[go: up one dir, main page]

WO1992002577A1 - Composes adhesifs - Google Patents

Composes adhesifs Download PDF

Info

Publication number
WO1992002577A1
WO1992002577A1 PCT/US1991/005409 US9105409W WO9202577A1 WO 1992002577 A1 WO1992002577 A1 WO 1992002577A1 US 9105409 W US9105409 W US 9105409W WO 9202577 A1 WO9202577 A1 WO 9202577A1
Authority
WO
WIPO (PCT)
Prior art keywords
composition
microfibers
matrix
weight parts
amount
Prior art date
Application number
PCT/US1991/005409
Other languages
English (en)
Inventor
Yoshinori Igarashi
Yukihiro Ohjubo
Stephen O. Friend
Robert W. Hausslein
James J. Barber
Paul Nahass
Original Assignee
Hyperion Catalysis International
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 Hyperion Catalysis International filed Critical Hyperion Catalysis International
Publication of WO1992002577A1 publication Critical patent/WO1992002577A1/fr

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M177/00—Special methods of preparation of lubricating compositions; Chemical modification by after-treatment of components or of the whole of a lubricating composition, not covered by other classes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/02—Fibres or whiskers
    • C08K7/04—Fibres or whiskers inorganic
    • C08K7/06—Elements
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/02—Printing inks
    • C09D11/03—Printing inks characterised by features other than the chemical nature of the binder
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/43—Thickening agents
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/66—Additives characterised by particle size
    • C09D7/67—Particle size smaller than 100 nm
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/70—Additives characterised by shape, e.g. fibres, flakes or microspheres
    • 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
    • C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
    • 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
    • C09J201/00—Adhesives based on unspecified macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K3/00—Materials not provided for elsewhere
    • C09K3/10—Materials in mouldable or extrudable form for sealing or packing joints or covers
    • C09K3/1025—Materials in mouldable or extrudable form for sealing or packing joints or covers characterised by non-chemical features of one or more of its constituents
    • C09K3/1028—Fibres
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/04—Carbon
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/02—Fibres or whiskers
    • C08K7/04—Fibres or whiskers inorganic
    • 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
    • C08L2666/54—Inorganic substances
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K3/00—Materials not provided for elsewhere
    • C09K3/10—Materials in mouldable or extrudable form for sealing or packing joints or covers
    • C09K2003/1034—Materials or components characterised by specific properties
    • C09K2003/1078—Fire-resistant, heat-resistant materials
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2200/00—Chemical nature of materials in mouldable or extrudable form for sealing or packing joints or covers
    • C09K2200/02—Inorganic compounds
    • C09K2200/0204—Elements
    • C09K2200/0208—Carbon
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2200/00—Chemical nature of materials in mouldable or extrudable form for sealing or packing joints or covers
    • C09K2200/02—Inorganic compounds
    • C09K2200/0239—Oxides, hydroxides, carbonates
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2200/00—Chemical nature of materials in mouldable or extrudable form for sealing or packing joints or covers
    • C09K2200/02—Inorganic compounds
    • C09K2200/0243—Silica-rich compounds, e.g. silicates, cement, glass
    • C09K2200/0247—Silica
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2200/00—Chemical nature of materials in mouldable or extrudable form for sealing or packing joints or covers
    • C09K2200/02—Inorganic compounds
    • C09K2200/0278—Fibres
    • C09K2200/0282—Carbon fibres
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2200/00—Chemical nature of materials in mouldable or extrudable form for sealing or packing joints or covers
    • C09K2200/04—Non-macromolecular organic compounds
    • C09K2200/0458—Nitrogen-containing compounds
    • C09K2200/047—Amides, imides, imines, N-oxides
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2200/00—Chemical nature of materials in mouldable or extrudable form for sealing or packing joints or covers
    • C09K2200/06—Macromolecular organic compounds, e.g. prepolymers
    • C09K2200/0607—Rubber or rubber derivatives
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2200/00—Chemical nature of materials in mouldable or extrudable form for sealing or packing joints or covers
    • C09K2200/06—Macromolecular organic compounds, e.g. prepolymers
    • C09K2200/0645—Macromolecular organic compounds, e.g. prepolymers obtained otherwise than by reactions involving carbon-to-carbon unsaturated bonds
    • C09K2200/0647—Polyepoxides

