EP1987080A1 - Multifunktionelle sternförmige präpolymere, deren herstellung und verwendung - Google Patents

Multifunktionelle sternförmige präpolymere, deren herstellung und verwendung

Info

Publication number
EP1987080A1
EP1987080A1 EP07722790A EP07722790A EP1987080A1 EP 1987080 A1 EP1987080 A1 EP 1987080A1 EP 07722790 A EP07722790 A EP 07722790A EP 07722790 A EP07722790 A EP 07722790A EP 1987080 A1 EP1987080 A1 EP 1987080A1
Authority
EP
European Patent Office
Prior art keywords
star
shaped
prepolymers
prepolymer
groups
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Withdrawn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
EP07722790A
Other languages
German (de)
English (en)
French (fr)
Inventor
Haitao Rong
Jürgen GROLL
Peter Greiwe
Gallus Schechner
Christine Mohr
Martin Möller
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.)
Henkel AG and Co KGaA
Original Assignee
SusTech GmbH and Co KG
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 SusTech GmbH and Co KG filed Critical SusTech GmbH and Co KG
Publication of EP1987080A1 publication Critical patent/EP1987080A1/de
Withdrawn legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/32—Polymers modified by chemical after-treatment
    • C08G65/329—Polymers modified by chemical after-treatment with organic compounds
    • C08G65/336—Polymers modified by chemical after-treatment with organic compounds containing silicon
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
    • A61K8/91—Graft copolymers
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q5/00—Preparations for care of the hair
    • A61Q5/12—Preparations containing hair conditioners
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F8/00—Chemical modification by after-treatment
    • C08F8/42—Introducing metal atoms or metal-containing groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C08G18/4833—Polyethers containing oxyethylene units
    • C08G18/4837—Polyethers containing oxyethylene units and other oxyalkylene units
    • C08G18/485—Polyethers containing oxyethylene units and other oxyalkylene units containing mixed oxyethylene-oxypropylene or oxyethylene-higher oxyalkylene end groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C08G18/50—Polyethers having heteroatoms other than oxygen
    • C08G18/5021—Polyethers having heteroatoms other than oxygen having nitrogen
    • C08G18/5036—Polyethers having heteroatoms other than oxygen having nitrogen containing -N-C=O groups
    • C08G18/5045—Polyethers having heteroatoms other than oxygen having nitrogen containing -N-C=O groups containing urethane groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C08G18/50—Polyethers having heteroatoms other than oxygen
    • C08G18/5096—Polyethers having heteroatoms other than oxygen containing silicon
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/71—Monoisocyanates or monoisothiocyanates
    • C08G18/718—Monoisocyanates or monoisothiocyanates containing silicon
    • 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
    • C09D171/00—Coating compositions based on polyethers obtained by reactions forming an ether link in the main chain; Coating compositions based on derivatives of such polymers
    • C09D171/02—Polyalkylene oxides
    • 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
    • C09D201/00—Coating compositions based on unspecified macromolecular compounds
    • C09D201/02—Coating compositions based on unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups
    • C09D201/10—Coating compositions based on unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups containing hydrolysable silane groups
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/373—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicones
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
    • A61K2800/40—Chemical, physico-chemical or functional or structural properties of particular ingredients
    • A61K2800/54—Polymers characterized by specific structures/properties
    • A61K2800/544—Dendrimers, Hyperbranched polymers
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
    • A61K2800/80—Process related aspects concerning the preparation of the cosmetic composition or the storage or application thereof
    • A61K2800/94—Involves covalent bonding to the substrate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2210/00—Compositions for preparing hydrogels

Definitions

  • Multifunctional star-shaped prepolymers their preparation and use
  • the present invention relates to coatings based on mutually crosslinkable star-shaped prepolymers and / or star-shaped prepolymer nanoparticle complexes with hydrophilic polymer arms which carry hydrolyzable SiIyI and / or siloxyl end groups at their free ends, and the production of coatings based thereon. Furthermore, the invention relates to the suitable for such coatings star-shaped prepolymers, their preparation and use in a variety of applications.
  • dirt and microbial Impurities be it proteins or cells, repel (Soil Repellency) or facilitate its detachment / washability (soil release). Since dirt, proteins, various polymers or cells usually adhere well to hydrophobic materials, there is a particular need for hydrophilic finished surfaces.
  • hydrophilic coatings include the hydrogel coatings based on polyethylene oxides or polyethylene glycols.
  • Various methods are proposed for producing such coatings.
  • WO 9952574 A1 describes a biomolecule-repellent coating prepared by immobilizing a terminal trichlorosilane-modified linear polyethylene glycol on vitreous surfaces.
  • hydrogel coating is known, which was prepared from star-shaped polyethylene oxides by means of electron irradiation.
  • EP 335308 A2 describes the use of prepolymers of polyethylene oxide diols and triols whose terminal OH groups have been reacted with polyisocyanates for the production of coatings with low nonspecific protein adsorption.
