EP1601706A1 - Composition de resine epoxy polymere - Google Patents

Composition de resine epoxy polymere

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Publication number
EP1601706A1
EP1601706A1 EP04714274A EP04714274A EP1601706A1 EP 1601706 A1 EP1601706 A1 EP 1601706A1 EP 04714274 A EP04714274 A EP 04714274A EP 04714274 A EP04714274 A EP 04714274A EP 1601706 A1 EP1601706 A1 EP 1601706A1
Authority
EP
European Patent Office
Prior art keywords
composition according
nanoparticles
bisphenol
polymeric composition
copolymer
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP04714274A
Other languages
German (de)
English (en)
Inventor
Christian Eger
Stephan Sprenger
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Evonik Operations GmbH
Original Assignee
Hanse Chemie AG
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 Hanse Chemie AG filed Critical Hanse Chemie AG
Priority to EP04714274A priority Critical patent/EP1601706A1/fr
Publication of EP1601706A1 publication Critical patent/EP1601706A1/fr
Withdrawn legal-status Critical Current

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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
    • C08J5/005—Reinforced macromolecular compounds with nanosized materials, e.g. nanoparticles, nanofibres, nanotubes, nanowires, nanorods or nanolayered materials
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/182—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing using pre-adducts of epoxy compounds with curing agents
    • C08G59/186—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing using pre-adducts of epoxy compounds with curing agents with acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/4007—Curing agents not provided for by the groups C08G59/42 - C08G59/66
    • C08G59/4014—Nitrogen containing compounds
    • C08G59/4021—Ureas; Thioureas; Guanidines; Dicyandiamides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/50—Amines
    • C08G59/56—Amines together with other curing agents
    • C08G59/58—Amines together with other curing agents with polycarboxylic acids or with anhydrides, halides, or low-molecular-weight esters thereof
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/03—Use of materials for the substrate
    • H05K1/0313—Organic insulating material
    • H05K1/0353—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement
    • H05K1/0373—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement containing additives, e.g. fillers
    • 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
    • C08J2363/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
    • 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
    • C08K3/34—Silicon-containing compounds
    • C08K3/36—Silica
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
    • H05K2201/02—Fillers; Particles; Fibers; Reinforcement materials
    • H05K2201/0203—Fillers and particles
    • H05K2201/0206—Materials
    • H05K2201/0209—Inorganic, non-metallic particles
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
    • H05K2201/02—Fillers; Particles; Fibers; Reinforcement materials
    • H05K2201/0203—Fillers and particles
    • H05K2201/0242—Shape of an individual particle
    • H05K2201/0257—Nanoparticles

