Classifications

• • 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
  • 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
  • C08K9/00—Use of pretreated ingredients
  • C08K9/08—Ingredients agglomerated by treatment with a binding agent
• • 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
  • C08L2666/18—Polyesters or polycarbonates according to C08L67/00 - C08L69/00; Derivatives thereof
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T428/00—Stock material or miscellaneous articles
  • Y10T428/249921—Web or sheet containing structurally defined element or component
  • Y10T428/249953—Composite having voids in a component [e.g., porous, cellular, etc.]
  • Y10T428/249971—Preformed hollow element-containing
  • Y10T428/249972—Resin or rubber element
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T428/00—Stock material or miscellaneous articles
  • Y10T428/26—Web or sheet containing structurally defined element or component, the element or component having a specified physical dimension
  • Y10T428/269—Web or sheet containing structurally defined element or component, the element or component having a specified physical dimension including synthetic resin or polymer layer or component
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T428/00—Stock material or miscellaneous articles
  • Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
  • Y10T428/2982—Particulate matter [e.g., sphere, flake, etc.]
  • Y10T428/2991—Coated
  • Y10T428/2998—Coated including synthetic resin or polymer

Definitions

• Filling material in particular for filling cavities, in particular of structural elements, manufacturing processes and structural elements
• the invention relates to a filling material, in particular for filling
• the filling material comprising particles which are coated with a reactive thermoset. Furthermore, the invention relates to a method for producing a filling material, in particular a filling material according to the invention, particles being coated with a reactive thermosetting plastic. The invention further relates to a structural element with a cavity.
• load-bearing metal parts are at the same time light and have high rigidity or strength.
• this goal can be achieved by designing metal parts in a sandwich construction, for example, and filling the cavities with a porous material such as foams.
• Such sandwiches are produced by gluing a foam core with two metal cover layers or by Foaming with, for example, a PUR reaction resin system.
• metal foams are also generally known, with the advantage that they have a higher energy absorption when deformed.
• the object of the present invention is to provide a filling material, a method for producing a filling material and a structural element which avoid the disadvantages of the prior art.
• the object is achieved by a filling material, in particular for filling cavities, in particular structural elements, the filling material comprising particles which are coated with a reactive thermosetting plastic, the reactive thermosetting plastic not flowing at room temperature in the unreacted state.
• the object is further achieved by a method for producing a filler material, in particular a filler material according to the invention, particles being coated with a reactive thermosetting plastic.
• the filling material can be introduced into cavities of structural elements in such a way that filling material is prevented from escaping, and, on the other hand, that the thermoset system - for example an epoxy resin system - is not both low-viscosity and at the same time comparatively highly reactive have to be.
• FIG. 1 shows a plurality of filler material particles of the filler material 3 according to the invention, the filler material particles being formed from particles 2 - in particular hollow body particles - which are essentially completely surrounded by a thermosetting plastic 1.
• FIG. 2 shows a structural element 4 which has a cavity which is filled with the filling material 3.
• the present invention relates to compositions for thermosets 1 or thermoset materials 1, in particular made of epoxy resin formulations, with a latent hardener - in particular a thermal hardener - which preferably form impact-modified epoxy resin systems with, for example, reactive liquid elastomers, which do not flow at room temperature in the unreacted state, ie which have a sufficiently high viscosity of typically more than 1000 Pas, preferably more than 2000 Pas and particularly preferably more than 3000 Pas at room temperature.
• Such formulations are preferably applied to the hollow spheres, ie to the particles 2, at elevated temperature or at room temperature using a centrifugal mixer.
• the coated balls can have a certain stickiness. If non-sticky coatings are required, the coatings can be coated with a dusted dry powder or partially crosslinked by adding a second, non-latent hardener immediately before coating.
