EP2553022A1 - Formulation convenant à une utilisation en tant que revêtement antigraffitis, présentant des propriétés mouillantes améliorées - Google Patents

Formulation convenant à une utilisation en tant que revêtement antigraffitis, présentant des propriétés mouillantes améliorées

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Publication number
EP2553022A1
EP2553022A1 EP11704763A EP11704763A EP2553022A1 EP 2553022 A1 EP2553022 A1 EP 2553022A1 EP 11704763 A EP11704763 A EP 11704763A EP 11704763 A EP11704763 A EP 11704763A EP 2553022 A1 EP2553022 A1 EP 2553022A1
Authority
EP
European Patent Office
Prior art keywords
polymer
iii
block
weight
formula
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Withdrawn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
EP11704763A
Other languages
German (de)
English (en)
Inventor
Manuel Friedel
Spomenko Ljesic
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
Evonik Degussa GmbH
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 Evonik Degussa GmbH filed Critical Evonik Degussa GmbH
Publication of EP2553022A1 publication Critical patent/EP2553022A1/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Withdrawn legal-status Critical Current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
    • C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
    • C09D183/04—Polysiloxanes
    • C09D183/08—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen, and oxygen
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/009—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone characterised by the material treated
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
    • C04B41/46—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with organic materials
    • C04B41/49—Compounds having one or more carbon-to-metal or carbon-to-silicon linkages ; Organo-clay compounds; Organo-silicates, i.e. ortho- or polysilicic acid esters ; Organo-phosphorus compounds; Organo-inorganic complexes
    • C04B41/4905—Compounds having one or more carbon-to-metal or carbon-to-silicon linkages ; Organo-clay compounds; Organo-silicates, i.e. ortho- or polysilicic acid esters ; Organo-phosphorus compounds; Organo-inorganic complexes containing silicon
    • C04B41/495—Compounds having one or more carbon-to-metal or carbon-to-silicon linkages ; Organo-clay compounds; Organo-silicates, i.e. ortho- or polysilicic acid esters ; Organo-phosphorus compounds; Organo-inorganic complexes containing silicon applied to the substrate as oligomers or polymers
    • C04B41/4961—Polyorganosiloxanes, i.e. polymers with a Si-O-Si-O-chain; "silicones"
    • C04B41/4966—Polyorganosiloxanes, i.e. polymers with a Si-O-Si-O-chain; "silicones" containing silicon bound to hydroxy groups, i.e. OH-blocked polysiloxanes
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/60—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone of only artificial stone
    • C04B41/61—Coating or impregnation
    • C04B41/62—Coating or impregnation with organic materials
    • C04B41/64—Compounds having one or more carbon-to-metal of carbon-to-silicon linkages
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
    • C08L83/04—Polysiloxanes
    • C08L83/08—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
    • C04B2111/10—Compositions or ingredients thereof characterised by the absence or the very low content of a specific material
    • C04B2111/1006—Absence of well-defined organic compounds
    • C04B2111/1012—Organic solvents
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
    • C04B2111/20—Resistance against chemical, physical or biological attack
    • C04B2111/25—Graffiti resistance; Graffiti removing

Definitions

  • Formulation suitable for use as an antigraffiti coating with improved wetting properties is
  • the invention relates to a composition which is suitable for the production of antigraffiti coatings comprising substantially water-soluble and substantially completely hydrolyzed, oligomeric organosiloxanes and at least one polyoxyalkylene block copolymer as wetting agent and water, and processes for their preparation as well as their Use.
  • the compositions according to the invention have improved film-forming properties which are manifested by the fact that, when applied, for example, but not exclusively, to porous, mineral substrates, coherent films without
  • Droplet formation can be generated to name just one of the most preferred uses.
  • Spray application applied formulations can be elaborately deleted with a brush to a continuous film.
  • the droplets sprayed in Example 1 of EP 1 193 302 A2 must be aftertreated with a brush to form a homogeneous film.
