be any natural or synthetic halogenated polyolefin elastomer.
  • the halogens employed in the halogenated polyolefinic elastomer are typically chlorine or bromine, although fluorine can also be used. Mixtures of halogens can also be employed in which case the halogen-containing polyolefinic elastomer will have more than one type of halogen substituted thereon.
  • halogenated polyolefins and their preparation are well known to those skilled in the art.
  • halogenated polyolefins include chlorinated natural rubber, chlorine- and bromine-containing synthetic rubbers including polychloroprene, chlorinated polychloroprene, chlorinated polybutadiene, hexachloropentadiene, butadiene/halogenated cyclic conjugated diene adducts, chlorinated butadiene styrene copolymers, chlorinated ethylene propylene copolymers and ethylene/propylene/non- conjugated diene terpolymers, chlorinated polyethylene, chlorosulfonated polyethylene, poly(2,3-dichloro-l,3-butadiene), brominated poly(2,3-dichloro-l,3-butadiene), copolymers of -haloacrylonitriles and 2,3-dichloro-l,3-butadiene, chlorinated poly(vinyl chloride) and the like including mixtures of such halogen-containing
  • the latex of the halogenated polyolefin can be prepared according to methods known in the art such as by dissolving the halogenated polyolefin in a solvent and adding a surfactant to the resulting solution. Water can then be added to the solution under high shear to emulsify the polymer. The solvent is then stripped to obtain a latex having a total solids content of from 10 to 60, preferably 25 to 50, percent by weight.
  • the latex can also be prepared by emulsion polymerization of chlorinated ethylenically unsaturated monomers. Chlorosulfonated polyethylene is especially effective when utilized as the halogenated polyolefin.
  • Chlorosulfonated polyethylene latex is commercially available and can be prepared by methods well known in the art such as, for example, dissolving polyethylene in carbon tetrachloride and subjecting the resulting solution to a mixture of chlorine gas and sulfur dioxide gas under high temperature and pressure. The carbon tetrachloride is then removed to produce a powder of chlorosulfonated polyethylene.
  • the latex of chlorosulfonated polyethylene can be prepared according to the general method for preparing lattices described above.
  • the preferred chlorosulfonated polyethylene typically has a molecular weight in the range of 50,000-150,000, preferably 60,000-120,000.
  • the chlorine content of the chlorosulfonated polyethylene is typically in the range of 20-50, preferably 25 to 45, percent while the sulfur content is typically in the range of 0.5 to 2, preferably 1.0 to 1.5, percent.
  • a latex of a copolymer of ⁇ -bromoacrylonitrile and 2,3-dichloro-l,3-butadiene is also particularly effective.
  • An example of such latex is described in U.S. Patent No. 5,496,884, incorporated herein by reference.
  • the halogenated polyolefin is present in the adhesive composition in an amount of 20 to 80, preferably 40 to 60, % dry weight (excluding water) based on the primary components of the inventive adhesive composition.
  • the adhesive can optionally include a maleimide-based compound such as an aliphatic or aromatic bismaleimide or polymaleimide.
  • Aromatic polymaleimides having from 2 to 100 aromatic nuclei wherein no more than one maleimide group is directly attached to each adjacent aromatic ring are preferred.
  • Particularly preferred aromatic polymaleimide compounds have the formula:
  • polymaleimides are common materials of commerce and are sold under different trade names by different companies, such as BMI-M-20 and BMI-S polymaleimides supplied by Mitsui Toatsu Fine Chemicals, Inc.
  • the aqueous adhesive composition can also optionally include other well known additives such as a metal oxide (for example, zinc oxide, lead oxide and zirconium oxide), lead-containing compounds (for example, polybasic lead salts of phosphorous acid and saturated and unsaturated organic dicarboxylic acids and anhydrides), plasticizers, fillers, pigments, surfactants, dispersing agents, wetting agents, reinforcing agents and the like, in amounts employed by those skilled in the adhesive arts.
  • a metal oxide for example, zinc oxide, lead oxide and zirconium oxide
  • lead-containing compounds for example, polybasic lead salts of phosphorous acid and saturated and unsaturated organic dicarboxylic acids and anhydrides
  • plasticizers for example, polybasic lead salts of phosphorous acid and saturated and unsaturated organic dicarboxylic acids and anhydrides
  • plasticizers for example, polybasic lead salts of phosphorous acid and saturated and unsaturated organic dicarboxylic acids and anhydrides
  • plasticizers for
  • Water preferably deionized water, is utilized in combination with the primary components and any optional components of the invention in order to provide an adhesive composition having a final solids content of between 5 and 60 weight percent, preferably between 30 and 50 weight percent.
  • the adhesive compositions may be prepared by any method known in the art, but are preferably prepared by combining and milling or shaking the ingredients and water in a ball-mill, sand-mill, ceramic bead-mill, steel bead-mill, high speed media-mill or the like.