Definitions

  • the invention relates to polymeric compositions based on epoxy resin.
  • epoxy resins are used extensively for adhesives (heat-curing one-component adhesives and room-temperature-curing two-component adhesives), as a resin component of composite materials, in particular fiber composite materials, for so-called coatings (coatings) and as a casting compound, for example for the casting of electronic components.
  • Epoxy resins are usually hard and brittle when cured. They have a low mechanical resistance, particularly against peeling and impact stresses.
  • the invention has for its object to provide a polymeric composition of the type mentioned, which has improved properties over the prior art mentioned.
  • the polymeric composition according to the invention contains the following components:
  • SANS small angle neutron control
  • Epoxy resins are monomers or prepolymers that contain an average of two or more epoxy groups per molecule. The reaction of these epoxy resins with a number of known hardeners leads to crosslinked or thermoset thermosets. Epoxy resins which can be used in the context of the invention are described, for example, in Ullmann's Encyclopedia of Industrial Chemistry, 6th edition, volume A12, page 285 ff.
  • the copolymer provided according to the invention must have reactive groups which can react with the epoxy groups of the epoxy resin and thus chemically bind the copolymer into the epoxy resin.
  • the term copoplymer in this context means that the polymer can react chemically with the epoxy resin through these reactive groups. Structurally, this copolymer with reactive groups can be a homo- or copolymer or oligomer.
  • the copolymer has a glass transition temperature T g of -20 ° C or less. After it has hardened, it forms what are known as rubber domains in the polymer according to the invention, which have the glass transition temperature mentioned.
  • the rubber domains are essentially phases containing only the copolymer, which are embedded in the epoxy resin and which cause a modification of the mechanical properties, in particular the impact resistance.
  • essentially only van der Waals forces can act between the copolymer molecules; in the border area to the epoxy resin matrix, due to the penetration of the copolymer into epoxy resin groups.
  • the polymer composition according to the invention is in a state which can be regarded as a borderline case between a true two-phase system (epoxy resin matrix with rubber domains) and an interpenetrating network.
  • Another component of the composition according to the invention are nanoparticles or nanoparticles with an average particle size d ⁇ of 5 to 150 nm.
  • Neutron small angle scattering (SANS small angel neutron scattering) is used as a method for measuring the average particle size. This measurement method is familiar to the person skilled in the art and does not require any further explanation here.
  • SANS measurement a particle size distribution curve is obtained, in which the volume fraction of particles of a corresponding size (diameter) is plotted against the particle diameter. The peak of such a SANS distribution curve, ie the largest volume fraction with particles of corresponding diameter, is defined as the average particle size.
  • the invention is based on the knowledge that the modification of epoxy resins with copolymers forming rubber domains on the one hand and nanoparticles or particles on the other hand brings about a clear and unexpected improvement in the mechanical properties of a cured polymer composition according to the invention.
  • thermosets After crosslinking and hardening, thermosets with a significantly improved fracture and impact resistance are obtained, with other important properties which are characteristic of thermosets, such as strength, heat resistance and resistance to chemicals, remaining essentially unaffected. It was not to be expected for the person skilled in the art that the combination of the modification of epoxy resin materials, known per se, with polymers on the one hand and nanoparticles on the other hand has a synergistic effect and one causes significant improvement in mechanical properties.
  • the epoxy resins can be, for example, glycidyl-based resins.
  • Glycidyl-based resins are obtainable by allowing epichlorohydrin to react with substances that have at least two reactive hydrogen atoms per molecule. These can be, for example, polyphenols, mono- and diamines, aminophenols, heterocyclic imides and amides, aliphatic diols and polyols and dimeric fatty acids.
  • the polyglycidyl-based epoxy resins are preferred.
  • Epoxy resins based on the diglycidyl ether of bisphenol A (DGEBA) are particularly preferred.
  • Epoxy resins based on epoxidized aliphatic or preferably cycloaliphatic dienes can also be used.
  • thermosetting material when a polymeric composition is used in the context of the invention, this term encompasses both the not yet crosslinked or hardened mixture of the corresponding constituents and a thermoset material produced therefrom.
  • the still reactive mixtures can be both one-component mixtures that can be caused to react by external influences (for example, heat-curing one-component adhesives) as well as multi-component mixtures in which, after the components have been mixed, curing to the thermosetting material begins (for example, two-component epoxy resin adhesive ).
  • the glass transition temperature T g of the domains is preferably at most -30 ° C., more preferably -40, -50 or -60 ° C. it does not exceed -100 ° C.
  • the preferred glass transition temperature also depends on the intended use of the polymeric compositions according to the invention. When used as structural adhesives in vehicle or aircraft construction, for example, high impact strength is important even at low temperatures in order to ensure sufficient strength of the bond even in the event of accidents (crash safety). Common test temperatures for the strength of structural bonds in automotive construction are, for example, -40 ° C, in aircraft construction -60 ° C.
  • the proportion of the copolymer in the polymeric composition according to the invention is preferably 2 to 30% by weight, more preferably 4 to 18% by weight.
  • the copolymers are usually not readily miscible with the epoxy resin.
