EP2064276A2 - Dispersions aqueuses de dioxyde de silicium pour formulations d'adhésifs et d'agents d'étanchéité - Google Patents

Dispersions aqueuses de dioxyde de silicium pour formulations d'adhésifs et d'agents d'étanchéité

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Publication number
EP2064276A2
EP2064276A2 EP07820366A EP07820366A EP2064276A2 EP 2064276 A2 EP2064276 A2 EP 2064276A2 EP 07820366 A EP07820366 A EP 07820366A EP 07820366 A EP07820366 A EP 07820366A EP 2064276 A2 EP2064276 A2 EP 2064276A2
Authority
EP
European Patent Office
Prior art keywords
dispersions
dispersion
adhesive
silica
aqueous
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Withdrawn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
EP07820366A
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German (de)
English (en)
Inventor
Dietrich Pantke
Peter-Nikolaus Schmitz
Hartmut Melzer
Rüdiger MUSCH
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.)
Nouryon Chemicals International BV
Original Assignee
Akzo Nobel Chemicals International BV
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
Priority claimed from DE102006044068A external-priority patent/DE102006044068A1/de
Application filed by Akzo Nobel Chemicals International BV filed Critical Akzo Nobel Chemicals International BV
Publication of EP2064276A2 publication Critical patent/EP2064276A2/fr
Withdrawn legal-status Critical Current

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Classifications

    • 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
    • C09D105/00—Coating compositions based on polysaccharides or on their derivatives, not provided for in groups C09D101/00 or C09D103/00
    • C09D105/16—Cyclodextrin; Derivatives thereof
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L5/00—Compositions of polysaccharides or of their derivatives not provided for in groups C08L1/00 or C08L3/00
    • C08L5/16—Cyclodextrin; Derivatives thereof
    • 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
    • C09J105/00—Adhesives based on polysaccharides or on their derivatives, not provided for in groups C09J101/00 or C09J103/00
    • C09J105/16—Cyclodextrin; Derivatives thereof
    • 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
    • Y10T428/28—Web or sheet containing structurally defined element or component and having an adhesive outermost layer