  • the adhesive composition may be applied to a substrate for bonding by spraying, dipping, brushing, wiping, roll-coating (including reverse roll-coating) or the like, after which the adhesive composition is permitted to dry.
  • the composition typically is applied in an amount sufficient to form a dry film thickness ranging from 2.5 to 25 ⁇ m, preferably from 5 to 7.5 ⁇ m.
  • the present adhesive typically is used as a one coat adhesive, although it can be used with a primer.
  • "one coat" adhesive means that the adhesive composition can provide sufficient bonding without the need for an additional and separate or distinct primer composition.
  • the coil metal is coated with the wet adhesive and then dried. Rubber is extruded over the coated coil metal profile and the assembly subsequently is cured in a hot air oven.
  • the adhesive composition can be used to bond any types of substrates or surfaces together, but it is particularly useful to bond a metal substrate or surface to a polymeric material substrate or surface.
  • the polymeric material can be any elastomeric material selected from any of the natural rubbers and olefinic synthetic rubbers including polychloroprene, polybutadiene, neoprene, styrene-butadiene copolymer rubber, acrylonitrile-butadiene copolymer rubber, ethylene-propylene copolymer rubber (EPM), ethylene-propylene-diene terpolymer rubber (EPDM), butyl rubber, brominated butyl rubber, alkylated chlorosulfonated polyethylene and the like.
  • the material may also be a thermoplastic elastomer such as those sold under the tradenames SANTOPRENE and ALCRYN by Monsanto and DuPont, respectively. This adhesive is particularly effective for bonding EPM and EPDM.
  • the metal substrate may be selected from any of the common structural metals such as iron, steel (including stainless steel and electrogalvanized steel), lead, aluminum, copper, brass, bronze, MONEL metal alloy, nickel, zinc and the like. Prior to bonding, the metal surface is typically cleaned according to one or more methods known in the art such as degreasing, grit-blasting and zinc-phosphatizing.
  • the adhesive composition typically is applied to the metal surface and the coated metal surface and elastomeric substrate are then brought together under heat and pressure to complete the bonding procedure.
  • the exact conditions selected will depend upon the particular elastomer being bonded and whether or not it is cured. In some cases, it may be desirable to preheat the metal surface prior to application of the adhesive composition to assist in drying of the adhesive composition.
  • the coated surface of the metal and the elastomeric substrate are typically brought together under a pressure of from 20 to 175 MPa, preferably from 20 to 50 MPa. If the elastomer is uncured, the resulting elastomer-metal assembly is simultaneously heated to a temperature of from 140°C to 200°C, preferably from 150°C to 170°C.
  • the assembly should remain under the applied pressure and temperature for a period of 3 minutes to 60 minutes, depending on the cure rate and thickness of the elastomeric substrate. If the elastomer is already cured, the bonding temperature may range from 90°C to above 180°C for 15 to 120 minutes.
  • the bonding process may be carried out by applying the elastomeric substrate as a semi-molten material to the metal surface as in, for example, an injection-molding process.
  • the process may also be carried out by utilizing compression molding, transfer molding or autoclave curing techniques. After the process is complete, the bond is fully vulcanized and ready for use in a final application.
  • aqueous adhesive composition having an approximately 45 percent solids content.
  • the adhesive composition is applied to bright stainless steel coil coupons and the coated coupons are heated (also known as pre-curing or pre-baking) to temperatures ranging from 93 °C to 232 °C to obtain a dry film thickness ranging from 2.5 to 15 ⁇ m.
  • EPDM rubber is milled to form a layer having a thickness of approximately 0.3 cm.
  • the rubber is preheated for 2 minutes at 93 °C and then contacted with the adhesive-coated substrate under minimal pressure.
  • the rubber-to-metal assembly then is cured for 3 minutes at 232°C.
  • This bonding method is intended to simulate commercially used rubber extrusion methods for producing a variety of parts such as automotive window channel.
  • Salt spray testing is performed by hanging the bonded test assemblies in a salt spray chamber that produces a 5% salt fog and maintains a temperature of 35°C.
  • the assemblies are tested for primary adhesion after 7 and 14 day exposures by hand peeling with needle nose pliers.
  • the adhesive compositions were applied to stainless steel and electrogalvanized steel coil coupons as described above in connection with Example 1.
  • the pre-bake temperature was 232°C. Rubber-to-metal assemblies were cured for 3 minutes at 232°C and for four minutes at 218°C.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Adhesives Or Adhesive Processes (AREA)

