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
  • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
  • C09J11/02—Non-macromolecular additives
  • C09J11/04—Non-macromolecular additives inorganic
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
  • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
  • C09C1/28—Compounds of silicon
  • C09C1/30—Silicic acid
  • C09C1/3081—Treatment with organo-silicon compounds
• • C—CHEMISTRY; METALLURGY
  • C01—INORGANIC CHEMISTRY
  • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
  • C01P2006/00—Physical properties of inorganic compounds
  • C01P2006/11—Powder tap density
• • C—CHEMISTRY; METALLURGY
  • C01—INORGANIC CHEMISTRY
  • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
  • C01P2006/00—Physical properties of inorganic compounds
  • C01P2006/19—Oil-absorption capacity, e.g. DBP values
• • C—CHEMISTRY; METALLURGY
  • C01—INORGANIC CHEMISTRY
  • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
  • C01P2006/00—Physical properties of inorganic compounds
  • C01P2006/22—Rheological behaviour as dispersion, e.g. viscosity, sedimentation stability
• • 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
• • 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
  • Y10T428/2993—Silicic or refractory material containing [e.g., tungsten oxide, glass, cement, etc.]
  • Y10T428/2995—Silane, siloxane or silicone coating

Definitions

• the invention provides adhesives which comprise silanized, structurally modified, pyrogenically prepared silicas.
• the invention further provides for the use of structurally modified, pyrogenically prepared silicas in adhesives.
• hotmelt adhesives for example, are hotmelt adhesives, dispersion-based adhesives, wet adhesives containing organic solvents, and contact adhesives.
• a feature common to all of these types of adhesive is that first the adhesive is applied in a processable form and then solidification occurs as a result, for example, of evaporation of the solvent or of cooling.
• the group of the chemically curing adhesives includes, for example, cyanoacrylate adhesives, methyl meth- acrylate adhesives, anaerobically curing adhesives, radiation-curing adhesives, phenol-formaldehyde resin adhesives, silicones, silane-crosslinked polymer adhesives, polyimide adhesives, epoxy resin adhesives and polyurethane adhesives.
• an adhesive which comprises silanized, structurally modified, pyrogenically prepared silicas containing on their surface fixed vinyl groups or vinylsilyl groups, with hydrophobic groups, such as trimethylsilyl and/or dimethylsilyl and/or monomethylsilyl, additionally being fixed on the surface.
• hydrophobic groups such as trimethylsilyl and/or dimethylsilyl and/or monomethylsilyl, additionally being fixed on the surface.
• Silanized silicas are known from the prior-art DE 102 39 424 Al, where they are used in coating materials in order to improve the scratch resistance of the coating's surface.
• EP 0 672 731 Al likewise discloses silanized pyrogenic silicas, but those silicas are not structurally modified and are used as thickeners for coating materials and resins.
• Pyrogenically prepared silicas are typically prepared by means of high-temperature hydrolysis from silicon tetrachloride, hydrogen and oxygen. Silicas prepared by temperature hydrolysis can be used for the adhesives according to the invention, and have the physicochemical data shown in Table 1 in the hydrophilic state prior to the silanization and structural modification. From Table 1, the pyrogenically prepared silicas Aerosil 200, Aerosil 150 and Aerosil 300 are preferred. Particularly preferred is the pyrogenically prepared silica Aerosil 300.
• the mixture is subsequently treated thermally at a temperature of 20 to 400 0 C over a period of 0.1 to 6 hours.
• the thermal treatment may take place under inert gas, such as nitrogen, for example.
• the temperature treatment may also take place in a plurality of stages at different temperatures.
• the surface modifier or modifiers can be applied using single-fluid, dual-fluid or ultrasonic nozzles.
• the surface modification can be carried out continuously or batchwise in heatable mixers and dryers with spraying devices.
• Suitable apparatus may include, for example the following: ploughshare mixers, plate dryers, fluidized-bed dryers or fluid-bed dryers.
• the structural modification of the silicas thus prepared takes place subsequently by means of mechanical action.
• Structural modification may if appropriate be followed by grinding. If appropriate, after the structural modification and/or grinding, a heat treatment may take place.