Definitions

  • the present invention concerns adhesive compounds, or more specifically it concerns adhesive compounds with superior adhesion characteristics against oily surfaces.
  • oil adhesiveness an adhesive with superior adhesion characteristics to the oily surface
  • oil adhesive agents with improved polymer compounds which contain epoxy resins, or with oil absorbing filler have been proposed.
  • these oil adhesive agents required various additives such as viscosity adjusting fillers, dilutants, anti-flow agents, or anti-settling agents.
  • a purpose of the present invention is to offer adhesive compounds with superior oil adhesion
  • the invention features an adhesive composition that includes an adhesive matrix and an amount of carbon microfibers having diameters less than 1 micron
  • the extent of adhesion improvement is determined by measuring lap shear and T-peel strength.
  • microfibers is between 0.1 and 30 weight parts per 100 weight parts of matrix, preferably between 0.5 and 10 weight parts, and more preferably between 0.75 and 3 weight parts.
  • Preferred microfibers have diameters no greater than 0.1 micron.
  • carbon microfibers which are tubes having graphitic layers that are substantially parallel to the microfiber axis and diameters between 3.5 and 70 nanometers, inclusive.
  • microfibers are preferably substantially free of a continuous thermal carbon overcoat and have a length to diameter ratio of at least 5.
  • Preferred matrix materials include thermoset and thermoplastic resins.
  • preferred resins include, e.g., epoxy resins, polyurethane resins,
  • polysulfides such as styrene-butadiene-styrene, styrene-isoprene- styrene, and styrene-ethylene-propylene-styrene triblock copolymers
  • polyvinylacetate polyamides
  • polyvinyl alcohol vinyl acetate-ethylene copolymer
  • ethylene-vinyl acrylate copolymer ethylene-acrylic acid copolymer
  • polyvinyl acetal acrylic resins, polycyanoacrylates, animal and fish glues, starch and other cellulosics, polychloroprene, amino resins, anaerobic adhesive
  • thermoplastic matrix may be in the form of hot melt adhesives.
  • One or more rubbers and/or colorants may also be added to the adhesive
  • composition preferably has an electrical conductivity of at least 10 -8 S/cm which is retained even at elevated temperatures.
  • the “yield value” is the shear stress at which a measurable shear rate is obtained. It may be measured by plotting the square root of the shear rate vs. the square root of the shear stress using data obtained from a viscometer, and then extrapolating the shear stress to zero shear rate. The value of the shear stress at zero shear rate is the yield value. In the absence of carbon microfibers, the yield value of the liquid is about zero. Preferably, yield values of at least 5 dynes/cm2 are obtained upon addition of 3 wt.% or less carbon microfibers. The compositions exhibit improved sag resistance compared to the liquids in the absence of the microfibers.
  • the composition may be in the form of an adhesive (including rubber-metal bonding agents), paint, or sealant.
  • Suitable liquids include organic and aqueous polymer solutions, low molecular weight polymers and resins which are liquids at room temperature, and polymer latices.
  • the composition may also be in the form of a lubricating grease (e.g., where the liquid is an oil prior to microfiber addition) , ink, or a flame-retardant composition such as an anti-drip paint; the latter takes advantage of the ability of the carbon microfibers to increase the sag resistance of the composition.
  • a lubricating grease e.g., where the liquid is an oil prior to microfiber addition
  • ink e.g., ink
  • a flame-retardant composition such as an anti-drip paint
  • microfibers and amounts thereof useful as viscosity and yield value modifiers are set fo ⁇ th above.
  • these compositions may contain one or more
  • colorants and preferably have electrical conductivities of at least 10 -8 S/cm. Again, the electrical
  • matrices which are solid at room temperature
  • Preferred matrices are thermoplastics and elastomers.
  • microfibers are described above.
  • the composites may be in the form of a plastic panel.
  • the invention further features a) an adhesive that includes a matrix to which carbon microfibers and at least one colorant have been added, and b) an adhesive that includes a matrix and carbon microfibers in an amount sufficient to impart an electrical conductivity of at least 10 -8 S/cm.