Abstract

L'invention concerne une composition adhésive aqueuse, destinée à fixer un substrat métallique à un substrat élastomère. Cette composition renferme un résol phénolique aqueux dispersable ou soluble, au moins un composé nitrosé aromatique ou un précurseur de composé nitrosé aromatique, et au moins une polyoléfine halogénée.
PCT/US1998/013762 1997-07-08 1998-06-30 Adhesif aqueux WO1999002583A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US88930097A 1997-07-08 1997-07-08
US08/889,300 1997-07-08

Publications (1)

Publication Number Publication Date
WO1999002583A1 true WO1999002583A1 (fr) 1999-01-21

Family

ID=25394875

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US1998/013762 WO1999002583A1 (fr) 1997-07-08 1998-06-30 Adhesif aqueux

Country Status (1)

Country Link
WO (1) WO1999002583A1 (fr)

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2000043131A2 (fr) * 1999-01-22 2000-07-27 Lord Corporation Adhesif a depot automatique
US6403673B2 (en) 2000-04-25 2002-06-11 3M Innovative Properties Company Water dispersed primers
WO2002048273A2 (fr) * 2000-12-14 2002-06-20 Henkel Kommanditgesellschaft Auf Aktien Liants aqueux caoutchouc-metal en une seule couche
WO2002057379A1 (fr) * 2001-01-18 2002-07-25 3M Innovative Properties Company Enduits a dispersion aqueuse
EP1683845A1 (fr) * 2005-01-21 2006-07-26 Advanced Elastomer Systems, L.P. Composition aqueuse adhésive et procédé de fixation d'un élastomère thermoplastique sur des substrats polaires
US7144630B2 (en) 2002-01-30 2006-12-05 Rohm And Haas Company Aqueous adhesive compositions for bonding elastomers
EP2006341A2 (fr) * 2006-04-13 2008-12-24 NOK Corporation Composition adhésive de vulcanisation
FR3017133A1 (fr) * 2014-02-06 2015-08-07 Michelin & Cie Composite de caoutchouc renforce d'au moins un element de renfort en acier adherise par une composition adhesive a base d'aldehyde aromatique et de polyphenol
FR3017070A1 (fr) * 2014-02-06 2015-08-07 Michelin & Cie Element de renfort en acier revetu par une composition adhesive a base d'aldehyde aromatique et de polyphenol

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0021186A1 (fr) * 1979-06-11 1981-01-07 Henkel Kommanditgesellschaft auf Aktien Liant à base de dispersions aqueuses pour déposer un caoutchouc sur un substrat par vulcanisation
US5200455A (en) * 1992-01-30 1993-04-06 Lord Corporation Aqueous adhesive compositions containing stabilized phenolic resins

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0021186A1 (fr) * 1979-06-11 1981-01-07 Henkel Kommanditgesellschaft auf Aktien Liant à base de dispersions aqueuses pour déposer un caoutchouc sur un substrat par vulcanisation
US5200455A (en) * 1992-01-30 1993-04-06 Lord Corporation Aqueous adhesive compositions containing stabilized phenolic resins