  • WO 03063926A1 discloses an ultra-thin hydrogel coating prepared from star-shaped isocyanate-terminated prepolymers with polyether polymer arms. Such hydrogel coatings effectively suppress nonspecific protein absorption on surfaces provided therewith.
  • R 1 is -CRVSi (OR 6 MRV (I)
  • R a is hydrogen or a linear or branched alkyl group having 1 to 6 carbon atoms
  • OR b is a hydrolyzable group
  • R ° is a linear or branched alkyl group having 1 to 6 carbon atoms
  • r is a number from 1 to 3
  • the silyl end groups R 1 are not attached to the end of the polymer arm via a polyisocyanate, which here and hereinafter also include diisocyanates, and which carry reactive or functional groups on the non-silyl end-group-bearing ends which may be present, which are reactive with themselves, with the substrate to be coated, optionally with entities introduced into the coating and / or with the silyl end groups.
  • Star-shaped prepolymers in the context of this invention are those which have polymer arms bound to a central unit, wherein the polymer arms are substantially star-shaped or radially bound to the central unit, that one end of the polymer arm is bonded to the central unit, while the other end not to this is bound.
  • Star-shaped prepolymer nanoparticle complexes in the sense of this invention are those which have polymer arms bonded to a nanoparticle, wherein the polymer arms are bonded to the nanoparticle in a substantially star-shaped or radial manner so that one end of the polymer is bound to the surface of the nanoparticle another end is not bound to the surface of the nanoparticle.
  • Star-shaped prepolymers and / or star-shaped prepolymer-nanoparticle complexes which are preferably used in the coating are particularly suitable in which the star-shaped prepolymer and / or the star-shaped prepolymer-nanoparticle complex have a plurality of polymer chains bonded to a central unit and in which case star-shaped prepolymer, the central unit is preferably a low-molecular-weight organochemical central unit and, in the case of the star-shaped prepolymer-nanoparticle complex, is preferably an inorganic oxidic nanoparticle.
  • Such star-shaped prepolymers to be used preferably in the coating according to the invention and / or star-shaped prepolymer-nanoparticle complexes have the following general formula (II):
  • Z stands for the central unit, which in the case of the star-shaped prepolymers determines the number of arms of the multi-arm prepolymers
  • A is a hydrophilic, inherently water-soluble polymer arm
  • B and X independently represent a chemical bond or a bivalent, low molecular weight organic radical having preferably 1 to 50 carbon atoms, wherein the silyl end groups R 1 does not have a polyisocyanate or diisocyanate at the end of
  • R 2 is a group which can be crosslinked with R 1 , the substrate and / or with itself, and m and n are in each case integers, in the case of the star-shaped prepolymers m ⁇ 1 and n ⁇ 0 and m + n having a value of 3 to 100, in the event that at least one radical R 2 is an isocyanate radical 4 to 100 and corresponds to the arm number of Z, and the m (XBR 1 ) groups and the n (XBR 2 ) groups independently may have different meanings, in the case of the prepolymer nanoparticle complexes m ⁇ 1 and n ⁇ 0 and m + n has a value of 3 up to a maximum value of 500,000.
  • Z preferably represents a glycerol residue, a polyvalent sugar, such as sorbitol or sucrose.
  • a polyvalent sugar such as sorbitol or sucrose.
  • Z is preferably a silica
  • Zinc oxide Zinc oxide, alumina, zirconia, calcium carbonate, titania, carbon,
  • the Group Z nanoparticles are either commercially available or are prepared in situ or ex situ, preferably by sol-gel techniques, Precipitation from aqueous and non-aqueous solution, gas phase synthesis (flame pyrolysis, chemical vapor deposition, etc.), mechanical processing (eg grinding, ultrasound) produced. With particular preference, these have a size of 0.5 to 200 nm, very particularly preferably 0.5 to 20 nm.
  • the polymer arms A are preferably attached via hydrolyzable silyl end groups to the nanoparticle surface of the residue Z.
  • attachment may also be via other surface reactive groups such as carboxyl groups, cationic groups (e.g., trialkylammonium groups), phosphonate groups, etc.
  • Particularly suitable for introducing the polymer arms on the nanoparticles are linear polyoxyalkylene diols, the two OH groups of which are reacted with silanes which are reactive toward OH groups, such as, for example, isocyanatosilanes.
  • Suitable compounds for introducing polymer arms onto the nanoparticle include polyether polyol, for example, VORANOL®, TERRALOX®, SYNALOX® and DOWFAX® from Dow-Chemical Corporation, SORBETH® from Glyco-Chemicals Inc., GLUCAM® from Amerchol Corp., or Lupranol® and Pluronic® from BASF.
  • polyether polyol for example, VORANOL®, TERRALOX®, SYNALOX® and DOWFAX® from Dow-Chemical Corporation, SORBETH® from Glyco-Chemicals Inc., GLUCAM® from Amerchol Corp., or Lupranol® and Pluronic® from BASF.
  • the wettability of the coatings according to the invention with water is a sensitive measure of their hydrophilicity or hydrophobicity.