  • Untreated droplets often tend to form sticky silicone resin films. Especially in building protection is therefore undesirable in the encountered there large surfaces a costly post-treatment by brush.
  • compositions of oligomeric organosiloxanes which are suitable as anti-graffiti coating, and which have improved film-forming properties when the composition is applied to a substrate. Another object was to provide a method for producing these compositions.
  • compositions of water-based, low-VOC oligomeric organosiloxanes containing very specific wetting agents and by this modification as
  • compositions of the invention comprise substantially water-soluble and substantially completely hydrolyzed, oligomeric organosiloxanes,
  • At least one wetting agent based on polyoxyalkylene block co-polymers in particular of ethylene oxide-propylene oxide-ethylene oxide (EO / PO / EO) triblock copolymers, and water, in which the organosiloxanes or mixtures thereof are used as co-condensates or block copolymers.
  • Co-condensates are present and derived from
  • At least two of the alkoxysilanes of the general formulas II, III, IV and V release substantially no more alcohol on crosslinking.
  • Alkoxysilanes obtained by hydrolysis and / or condensation in the presence of a defined amount of water and optionally an acid after removal of the hydrolysis alcohol and optionally adding water to organosiloxanes can preferably be prepared as disclosed in EP 0 846 717 and EP 1 193 301 A2.
  • the disclosure content of EP 0 846 717 and EP 1 193 301 A2 is fully incorporated into the content of the present invention.
  • the invention thus relates to a composition comprising substantially water-soluble and substantially completely hydrolyzed, oligomeric organosiloxanes, at least one wetting agent and water, and
  • A is an aminoalkyl radical H 2 N (CH 2 ) f (NH) g (CH 2 ) h (NH) m (R 7 ) n - in which
  • B is a fluoroalkyl radical R 4 -Y- (CH 2 ) 2 - in the structural element derived from the general formula III,
  • R 6 -Si (R 5 ) u (OR 1 ) 3-u (IV), wherein R 5 is a linear or branched alkyl group having 1 to 4 carbon atoms, in particular methyl (CH 3 -) and u 0 or 1 in formula IV,
  • D is an alkyl radical R 6 - in the structural element derived from the
  • R 1 in formulas II, III, IV and / or V independently of one another is a linear, branched or cyclic alkyl group having 1 to 8 C atoms or an aryl group, preferably R 1 is independently methyl, ethyl or propyl; with R 2 , R 3 and / or R 5 in the abovementioned formulas independently correspond to a linear or branched alkyl radical having 1 to 4 C atoms, preferably independently of methyl or ethyl, and
  • HX is an acid, where X is an inorganic or organic acid radical, where x, y and u are independently 0 or 1 and a, b, c, d and e are each independently of the other integer a> 0, b> 0, c> 0, d> 0, e> 0 and (a + b + c + d)> 2, preferably (a + b + c + d)> 4, more preferably (a + b + c + d)> 10, with X being, for example, chloride, nitrate, formate or acetate, or (ii) wherein the organosiloxanes are co-condensates or block co-condensates or mixtures thereof derived from at least two of The aforementioned alkoxysilanes of the general formulas II, III, IV and V are preferably derived in molar ratio from the formulas II and II 1: ⁇ 3.5 or else with a, bc and d in moles of
  • the wetting agent is a polyoxyalkylene block co-polymer or a
  • the aqueous composition when used in a suitable concentration, a hydrophobicizing and oleophobicizing effect is achieved.
  • the composition contains oligomeric
  • Organopolysiloxanes having (a + b + c + d)> 4 and optionally monovalent inorganic or organic acids or their derivatives from the hydrolysis and / or condensation step of the alkoxysilanes, wherein the aqueous oligomers
  • Organosiloxanes preferably have a pH between 1 to 8, preferably between 1 to 6, most preferably between 1 to 5.