• the structural modification may take place for example with a ball mill or with a continuously operating ball mill. Grinding may take place, for example, by means of an air-jet mill, toothed-disc mill or pinned-disc mill. Heat treatment may take place batchwise, in a drying oven, for example, or continuously, in a fluid bed or fluidized bed, for example. Heat treatment may take place under inert gas, nitrogen for example.
• the adhesives preferably contain 1% to 40%, preferably 2% to 30%, more preferably 4% to 10% by weight of the structurally modified, pyrogenically prepared silicas.
• the adhesive comprises as its base polymer compounds selected from the group consisting of epoxy resins, unsaturated polyester resins, polyurethane, silane-terminated polymers, vinyl ester resins, acrylates, polyvinyl acetate, polyvinyl alcohol, polyvinyl ethers, ethylene-vinyl acetate, ethylene-acrylic acid copolymers, polyvinyl acetates, polystyrene, polyvinyl chloride, styrene-butadiene rubber, chloroprene rubber, nitrile rubber, butyl rubber, polysulphide, polyethylene, polypropylene, fluorinated hydrocarbons, polyamides, saturated polyesters and copolyesters, phenol-formaldehyde resins, cresol-/resorcinol-formaldehyde resins, urea- formaldehyde resins, melamine-formaldehyde resins, polyimides, polybenzimidazoles, polys
• the structurally modified, pyrogenically prepared silica can also be introduced into an epoxy resin, with this resin then being admixed to the adhesive.
• Adhesives are products which, in accordance with their respective chemical composition and the physical state prevailing at the time of application to the adherends, allow wetting of the surfaces and, in their bonded joint, form the adhesive layer needed for the transmission of force between the adherends.
• adhesives comprise similar components in addition to the base polymer, such as, for example, solvents (ketones for example) , water, fillers (chalk for example) , thixotropic agents (pyrogenic silica for example) , adhesion promoters (silanes for example) , colour pastes (pigment-grade carbon black for example) and also further additives (for example, catalysts, ageing inhibitors) .
• Epoxy resins are used preferably as base polymers for adhesives.
• Epoxy resins are prepared for example by condensing 2, 2-bis (4-hydroxyphenyl) propane and epi- chlorohydrin in a basic medium. Depending on the equivalents of both reactants that are employed, the products are glycidyl ethers with different molar masses. In recent years, epoxy resins from bisphenol F, novolak epoxy resins, and cycloaliphatic and heterocyclic epoxy resins have also acquired importance.
• crosslinking agents used for epoxy resins include polyamines, polyamino- amides, carboxylic anhydrides and dicyandiamides .
• amine curing agents a distinction is made between aliphatic, cycloaliphatic, aromatic and araliphatic polyamines. Curing takes place without elimination of reaction products. It generally involves the addition of a reactive hydrogen atom to the epoxide group, with formation of a hydroxyl group.
• Unsaturated polyester resins are used preferably as base polymers for adhesives. They are obtained by polycondensation of unsaturated and saturated dicarboxylic or polycarboxylic acids with alcohols. Given a suitable reaction regime, the double bonds remain in the acid and/or alcohol and permit polymerization reactions with unsaturated monomers, styrene for example.
• Unsaturated dicarboxylic acids used with preference are as follows: maleic anhydride, maleic acid, fumaric acid.
• Saturated dicarboxylic acids used with preference are as follows: ortho-phthalic acid and ortho-phthalic anhydride, isophthalic acid, terephthalic acid, tetra- hydrophthalic acid, hexahydrophthalic acid, adipic acid, azelaic acid, sebacic acid, hexachloroendo- methylenetetrahydrophthalic acid, tetrabromophthalic acid.
• Glycols used with preference are as follows: propylene 1,2-glycol, ethylene glycol, butylene glycol, neopentyl glycol, 2, 2, 4-trimethylpentane-l, 3-diol, dibromoneo- pentyl glycol, diethylene glycol, triethylene glycol, dipropylene glycol, pentaerythritol diallyl ether, dicyclopentadiene .
• Monomers for the crosslinking used with preference are as follows: styrene, alpha-methylstyrene, meta- and para-methylstyrene, methyl methacrylate, diallyl phthalate, triallyl cyanurate .