  • the contact angle of a water droplet on a planar substrate in the surrounding medium air results from the surface energies of the coating and the water as well as the interfacial energy between water and the coating according to the Young's equation. In the case of maximum hydrophilicity, the contact angle approaches 0 °. In the case of maximum hydrophobicity, the contact angle approaches 180 °.
  • the advancing contact angle and the receding contact angle are often measured dynamically by means of a Wilhelmy balance according to DIN EN 14370. Ideally, the difference between the two should be zero.
  • the coatings according to the invention have both a progressive and a withdrawing water contact angle of at most 90 °, more preferably at most 60 °, particularly preferably at most 55 ° and very particularly preferably at most 50 °. In many cases, however, water contact angles of 40 ° and less are achieved.
  • radicals R 1 are dimethylethoxysilyl-CRY, dimethylmethoxysilyl-CRY, diisopropylethoxysilyl-CRY, methyldimethoxysilyl-CRY, methyldiethoxysilyl-CR a 2 -,
  • B is in the star-shaped prepolymer of the general formula (II) for a chemical bond or a bivalent, low molecular weight organic radical having preferably 1 to 50, in particular 2 to 20 C-atoms.
  • divalent low molecular weight organic radicals include aliphatic, heteroaliphatic, araliphatic, heteroaraliphatic, cycloaliphatic, cycloheteroaliphatic and aromatic and heteroaromatic radicals. Particularly preferred are short-chain aliphatic and heteroaliphatic radicals.
  • suitable radicals include
  • those coatings are preferred which are obtained from star-shaped prepolymers and / or star-shaped prepolymer-nanoparticle complexes of the general formula (II) in which two adjacent or all radicals B in the group BR 1 are not more than one, preferably no hydrogen bonds to one another can build up.
  • Such a low hydrogen crosslinking coating provides greater flexibility in the orientation of the polymer arms A, which in turn results in more uniform distribution of the prepolymers or prepolymer-nanoparticle complexes and in obtaining a uniform, closed coating.
  • the presence of a particularly large number of cross-links or particularly strong crosslinks due to hydrogen bonds can lead to the materials becoming too viscous to be used in typical application formulations.
  • radical B of the star-shaped prepolymer of the general formula (II) in the group BR 1 contains at most one urethane group, one ester or one urea group.
  • the present invention relates to coatings of crosslinked star-shaped prepolymers of the general formula (II) in which the radical R 2 is preferably selected from the group consisting of isocyanate radicals, (meth) acrylate radicals, oxirane radicals, alcoholic OH groups, primary and secondary amino groups, Thiol groups and silane groups. If silane groups are used as R 2 groups, these may also have the general formula (I), but must differ from R 1 in at least one of the groups R a , R b and R c and / or the numerical value of r.
  • R 2 is preferably selected from the group consisting of isocyanate radicals, (meth) acrylate radicals, oxirane radicals, alcoholic OH groups, primary and secondary amino groups, Thiol groups and silane groups. If silane groups are used as R 2 groups, these may also have the general formula (I), but must differ from R 1 in at least one of the groups R a , R b and R c and / or the
  • R 2 in coatings is particularly preferably an isocyanate, oxirane or OH group.
  • hydrogel coating according to the invention over known hydrogel coatings is that their properties can be specifically defined by an appropriate selection of the R 1 and R 2 radicals and their relationship to one another. For example, wettability, water swellability, and protein and cell repellency can be affected by selective adjustment of the R 1 / R 2 ratio.
  • the coatings according to the invention contain star-shaped prepolymers whose polymer arms, in and of themselves, are soluble in water.
  • the preferred star-shaped prepolymers of general formula (II) preferably have polymer arms A which are selected from the group consisting of poly-C 2 -C 4 -alkylene oxides, polyoxazolidones, polyvinyl alcohols, homopolymers and copolymers containing at least 50 wt .-% N -Vinylpyrrolidone copolymerized, homo- and copolymers containing at least 30 wt .-% acrylamide and / or methacrylamide in copolymerized form, homopolymers and copolymers containing at least 30 wt .-% of acrylic acid and / or methacrylic acid in copolymerized form.
  • Polymer arms A which consist of polyethylene oxide or ethylene oxide / propylene oxide copolymers are particularly preferred. If the very particularly preferred ethylene oxide / propylene oxide copolymers are used, a propylene oxide content of at most 60% by weight, preferably at most 30% by weight and particularly preferably at most 20% by weight, is recommended.
  • the indices m and n of the star-shaped prepolymers used in the coatings and / or star-shaped prepolymer-nanoparticle complexes are in each case integers, where m ⁇ 1 and n ⁇ 0, and m + n in the case of star-shaped prepolymers preferably has a value of 3 to 100 and, in the case of prepolymer-nanoparticle complexes, preferably from 3 to a maximum value of 500,000.
  • the indices m and n stand for integers, where m ⁇ 1 and n ⁇ 0, and m + n preferably a value of 3 to 100, or 3 to 50, in particular 4 to 10 and particularly preferably 6 to 10 and matches the arm count of Z.