  • compounds such as alkali metal halides, in particular sodium or potassium chloride, alkali metal acetates, alkyl formates, alkali metal nitrates or compounds of the aminoalkyl radical with inorganic or organic acid radicals are to be understood, as shown in formula I.
  • structural elements are each the Expressions in the square brackets, such as [Si (C) (R 5 ) u (OH) i -u O] c or
  • Organosiloxanes linear, branched, cyclic and / or spatially crosslinked structures or structural regions of the structural elements having M, D, T structures.
  • organosiloxanes which have only a negligible content of hydrolyzable alkoxy groups, -OR 1 - therefore not represented in idealized formula I, where they are shown as -OH.
  • the content is considered to be negligible if it results in a solvent content in the total composition of less than 5 wt .-% to 0 wt .-% or
  • the polyoxyalkylene block copolymer contains at least two different alkylene oxide groups, in the sense of substituted or
  • HO (EO) v [Z] r - (EO) v -H (VI) is -CH Z (CH 3) -CH 2 -O-, - (CH 2) 3 -O -, - (CH 2 ) 4 -O- or -CH (C 6 H 6 ) -CH 2 -O-, more preferably with Z equal to -CH (CH 3 ) -CH 2 -O-, and EO in each case equal to -CH 2 - CH 2 - each of v is independently an integer size, that the hydrophilic part EO is 5 to 95% by weight of the block co-polymer, and r is an integer size each, that the hydrophobic part Z is one
  • the polyoxyalkylene block co-polymer is a triblock co-polymer of ethylene oxide blocks [EO], propylene oxide blocks [PO] and ethylene oxide blocks [EO].
  • r is in each case an integer number of the size such that the hydrophobic part Z, in particular with Z equal to -CH (CH 3 ) -CH 2 -O-, of the polyoxyalkylene block co-polymer has a molecular weight between 450 and 3400, in particular between 900 to 3400 g / mol
  • v is in each case an integer number of the size which corresponds to the hydrophilic part EO, with EO equal to -CH 2 -CH 2 -O-, from about 10 to 90% by weight of the block co Polymers.
  • each r is an integer size, that the hydrophobic portion Z of the polyoxyalkylene block co-polymer has a molecular weight in the range of 1100 to 2300 g / mol, and v is an integer of the size the hydrophilic part EO is about 10 to 80% by weight of the block co-polymer.
  • r means an integer number of size that the hydrophobic part Z of the polyoxyalkylene block co-polymer has a molecular weight in the range of about 1750 g / mol plus plus / minus 50 g / mol, and v independently one whole each
  • the number of the size is that the hydrophilic part EO is about 80 wt% with plus minus 10 wt% of the block co-polymer.
  • the molecular weight is understood as the average molecular weight and can preferably be determined by the hydroxyl value.
  • the expert is the
  • v can be in the range from 10 to 500, in particular between 10 and 300, preferably between 10 and 250, particularly preferably between 10 and 200, very preferably v independently between 40 and 100 or v with 70 plus /. minus 10.
  • numbers in the range of 10 to 100 are preferred, especially between 10 to 70, more preferably between 10 to 60, most preferably r is about 30 plus / minus 5.
  • the triblock co-polymers used according to the invention can be present in liquid or solid form.
  • the molecular weight of the triblock copolymers is between 940 and 10,000, preferably between 1,000 and 10,000.
  • the molecular weights for the two ethylene oxide blocks may be around 7,000 down to 980, 550, 500 or 400.
  • Propylene oxide blocks are preferably in the range of 450 to 3300,
  • each v is independently an integer and the two ethylene oxide blocks between 10 to 90 wt .-%, preferably between 20 to 85 wt .-% plus / minus 5% by weight with respect to the total polyoxyalkylene block co-polymer.
  • the preferred triblock co-polymer may have the combination of on average v independently equal to or equal to 70 ⁇ 10 and r equal to 30 ⁇ 5, respectively.