Definitions

  • the invention relates to aqueous dispersions based on silica and hydroxyl-containing water-soluble compounds, a process for their preparation and their use as a component in the production of sealants and adhesives and
  • Coatings - especially for the production of adhesive coatings gen - and the resulting sealant or K ⁇ ebstoffformultechniken and a method for joining the one-sided or double-coated substrates using these formulations.
  • aqueous silica dispersions there is a wide range of applications, e.g. as a binder in the foundry and steel sector in the area of investment casting, as an additive for the modification of
  • silica products for different applications is known. While solid SiO 2 products are often used to control rheological properties, as fillers or adsorbents, silica dispersions (for example, silica sols) are dominated by the use as binders of various inorganic compounds
  • EP-A 0 332 928 discloses the use of polychloroprene latices in the presence of silica sols as an impregnation layer in the production of fire protection elements.
  • FR-A 2 341 537 and FR-A 2 210 699 fumed silicas in combination with Polychloroprenlatices for the production of flame-resistant foam or
  • EP 1652879 A1 describes coatings of fiber products with aqueous dispersions of polychloroprene and silica sols for producing textile-reinforced and fiber-reinforced concrete.
  • open time according to DIN 16920 is understood to mean the time after the adhesive application within which wet adhesion is possible. to extend the processing time (open time). Although the replacement of these resins by silica dispersions increases the temperature resistance of the bonds, it reduces the "open time.”
  • silica dispersions to aqueous resinous
  • pot life is understood to mean the time in which the formulation can be processed after mixing in at least one further dispersion. According to the prior art, (Ullmann, Encyklopadie der ischen Chemie, Volume 14, 4th edition, p. can be achieved by adding
  • Solvents and / or plasticizers accelerate the setting speed and lower the film-forming temperature. By this measure, however, the heat level of the coating or the adhesive seam is reduced.
  • a higher thermal state can be achieved by adding a second dispersion based on resorcinol or mefamine resin or inorganic salts such as e.g. Achieve chromium nitrate.
  • these two-component dispersion formulations are limited in their "pot life" to a few hours.
  • aqueous dispersions based on polychloroprene, acrylate, chlorinated rubber, styrene-butadiene or reactive systems based on epoxy resin and based on unsaturated polyesters were used.
  • the penetration of the rovings takes place by coating the filaments in the roving production or by soaking the rovings before or after the textile production.
  • the curing or crosslinking of the polymeric phase is carried out before the reinforcement textiles are introduced into the concrete. Thereafter, the treated rovings or textiles are embedded in fine concrete.
  • G aqueous dispersions based on polychloroprene, acrylate, chlorinated rubber, styrene-butadiene or reactive systems based on epoxy resin and based on unsaturated polyesters were used.
  • the penetration of the rovings takes place by coating the filaments in the roving production or by soaking the rovings before or after the textile production.
  • the present invention was thus based on the object of providing aqueous silicon dioxide dispersions which, in aqueous polymer-containing adhesive dispersions, have a rapid setting and / or a long open time and high initial strength after application to the substrates to be coated or bonded. It would also be advantageous if the resulting dry coating or adhesive films have high water resistance and heat resistance. Furthermore, a reduced residual monomer content would be advantageous.
  • dispersions comprising silicon dioxide dispersion and certain water-soluble organic compounds have these properties.
  • the present invention thus relates to aqueous dispersions, characterized in that they
  • (B) contain at least one water-soluble hydroxyl-containing organic compound.
  • the water-soluble hydroxyl-containing organic compounds according to the invention are dissolved in the Siiiciumdioxid dispersion before. Undissolved portions are separated before use.
  • These dispersions comprising components (a) and (b) are also referred to below as dispersions according to the invention in the following.