  • the central unit therefore has, as a rule, 3 to 100, preferably 5 to 50, in particular 6 to 10 skeletal atoms which serve as attachment points for the arms.
  • the indices m and n stand for integers, where m ⁇ 1 and n ⁇ 0, and m + n preferably have a value of 3 to 500,000.
  • n is 0, the star-shaped prepolymer corresponding to a completely R 1 -modified prepolymer which preferably has 5 to 50 and in particular 4 to 10, particularly preferably 6 to 10 polymer arms.
  • the ratio n / m moves between 99/1 and 1/99, preferably 49/1 and 1/49, and especially 9/1 and 1/9.
  • the star-shaped prepolymer of the coatings according to the invention preferably has a number-average molecular weight in the range from 200 to 50,000, more preferably from 1,000 to 30,000 and very particularly preferably from 5,000 to 20,000 g / mol.
  • the star-shaped prepolymer preferably contains at least 0.05% by weight, more preferably at least 0.1% by weight and most preferably at least 0.15% by weight of silicon.
  • the coating according to the invention additionally contains foreign materials of organic, inorganic or natural origin, which are simply referred to below as entities.
  • An entity is preferably selected from the group consisting of biologically active substances, pigments, dyes, fillers, silicic acid units, nanoparticles, organosilanes, biological cells, receptors or receptor-bearing molecules or cells and physically incorporated in the coating and / or on this or in this covalently bound.
  • bioactive materials such as drugs, biocides, oligonucleotides, peptides, proteins, signaling agents, growth factors, cells, carbohydrates and lipids, inorganic components such as apatites and hydroxyapatites, quaternary ammonium salt compounds, bisguanidines, quaternary compounds
  • Pyridinium salt compounds compounds of phosphonium salts, Thiazoylbenzimidazole, sulfonyl compounds, salicylic or organometallic and organometallic compounds. Preference is given to antibacterial substances such as, for example, peptides, metal colloids and quaternary ammonium and pyridinium salt compounds.
  • silanol groups capable of condensation Si-OH
  • hydrolysis-stable Si-R ' bonds on the same silicon atom the latter hydrolysis-stable bond usually being present in a covalent Si-C single bond.
  • the said functionalized silanes are low molecular weight compounds, but also oligomeric or polymeric compounds fall under the term "organically functionalized silanes", it is essential that in the same molecule both silanol-hydrolyzable Si-OR " groups and non-hydrolyzable Si-R ' Groups are present.
  • cationic adhesive groups eg, --NR ' " 3 + groups
  • anionic adhesive groups eg, -SO 3 "
  • redox active groups eg, quinone / hydroquinone residues
  • dye groups eg, azo dye molecules, stilbene based brighteners
  • groups with biological / pharmacological Activity for example also saccharide or polysaccharide molecular units, peptides or protein units and other organic structural motifs
  • groups for covalent attachment to substrates for example epichlorohydrin residues, cyanuric chloride cystine / cysteine units and the like
  • groups with bactericidal activity for example NR '" 3 + - Groups with very long R "' alkyl radicals
  • catalytically active groups such as transition metal complexes with organic ligands
  • radical R ' examples include, for example, epoxy, aldehyde, acrylate and methacrylate groups, anhydride, carboxylate or hydroxy groups.
  • the functionalities described here are not to be understood as a complete listing in terms of a selection of examples.
  • the organosilanes therefore serve not only as a crosslinking aid, but at the same time as a functionality distributor. This gives directly a hydrogel coating according to the invention with desired functionalities.
  • Entities also include nanoparticulate metal or semimetal oxides.
  • those of silicon, zinc, titanium, aluminum, zirconium are suitable.
  • silica particles with a diameter of about 1 to 500 nm are preferred.
  • Such SiO 2 particles, including their surface-modified or -functionalized derivatives, can contribute to improving the mechanical properties of the layers.
  • Another group of entities are inorganic pigments.
  • the coatings according to the invention having reactive silyl groups readily bind to them via stable covalent bonds. If a hydrogel according to the invention, ie a coating according to the invention which is mixed with pigments, is applied to a surface on which the hydrogel can bind, the result is bound, pigmented surface coatings. If organic pigments are to be incorporated into the hydrogel, or if one Adhesion of the hydrogel is to be ensured on organic surfaces, so in the coating according to the invention organosilanes can be incorporated with appropriate adhesion groups (eg cationic groups, as described above). In this way, means and methods are possible by which pigments can be well anchored, for example, on hair.
  • adhesion groups eg cationic groups, as described above
  • mica or effect pigments pearlescent pigment
  • special optical effects on hair are made possible (“glitter hair”).
  • colored inorganic or organic pigments for example lapis lazuli, pyrolopyrroles
  • particularly intensive or stable hair colors are obtained.
  • the incorporation of the entities is preferably carried out by co-adsorption from solutions containing the star-shaped prepolymer and / or the star-shaped prepolymer-nanoparticle complex and the foreign constituent.