  • the molecular weights are preferably in a range of 4,000 to 15,000, more preferably 10,000 to 15,000, more preferably 13,000 to 14,600. Examples thereof
  • EO / PO / EO polymers have a molecular weight distribution of EO together 4000 and PO of 1000 at a molecular weight of 5000, or EO together 1200 and PO of 4800 and together 16000, or EO together 8500 and PO of 1500 and together of 10000 , or EO together 10400 and PO of 2600 and together of 13000, or also of EO together 1 1680 and PO of 2920 and together of 14600 on.
  • liquid and solid triblock copolymers as a mixture / blend in the composition.
  • 80 to 98 wt .-% of the total composition of triblock co-polymers of the liquid polymer and 2 to 20 wt .-% of the solid polymer are used, preferably 85 to 95 wt .-% of the liquid polymer and 5 bis 15% by weight of the solid polymer, more preferably 88 to 92% by weight of the liquid and 8 to 12% by weight of the solid polymer in a polyoxyalkylene block copolymer blend.
  • the present composition is essentially free from volatile solvents, preferably from hydrolysis alcohol, and in particular does not release any hydrolysis alcohol when crosslinked.
  • volatile solvents preferably from hydrolysis alcohol
  • the content of organic solvents, in particular volatile solvents, in the total composition is preferably below 5 wt .-% to 0 or 0.0001 wt .-%, or to
  • Detection limit with all components in the composition in total 100 wt .-%.
  • the content of organic solvents is particularly preferred in the total composition between 3 to 0.0001 wt .-%, in particular 1, 0 to 0.0001 wt .-%, preferably between 0.5 to 0.0001 wt .-% or to
  • Volatile solvents include alcohols, such as methanol, ethanol, isopropanol, n-propanol, and alkoxy groups which hydrolyze to alcohols, or methoxyethanol, which are either added to the formulation or formed by hydrolysis of the alkoxysilanes, and all others
  • solvents such as ketones, ethers and the like.
  • the active substance content of the composition of oligomeric organopolysiloxanes in the total composition according to the invention is between 0.001 to 60 wt .-%, in particular between 0.1 to 50 wt .-%, preferably between 0.5 to 30 wt .-%, particularly preferably 1 to 20 Wt .-%, most preferably 1, 5 to 15 wt .-%.
  • the content of the wetting agent is in the total composition
  • the wetting agent is at least one polyoxyalkylene block co-polymer or a mixture of these, preferably a wetting agent of the general formula VI.
  • the content is 0.01 to 3 wt .-%,
  • the wetting agents mentioned are from 0.1 to 2% by weight, in particular from 0.2 to 1.5% by weight, more preferably from 0.25 to 1.5% by weight, very particularly preferably at 0.3 to 1 wt .-%.
  • this composition may advantageously have inorganic particles or fillers such as silica, precipitated silica, flame silicic acid, quartz, titanium dioxide, calcium carbonate, gypsum, ATH, alpha and gamma Al 2 O 3, magnesium hydroxide / oxide, iron oxides in order to increase their abrasion resistance and scratch resistance , Clay minerals, phyllosilicates, cerium oxide, yttrium oxide, calcium oxide,
  • Germanium oxide and corresponding hydroxides and oxide hydrates and mixtures of at least two of the aforementioned compounds with one another or other metal oxides known to those skilled in the art are present.
  • the stated particles or fillers may be added as a powder, paste or in aqueous dispersion, optionally in stabilized dispersions.
  • a composition comprising a
  • Silica dioxide a flame-silica, a precipitated silica or mixtures thereof has proven to be particularly advantageous in spray application.
  • aqueous dispersion in particular as an aqueous dispersion or as an aqueous dispersible flame or precipitated silica used in the preparation of the composition.