• Polyurethane resins are used preferably as base polymers for adhesives.
• the polyurethanes are derived from isocyanic acid. As an extremely reactive compound, it undergoes addition very readily with compounds which possess an active hydrogen atom. In the course of this reaction the double bond between the nitrogen and the carbon is cleaved, the active hydrogen becoming attached to the nitrogen and the oxygen-combining radical to the carbon, to form a urethane group.
• reaction partners which are starting products having at least two functional groups, such as di- or triisocyanates, for example diphenylmethane 4, 4-diisocyanate (MDI) with polymeric fractions, or reaction product of tolylene diisocyanate (TDI) and polyols, and polyhydric alcohols
• di- or triisocyanates for example diphenylmethane 4, 4-diisocyanate (MDI) with polymeric fractions, or reaction product of tolylene diisocyanate (TDI) and polyols, and polyhydric alcohols
• Alcohols of this kind may also be present, for example, in the form of saturated polyesters, which are prepared with an excess of polyalcohols .
• Solvent-borne polyurethane adhesives are available as physically setting systems and as chemically reacting systems.
• the polymer takes the form of a high molecular mass hydroxyl polyurethane, the solvent used being, for example, methyl ethyl ketone.
• the chemically reacting systems include additionally hydroxyl polyurethane and a further polyisocyanate as crosslinker and as a second component .
• Dispersion-based adhesives comprise a high molecular mass polyurethane in dispersion in water.
• the isocyanate component is in "capped” or “blocked” form in a compound which eliminates the isocyanate component only at a relatively high temperature .
• Reactive polyurethane hotmelt adhesives are prepared by using relatively high molecular mass, crystallizing and meltable diol and isocyanate components. These components are applied as hotmelt adhesives at temperatures from around 70 0 C to 120 0 C to the adherends . After cooling, the bond acquires a sufficient initial strength, which allows rapid further processing. Subsequently, as a result of additional moisture exposure of the reactive isocyanate groups still present, crosslinking then takes place via urea bonds, to form the adhesive layer polymer.
• Silane-terminated polymers are used preferably as base polymers for adhesives.
• silane-terminated polymers or else "silane- modified polymers” embraces all of those prepolymers which, either at the chain ends or pendently, carry silyl groups having at least one hydrolysable bond, but whose polymer backbone does not contain the siloxane bond typical of siloxanes.
• any silane-modified polymer irrespective of its chemical structure, will have the qualities of a hybrid: the curing is similar to that of the silicones, and the other properties are shaped by the various possible polymer backbones between the silyl groups.
• Silane-terminated or silane- modified polymers can be classed in terms of their structure between the polyurethanes and the silicones.
• the synthesis of the silane-modified polymer encompasses a number of stages.
• the initial basis is dihydric or trihydric polyoxypropylene glycol, which is converted into the corresponding bisallyl compound. That compound is reacted to form the desired end product, bis (3- (methyldimethoxysilyl) propyl) polyoxypropylene .
• sealants and adhesives based on silicone-modified polymers for example, the reaction of NCO-terminated prepolymers with correspondingly reactive aminosilanes or mercaptosilanes .
• the polymer backbone may contain all of the conceivable rational structural elements, such as ether, ester, thioether or disulphide bridges.
• an NH 2 -, SH- or OH- terminated prepolymer can be reacted with an isocyanate silane, is likewise conceivable.
• the addition of terminal mercapto groups either in the prepolymer or in the silane to C-C double bonds offers a further route of technical interest.
• Vinyl ester resins are used preferably as base polymers for adhesives.
• vinyl ester resins possess a certain relationship to the UP resins, in particular as far as curing reaction, processing technology and field of use are concerned.
• These resins are polyadducts of liquid epoxy resins and acrylic acid. As a result of reduction of ester groups in the molecule chain, these resins have better hydrolysis resistance in tandem with effective elasticity and impact toughness.
• Monomers used for crosslinking are the same as for the unsaturated polyester resins, styrene in particular.
• Acrylates are used preferably as base polymers for adhesives.
• the collective term "acrylate-based adhesives" encompasses all of the reactive adhesives whose curing takes place via the carbon-carbon double bond of the acrylic group.