• the particles are hollow, preferably in the form of hollow spheres, and particularly preferably are coated substantially uniformly. Because the particles are hollow inside, it is possible to make the filling material particularly light. This makes it possible, on the one hand, to give structural elements great stability without, however, being associated with excessive weight gain. If the particles are designed as spheres - in particular as hollow spheres - their surface to be coated with the thermoset material is comparatively small and their stability against acting forces is also comparatively large.
• thermoset is essentially indefinitely stable in storage at room temperature and, in particular, is modified with impact resistance. This makes it possible to store the thermoset material for a long time and to ensure a logistically comparatively inexpensive and therefore inexpensive production of the filler material.
• the main part of the crosslinking of the thermosetting plastic can then take place in the course of complete curing in a cavity of a structural element into which the particles to be coated have been filled. This curing takes place e.g. in the automotive industry in such a way that the coated particles are either introduced into the cavity before the KTL (cathodic dip coating) and hardened in the body-in-white furnace, or introduced into the cavity after the KTL and hardened in the paint furnace.
• thermosetting systems which are stable in storage at room temperature in the uncrosslinked state and have a sufficiently high viscosity of typically more than 1000 Pas, preferably more than 2000 Pas and particularly preferably more than 3000 Pas at room temperature. They typically consist of mixtures of so-called solid resins or adducts (ie with diphenols or dicarboxylic acids to diglycidyl ethers of diphenols pre-extended at room temperature) with liquid diglycidyl ethers, toughness improvers such as thermoplastics e.g. B.
• poly-p-phenylene oxide polyalkylene oxide glycidyl ether or reactive liquid rubbers and fillers.
• Typical molecular weights of the solid resins or adducts are in the range 800-100000 daltons, preferably 900-8000 daltons.
• Latent hardeners such as dicyandiamide or other substituted ureas are preferably used as hardeners, which harden at temperatures above 160 ° C.
• Enable cross-linking reaction In addition to latent hardeners, it is also possible to add conventional epoxy hardeners such as polyphenols, mercaptans, amines or carboxylic acids or carboxylic anhydrides to the adhesive system immediately before coating and to achieve a partial crosslinking of the coating. It is also possible to immediately before the
• Coating process additionally add diisocyanates to the adhesive system and thus achieve a pre-crosslinking via the ⁇ -hydroxy groups of the epoxy adducts.
• the additional pre-crosslinking leads to higher molecular weights, thus increasing the glass transition temperature and reducing the stickiness.
• Such systems are tack-free if the
• Glass transition temperature of the uncrosslinked and pre-crosslinked adhesive layer is greater than 30 ° C.
• the coating is preferably chosen to be as thin as possible, particularly in lightweight applications.
• the proportion by weight of the adhesive in relation to the ball is 5 to 80%, preferably 20 to 50% and in particular 30%.
• the thickness of the coating is 2 to 200 ⁇ m, preferably 5 to 100 ⁇ m, particularly preferably 10 to 80 ⁇ m and in particular 50 ⁇ m.
• the coated particles form filler particles which have a sticky or a dry surface.
• the coated spheres or the coated particles can have a certain stickiness, which can be advantageous in particular for filling cavities in structural elements on account of the then possible adhesion to the inner wall.
• it is also quite advantageous for other applications that the coated particles are not sticky. If this is the case, it is possible according to the invention that the coating is dusted with a dry powder.
• the dry powder can be used according to the invention to adjust the stickiness or adhesion of the coating.
• the filler material particles are dusted with a powder, the powder being in particular thermoplastic powder and / or a latent hardener of the thermoset and / or an inert filler.
• a thermoplastic powder is that it can contribute to toughness. This is possible when using poly (vinyl butyral) powder and / or polyamide powder.
• powdered minerals or fillers such as calcium carbonates, wollastonites, quartz flours or pyrogenic silica are also possible.
• the powder can exclusively or in combination with other substances also have a hardener, in particular micronized, solid and latent, such as dicyadiamide.
• part of the hardener is added to the formulation of the thermosetting plastic, while the rest of the hardener is dusted on in the form of a powder.
• an organic or mineral filler it is possible for an organic or mineral filler to be used as the powder intended for dusting.