  • polyurethane compounds, etc. can be mentioned as a curing type (i.e., thermoset) compound used in the adhesive compounds covered by the present invention.
  • a curing type i.e., thermoset
  • epoxy resin is the most preferable due to its superior adhesion to metal.
  • the compounds covered by the present invention can be prepared by various types of curing such as room-temperature curing, heat curing, and photo-curing
  • curing compound used, or the curing agent, curing accelerator, and/or bridging agent which are used as required.
  • they can be prepared either in a single or binary liquid formula depending on the composition of the compound and the type of curing.
  • epoxy type compounds which contain epoxy groups
  • condensation products between epichlorohydrin and polyhydroxy alcohol or polyhydroxy phenol such as
  • Bisphenol-F Bisphenol-A, ethyleneglycol, butanediol, glycerine, or erythritol; condensation products between epichlorohydrin and Novolak resin such as phenol Novolak resin, cresol Novolak resin; cyclic hydrocarbon epoxy compounds; glycidylester type epoxy compounds;
  • glycidylamine type epoxy compounds include heterocyclic epoxy compounds; epoxy compounds derived from polyolefin polymers or co-polymers; epoxy compounds obtained from glycidylmethacrylate polymers or co-polymers; epoxy compounds obtained from glycerides of unsaturated fatty acids; polyalkylene-ether type epoxy compounds; and bromine or fluorine containing epoxy compounds can be listed as specific examples.
  • epoxy compounds derived from polyolefin polymers or co-polymers include epoxy compounds obtained from glycidylmethacrylate polymers or co-polymers.
  • epoxy compounds obtained from glycerides of unsaturated fatty acids include polyalkylene-ether type epoxy compounds; and bromine or fluorine containing epoxy compounds.
  • Reaction products between isocyanate compounds and active hydrogen compounds can be listed as specific examples of polyurethane based curing type compounds.
  • polyisocyanate prepolymers which contain more than two isocyanate radicals in the molecule can be listed.
  • Various polyisocyanates including aliphatic, aromatic, and alicyclic
  • polyisocyanates can be used as a polyisocyanate that gives the pre-polymers. It is also possible to use these compounds together with pre-polymers.
  • Polyol compounds and polyamine compounds can be mentioned as examples of active hydrogen compounds.
  • Polyhydroxy alcohols such as ethyleneglycol, 1,4-butanediol, pentaerythritol, glycerine, ethyleneglycol, propyleneglycol, polyetherpolyols obtained by the
  • substitution polymerization between the aforementioned polyhydroxy alcohols and alkyleneoxides polyesterpolyols obtained by the condensation reaction between polyhydroxy alcohols and polybasic acids, and polyesterpolyols obtained by other methods, acrylpolyols, castor oil polyol and its derivatives, and epoxypolyols can be listed as polyol compounds.
  • polyamine compounds such as aliphatic polyamines and aromatic polyamines can be listed as polyamine compounds.
  • reaction products between phenol compounds and formaldehyde can be listed as specific examples.
  • monovalent or polyvalent phenols such as phenol, cresol, xylenol, para-t-butylphenol, resorcinol,
  • nonylphenol hydroquinone, catechol, etc. can be listed.
  • Epoxy compounds are normally used together with a curing agent.
  • the type of curing agent is selected depending on the intended type of curing.
  • aliphatic polyamines such as ethylenediamine, di-ethylenetriamine, tri-ethylenetetramine, tetra-ethylenepentamine, di-propylenediamine, di-ethylaminopropylamine,
  • hexamethylenediamine menthenediamine, isochorondiamine, bis (4-amino-3-methyldicyclohexyl)methane, diamino-dicyclohexylmethane, bis (aminomethyl) cyclohexane, N-aminoethylpiperidine, 3,9-bis (3-aminopropyl)-2,4,8,10-tetraoxa-spiro(5,5)undecan, m-xylenediamine; aromatic polyamines such as methaphenylenediamine,
  • diaminodiphenylmethane diamino-diphenylsulfone, diamino-diethyl-diphenylmethane, etc.
  • secondary or tertiary amines such as benzyldimethylamine, 2- (dimethylaminomethyl) phenol, 2,4,6,-tris (dimethylaminomethyl) phenol, tetramethylguanizine, N,N'-dimethylpiperidine, triethylenediamine, 1,8-diazabiscyclo(5,4,0) undecene, triethanolamine,
  • piperidine pyrolysine, polyamidamine, boron-monoethylamine-fluoride complex, etc.; anhydride such as methylnasic anhydride, dodecenylsuccinic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic
  • anhydride methylcondomethylene-tetrahydrophthalic anhydride, chlorend acid anhydride, ethyleneglycoltrimeritate anhydride ester, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, etc.;
  • imidazole derivatives such as imidazole, 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1-benzyl-2-methylimidazole, 1-cyanoethyl-2-methylimidazole, l-cyanoethyl-2- phenylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-methylimidazole-trimeritate, 1-cyanoethyl-2-phenylimidazole-trimeritate, 2, 4-diamino-6- ⁇ 2'-methylimidazole-(1') ⁇ -ethyl-S-triazine, 2,4-diamino-6- ⁇ 2'-undecylimidazole
  • the compound covered by the present invention is prepared by photo-curing, the use of aromatic diazonium salts, sulphonium salts, etc. which are known as ultraviolet curing catalysts is desirable.
  • the amount of these curing agents is normally determined so that the ratio between the amount of active hydrogens contained in these curing agents and the amount of epoxy radicals contained in the epoxy compounds become, for example, 1:0.8-1.2 (equivalent ratio).
  • a curing accelerator can be used with the compounds covered by the present invention as required.
  • tetriary amines such as 2,4,6-tris (dimethylaminomethyl) phenol, 2- (dimethylaminomethyl), 1,8-diazobicyclo(5,4,0)undecene and its salts, adipic acid dihydrazide, isophthalic dihydrazide, sebacic acid dihydrazide,
  • accelerators is determined depending on the type of accelerator, the curing conditions, etc.
  • a carbon microfiber whose diameter (D) is within the range of 3.5-70 nm or more preferably 7-25 nm, and whose length (L) is greater than at least 5 times the diameter or L/D>5 is used as the carbon microfiber which is the second component of the compounds covered by the present invention.
  • the desirable range for L/D is 10 2 -10 4 .
  • the carbon microfiber consists of an outer layer which is formed by many continuous annular layers made of uniformly aligned carbon atoms and an inner core. It is desirable for the microfiber to be practically in a cylindrical form in which the outer layer and the inner core are aligned concentric to the cylindrical center of the microfiber. Further, it is desirable for the inner core to be hollow, or for the inner core to contain carbon atoms whose alignment is not as uniform as the alignment of the outer layer, for the uniformly aligned carbon to be graphite, and for the inner core to have a diameter greater than about 2 nm.
  • the individual microfibers may form intertwined flocks with each other.
  • Such carbon microfiber can be prepared by the following procedures. Suitable metalcontaining particles such as iron, cobalt, or nickel particles carried on alumina, and suitable carbon
  • the dry weight ratio between the carbon containing organic material and the metal containing particles is at least 100/1.
  • the carbon microfiber can be surfaced- treated with a coupling agent, ultraviolet, plasma, etc. (e.g., as described in McCarthy et al., U.S.S.N. 351.967 entitled “Surface Treatment of Carbon Microfibers” filed May 15, 1989 and assigned to the same assignee as the present application and which is hereby incorporated by reference) prior to use as long as it is to such a degree that it does not adversely affect the oil adhesion effects.
  • a coupling agent ultraviolet, plasma, etc.
  • the compounds covered by the present invention can be mixed with rubber as required.
  • the rubber used for this purpose may be butadiene rubber, styrene-butadiene rubber, acrylonitrile-butadiene rubber, ethylene-propylene rubber, isoprene rubber, chloroprene rubber, butylrubber, acryl rubber, etc. Active radicals such as carboxyl radical, epoxy radical, or hydroxy radical may be introduced into these rubbers as required.
  • the method for mixing the rubber is not particularly restricted.
  • rubber into the compound gives resilience to the cured product, and also improves the adhesion characteristics.
  • various additives such as a elastomer, pigment, leveling agent, tackiness imparting agent, anti-foam, heat stabilizer, photo stabilizer, fillers, etc. can be added as required to the compounds covered by the present invention.
  • other electrically conductive or oil absorbing fillers such as carbon black, graphite powder, or carbon fibers can be added together with the carbon microfibers.
  • R-1309 ACR Co. manufacturer, acryloritrile-butadiene rubber 30% containing epoxy resin
  • Carbon black Asahi Carbon manufacturer, HS-500 • Carbon fiber: Hicarbon A-6000, diameter 7 ⁇ m, length 0.5 mm