  • so-called adducts or prepolymers are therefore generally first prepared by chemically reacting the copolymers with an excess of epoxy resin. These adducts can be mixed with all common epoxy resins. In the context of the invention it is therefore not necessary for the copopolymer to have reactive groups when mixed with the other constituents of the polymeric composition.
  • this epoxy resin component having a molar excess of epoxy groups compared to the reactive groups compared to the reactive groups of the copolymer.
  • the rubber domains in the cured composition preferably have an average size determined by
  • SEM or TEM from 0.05 to 20 ⁇ m, more preferably 0.1 to 10 ⁇ m, more preferably 0.2 to 4 ⁇ m.
  • copolymers examples include 1,3-diene polymers with carboxyl groups and other polar ethylenically unsaturated comonomers.
  • Butadiene, isoprene or chloroprene can be used here, butadiene is preferred.
  • polar, ethylenically unsaturated comonomers are acrylic acid, methacrylic acid, lower alkyl esters of acrylic or methacrylic acid, for example their methyl or ethyl esters, amides of acrylic or methacrylic acid, fumaric acid, itaconic acid, maleic acid or their lower alkyl esters or half esters , or maleic or itaconic anhydride, vinyl esters such as vinyl acetate or in particular acrylonitrile or methacrylonitrile.
  • Very particularly preferred copolymers are carboxyl-terminated butadiene-acrylonitrile copolymers (CTBN) or amino-functional butadiene-acrylonitrile copolymers (ATBN), which are offered in liquid form under the trade name Hycar by the company Noveon (formerly B. F. Goodrich). These have molecular weights between 2000 and 5000 and acrylonitrile contents between 10% and 30%. Specific examples are Hycar CTBN 1300 X 8, 1300 X 13, 1300 X 18 or ATBN 1300 X 16.
  • hardening systems known and known to the person skilled in the art are provided for hardening the epoxy resin.
  • guanidines substituted guanidines, substituted ureas, melamine resins, guanamine derivatives, cyclic tertiary amines, aromatic amines and / or their can be used as thermally activatable or latent hardeners for the epoxy resin Mixtures are used.
  • the hardeners can be included stoichiometrically in the hardening reaction, but they can also be catalytically active.
  • substituted guanidines are methylguanidine, dimethylguanidine, trimethylguanidine, tetramethylguanidine, methylisobiguanidine, dimethylisobiguanidine, tetramethylisobiguanidine, hexamethylisobiguanidine, hepamethylisobiguanidine and very particularly cyanoguanidine (dicyandiamide).
  • Alkylated benzoguanamine resins, benzoguanamine resins or methoxymethylethoxyethylbenzoguanamine may be mentioned as representatives of suitable guanamine derivatives.
  • Dicyandiamide is suitable for heat-curing one-component paste adhesives. This ensures good storage stability of the composition.
  • catalytically active substituted ureas can be used. These are, in particular, p-chlorophenyl-N, N-dimethylurea (monuron), 3-phenyl-1,1-dirnethylurea (fenuron) or 3,4-dichlorophenyl-N, N-dimethylurea (diuron).
  • catalytically active tertiary acrylic or alkyl amines such as, for example, benzyldimethylamine, tris (diethylamino) phenol, piperidine or piperidine derivatives, can also be used.
  • compositions according to the invention can furthermore contain customary other auxiliaries and additives, such as, for example, plasticizers, diluents, rheology aids, wetting agents, anti-aging agents, stabilizers and / or color pigments.
  • compositions according to the invention can be formulated as one-component adhesives, these being formulated both as highly viscous adhesives which can be applied warm can be used as thermally curable hot melt adhesives.
  • compositions according to the invention can also be formulated as two-component epoxy adhesives, in which the two reaction components are only mixed with one another shortly before application, the curing then taking place at room temperature or at moderately elevated or reduced temperature.
  • the reaction components known per se for two-component epoxy adhesives for example di- or polyamines, a terminated polyalkylene glycols (e.g. Jeffamine, amino-poly-THF) or polyaminoamides, can be used as the second reaction component.
  • Other reactive partners can be mercapto-functional prepolymers such as the liquid thiokol polymers.
  • the epoxy compositions according to the invention can also be cured with carboxylic anhydrides as the second reaction component.
  • the proportion of the hardener based on the total amount of epoxy resin and hardener can preferably be between 4 and 50% by weight.
  • the nanoparticles are preferably selected from the group consisting of silicon dioxide, carbonates (for example chalk) and montmorillonite. Silicon dioxide nanoparticles as disclosed in WO-A-02/083776 are particularly preferred.
  • the nanoparticles are preferably surface-modified in order to prevent or reduce their agglomeration and to facilitate their incorporation into the resin matrix. In the case of silicas, a preferred surface modification is the silanization with suitable silanes.
  • the silanes can have hydrolyzable and non-hydrolyzable, optionally functional groups.
  • hydrolyzable groups are halogen, alkoxy, alkenoxy, acylox, oximino and amino groups.
  • functional nelle, non-hydrolyzable groups are vinyl, aminopropyl, chloropropyl, aminoethylaminopropyl, glycidyloxypropyl, mercapto propyl or methacryloxypropyl groups.
  • non-hydrolyzable, non-functional groups are monovalent C x to C 8 hydrocarbon residues.
  • inventively usable silanes are: ⁇ - aminopropyltrimethoxysilane, ⁇ -Aminopropylmethyldiethoxy- silane, ⁇ -amino-Propyldimethylmethoxysilan, Glycidyloxypro- pyltrimethoxysilan, methacryloxypropyltrimethoxysilane, chloropropyl, vinyl methyl, nyltrispropenoxysilan Vi, Vinyldimethylbutanoximsilan, Vinyltrisbutanonoximsilan, trimethylchlorosilane, vinyldi- methylchlorosilane, dimethylchlorosilane, Vinylmethylchlorsi - lan.
  • the silanes are preferably used in a concentration of 40 to 200 mol% and particularly preferably from 60 to 150 mol%, based on the molar amount of silanol groups on the surface of the nanoparticles.
  • the average particle size d ⁇ . the nanoparticles is preferably between 6 and 100 nm, more preferably 6 and 40 nm, more preferably 8 and 30 nm, more preferably 10 and 25 nm.