  • Aqueous silica dispersions have been known for a long time. Depending on the manufacturing process, they are available in different forms. g, py g, ggg.
  • Fatty acid sols are colloidal solutions of amorphous silica in water, which are also commonly referred to as silica sols but are referred to as silica sols for short.
  • the silica is present in the form of spherical and surface-hydroxylated particles.
  • the particle diameter of the loColloidteilchen is usually 1 to 200 nm, wherein the particle size correlating BET specific surface area (determined by the method of GN Sears, Analytical Chemistry Vol. 28, N. 12, 1981-1983, December 1956) at 15 up to 2000 m 2 / g.
  • This correlation can be represented as follows: Assuming that silica sols are present as spherical primary particles and have a density of 2.2 g / cm 3 , this results in a factor of 2750. This factor divided by the specific surface area gives the particle size in nm (For the determination of the factor, see Ralph K. Her, The Chemistry of Silica, John Wiley & Sons New York 1979, pp. 465 f.). The surface of the SiO 2 particles has a charge which is counterbalanced by a corresponding counterion which results in the stabilization of the colloidal solution.
  • the alkaline stabilized silicic acid have a pH of 7 to 3 1.5 and contain, for example, small amounts of Na 2 O, K 2 O, Li 2 O, ammonia, organic nitrogen bases, tetraalkylammonium hydroxides or alkali metal or ammonium aluminates as alkalizing agents.
  • Silica sols may also be slightly acidic as semi-stable colloidal solutions.
  • the solids concentrations of the silica sols are preferably from 5 to 60% by weight of SiO 2 .
  • the production process for silica sols essentially goes through the production steps of dealkalization of water glass by means of ion exchange, adjustment and stabilization of the respectively desired particle sizes (distribution) of the SKV particles, adjustment of the respectively desired
  • SiOr particles leave the colloidally dissolved state. This explains the presence of the discrete primary particles,
  • Silica gels are colloidally shaped or unshaped silicas of elastic to solid consistency with a loose to dense pore structure.
  • the silica is in the form of highly condensed polysilicic acid.
  • On the surface are siloxane and / or silanol groups.
  • the silica gels are prepared from water glass by reaction with mineral acids.
  • fumed silica and precipitated silica.
  • water glass and acid such as H 2 SO 4
  • Agglomerate and agglomerates verwachs n specifi h O gg 30 to 800 m 2 / g (determined according to test specification: DIN 66131) and the primary particle size at 5 to 100 nm.
  • the primary particles of these present as solid silicas are usually firmly networked to secondary agglomerates , The particle size data are average
  • Pyrogenic silica can be prepared by flame hydrolysis or by the arc process.
  • the dominant synthesis method for fumed silicas is flame hydrolysis, in which tetrachlorosilane is decomposed in an oxyhydrogen flame.
  • the resulting silica is X-ray amorphous.
  • Pyrogenic silicic acids have significantly less OH groups than precipitated silica on their virtually pore-free surface.
  • the fumed silica prepared via flame hydrolysis generally has a specific surface area of 50 to 600 m 2 / g (determined according to DIN 66131) and a particle size of 5 to 50 nm, and the silica prepared by the arc process has a specific surface area of 25 to 300 m 2 / g (determined according to DIN 66131) and a particle size of 5 to 500 nm.
  • Primary particles of these present as solid silicas usually crosslinked to secondary agglomerates.
  • the particle size data are average particle sizes which include the size of primary particles and any agglomerates present therefrom.
  • an SiO 2 raw material present as an isolated solid such as, for example, pyrogenic or precipitated silica
  • this is converted into an aqueous SiO 2 dispersion by dispersing.
  • Dispersants of the prior art are used to prepare the silica dispersions, preferably those suitable for producing high shear rates, e.g. Ultratorrax or dissolver discs
  • aqueous silicon dioxide dispersions whose SiO 2 particles have a primary particle size of 1 to 400 nm, preferably 5 to 100 nm and particularly preferably 8 to 60 nm.
  • precipitated silicas they are ground for particle reduction.