  • the dispersion characteristics (O: good, X: poor) were evaluated by using a three-roll kneader.
  • Adhesion objects were prepared by soaking two steel plates with 1.6x25x100 mm and 0.8 ⁇ 25 ⁇ 200 mm
  • rust protecting oil (RL-55; Idemitsu Kosan manufacturer), and then leaving them standing vertically over night. Compounds were coated on these objects, and then two plates were immediately pressed together. The plates were clamped and cured at 180°C for a period of 30 minutes, or 140°C for a period of 60 minutes. The thickness of the compound was adjusted to 0.25 mm. Subsequently, the tensile breaking strength and T-type peeling strength were measured. Incidentally, the tensile speed was 5 mm/min for the measurement of the tensile breaking strength, and 50 mm/min for the
  • the compounds covered by the present invention give superior oily surface adhesion characteristics with a relatively small amount of carbon microfiber addition as compared to the amount of carbon black or carbon fiber conventionally used as oil absorbing filler. Further, the addition of carbon microfiber resulted in the resilience and
  • the compounds covered by the present invention have superior oily surface adhesiveness, storage stability, and applicability, and they are, for example, extremely suitable for the adhesion of edging parts of automobiles which contain an oily surface.
  • the compounds covered by the present invention contain dispersed carbon microfibers, they have an advantage of improved electric conductivity.
  • the sample had good electrical conductivity (110 kohms from bead to panel).
  • This example demonstrates the improvement in lap shear strength of adhesives upon addition of carbon microfibers.
  • Araldite AW-105 an epoxy resin commercially available from Ciba-Geigy
  • HV-953 curing agent also available from Ciba-Geigy
  • 1.4 parts carbon microfibers as described above
  • the bond thickness of the epoxy adhesive was 0.012 in.
  • the lap shear strength of the adhesive bond was then measured and compared to that of the epoxy resin alone applied to identical surfaces. The results are shown below.
  • This example also demonstrates the improvement in lap shear strength of adhesives upon addition of carbon microfibers.
  • Epon 828 an epoxy resin commercially available from Shell
  • Epon V-40 curing agent also available from Shell
  • was combined with 1.34 parts carbon microfibers (as described above) per hundred parts epoxy resin, and cured at 25 °C overnight, then at 150°C for 1 hour. It was then applied to (a) the clean surface of an aluminum substrate (substrate thickness 0.125 in.) and (b) to the same surface coated with WD-40 to make it oily.
  • This example describes the ability of carbon microfibers compared to fumed silica to modify the viscosity and impart yield values to liquids.
  • Dispersions of carbon microfibers and three types of commercially available fumed silica were prepared in the following media:
  • 1 DOP is dioctyl phthalate.
  • fumed silica All available from Degussa
  • Aerosil 200 hydrophilic
  • Aerosil COK 84 hydrophilic with 15% alumina added
  • Aerosil R202 hydrophobic
  • DOP and toluene only carbon microfiber and Aerosil 200-containing dispersions were prepared.
  • Each dispersion was prepared by adding the thickening agent (carbon microfibers or fumed silica) to the thickening agent (carbon microfibers or fumed silica) to the thickening agent (carbon microfibers or fumed silica) to the thickening agent (carbon microfibers or fumed silica) to
  • Viscosity readings were taken at 5, 10, 20, 50, and 100 rpm using the LV-1, LV-2 , LV-3, and helipath spindles. Viscosity was reported at 50 rpm for most runs, corresponding to a shear rate of about 10 sec -1 .
  • Microfibers (wt.%1
  • the yield values of the various thickened media were obtained by plotting the square root of the shear rate vs. the square root of the shear stress using data obtained from the viscometer, and extrapolating the stress value to zero shear rate to determine the yield value.
  • the carbon microfibers were also easier to handle than the fumed silicas because they were more easily wet by the media, had a lower initial viscosity (thereby facilitating pouring and cleaning), and created less of a dusting problem. In turn, this lead to enhanced accuracy in formulation and ease of processing.
  • This example illustrates the ability of carbon microfibers to increase viscosity.
  • Viscosity (poise)