• the curing of the acrylate adhesives is accomplished by addition polymerization, in the course of which an initiator triggers a chain reaction leading to a continuous curing of adhesive.
• the polymerization of the "acrylate" adhesives can be initiated by means of free radicals or alternatively, in the case of the alpha-cyanoacrylates, by means of anions.
• the acrylate adhesives are also subdivided into the following groups:
• sealants based on polyacrylic esters or acrylic ester copolymers and polymethacrylic esters a distinction is made between solvent-borne and aqueous systems.
• Polyacrylate sealants cure physically by evaporation of the solvent or of the dispersion water.
• Polyvinyl alcohols are used preferably as base polymers for adhesives.
• Polyvinyl ethers are used preferably as base polymers for adhesives.
• the following three polymers in particular are of interest as base materials for adhesives: polyvinyl methyl ethers, polyvinyl ethyl ethers, polyvinyl isobutyl ethers
• polyvinyl ethers at moderate degrees of polymerization are tacky plasticizing resins possessed of very good adhesion properties to porous and smooth surfaces.
• Polyvinyl methyl ether is notable in particular for the fact that, owing to its water- solubility, it can be moistened again and therefore, for example, as a mixture with dextrin or animal glues, used as a gum on label papers, endows them with improved adhesion.
• polyvinyl ethers are also employed in pressure-sensitive adhesives.
• Ethylene-acrylic acid copolymers are used preferably as base polymers for adhesives. They are copolymers of ethylene and of acrylic acid and/or acrylic esters. These copolymers, which combine the chemical resistance of polyethylene with the good properties of the acid and/or ester moiety, represent important base polymers for hotmelt adhesives.
• the ester component used is preferably ethyl acrylate.
• Polyvinylacetals are used preferably as base polymers for adhesives. Polyvinylacetals come about through the action of aldehydes on alcohols. The most important acetals for adhesives manufacture are polyvinylformal and polyvinylbutyral . Both serve as a plasticizing component for phenolic resin-based adhesives. Polyvinylbutyral, moreover, finds application as an adhesive film in laminated safety glass.
• Polystyrenes are used preferably as base polymers for adhesives.
• the monomer is in use as a constituent for adhesive base materials predominantly in two areas: as a copolymer with plasticizing monomers, particularly butadiene, for the preparation of styrene-butadiene dispersions; and as a "polymerizable" solvent for copolymerization with unsaturated polyesters.
• Polyvinyl chloride is used preferably as base polymer for adhesives. It is used more particularly for plastisol adhesives, and also as a copolymer with vinyl acetate to give vinyl chloride/vinyl acetate copolymers in solvent-based adhesives, dispersion-based adhesives, heat-sealing adhesives, and as a high-frequency welding assistant.
• Styrene-butadiene rubber is used preferably as base polymer for adhesives.
• Styrene-butadiene rubber is a typical example of a thermoplastic elastomer, combining the application properties of elastomers with those of thermoplastics.
• the styrene-butadiene copolymer (SBS) and the styrene-isoprene copolymer (SIS) are what are called triblock copolymers, constructed linearly of successive identical monomer units in individual blocks.
• the end blocks are polystyrene segments, while the middle block is polybutadiene (styrene-butadiene- styrene block copolymer, SBS) or else isoprene (styrene-isoprene-styrene block polymer, SIS) .
• the ratio of styrene fraction to butadiene fraction or of styrene fraction to isoprene fraction is approximately 1:3.
• an "internal plasticizing" is achieved.
• a particular advantage of these rubber copolymers is their ability to form adhesive layers having good adhesion properties and high flexibility. Significant application therefore exists in situations where the adhesively bonded adherends are subject in practical use to high deformation stresses, such as in footwear or with rubber/rubber or rubber/metal bonds, for example.
• Butyl rubber is used preferably as base polymer for adhesives.
• Butyl rubber is a copolymer composed of a predominant fraction of isobutylene with isoprene. Within this linear chain molecule there exist, in the form of the long polyisobutylene segments, very high chain fractions of saturated character, at which no further crosslinking is possible.