Cited By (20)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2000043131A2 (fr) * 1999-01-22 2000-07-27 Lord Corporation Adhesif a depot automatique
WO2000043131A3 (fr) * 1999-01-22 2000-09-28 Lord Corp Adhesif a depot automatique
US7109265B2 (en) 1999-01-22 2006-09-19 Lord Corporation Autodepositable adhesive
US6521687B2 (en) 1999-01-22 2003-02-18 Lord Corporation Autodepositable adhesive
US6403673B2 (en) 2000-04-25 2002-06-11 3M Innovative Properties Company Water dispersed primers
WO2002048273A3 (fr) * 2000-12-14 2002-08-29 Henkel Kgaa Liants aqueux caoutchouc-metal en une seule couche
US6902760B2 (en) 2000-12-14 2005-06-07 Henkel Kommanditgesellschaft Auf Aktien Aqueous one-coat rubber-metal bonding agents
AU2002231657B2 (en) * 2000-12-14 2006-06-01 Henkel Kommanditgesellschaft Auf Aktien Aqueous single layer rubber-metal binding agents
WO2002048273A2 (fr) * 2000-12-14 2002-06-20 Henkel Kommanditgesellschaft Auf Aktien Liants aqueux caoutchouc-metal en une seule couche
WO2002057379A1 (fr) * 2001-01-18 2002-07-25 3M Innovative Properties Company Enduits a dispersion aqueuse
KR100965485B1 (ko) * 2002-01-30 2010-06-24 롬 앤드 하스 캄파니 탄성중합체 결합용 수성 접착제 조성물
US7144630B2 (en) 2002-01-30 2006-12-05 Rohm And Haas Company Aqueous adhesive compositions for bonding elastomers
EP1683845A1 (fr) * 2005-01-21 2006-07-26 Advanced Elastomer Systems, L.P. Composition aqueuse adhésive et procédé de fixation d'un élastomère thermoplastique sur des substrats polaires
EP2006341A2 (fr) * 2006-04-13 2008-12-24 NOK Corporation Composition adhésive de vulcanisation
EP2006341A4 (fr) * 2006-04-13 2011-11-09 Nok Corp Composition adhésive de vulcanisation
FR3017133A1 (fr) * 2014-02-06 2015-08-07 Michelin & Cie Composite de caoutchouc renforce d'au moins un element de renfort en acier adherise par une composition adhesive a base d'aldehyde aromatique et de polyphenol
FR3017070A1 (fr) * 2014-02-06 2015-08-07 Michelin & Cie Element de renfort en acier revetu par une composition adhesive a base d'aldehyde aromatique et de polyphenol
WO2015118041A1 (fr) * 2014-02-06 2015-08-13 Compagnie Generale Des Etablissements Michelin Elément de renfort en acier revêtu par une composition adhésive à base d'aldéhyde aromatique et de polyphénol
WO2015118042A1 (fr) * 2014-02-06 2015-08-13 Compagnie Generale Des Etablissements Michelin Composite de caoutchouc renforcé d'au moins un élément de renfort en acier adhérisé par une composition adhésive à base d'aldéhyde aromatique et de polyphénol
US10864774B2 (en) 2014-02-06 2020-12-15 Compagnie Generale Des Etablissements Michelin Rubber composite reinforced by at least one steel reinforcing element rendered adhesive by an adhesive composition containing aromatic aldehyde and polyphenol

Similar Documents

Publication Publication Date Title
US5200455A (en) Aqueous adhesive compositions containing stabilized phenolic resins
US5162156A (en) Phenolic resin adhesion promoters and adhesive compositions, and bonding method employing same
CA2179633C (fr) Compositions primaires et adhesives a base de polyolefines chlorees a haute teneur en chlore
US7820747B2 (en) Method for preparing adhesives from stable butadiene polymer latexes
CA2359054C (fr) Adhesif a depot automatique
JP4064831B2 (ja) エラストマを接合させるための水性接着剤組成物
US5093203A (en) Polychloroprene-based adhesive system
WO1999002583A1 (fr) Adhesif aqueux
US6841600B2 (en) Environmentally friendly adhesives for bonding vulcanized rubber
EP0705315B1 (fr) Adhesif pour caoutchouc de copolymere acrylnitrile-butadiene
CA2462612C (fr) Adhesifs sans danger pour l'environnement destines au collage de caoutchouc vulcanise
KR102624257B1 (ko) 수계 1액형 접착제 조성물

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A1

Designated state(s): CA CN JP NO

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): AT BE CH CY DE DK ES FI FR GB GR IE IT LU MC NL PT SE

DFPE Request for preliminary examination filed prior to expiration of 19th month from priority date (pct application filed before 20040101)
121 Ep: the epo has been informed by wipo that ep was designated in this application
NENP Non-entry into the national phase

Ref country code: JP

Ref document number: 1999508761

Format of ref document f/p: F

122 Ep: pct application non-entry in european phase
NENP Non-entry into the national phase

Ref country code: CA