  • the star-shaped prepolymers and / or prepolymer-nanoparticle complexes can be chemically reacted with said bioactive materials or reacted on the surface as a mixture with unmodified star-shaped prepolymers and / or prepolymer-nanoparticle complexes.
  • the substrates to be coated with the coatings according to the invention are fundamentally subject to no restrictions.
  • the substrates may have regular or irregularly shaped, smooth or porous surfaces.
  • Suitable surface materials include glassy surfaces such as glass, quartz, silicon, silica or ceramics, or semiconductor materials, metal oxides, metals and metal alloys such as aluminum, titanium, zirconium, copper, tin and steel. Also composites such as glass fiber reinforced or carbon fiber reinforced plastics (GRP, CFRP), polymers such as polyvinyl chloride, polyethylene, polymethylpentenes, polypropylene, generally polyolefins, elastomeric plastics such as polydimethylsiloxane, polyesters, fluoropolymers, polyamides, polyurethanes, poly (meth) acrylates and copolymers, blends and composites The aforementioned materials are suitable as substrates.
  • GRP glass fiber reinforced or carbon fiber reinforced plastics
  • polymers such as polyvinyl chloride, polyethylene, polymethylpentenes, polypropylene, generally polyolefins, elastomeric plastics such as polydimethylsiloxane, polyesters, fluoro
  • cellulose and natural fibers such as cotton fibers, wool and hair can be used as substrates.
  • mineral surfaces such as paints or grout material can serve as substrates.
  • substrates it is advisable in some cases to pretreat the surfaces.
  • Particularly preferred substrate materials are glassy or generally inorganic surfaces, since in these directly a connection via relatively hydrolysis-stable bonds, for example Si-O-Si, or Si-O-Al takes place and thus a surface preparation is not necessary.
  • ceramic, plastic and metal substrates offers, for example, an application in the equipment of showers, windows, aquariums, glasses, dishes, sinks, toilets, work surfaces, or kitchen appliances, such as refrigerators or cookers with a light cleanable temporary or permanent equipment that allows for complete drainage of water, as well as repels proteins and bacteria.
  • Another object of the present invention is a method for producing the coatings of the invention on a substrate, wherein a solution of a star-shaped prepolymer and / or star-shaped prepolymer nanoparticle complex (as defined above) is applied to the substrate to be coated, and before, simultaneously or followed by an at least partial crosslinking reaction of the silyl end groups and the optionally present reactive groups of the non-silyl end-bearing-carrying ends with one another and / or with the substrate.
  • a star-shaped prepolymer and / or star-shaped prepolymer nanoparticle complex as defined above
  • the process is preferably carried out with the star-shaped prepolymers and / or star-shaped prepolymer-nanoparticle complexes of the general formula (II).
  • a foreign material for example an entity selected from the group consisting of biological active substances, pigments, dyes, fillers, silicic acid units, nanoparticles, organosilanes, biological cells, receptors or receptor-bearing molecules or cells, or precursors of the abovementioned entity brought into contact with the star-shaped prepolymers.
  • the introduced entities may in this case be physically incorporated into the network of crosslinked star-shaped prepolymers and / or star-shaped prepolymer-nanoparticle complexes or bound to the surface of the coating ionically by van der Waals or hydrogen bonds, or chemically via covalent bonds, preferably via reactive end groups of the star-shaped prepolymer are bound.
  • silica units are introduced into the coating as entities, this can be done by mixing a solution of the star-shaped prepolymers with a hydrolyzable one Silica precursors, such as a tetraalkoxysilane (for example, tetraethoxyorthosilane, TEOS), preferably in the presence of a catalyst, such as an acid, or a base, take place.
  • Silica precursors such as a tetraalkoxysilane (for example, tetraethoxyorthosilane, TEOS)
  • a catalyst such as an acid, or a base
  • the attachment of the silica units to the star-shaped Prepolymer can be carried out via van der Waals bonds, ionic or via hydrogen bonds.
  • the bonding preferably takes place covalently via a C-Si-O-Si constellation (detection Raman or IR) to reactive end groups of the star-shaped prepolymer used in the coatings according to the invention and / or star-shaped prepolymer-nanoparticle complex.
  • the water contact angle (advancing as well as receding) of a coating according to the invention is measured by means of a Wilhelmy balance according to DIN EN 14370 on a planar, smooth surface preferably 0.0001 to 90 °, more preferably 0.001 to 60 ° and most preferably to 50 ° or not more than 40 °.
  • the water contact angle hysteresis is preferably not more than 10 °, more preferably not more than 5 °.
  • the bonding of the silicic acid units with one another can take place in the coating via hydrogen bridges or via ionic interaction.
  • covalent -Si-O-Si bridges are preferred (detectable by IR).
  • the effect of the TEOS within the layer can be understood as a crosslinking effect, wherein layers without crosslinker (TEOS) are usually more hydrophilic, that is, characterized by a lower contact angle, for example in the range of 30 °.