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Nanotechnology (AREA)
  • Adhesives Or Adhesive Processes (AREA)

Abstract

Compositions adhésives comprenant une matrice et des microfibres de carbone dont les diamètres sont inférieurs à un micron. L'invention concerne également des compositions comprenant un liquide ainsi qu'une quantité desdites microfibres de carbone suffisantes pour augmenter la valeur de viscosité et/ou de contrainte de cisaillement du liquide par rapport aux valeurs de ces propriétés en l'absence des microfibres de carbone.
PCT/US1991/005409 1990-07-30 1991-07-30 Composes adhesifs WO1992002577A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US55925490A 1990-07-30 1990-07-30
US559,254 1990-07-30

Publications (1)

Publication Number Publication Date
WO1992002577A1 true WO1992002577A1 (fr) 1992-02-20

Family

ID=24232913

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US1991/005409 WO1992002577A1 (fr) 1990-07-30 1991-07-30 Composes adhesifs

Country Status (2)

Country Link
AU (1) AU8322991A (fr)
WO (1) WO1992002577A1 (fr)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5602221A (en) * 1993-11-10 1997-02-11 Minnesota Mining And Manufacturing Company Pressure sensitive adhesives with good low energy surface adhesion
US5616670A (en) * 1993-11-10 1997-04-01 Minnesota Mining And Manufacturing Company Pressure sensitive adhesives with good oily surface adhesion
US5654387A (en) * 1993-11-10 1997-08-05 Minnesota Mining And Manufacturing Company Pressure sensitive adhesives
US5683798A (en) * 1993-11-10 1997-11-04 Minnesota Mining And Manufacturing Company Tackified pressure sensitive adhesives
WO1998031766A1 (fr) * 1997-01-17 1998-07-23 Federal-Mogul Technology Limited Materiau d'etancheite
WO2013162840A1 (fr) * 2012-04-26 2013-10-31 Dow Global Technologies Llc Composition adhésive époxy

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4472541A (en) * 1982-10-01 1984-09-18 The Bendix Corporation Secondary matrix reinforcement using carbon microfibers
JPS61218669A (ja) * 1985-03-23 1986-09-29 Asahi Chem Ind Co Ltd 炭素質繊維含有塗料組成物
US4778716A (en) * 1987-03-26 1988-10-18 Basf Corporation Method of increasing the toughness of fiber-reinforced composites without loss of modulus
EP0325236A2 (fr) * 1988-01-19 1989-07-26 Yazaki Corporation Matériau composite à base de résine contenant des fibres de graphite
JPH01282276A (ja) * 1988-05-10 1989-11-14 Asahi Chem Ind Co Ltd 炭素質繊維含有接着剤
JPH01287151A (ja) * 1988-05-13 1989-11-17 Asahi Chem Ind Co Ltd ゴム組成物

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4472541A (en) * 1982-10-01 1984-09-18 The Bendix Corporation Secondary matrix reinforcement using carbon microfibers
JPS61218669A (ja) * 1985-03-23 1986-09-29 Asahi Chem Ind Co Ltd 炭素質繊維含有塗料組成物
US4778716A (en) * 1987-03-26 1988-10-18 Basf Corporation Method of increasing the toughness of fiber-reinforced composites without loss of modulus
EP0325236A2 (fr) * 1988-01-19 1989-07-26 Yazaki Corporation Matériau composite à base de résine contenant des fibres de graphite
JPH01282276A (ja) * 1988-05-10 1989-11-14 Asahi Chem Ind Co Ltd 炭素質繊維含有接着剤
JPH01287151A (ja) * 1988-05-13 1989-11-17 Asahi Chem Ind Co Ltd ゴム組成物