  • the particle size of silica sol particles can be calculated from the BET surface area as described above. Primary particles as well as in the form of agglomerates.
  • the expression "average particle size" in accordance with the invention means the mean particle size determined by means of ultracentrifugation and includes the size of primary particles and any agglomerates present therefrom (see: HG Müller, Progr. Colloid Polym., Sci 107, 180-188 (1997)). The weight average is given).
  • Preferred dispersions of the invention are those in which the SiOr particles of the silica dispersion (a) are present as discrete uncrosslinked primary particles.
  • Such preferred dispersions according to the invention containing discrete uncrosslinked primary particles are, in particular, silica sols.
  • the SiO 2 particles have hydroxyl groups on the particle surface.
  • aqueous silica sols as aqueous silicon dioxide dispersions.
  • Suitable silica sols are also commercially available, for example from H.C. Starck GmbH (Levasil®).
  • Water-soluble hydroxyl-containing organic compounds in the context of the invention are to be understood as meaning all linear or cyclic oligomers or polymers which contain hydroxyl groups in the OHgomer- or polymer chain and are water-soluble.
  • oligomers are to be understood as meaning those compounds having up to 10 repeat units and a molecular weight of less than 1000, and polymers having more than 10 repeat units, in which case the repeat units may be the same or different.
  • Preferred examples of OH-containing oligomers and polymers are hydroxyalkylcelluloses, polyvinyl alcohols or cyclodextrins.
  • Preferred OH-group-containing oligomers or polymers are cyclodextrins in the context of the invention.
  • cyclodextrins are based on the possibility that water molecules inside the tubular cyclodextrins can be exchanged for hydrophobic guest molecules. Examples of such monomers or low molecular weight compounds can be found in the yearbook of Heinrich-Heine - University of Düsseldorf 2002, article by H. Ritter and M. Tabatabai (www.uni-duesseldorf.de/home/helpbuch/2002/ritter/index_html) ,
  • the inclusion of low molecular weight guest molecules or compounds can be carried out at most in the equimolar range, ie the ratio of cyclodextrin: guest molecule is less than or equal to 1: 1.
  • the diameter of the guest molecules should be 0.95 nm maximum for Cavamax W6, 0.78 nm maximum for Cavamax W6 and 0.57 nm maximum for Cavamax W8. (Fig. 10).
  • Cydodextrins as water-soluble hydroxyl group-containing organic compounds in the compositions according to the invention have the advantage that the Rcstmonomergehalt can be significantly reduced in the resulting dispersions.
  • Suitable Cydodextrins are unsubstituted and substituted Cydodextrins.
  • Preferred cyclodextrins are ⁇ -, ß- and ⁇ -Cyclodcxlri ⁇ e and their ester, alkyl ether, hydroxyalkyl ether. Alkoxycarbonylalkylether-, Carboxyalkylcther derivatives or their salts .
  • methyl- ⁇ -cyclodextrin particularly preferred are methyl- ⁇ -cyclodextrin, methyl- ⁇ -cyclodextrin, methyl- ⁇ -cydodextrin, ethyl- ⁇ -cyclodextrin, ⁇ -butylcyclodextrin, butyl- ⁇ -cyclodextrin, butyl- ⁇ -cyclodextrin, 2,6-DimethyU ⁇ -cyclode ⁇ triii, 2,6-dimethyl-.beta.-cycl ⁇ dexirin, 2,6-Ditn ⁇ hyl- ⁇ -cyclodexlri ⁇ , 2,6-DJethyl-ß-cydodex.lrin, 2,6-dibutyl-ß-cyclodcxtrin, 2.3 , 6-trimethyl- ⁇ 'Cyclodextri ⁇ , 2,3,6-TrJmcthyl-ß-cyclodcxtrin, 2,3,
  • the mono-, di- or triether-substituted, mono-, di- or triester-substituted or monocKterZ-diether-substituted derivatives are generally obtained by the preparation of ⁇ - , ⁇ - and ⁇ -cyclodextrins with alkylating agents such as dimethyl sulfate or alkyl halides m from 1 to 30 carbon atoms, for example methyl, ethyl, propyl, bulyl, pentyl , hexyl, heptyl, octyl chloride, bromide or iodide and / or esterification with acetic acid or succinic acid in the presence of acids ,
  • alkylating agents such as dimethyl sulfate or alkyl halides m from 1 to 30 carbon atoms, for example methyl, ethyl, propyl, bulyl, pentyl , hexyl, h
  • Cydodextrins are likewise commercially available, for example from Wicker (Cavamax® and CavasoK®).
  • a further object of the invention is the use of the dispersions according to the invention as a component in the production of adhesives and sealants using polymer dispersions (c) and the resulting adhesives and sealants.