  • the maximum half width of the distribution curve of the particle size of the nanoparticles is preferably at most 1.5. ⁇ , more preferably at most 1.2 d- ⁇ , more preferably at most 0.75 cL ⁇ .
  • the width at half maximum of the distribution curve is the width (in nm) of the distribution curve at half the height, i.e. at half the particle volume fraction at the distribution curve peak d- ⁇ or (in other words) the width of the distribution curve at half the height of the Y axis (relative to Height of the curve at d- ⁇ ).
  • the nanoparticles can have a mono- or multimodal distribution curve. In the case of a monomodal distribution curve, this has only a maximum.
  • a multimodal distribution curve has two or more maxima, within In the range from 5 to 150 nm mentioned there are two or more maxima d ⁇ of the curve.
  • particles with bi- or trimodal distribution curves are preferred.
  • the width of the half-value curve is determined separately for each maximum.
  • the invention also relates to an adhesive which contains a polymeric composition according to the invention.
  • a polymeric composition according to the invention One and two-component epoxy resin adhesives and their possible use, in particular for structural bonds in vehicle and aircraft construction, have already been explained above.
  • the epoxy resins are preferably selected from the group consisting of bisphenol A and bisphenol F-based resins.
  • the proportion of nanoparticles in the polymeric composition for adhesives is preferably 0.5 to 5% by weight, more preferably 1 to 3% by weight. It has been found that adhesives according to the invention with nanoparticle contents of significantly more than 2% by weight no longer achieve any significant improvement in impact strength (measured by tensile shear tests according to DIN 55283).
  • the invention further relates to composite materials which contain polymeric compositions according to the invention.
  • these are fiber composite materials such as glass fiber or carbon fiber composite materials.
  • the polymeric composition of the invention in such a composite is the impregnation resin.
  • the impregnation resin is the matrix resin in which the fibers or fabrics are embedded, regardless of the embedding process. Due to the very small particle size of the nanoparticles, a polymer composition according to the invention as an impregnating resin can also penetrate tightly packed reinforcing fibers, as are intended for highly stressed composite materials. The advantageous mechanical properties of the composition according to the invention can thus develop in the entire component.
  • the epoxy resins are preferably selected from the group consisting of bisphenol A and bisphenol F-based resins, novolak resins and aromatic glycidylamines.
  • the proportion of the nanoparticles in the polymeric composition is preferably 3 to 20% by weight, more preferably 6 to 10% by weight.
  • Composite materials according to the invention can be used, for example, for the production of printed circuit boards, structural components for vehicles and airplanes, sports equipment, radar masts, windmill blades or the like.
  • the invention further relates to coatings which contain a polymeric composition according to the invention.
  • coatings can be, for example, paints, varnishes or other coatings.
  • the epoxy resins of the polymeric composition according to the invention are preferably selected from the group consisting of bisphenol A and bisphenol F-based resins and epoxidized cycloaliphatics.
  • the proportion of the nanoparticles in the polymeric composition is preferably 10 to 50% by weight, more preferably 20 to 50% by weight.
  • the invention also relates to casting compounds which contain a polymeric composition according to the invention.
  • Potting compounds are used in the electrical and electronics industry as electrical insulating resins, for example when casting coils or transformers, or as a so-called die-attach adhesive for gluing components onto printed circuit boards.
  • the casting compound the impregnating resin
  • the epoxy resins are preferably selected from the group consisting of bisphenol A and bisphenol F-based resins and the epoxidized cycloaliphatics.
  • the proportion of the nanoparticles in the polymeric composition is preferably 10 to 50% by weight, more preferably 20 to 50% by weight.
  • the invention thus also relates to the use of a polymeric composition according to the invention for producing a product selected from the group consisting of adhesives, composite materials, coatings and casting compounds.
  • thermosetting one-component adhesives Formulation of thermosetting one-component adhesives.
  • Heat-curing one-component adhesives were used in accordance with the recipe in Table 1 below.
  • the figures in the table are parts by weight.
  • Examples 1 and 2 are examples according to the invention, control 1 is an epoxy resin, control 2 is an epoxy resin with a CTBN copolymer
  • DGEBA diglycidyl ether of bisphenol A
  • Nanoadduct monomodal Si0 2 with ad_, aJ . of 20 nm in an adduct of DGEBA epoxy resin and the CTB rubber Hycar 1300 X 13.
  • Cabot TS 720 ' Pyrogenic silica as a thixotropic agent
  • Dyhard 100 SF hot hardener based on dicyandiamide
  • Dyhard UR 300 hardening accelerator based on monuron (p-chlorophenyl-N, -dirnethylurea)
  • Control 3 is a comparative example without nanoparticles.
  • Nanopox 40 wt .-% nano-Si0 2 with ad ⁇ of 20 nm in DGEBA.
  • Polypox P 502 hardener based on isophoronediamine (manufacturer UPPC)
  • the one-component adhesives in Table 1 and components A and B of the two-component adhesives in Table 2 were applied to untreated aluminum for tensile shear tests in accordance with DIN 55283. The thickness of the adhesive layer was adjusted to 0.5 mm using glass beads.
  • the adhesives in Table 1 were cured at 120 ° C. for 1 hour and then at 180 ° C. for two hours.
  • the two-component adhesives in Table 2 were cured for 24 hours at room temperature and for two hours at 60 ° C.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Medicinal Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Nanotechnology (AREA)
  • Materials Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Physics & Mathematics (AREA)
  • Composite Materials (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Epoxy Resins (AREA)