  • the content of the aforementioned inorganic particles or fillers such as silica, flame silica and / or
  • Precipitated silica between 0.001 to 10 wt .-% with respect to the
  • Total composition in particular between 3 to 0.1 wt .-%, preferably between 2.5 to 0.2, particularly preferably between 2 to 0.25 wt .-%. In this case, further 0.6 to 0.02 wt .-%, 0.5 to 0.04 wt .-% and most preferably 0, 4 to 0.05 wt .-% of a content of silica, flame silicic acid and / or Precipitated silica relative to the total composition.
  • Preferred average particle sizes (primary particles) or aggregate sizes of the flame silica (d50) are between 1 nm and 500 nm, preferably between 1 nm and 250 nm, particularly preferably between 1 nm and 150 nm.
  • Preferably used stabilized aqueous dispersions of flame silicic acid have a content of 12 to 50 wt .-% with respect to the entire aqueous dispersion, wherein usually the particle sizes or sizes of
  • compositions include organopolysiloxanes at 0.001 to 60% by weight, the wetting agent at 0.001 to 5% by weight and optionally inorganic particles or fillers such as silica, flame silicic acid and / or precipitated silica at 0.001 to 10% by weight, respectively on the
  • compositions may also contain small amounts of water-soluble solvent.
  • a composition according to the invention comprises, for example, 1 to 15% by weight of organopolysiloxanes, 0.01 to 2% by weight of the wetting agent, in particular of the polyoxyalkylene block co-polymer, preferably of the formula VI; optionally from 0.1 to 3% by weight of inorganic particles or fillers, such as silicon dioxide,
  • compositions are substantially storage stable. This means they do not show any visible changes like cloudiness or
  • the composition can be made homogeneous again by stirring.
  • composition according to the invention may contain at least one of the following components from the series pigments, fillers, binders, crosslinkers, optical brighteners, paint assistants or other auxiliaries.
  • Organosiloxanes and preferably VOC-free organosiloxanes, in particular of the general formula I, the following alkoxysilanes are preferably used, hydrolyzed and / or condensed and VOC-free:
  • alkoxysilane of the formula II aminopropyltriethoxysilane
  • alkoxysilane of the formula III tridecafluoro-1,1,2,2-tetrahydrooctyl-1-trimethoxysilane or tridecafluoro-1,1,2,2-tetrahydrooctyl-1-triethoxysilane,
  • alkoxysilane of the formula IV dimethyldimethoxysilane, dimethyldiethoxysilane,
  • alkoxysilane of the formula V methyltrimethoxysilane, methyltriethoxysilane,
  • the organosiloxanes are prepared, for example-but not exclusively
  • EP 0 846 717 A2 and EP 1 193 302 A2 are fully incorporated by reference and made the subject of the present application.
  • the invention also provides a process for the preparation of a
  • composition as well as a composition obtainable by this method by
  • Organosiloxane or a mixture of organosiloxanes which are derived from alkoxysilanes of the formulas II, III, IV and / or V, in particular as named in claim 1, and have crosslinking structural elements which form chain-like, cyclic, crosslinked and / or spatially crosslinked structures, preferably at least one structure in idealized form of the general formula I corresponds, or
  • polyoxyalkylene block co-polymer or a mixture of polyoxyalkylene block co-polymers comprising at least two different alkylene oxide groups each having 1 to 8 C atoms, in particular having 1 to 5 C atoms, as defined above, and a molecular weight in the range of 450 to 15,000, preferably 940 to 15,000, preferably 1000 to 15,000 or a mixture thereof
  • aqueous, oligomeric organosiloxanes in particular aminoalkyl, aminopropyl / methyl and fluoroalkyl-functional organosiloxanes, with a triblock copolymer or a mixture of these polymers and
  • silica such as precipitated silica or flame silica.
  • the mixing may be carried out by separately or jointly stirring the polymers and / or the silica into the aqueous organosiloxanes.
  • an aqueous dispersion or an aqueous dispersible flame or precipitated silica is mixed with an aqueous organosiloxane-containing composition of the silica.