  • TEOS layers without crosslinker
  • additional crosslinkers for example TEOS or functional alkoxysilanes, represents a further possibility for individually adjusting the properties of the coatings.
  • the ultra-thin hydrogel coatings are applied to the substrate, for example, by depositing the star-shaped prepolymers and / or star-shaped prepolymer nanoparticle complexes by processes known per se on the surface to be coated from a solution of the prepolymers which may already be partly pre-crosslinked therein , and simultaneously or subsequently crosslinking the reactive groups with each other and with the substrate surface.
  • the coating measures will be selected so that the coating thickness, preferably does not exceed a value of 500 .mu.m, more preferably 200 .mu.m and most preferably 100 .mu.m.
  • a coating must simultaneously meet many different requirements in terms of, for example, the mechanical properties, water wetting and wetting behavior, protein and bacteria repellency, and the like.
  • an ultrathin or thin layer with a layer thickness of 0.1 to 100 nm, in particular of 1 to 50 nm is often sufficient to achieve the desired effects, while in applications, for example due to a high mechanical Claiming the surface, thicker layers with a layer thickness of, for example, 50-500 microns are desired, and for some applications, such as those that provide for the presence of nanoparticles in the coating, larger layer thicknesses such as 1000 microns may be desired.
  • the hydrophilicity of the hydrogel coatings of the invention remains largely uninfluenced by the layer thickness. In other words, the dirt, protein and cell repellency properties are retained independent of the thickness of the layer.
  • Another object of the present invention are the star-shaped prepolymers of general formula (II) wherein m and n are independently of one another ⁇ 1 and R 2 is not R 1 or OH. Particular embodiments of this object are described in claims 34 to 48.
  • all solvents which have little or no reactivity with the reactive end groups of the star-shaped prepolymer are generally suitable. Examples are water, alcohols, water / alcohol mixtures, aprotic solvent or mixtures thereof.
  • Suitable aprotic solvents are, for example, ethers and cyclic ethers such as tetrahydrofuran (THF), dioxane, diethyl ether, tert-butyl methyl ether, aromatic hydrocarbons such as xylene and toluene, acetonitrile, propionitrile and mixtures of these solvents.
  • THF tetrahydrofuran
  • dioxane diethyl ether
  • tert-butyl methyl ether aromatic hydrocarbons
  • aromatic hydrocarbons such as xylene and toluene
  • acetonitrile such as xylene and toluene
  • propionitrile propionitrile
  • protic solvents such as water or alcohols, for example methanol, ethanol, n-propanol, 2-propanol, n-propanol Butanol and tert-butanol, as well as their mixtures with aprotic solvents.
  • protic solvents such as water or alcohols, for example methanol, ethanol, n-propanol, 2-propanol, n-propanol Butanol and tert-butanol, as well as their mixtures with aprotic solvents.
  • water and mixtures of water with aprotic solvents are suitable in addition to the abovementioned aprotic solvents.
  • the solvent is water or a mixture of water with aprotic solvents.
  • Suitable amounts of the star-shaped prepolymers and / or star-shaped prepolymer nanoparticle complexes in the application mixtures used in the coating process of the invention depend on the layer thicknesses which are most suitable for the respective application. Frequently, amounts of, for example, about 0.005 to 50 wt .-%, preferably 0.1 to 10 wt .-% of. Depending on the affinity of the substrate and the type of application, it is also possible to use both application mixtures with a higher or even lower content of star-shaped prepolymers and / or star-shaped prepolymer-nanoparticle complexes.
  • the application mixtures may for example also have the form of pastes or creams.
  • star-shaped prepolymers of the general formula (II) according to the invention which are used in the coatings according to the invention and the process according to the invention for producing a coating, is carried out by functionalizing suitable star-shaped prepolymer precursors in analogy to known functionalization processes of the prior art.
  • the prepolymer precursors of the prepolymers according to the invention are in turn also star-shaped prepolymers, which already have the above-described star-shaped structure, ie at least three inherently water-soluble polymer arms, and which at the ends of the polymer arms each have a suitable functional group R 3 , which in the aforementioned reactive groups B-R 1 or BR 2 can be converted.
  • the prepolymer precursors of the prepolymers of the invention can be represented by the general formula (III) as Z- (XAR 3 ) m + n , where Z, X 1 A 1 m and n have the same meaning as the corresponding radicals and indices of star-shaped prepolymers according to the invention and R 3 represents a functional group which can be converted into the abovementioned reactive groups BR 1 or BR 2 .
  • R 3 examples include OH groups bound to aliphatic or aromatic carbon atoms, thiol groups, primary or secondary amine groups and halogen atoms such as chlorine, bromine or iodine.
  • a particularly preferred precursor relates to the primary and secondary OH groups, the so-called star-shaped polyether polyols.
  • These prepolymer precursors are prepared by polymerization of the appropriate monomers using multifunctional small molecules such as sorbitol initiator and may optionally be further modified to generate at their ends a group -R 3 of the invention. Due to the statistical nature of the polymerization reaction, the above information on the polymer arms of the prepolymers of the invention, in particular with respect to the arm length and number of arms (m + n) as a statistical mean.