  • dispersions of the invention can be used as a component in the preparation of dichrofaces and coatings-in particular for the production of adhesive coatings
  • Emulators or dispersants are dispersed in water.
  • examples are latexes of polymers of dienes or olefinically unsaturated monomers and copolymers thereof, such as polystyrene-butadiene latex, acrylonitrile-butadiene-latex, polychloroprene latex, latex of a copolymer of chloroprene and dichlorobutadiene, latex of chlorinated polyisoprene or (meth) acrylate -Latex.
  • these polymers (c) may also be water-soluble, e.g. Polyvinylpyrralidon
  • the polymer dispersions (c) may contain one or more such polymer dispersions.
  • polymer dispersions (c) whose viscoplastic properties of the dry films are in or in the region of the pressure-sensitive adhesive range.
  • the film production took place from the dispersions at room temperature. From the films boards were pressed at 100 0 C and determined in red & tionsrheometer the storage modulus G 'at temperatures of 30 C to 100 u 0 C for measurement.
  • the memory module should be in the range of 0.02 to 2 MPa. If the storage modulus G is less than 0.02 MPa, then the addition of the dispersion according to the invention increases the storage modulus, but the internal strength of the polymer dispersion e (cohesion) is too low, so that the adhesive film cohesively fails in the test. If the storage modulus G 'is greater than 2 MPa, then the adhesive film is too hard and the adhesion to the substrate is insufficient.
  • the dispersions according to the invention containing the components (a) and [d] (b) preferably have a content of dispersed silicon dioxide (a) of 99.9% by weight to 25% by weight , preferably of 99.5% by weight . -% to 45 wt .-%.
  • the proportions of the water-soluble polymers or oligomers (b) in the dispersions are from 0.1% by weight to 75% by weight, preferably from 0.5% by weight to 55% by weight , the process inputs being based on refer to the weight of non-volatile components and add to 100 wt .-%.
  • the formulations contain the dispersions of the invention in the range from 3% to 45% by weight, preferably 5% Gcw , -% . to 30% by weight.
  • the polymer dispersions (c) are in the formulations m 97 wt . % to 55 wt .-%, preferably to 95 wt .-% to 70 wt .-%, wherein the percentages are based on the weight of non-volatile components and add to 100 wt .-%.
  • fillers such as Quaizmehl, quartz sand, barite, calcium carbonate,
  • Chalk, dolomite or talc optionally together with Netzii ⁇ itteln, for example Polyphosphatcn, such as sodium hexamctaphosphate, naphthalenesulfonic acid, ammonium or Nadiumpolyacryl-Situresalze be added, wherein the fillers in amounts of 10 to 60 wt . %, preferably from 20 to 50% by weight, and the wetting agents in amounts of from 0.2 to 0.6% by weight, all data relating to the nonvolatile components being added. Further suitable, optionally used adjuvants are, for example, in amounts of 0.01 . to 1 wt .
  • organic thickening agents such as Celluloscderivate, Algi ⁇ ate, starch, starch derivatives, polyurethane Verdicku ⁇ gsstoff or polyacrylic acid or in amounts of 0.05 to 5 Gcw .-%, based on non-volatile components, to be used inorganic thickening, such as for example bentonites.
  • fungicides can also be added to the dispersion according to the invention. These come in amounts of 0.02 to 1 wt .-%. based on non-volatile components used. Suitable fungicides are, for example, phenol and cresol derivatives or organotin compounds.
  • tackifying resins so-called adhesive resins, such as. unmodified or modified natural resins, such as rosin esters, carbonyl hydrogen resins or synthetic resins, such as phthalate resins, are added in dispersed form to the polymer dispersion according to the invention (see, for example, "Klebharze” R. Jordan, R. Htnterwaldner, pp. 75-115, Hinterwaldner Verlag, Kunststoff 1994). Alkylpbenol resin and terpene phenolhar are preferred: _>
  • Dispersions with softening grölier 70 0 C more preferably greater than 110 0 C.
  • Plasticizers such as those based on adipate, phthalate or phosphate may be present to erf indungschtee ⁇ dispersions in amounts of 0.5 to tenth parts by weight, based on non-volatile Shares are added.
  • organic solvents such as aromatic hydrocarbons, e.g. Toluene or xylene, ethers, e.g. Dioxane, ketones, e.g. Acetone, or methyl ethyl ketone, esters, e.g. Butyl acetate or ethyl acetate, or mixtures thereof in amounts of up to 10% by weight based on the total adhesive formulation