  • Precipitated silicic acids can be avoided as a rule a complex homogenization under high stirring speeds.
  • an alkaline stabilized flame silica with a content of 10 to 50 wt .-% in the aqueous dispersion, preferably by 20 ⁇ 1 wt .-% with respect to the
  • Dispersion can be used.
  • the viscosity of this dispersion is advantageously set to less than or equal to 300 mPa s (measured at shear rates of 100 s -1 measured in accordance with DIN EN ISO 32 19) and the pH is in the range from 9 to 10.
  • a stabilizing agent it is possible, for example not exclusively - potassium hydroxide should be present
  • Flame silica particles may be as explained above.
  • Particularly preferred is an aqueous dispersion of a flame or silica, aqueous
  • Silica added to the organosiloxanes.
  • a polyoxyalkylene block co-polymer or a mixture of polyoxyalkylene block co-polymers is mixed with the organosiloxane, wherein the polyoxyalkylene block co-polymers at least two different
  • HO (EO) v [Z] r - (EO) v -H (VI) is -CH Z (CH 3) -CH 2 -O-, - (CH 2) 3 -O-, - (CH 2 ) 4 is -O- or -CH (C 6 H 6 ) -CH 2 -O- and EO is -CH 2 -CH 2 -, v is independently an integer of size, that the hydrophilic part EO is 5 to 95 Weight percent of the block co-polymer and r is an integer size means that the hydrophobic part Z has a molecular weight of at least 450 g / mol.
  • the above-described triblock co-polymers having the stated molecular weights total or the PO, EO blocks, v, r and / or weight percent of EO blocks in the block co-polymers can be used.
  • Particular preference is given here to polyoxyalkylene block copolymers of the formula VI in which r is an integer of the size such that the hydrophobic part Z of the polyoxyalkylene block co-polymer has a molecular weight in the range of 1750 g / mol plus / minus 50 g / mol, and v is independently an integer of the size that the hydrophilic part EO is about 80 wt% plus plus 10 wt% of the block co-polymer.
  • the polyoxyalkylene block co-polymers used to prepare the composition may preferably also have EO parts of different lengths.
  • the values of the numbers of the two v in formula VI are independent of each other and may therefore differ significantly.
  • the organosiloxane can also be stirred into an aqueous flame or precipitated silica dispersion to prepare the composition and then the polyoxyalkylene block co-polymers are stirred in.
  • an aqueous dispersion of a flame or precipitated silica may first be stirred into aqueous organosiloxanes and then the polyoxyalkylene block co-polymers mixed therewith.
  • compositions thus obtained may preferably be diluted further with water or expediently a suitable solvent, for use on inorganic materials, preferably porous inorganic substrates, such as concrete, sand-lime brick, bricks, paving stones, in particular according to DIN 18 501 screed, granite, marble, Sandstone, natural stone content of 1 to 20 wt .-% of oligomeric organosiloxanes for optimum results in terms of film-forming properties and the oleophobic and hydrophobic effect has been found to be particularly preferred.
  • a suitable solvent for use on inorganic materials, preferably porous inorganic substrates, such as concrete, sand-lime brick, bricks, paving stones, in particular according to DIN 18 501 screed, granite, marble, Sandstone, natural stone content of 1 to 20 wt .-% of oligomeric organosiloxanes for optimum results in terms of film-forming properties and the oleophobic and hydrophobic effect has been found to be particularly preferred.
  • compositions obtainable according to the invention can be diluted with water in virtually any ratio, in particular between 1: 100 to 100: 1 and in all ratios lying therebetween.
  • the invention also provides the use of the invention
  • composition or a method in which a one to four times applied to a substrate, wherein after each application, a drying and / or crosslinking step, and the application is preferably carried out by spraying.
  • the composition may be applied more dilute to the surface upon first spraying than on second or further spray application.