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5602221A (en) * 1993-11-10 1997-02-11 Minnesota Mining And Manufacturing Company Pressure sensitive adhesives with good low energy surface adhesion
US5616670A (en) * 1993-11-10 1997-04-01 Minnesota Mining And Manufacturing Company Pressure sensitive adhesives with good oily surface adhesion
US5654387A (en) * 1993-11-10 1997-08-05 Minnesota Mining And Manufacturing Company Pressure sensitive adhesives
US5683798A (en) * 1993-11-10 1997-11-04 Minnesota Mining And Manufacturing Company Tackified pressure sensitive adhesives
US5708110A (en) * 1993-11-10 1998-01-13 Minnesota Mining And Manufacturing Company Pressure sensitive adhesives with good low energy surface adhesion
US5708109A (en) * 1993-11-10 1998-01-13 Minnesota Mining And Manufacturing Company Pressure sensitive adhesives with good oily surface adhesion
US5756584A (en) * 1993-11-10 1998-05-26 Minnesota Mining And Manufacturing Company Tackified pressure sensitive adhesives
US5883149A (en) * 1993-11-10 1999-03-16 Minnesota Mining And Manufacturing Company Tackified pressure sensitive adhesives
WO1998031766A1 (fr) * 1997-01-17 1998-07-23 Federal-Mogul Technology Limited Materiau d'etancheite
US6177504B1 (en) 1997-01-17 2001-01-23 Federal-Mogul Technology Limited Sealing material
WO2013162840A1 (fr) * 2012-04-26 2013-10-31 Dow Global Technologies Llc Composition adhésive époxy
CN104245875A (zh) * 2012-04-26 2014-12-24 陶氏环球技术有限责任公司 环氧粘合剂组合物

Also Published As

Publication number Publication date
AU8322991A (en) 1992-03-02

Similar Documents

Publication Publication Date Title
CA2304539C (fr) Revetements epoxyde insonorisants flexibles
KR20150003373A (ko) 에폭시 접착제 조성물
CN1433453A (zh) 具有与浸油金属表面改进粘合性的环氧基增强补片
CN105705585B (zh) 用于改进的冲击强度和柔性的树脂组合物的添加剂
US4695598A (en) Epoxy resin coating composition
EP1715003A1 (fr) Compositions de résine epoxy résistantes aux chocs
TW200831410A (en) Surface-modified, structurally modified fumed silicas
EP0309903B2 (fr) Compositions durcissables à base d'époxyde et de caoutchouc ayant une bonne adhésion directe aux métaux
EP3632982A1 (fr) Matériau de moulage, et matériau composite renforcé par des fibres
CN112654666A (zh) 片状模塑料及纤维增强复合材料
JP3516798B2 (ja) 室温硬化性２液混合型組成物
CN110669471A (zh) 一种环保型高强度有机硅胶粘剂及其制备方法
JPS58168619A (ja) エポキシ樹脂組成物
WO1992002577A1 (fr) Composes adhesifs
JP4475687B2 (ja) コンクリート構造体用二液型エポキシ樹脂接着剤、およびそれを用いたコンクリート構造体の補修・補強方法
JP2005187683A (ja) 樹脂塗膜用プライマー
JP2000169820A (ja) 接着剤組成物
JP3661358B2 (ja) 液状エポキシ樹脂組成物およびコンクリート構造物の補修・補強方法
JPH11323297A (ja) 接着剤組成物
JP4765208B2 (ja) エポキシ樹脂組成物およびそれを用いたコンクリート構造体の補修・補強方法
JPS6268874A (ja) 接着剤組成物
US9018282B2 (en) Homogenous dispensing process for an epoxy-composition with high filler content
JPS60210688A (ja) 防汚処理方法
JPH02292381A (ja) 接着剤組成物
JP2010006936A (ja) 混合増粘型硬化性樹脂組成物及び硬化性樹脂組成物における増粘方法

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A1

Designated state(s): AU BB BG BR CA CS FI HU JP KP KR LK MC MG MN MW NO PL RO SD SU

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): AT BE BF BJ CF CG CH CI CM DE DK ES FR GA GB GN GR IT LU ML MR NL SE SN TD TG

NENP Non-entry into the national phase

Ref country code: CA

122 Ep: pct application non-entry in european phase
122 Ep: pct application non-entry in european phase
122 Ep: pct application non-entry in european phase
122 Ep: pct application non-entry in european phase