  • organic solvents such as aromatic hydrocarbons, e.g. Toluene or xylene, ethers, e.g. Dioxane, ketones, e.g. Acetone, or methyl ethyl ketone, esters, e.g. Butyl acetate or ethyl acetate, or mixtures thereof in amounts of up to 10% by weight based on the total adhesive formulation
  • organic solvents such as aromatic hydrocarbons, e.g. Toluene or xylene, ethers, e.g. Di
  • the proportions of the individual components are chosen such that the resulting formulation according to the invention comprises components (a), (b) and (c) and optionally further
  • the dispersions according to the invention are outstandingly suitable as adhesives or coating agents for various substrates.
  • substrates such as wood, paper, plastics, textiles, leather, rubber or inorganic materials such as Keram ik, earthenware,
  • the adhesive and sealant formulations according to the invention exhibit a high initial strength and the resulting dry coating or adhesive films have a high water resistance and heat resistance compared with known adhesive formulations
  • the present invention furthermore relates to the use of the adhesive and sealant molds according to the invention as adhesives or coating adhesives, the use as contact adhesives, pressure-sensitive adhesives, flock adhesives or laminating adhesives, or agents for coating and impregnating Fader products for the manufacture of textile or fiber reinforced concrete or other cement based products.
  • the application of the polymer dispersions of the invention may be carried out in known manners, e.g. by brushing, pouring, knife coating, spraying, rolling or dipping.
  • the drying of the coating or adhesive film can at room temperature or elevated
  • substrates which are coated or bonded with a formulation according to the invention and a method for bonding the substrates coated on one or both sides using the formulations.
  • TMA Thermo-mechanical analysis
  • the dispersions are dried in a Teflon dish as a film and that for 3 days at room temperature, for 1 hour at 80 0 C and then again for 3 days at room temperature, with a film to be formed with a thickness of 1.0 mm to 1.5 mm. It is measured with a Perkin Elmer DMA 7 device at a load of 500 mN and a temperature program of pp, gp substrate. This measurement correlates with the determination of the heat resistance of the bonds in the heating cabinet.
  • Example of such a heat resistance test The test specimens are loaded with 4 kg and placed in a heating cabinet within 30 min. tempered to 4O 0 C. Subsequently, the test specimens with a linear heating rate of 0.5 o C / min. heated to 15O 0 C. The softening temperature, ie the temperature at 0 C at which the adhesion fails under the 4 kg load, is registered.
  • the test is carried out in accordance with EN 1392. On two test pieces of linen measuring 100 ⁇ 30 mm, a 100 ⁇ m thick wet film of the formulation is applied and ventilated at room temperature. Subsequently, the specimens are shock activated for 10 seconds and joined together at 4 bar. There is a tear test on a commercial tensile testing machine at room temperature. The strength values are determined after one day.
  • the viscoelastic properties are determined as a function of the temperature of 100 0 C to 20 0 C with a cooling rate of 4 0 C / min at a measuring frequency of 1 Hz and a deformation of 0.05.
  • Determination of the crosslinking behavior takes place on a moving The rheometer of the company Alpha Technologies. The test is carried out according to the method ASTM D 5289-95. This standard is equivalent to ISO 6502-1991 and DIN 53529 Part 3. The measurement is usually carried out at temperatures of 100 0 C to 200 0 C. The deformation resistance is measured by the increasing cross-linking increases as a thrust or torque. Indicated is the minimum force at
  • test specimens are cut out, dimensions 20 x 60 mm.
  • a 100 ⁇ m thick wet of the adhesive formulation is applied with a brush on a surface to be bonded of 10 x 20 mm and ventilated for 1 hour at room temperature.
  • the test pieces are shock activated for 10 seconds and pressed against each other so that only the adhesive surfaces are joined at an angle of 180 ° to each other.
  • the composite is pressed in the press for 10 seconds with 4 bar (effective).