  • the spray application can be repeated as often as desired
  • compositions may include dipping, brushing, rolling, knife-coating, triturating, polishing or flooding.
  • essentially contiguous films are preferred on the
  • a suitable for the process used concentration of organosiloxanes in the composition is set. Depending on the processing method, therefore, the concentration may range from 0.01% by weight of organosiloxanes to as much as 99.5% by weight in the composition.
  • the application methods are well known to the respective person skilled in the art.
  • a coating applied to a substrate can be cured under ambient conditions and / or by an additional thermal and / or photochemical treatment or set with the substrate.
  • inorganic or organic substrates can thus be treated with a composition according to the invention, or a composition according to the invention can be used as starting material component in
  • the invention also provides the use of a composition of substantially completely hydrolyzed, oligomeric organosiloxanes and
  • Polyoxyalkylene block co-polymers and optionally silicon dioxides are preferred.
  • Water-based precipitated silica or flame-silica in particular according to one of claims 1 to 15, for the treatment, modification, preparation of formulations, substrates, articles, coatings, organic or
  • inorganic materials or composite materials or for the coating of substrates for hydrophobization and oleophobization and for the dirt and ink repellent finishing of surfaces or porous substrates, mineral building materials, metals, plastics, for the protection of buildings and facades, for the silanization of fillers and pigments for the improvement of the rheological properties of polymer dispersions and emulsions, for hydrophobization and oleophobization as well as dirt and ink repellent
  • the end product according to the invention or the composition of the invention is usually liquid and low to slightly viscous, the viscosity is in particular for a spray application below 1500 mPa s to 0.001 mPa s, preferably between 1000 and 1 mPa s, preferably below 300 mPa s , preferably below 200 mPa s, more preferably below 100 mPa s, better between 100 mPa s and 1 mPa s, further preferred ranges are from 200 to 1 mPa s, in particular from 100 and 10 mPa s (the viscosity is determined according to DIN 53015) ).
  • Figure 1 shows a coating of a specimen with unmodified
  • FIG. 2 shows a coating of a test specimen after two times
  • FIG. 3 shows a coating of a test specimen after two times
  • Example 3 as Example 2, but without the addition of flame silica.
  • Comparative composition without the inventive wetting agent shows a significant droplet formation (1).
  • the formation of droplets (1) is clearly visible in the figure at the points which reflect the light more strongly. The educated
  • FIG. 3 shows a
  • FIG. 3 shows a comparative composition - according to Example 1 without wetting assistant - after two spray applications with intermediate drying.
  • Figure 3 shows a clear
  • Table 1 show that the cleaning of conventional graffiti paints with excellent results is possible when treating concrete with mixtures according to the invention. A Ci value of> 80 is considered an excellent cleaning result. At the same time, the stickiness of the surface corresponds to that of the untreated comparison body. Table 1 :
  • the concrete slabs are sprayed with Edding 800 permanent marker black, acrylic paint RAL 3000 flame red, Genius Pro Aqua multicolour spray varnish high gloss gentian blue.
  • the three color stains are dried for 60 min at room temperature, followed by cleaning with a chemical cleaner N-methylpyrrolidone (NMP). This is done by allowing the cleaner to act on the spray paint for 10 minutes, then rinsing under running water and gently brushing the surface off.
  • the specimens are then dried at 60 ° C for 15 min and cooled to RT. This process is performed a total of 10 times.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Structural Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Polymers & Plastics (AREA)
  • Medicinal Chemistry (AREA)
  • Health & Medical Sciences (AREA)
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Abstract

L'invention concerne une composition qui convient à la réalisation de revêtements antigraffitis, contenant des organosiloxanes oligomères, pour l'essentiel solubles dans l'eau, et pour l'essentiel entièrement hydrolysés ainsi qu'au moins un copolymère à blocs de polyoxyalkylène en tant qu'agent mouillant, et de l'eau. L'invention concerne également un procédé de fabrication de cette composition, ainsi que sur son utilisation. Les compositions selon l'invention présentent des propriétés filmogènes améliorées, qui se manifestent par le fait que, lors de l'application, par exemple sur des subjectiles minéraux poreux, des films cohérents peuvent être produits sans former de gouttelettes.