  • Suitable starting materials for the conversion of the end groups R 3 of the star-shaped prepolymer precursor into the groups BR 1 are generally all functional silane derivatives which have a functional group which is reactive with the end groups of the prepolymer precursor.
  • Examples are amino silanes such as (3-aminopropyl) triethoxysilane and N- (2-aminoethyl) (3-aminopropyl) trimethoxysilane, (meth) acrylate silanes such as (3-methacryloxypropyl) trimethoxysilane, (methacryloxymethyl) triethoxysilane (methacryloxymethyl) methyldimethoxysilane and (3- Acryloxypropyl) trimethoxysilane, isocyanato-silanes such as (3-isocyanatopropyl) trimethoxysilane, (3-isocyanatopropyl) triethoxysilane, (isocyanatomethyl) methyl-d
  • Triethoxysilyl butyraldehydes epoxy silanes such as (3-glycidoxypropyl) trimethoxysilane, anhydride silanes such as 3- (triethoxysilyl) propyl succinic anhydride, halogen silanes such as
  • Chloromethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, hydroxylsilanes such as hydroxymethyltrietoxysilanes, and tetraethylsilicate (TEOS), which are commercially available, for example from Wacker Chemie GmbH (Burghausen), Gelest, Inc. (Morrisville, USA) or ABCR GmbH & Co. KG (Karlsruhe) are available or can be prepared by known methods. Isocyanato-silanes or anhydride-silanes are particularly preferably reacted with hydroxy-terminated (R 3 OH) star-shaped polymers of the general formula (III).
  • Suitable starting materials for the conversion of the terminal groups R 3 of the star-shaped prepolymer precursor into the groups BR 2 are generally all diisocyanates, both aromatic and aliphatic, in question. Preference is given to diisocyanates whose isocyanate groups differ in their reactivity; in particular, aliphatic and cycloaliphatic diisocyanates, such as isophorone diisocyanate (IPDI), are preferred.
  • IPDI isophorone diisocyanate
  • urethane groups are likewise formed in the radical B.
  • the radical "B" within the star-shaped prepolymers according to the invention may have a different meaning in each of the m + n polymer arms.
  • star-shaped prepolymers of the general formula (II) according to the invention are prepared which carry both BR 1 and BR 2 groups, preference is given to initially introducing BR 1 groups as described above, but not all R 3 groups be implemented in the star-shaped prepolymer of the general formula (III). In this way, star-shaped prepolymers carrying both -R 1 and -R 2 groups are obtained, this being the special case where -R 2 is -R 3 .
  • the remaining or a part of the remaining R 3 groups - as described - can be modified to form R 2 or BR 2 .
  • R 2 or BR 2 For example, when -R 2 represents a (meth) acrylate group, one obtains by esterification of the remaining OH groups with (meth) acrylic anhydride. In most cases, this is also possible in a reverse reaction sequence, ie, the group -R 3 of the star-shaped prepolymers can first be converted to -R 2 and then reacted with a functional alkoxysilane to introduce the group -R 1 .
  • Another object of the present invention are derivatives of the prepolymers of the invention, which are obtained by reaction of the groups R 1 and / or R 2 with the abovementioned Entites and claimed in claims 48 and 49.
  • star-shaped prepolymers according to the invention of claim 33 In addition to the star-shaped prepolymers according to the invention of claim 33, other star-shaped prepolymers can be used to form the coatings according to the invention, as long as they satisfy the conditions according to the invention as defined in claim 1.
  • star-shaped prepolymers in which the silyl groups-bearing molecules are attached via diisocyanates are less suitable for uniformly dense coatings than star-shaped prepolymers of the general formula (II) in which B contains at most one urethane or urea bond.
  • Particularly dense layers make it possible to protect the substrates from a much wider range of soiling.
  • Star-shaped prepolymers known from the literature can only be used under the abovementioned conditions in the coatings according to the invention and in the coating method according to the invention.
  • EP 0931800 A1 relates to a silylated polyurethane which has been prepared by first reacting a polyol with stoichiometrically lower diisocyanate and subsequently reacting the resulting isocyanate-hydroxy polyol with isocyanatosilanes.
  • US 2003 0153712 A1 describes a polyurethane prepolymer having terminal alkoxysilane and hydroxy groups.
  • a polyether diol was first reacted with stoichiometric diisocyanate, the resulting isocyanate-hydroxy compound was then further reacted with an aminosilane to introduce the silyl groups.
  • EP 0935627 A1 discloses a polyether-based star-shaped prepolymer which carries two differently reactive functional groups R 1 and R 2 at its free ends.
  • R 1 is an isocyanate group
  • R 2 is a non-reactive group under normal conditions with R 1 .
  • All OH groups of the Polyether polyols first reacted with stoichiometrically excess diisocyanates and the NCO prepolymers thus obtained further treated with a stoichiometric underschüssigen bifunctional compound carrying a terminal isocyanate-reactive group and another terminal non-isocyanate-reactive group.