• the particles are preferably coated with the thermoset in a centrifugal mixer.
• the rotation of an arm at high speed in a first direction combined with the rotation of a basket attached to the arm in the opposite direction causes a very strong and extremely rapid mixing of the in the material in the machine takes place, even if the viscosity of the thermosetting material, for example, is comparatively large, in particular exceeds a value at which spraying of the material would be possible.
• the viscosity can be adjusted via the temperature, and the adhesive system is advantageously heated until the viscosity is 20 - 50 Pas.
• Example 1 Coated balls, sticky surfaces, resin system (SikaPower® 496/3).
• Balls and adhesive (total amount 70 g) were weighed in a beaker and heated to 80 ° C. The coating was carried out in a speed mixer DAC 150 FV (centrifugal mixer from Hauschild). Homogeneously coated, slightly sticky balls are obtained which can be easily conveyed. The slightly sticky balls were placed in a cylindrical mold treated with a release agent as an example of a cavity of a structural element and cured at 180 ° C. for 30 minutes. You get a stiff cylinder.
• the layer thicknesses were measured at 200 times magnification.
• the coating turned out to be homogeneous and corresponded to the calculated layer thickness.
• Example 2 Coated balls, dry surfaces, tough modified epoxy resin system, dusted with Butvar.
• Example 2 Thermoset or adhesive and processing method as in Example 1. The example with 30% by weight of adhesive (70 g total weight) was repeated. Immediately after coating, the balls were dusted with 5 g of Polyvinylbutyral Movital 60HH. Free-flowing balls are obtained. When placed in a cylindrical shape, a rigid cylinder is obtained after curing at 180 ° C for 30 minutes.
• Example 3 Coated balls, tough modified epoxy resin system
• a reactive toughened epoxy adhesive was prepared by mixing 100 g of an adduct of bisphenol A diglycidyl ether with dimeric fatty acid (epoxy value 2.8 epoxy equivalents / kg) with 100 g solid epoxy resin (GT 7004, manufacturer Vantico AG, epoxy value 1.4 epoxy equivalents / kg) and 50g liquid epoxy resin (GY 250, manufacturer Vantico) at 90 ° C in a planetary mixer.
• a reactive polyol polyol with epoxy end groups
• 130 g of light filler extendospheres, to reduce the density of the thermoset
• 6.5 g of pyrogenic silica Cabosil TS 720, manufacturer Cabot
• 12.2 g of dicyandiamide are added to the homogeneous mixture.
• the reactive polyol with epoxy end groups was prepared as follows: 200 g of PolyTHF 2000 (PTMEG, polytetramethylene ether glycol, 2000 g / mol molecular weight), OH number 57.5 mg / g of KOH) were dried under vacuum at 100 ° C. for 30 minutes. Then 47.5 g of IPDI (isophorone diisocyanate) and 0.04 g of dibutyltin dilaurate were added. The reaction was carried out under vacuum at 90 ° C. until the NCO content was constant at 3.6% after 2.5 hours (theoretical NCO content: 3.7%).
• T-peel and tensile shear test specimens are produced with the adhesive and cured at 180 ° C for 30 min. The following mechanical values are obtained:
• thermoset produced in this way to the particles
• spheres filler particles
• the hollow bodies or the particles in particular hollow steel balls, as described in Examples 1 and 2
• the thermoset in the centrifugal mixer and coated with them.
• Example 4 Coated balls, dry surfaces, tough modified epoxy resin system, dusted with an inert filler.
• thermoset or adhesive in Example 3 was produced with 6.1 g of dicyandiamide. 49 g of steel balls or hollow steel balls and 21 g of adhesive were converted into coated balls in a speed mixer, then the balls, ie the filler particles, were dusted with 250 mg of dicyandiamide in 1 g of pyrogenic silica. Dry coated balls are obtained.

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• Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Health & Medical Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Paints Or Removers (AREA)
• Compositions Of Macromolecular Compounds (AREA)
• Powder Metallurgy (AREA)

Priority Applications (4)

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Cited By (16)

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Citations (6)

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• 2004
  • 2004-05-19 EP EP20040102229 patent/EP1598393A1/de not_active Withdrawn
• 2005
  • 2005-05-19 JP JP2007517261A patent/JP4813472B2/ja not_active Expired - Fee Related
  • 2005-05-19 EP EP05742838A patent/EP1751238A1/de not_active Withdrawn
  • 2005-05-19 US US11/597,251 patent/US20090042013A1/en not_active Abandoned
  • 2005-05-19 CA CA 2567536 patent/CA2567536A1/en not_active Abandoned
  • 2005-05-19 WO PCT/EP2005/052303 patent/WO2005113689A1/de not_active Ceased

Patent Citations (6)

Non-Patent Citations (2)

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