  • the KASX test specimens are loaded with 4 kg and placed in a heating cabinet within 30 min. tempered to 40 0 C. Subsequently, the test specimens with a linear heating rate of ö, 5 ° C / min. heated to 150 0 C. The softening temperature, ie the temperature at 0 C at which the adhesion fails under the 4 kg load in the shear test, is registered. In each case 4 individual measurements are carried out.
  • the adhesive surfaces are illuminated for 10 seconds with an infrared radiator from Funk (shock activator
  • test specimens are stored at 23 ° C and 50% relative humidity.
  • the silica dispersion (a) was placed in closable glass bottles and added the water-soluble hydroxyl-containing polymer or oligomer (b) with stirring. After a stirring time of 1 hour, the glass bottles were sealed and stored.
  • the polymer dispersion (c) was placed in a beaker.
  • the dispersion according to the invention and, if necessary, additives and optionally adhesive adjuvants were then added with stirring. After a storage time of 24 hours, the Fonnultechnik was used for the experiments.
  • Dispersion I Silica D + 7% by weight of cyclodextrin F, (Tab.l batch 4)
  • Tab 2b Vulkameter data, maximum force (S'max)
  • Fig. 2 Course of the measurements of the resistance to thermal stress of films from dispersions according to Tab. 2a-c, batches 15, 18, 19
  • Dispersion I SiHcium dioxide D + 7% by weight of cyclodextrin F, (Tab.l batch 4)
  • Dispersion II silicon dioxide D + 5% by weight of cyclodextrin F (Tab 1 batch 4)
  • Tab 3b Vulkameter data, maximum force (S'max)
  • Resin-free formulations of the invention 21 and 23 a significantly higher resistance to thermal stress and the best crosslinking behavior.
  • the curve is shown in Fig. 3 and 4.
  • Dispersion I Silica D + 7% by weight of cyclodextrin F, (Tab.l batch 4)
  • Dispersion II Silica D + 5% by weight of cyclodextrin F (Tab. 1 batch 4)
  • Tab 4b Vulkameter data, maximum force (S'max)
  • the polymer dispersions L with a higher content of hydroxyl groups shows a better crosslinking behavior than the same polymer dispersion K with a lower content of hydroxyl groups.
  • Fig.5 cooling test with polymer dispersions S, T, N, and U Bohlin VOR 100 0 C> 20 0 C, 4 ° C / min, frequency: 1 Hz
  • Fig.6 cooling test with polymer dispersions W, X and V Bohlin VOR: 100 ° C> 20 0 C, 4
  • Fig.7 cooling test with polymer dispersions O, P and M Bohlin VOR 100 0 C> 20 0 C, 4 ° C / min, frequency: 1 Hz
  • Fig. 8 Cooling test Bohlin with polymer dispersions K and L VOR: 100 0 C> 20 0 C, 4 ° C / min, frequency: 1 Hz
  • the dispersions W and X satisfy the criteria of the present invention, while the adhesive dispersion V is too soft, i. the curve is below the desired range of 0.2 MPa.
  • Fig.7 meet the dispersions O and P, the criteria of the invention, while the dispersion M is too soft for the adhesive, ie the storage modulus of the polymer decreases rapidly with increasing temperature and is already at temperatures above 50 0 C below the desired range of 0.2 MPa.
  • both dispersions K and L fulfill the criteria according to the invention Polymer dispersion N and Z
  • formulation contains, in addition to the polymer dispersion, this silica dispersion
  • N spoke modulus G at temperatures of 30 0 C to 100 0 C outside the range of 0.02 to 2 MPa s
  • N storage modulus G at temperatures of 30 0 C to 100 0 C outside the range of 0.02 to 2 MPa s
  • N storage modulus G at temperatures of 30 0 C to 100 0 C outside the range of 0.02 to 2 MPa s nb not determined.
  • Particularly preferred polymer dispersions whose viscoelastic properties (G Speichermodui) at temperatures of 3O 0 C to 100 0 C are in the range of 0.02 to 2 MPa s show in combination with the inventive silica dispersion, the best peel strengths of the bonded substrates, and show the highest crosslinking (S'max), cf. in particular experiments 42, 48, 57, 60, 69, 72. This also applies to the experiments 45 and 51, of which the corresponding memory module curves are not present.
  • Residual monomer shown by the example polychloroprene latex, significantly reduced.
  • Dispersion III Silica D + 0.9% by weight of cyclodextrin G (Tab 1 batch 6)
  • Dispersion V Silica D + 2.5% by weight of cellulose compound AB
  • Dispersion VI Silica D + 2.5% by weight of cellulose compound AC
  • Fig.9 cooling test with polymer dispersions AD, Bohlin VOR 100 0 C> 20 0 C, 4 ° C / min, frequency: 1 Hz
  • Tab 12b Force at which the roving slips out of the concrete test specimen.