Abstract

La présente invention concerne une composition polymère contenant a) au moins une résine époxy, b) au moins un copolymère qui présente des groupes réactifs avec des résines époxy et une température de transition vitreuse Tg inférieure ou égale à -20° C, ainsi que c) des nanoparticules qui présentent une taille particulaire moyenne dmax de 5 à 150 nm, mesurée au moyen d'une diffusion des neutrons aux petits angles (SANS). La composition selon cette invention permet de produire des adhésifs, des matériaux composites, des revêtements et des matériaux d'étanchéité présentant des caractéristiques mécaniques améliorées, notamment une meilleure résistance aux chocs.
EP04714274A 2003-03-11 2004-02-25 Composition de resine epoxy polymere Withdrawn EP1601706A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP04714274A EP1601706A1 (fr) 2003-03-11 2004-02-25 Composition de resine epoxy polymere

Applications Claiming Priority (6)

Application Number Priority Date Filing Date Title
EP03005538 2003-03-11
EP03005538 2003-03-11
EP03005377A EP1457509B1 (fr) 2003-03-11 2003-03-12 Composition de polymère à base de résine Epoxy
EP03005377 2003-03-12
EP04714274A EP1601706A1 (fr) 2003-03-11 2004-02-25 Composition de resine epoxy polymere
PCT/EP2004/001871 WO2004081076A1 (fr) 2003-03-11 2004-02-25 Composition de resine epoxy polymere

Publications (1)

Publication Number Publication Date
EP1601706A1 true EP1601706A1 (fr) 2005-12-07

Family

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Family Applications (2)

Application Number Title Priority Date Filing Date
EP03005377A Expired - Lifetime EP1457509B1 (fr) 2003-03-11 2003-03-12 Composition de polymère à base de résine Epoxy
EP04714274A Withdrawn EP1601706A1 (fr) 2003-03-11 2004-02-25 Composition de resine epoxy polymere

Family Applications Before (1)

Application Number Title Priority Date Filing Date
EP03005377A Expired - Lifetime EP1457509B1 (fr) 2003-03-11 2003-03-12 Composition de polymère à base de résine Epoxy

Country Status (4)

Country Link
US (1) US9175145B2 (fr)
EP (2) EP1457509B1 (fr)
CA (1) CA2518618C (fr)
WO (1) WO2004081076A1 (fr)

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Publication number Priority date Publication date Assignee Title
EP1236765A1 (fr) 2001-02-28 2002-09-04 hanse chemie GmbH Dispersion de silice
EP1529807A3 (fr) * 2003-10-16 2006-01-25 Nitto Denko Corporation composition de résine époxy déstinée à l'encapsulation de semi-conducteurs et dispositif a semi-conducteurs optiques
EP1634921A1 (fr) * 2004-09-10 2006-03-15 hanse chemie GmbH Composition de résine polymérique.
EP1805260B1 (fr) * 2004-10-27 2009-10-14 E.I. Du Pont De Nemours And Company Composition d'un revetement auto-adhesif
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WO2004081076A1 (fr) 2004-09-23
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CA2518618A1 (fr) 2004-09-23
US20070191556A1 (en) 2007-08-16
EP1457509B1 (fr) 2006-06-28
US9175145B2 (en) 2015-11-03

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