• the sole crosslinkable component is the isoprene molecule, and so the overall properties of the butyl rubber are determined by the fraction of the number of double bonds, predetermined by the isoprene. The reactivity can be further influenced by incorporation of monomers containing chlorine or bromine.
• Polysulphides are used preferably as base polymers for adhesives.
• Raw materials for polysulphide sealants have long been known under the trade name Thiokol®.
• Polysulphide polymers are obtained by reacting dichloroethylformal with sodium polysulphide. The molecular weight of the liquid polymers is between 3000 and 4000. By reaction with an oxidizing agent, manganese dioxide for example, they can be converted into an ultimate rubber-elastic state.
• Polyethylenes are used preferably as base polymers for adhesives.
• the low molecular mass types with melt indices in the range from 2 to 2000 g/10 min, have found use, in combination with tackifying resins and microwaxes, as hotmelt adhesives in the paper and cardboard industry.
• Fluorinated hydrocarbons are used preferably as base polymers for adhesives.
• Polyfluoro-ethylene-propylene is a copolymer of tetrafluoroethylene and hexafluoro- propylene and has been studied as a base material for hotmelt adhesives. The advantage of these products lies in the high long-term temperature durability.
• Polyamides are used preferably as base polymers for adhesives.
• the polyamides represent some of the most important base materials for the physically setting hotmelt adhesives.
• Suitable for the preparation of the polyamides are the reactions described below, which typically take place in the melt under a nitrogen atmosphere: polycondensation of diamines with dicarboxylic acids; polycondensation of aminocarboxylic acids; polycondensation from lactams; polycondensation of diamines with dimerized fatty acids.
• Saturated polyesters and copolyesters are used preferably as base polymers for adhesives.
• Saturated polyesters and copolyesters come about through polycondensation from dicarboxylic acids and diols. They are an important base material for hotmelt adhesives .
• Phenol-formaldehyde resins are used preferably as base polymers for adhesives. These polymers come about through a polycondensation reaction between phenol and formaldehyde, forming highly crosslinked phenolic resins which are used as a base material for adhesives for - for example - aircraft construction. Pure phenol- formaldehyde resins are generally too brittle. For this reason they are modified with thermoplastic polymers by copolymerization or cocondensation, for example with polyvinylformal, polyvinylbutyral, polyamides, epoxy resins or elastomers, for example polychloroprene and nitrile rubber.
• the polybenzimidazoles are likewise to be classed as adhesives of high heat resistance. They come about through a polycondensation reaction from aromatic tetramines with dicarboxylic acid.
• Polysulphones are used preferably as base polymers for adhesives.
• the polysulphones likewise belong to the group of heat-resistant adhesives. They are obtained, for example, through a polycondensation reaction from dihydroxydiphenyl sulphone with bisphenol A.
• the adhesives of the invention are used preferably in casting compounds, which are used as a coating in the electrical and electronics industries.
• the structural modification of the silanized silicas is accomplished by mechanical action in a continuously operating ball mill with optional subsequent grinding. Grinding may also be followed by heat treatment. Grinding is accomplished by means of an air-jet mill, toothed-disc mill or pinned-disc mill. Heat treatment takes place batchwise in a drying oven or may take place continuously in a fluidized-bed or fluid-bed dryer. Table 2 below shows the reaction conditions of the individual silicas used from Table 1.
• Temperature treatment temperature treatment after grinding
• Example 2 the rheological properties of the structurally modified, pyrogenic silicas used are determined in the epoxy resin Renlam Ml (Huntsman) .
• the respective viscosities with comparison products and with the structurally modified silicas used in the invention are ascertained.
• the viscosities are measured before and after addition of the silica.
• the inventive silica S 4 can be incorporated very rapidly into Palatal A 410, within 58 sec.
• the comparative example requires a time of 196 sec. Hence a time saving is produced of approximately 30%.

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• Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Inorganic Chemistry (AREA)
• Adhesives Or Adhesive Processes (AREA)
• Pigments, Carbon Blacks, Or Wood Stains (AREA)
• Silicon Compounds (AREA)

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• 2007
  • 2007-05-22 DE DE102007024099A patent/DE102007024099A1/de not_active Ceased
• 2008
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