Abstract

L'invention concerne des dispersions aqueuses, caractérisées en ce qu'elles contiennent (c) au moins une dispersion aqueuse de dioxyde de silicium avec un diamètre moyen de la particule SiO2 de 1 à 400 nm et (d) au moins un composé organique hydrosoluble contenant des groupements hydroxy. L'invention concerne également leur procédé de fabrication et leur utilisation dans des formulations d'adhésifs ou de revêtements.
EP07820366A 2006-09-20 2007-09-20 Dispersions aqueuses de dioxyde de silicium pour formulations d'adhésifs et d'agents d'étanchéité Withdrawn EP2064276A2 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102006044068A DE102006044068A1 (de) 2006-05-11 2006-09-20 Wässrige Siliciumdioxid Dispersionen für Dicht- und Klebstoffformulierungen
PCT/EP2007/059922 WO2008034856A2 (fr) 2006-09-20 2007-09-20 Dispersions aqueuses de dioxyde de silicium pour formulations d'adhésifs et d'agents d'étanchéité

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EP2064276A2 true EP2064276A2 (fr) 2009-06-03

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EP07820366A Withdrawn EP2064276A2 (fr) 2006-09-20 2007-09-20 Dispersions aqueuses de dioxyde de silicium pour formulations d'adhésifs et d'agents d'étanchéité

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US (1) US8946338B2 (fr)
EP (1) EP2064276A2 (fr)
CN (1) CN101558111B (fr)
WO (1) WO2008034856A2 (fr)

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GB0905951D0 (en) 2009-04-06 2009-05-20 Univ Ulster Method of manufacture of a composite concrete article
US10434569B2 (en) 2014-01-23 2019-10-08 Les Produits Industriels De Haute Temperature Pyroteck Inc. Filtration device for the filtration of a liquid metal or an alloy thereof, and a filtration method using said filtration device
BR112016017106B1 (pt) * 2014-01-23 2022-04-19 Les Produits Industriels De Haute Température Pyrotek Inc Composição para a preparação de um tecido endurecido, tecido termoplástico, tecido endurecido e dispositivo de filtração
WO2016004381A1 (fr) * 2014-07-03 2016-01-07 Advanced Materials Technology Compositions de milieux poreux et procédés de production associés
EP3825375A1 (fr) 2019-11-20 2021-05-26 Covestro Deutschland AG Collage humide des adhésifs de pulvérisation 1k à base de polychloroprène stables au stockage
KR20230137391A (ko) * 2021-02-25 2023-10-04 노블 파나시아 랩스, 인크. 제어된 약물 방출을 위한 유기 초분자 혈관구조체의 어셈블리(assembly of organic supramolecular vessels for controlled drug release)
CN114409279B (zh) * 2022-01-24 2024-03-29 广东卫屋防火科技有限公司 一种防火夹层胶及其制备方法及包含其的防火玻璃

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Also Published As

Publication number Publication date
WO2008034856A2 (fr) 2008-03-27
CN101558111B (zh) 2013-07-17
CN101558111A (zh) 2009-10-14
US20100029810A1 (en) 2010-02-04
US8946338B2 (en) 2015-02-03
WO2008034856A3 (fr) 2008-06-05

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