EP11704763A 2010-04-01 2011-02-14 Formulation convenant à une utilisation en tant que revêtement antigraffitis, présentant des propriétés mouillantes améliorées Withdrawn EP2553022A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102010003579A DE102010003579A1 (de) 2010-04-01 2010-04-01 Formulierung geeignet zur Verwendung als Antigraffiti-Beschichtung mit verbesserten Benetzungseigenschaften
PCT/EP2011/052110 WO2011120735A1 (fr) 2010-04-01 2011-02-14 Formulation convenant à une utilisation en tant que revêtement antigraffitis, présentant des propriétés mouillantes améliorées

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EP2553022A1 true EP2553022A1 (fr) 2013-02-06

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US (1) US20130040058A1 (fr)
EP (1) EP2553022A1 (fr)
JP (1) JP2013523923A (fr)
CN (1) CN102939342A (fr)
AU (1) AU2011234795A1 (fr)
DE (1) DE102010003579A1 (fr)
WO (1) WO2011120735A1 (fr)

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WO2011121027A1 (fr) 2010-04-01 2011-10-06 Evonik Degussa Gmbh Mélange durcissable
DE102011007142A1 (de) 2011-04-11 2012-10-11 Evonik Degussa Gmbh Lösung umfassend Propyl-funktionelle Alkali-Siliconate, Silikate sowie Verfahren zu deren Herstellung
DE102011007137A1 (de) 2011-04-11 2012-10-11 Evonik Degussa Gmbh Lösung umfassend organofunktionelle Alkali-Siliconate, Silicate sowie Verfahren zu deren Herstellung
DE102011086362A1 (de) 2011-11-15 2013-05-16 Evonik Industries Ag Zusammensetzung umfassend Block-Co-Kondensate von Propyl-funktionellen Alkali-Siliconaten und Silicaten sowie Verfahren zu deren Herstellung
US10106724B2 (en) 2012-11-19 2018-10-23 3M Innovative Properties Company Method of contacting hydrocarbon-bearing formations with fluorinated ionic polymers
US9890294B2 (en) 2012-11-19 2018-02-13 3M Innovative Properties Company Composition including a fluorinated polymer and a non-fluorinated polymer and methods of making and using the same
US10093827B2 (en) 2013-03-15 2018-10-09 Conservation Technologies, Llc Protective water reversible clear coating for substrates
US11697746B2 (en) 2013-03-15 2023-07-11 Conservation Technologies, Llc Protective water reversible clear coating for substrates
DE102014206359A1 (de) 2014-04-03 2015-10-08 Evonik Degussa Gmbh VOC-arme Dialkyl-funktionelle Alkoxysiloxane, Verfahren und deren Verwendung als hydrophobierende Imprägniermittel für mineralische Baustoffe
WO2016036415A1 (fr) 2014-09-02 2016-03-10 Apple Inc. Interface utilisateur de message électronique
BR112018015388B1 (pt) 2016-01-27 2022-12-27 Momentive Performance Materials, Inc Composição de revestimento elastomérica, revestimentos arquitetural e anti-sujeira e/ou anti-mancha e/ou antiincrustação de camada única compreendendo dita composição e método para prepará-la
EP3450508B1 (fr) 2017-08-23 2023-01-25 Conservation Technologies, LLC Revêtement de protection réversible à eau pour substrats

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JP2013523923A (ja) 2013-06-17
AU2011234795A1 (en) 2012-11-01
DE102010003579A1 (de) 2011-10-06
CN102939342A (zh) 2013-02-20
WO2011120735A1 (fr) 2011-10-06
US20130040058A1 (en) 2013-02-14

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