  • Such prepolymers can be used, for example, for coating surfaces.
  • hydrogel coatings of the invention prepared using star-shaped prepolymers and / or star-shaped prepolymer nanoparticle complexes effectively prevent the adsorption of proteins and cells and can be used for many applications, such as in the hygiene and bioanalytical field. Therefore, such use is inter alia subject of the present invention.
  • Another object of the present invention is the use of star-shaped prepolymers according to the invention, their derivatives and / or star-shaped prepolymers used in the coating compositions of the invention and / or star-shaped prepolymer nanoparticle complexes in anti-soiling agents for the temporary or permanent finishing of surfaces.
  • An essential prerequisite for this is the hydrophilic surface behavior with simultaneously low contact angle hysteresis.
  • the hydrophilicity of the surface on the one hand impedes the adsorption and adhesion of proteinaceous and greasy stains and on the other hand allows efficient wetting with cleaning agent, whereby impurities can be separated from the substrate more easily than with hydrophobic surfaces.
  • the dewetting characterized by the low contact angle hysteresis, or the complete draining of the cleaning solution also effectively prevents the re-deposition of dirt on the freshly cleaned surfaces.
  • star-shaped prepolymers according to the invention their derivatives and / or those used in the coating compositions according to the invention star-shaped prepolymers and / or star-shaped prepolymer-nanoparticle complexes consist in their use as additives in detergents and detergents for hard and soft surfaces, as used for example in the sanitary or kitchen area, to prevent or reduce staining or re-soiling Hair care products, textile treatment agents, wall, facade and joint treatment agents, in agents for the treatment of vehicles such as automobiles, aircraft, ships or boats (anti-fouling) and in means for internal and external coating of containers to, for example, a lossless emptying of the container or in means for coating bioreactors and heat exchangers, for example, to prevent the adhesion of microorganisms.
  • a further use according to the invention of the star-shaped prepolymers according to the invention, their derivatives and / or the star-shaped prepolymers and / or star-shaped prepolymer-nanoparticle complexes used in the coating compositions according to the invention is the use in coatings for influencing the growth or the crystallization of solids on the surface. Due to their dense structure, their hydrophilicity and their ease of chemical functionalization - for example by entities - can be adjusted with the hydrogel layers according to the invention in principle, the biological situation in Biomineralmaschinesvorêtnam. An example of a typical biomineralisation process is the formation of shells of calcium carbonate, which is controlled by specifically structured and functionalized hydrophilic polymer layers.
  • hydrophilic polymers can either promote and / or control the growth of solids from solution, or prevent them from occurring.
  • As a technically and economically relevant growth process here is calcium crystallization on surfaces to call.
  • the hydrogel layers according to the invention if appropriate by adding suitable entities, the growth of lime can be prevented.
  • the Kaikabscheidung is beyond the substrate effect described here also prevented by dewatering water as mentioned above on the coated surfaces and thus crystallization is prevented due to this simple physical effect.
  • the hydrogel-based anti-scale coating may be permanent or temporary.
  • a further use according to the invention of the star-shaped prepolymers according to the invention, their derivatives and / or those used in the coating compositions according to the invention star-shaped prepolymers and / or star-shaped prepolymer-nanoparticle complexes is given in the production of microarrays or sensors for bioanalytical purposes or for coating microfluidic components or for the coating of microcannules and capillary systems, for example for the introduction of genetic material into cells.
  • the hydrogel coating on the one hand allows a selective coupling of biomolecules to the coating, if for example they have receptors bound as an entity, on the other hand it is distinguished by a particularly low affinity for non-specific binding of biomolecules. Therefore, the hydrogel coatings are particularly suitable as a coating base of substrates for Bioanalysesysteme.
  • Articles of the present invention are therefore also anti-soiling agents, detergents and detergents for hard and soft surfaces, hair care products, textile treatment agents, wall, facade and joint treatment agents, vehicle treatment agents, means for coating containers inside and outside, bioreactors and heat exchangers containing the star-shaped prepolymers of the invention.
  • a further use according to the invention of the star-shaped prepolymers, their derivatives and / or the star-shaped prepolymers and / or star-shaped prepolymer-nanoparticle complexes used in the coating compositions according to the invention is the finishing of surfaces with modified, in particular reduced, friction properties. Applying, for example, the coatings on textiles, so it is a more pleasant handle generated, when applied to hair, for example, the combability is improved.
  • a further use according to the invention of the star-shaped prepolymers, their derivatives and / or the star-shaped prepolymers and / or star-shaped prepolymer-nanoparticle complexes used in the coating compositions according to the invention consists in the hydrogel coating on textiles either due to the hydrogel structure itself or by additional functionalities preferably be introduced by the abovementioned Entities to fix or retain dyes on the fiber.
  • additional functionalities preferably be introduced by the abovementioned Entities to fix or retain dyes on the fiber.
  • a color protection effect is achieved, which can be used, for example, in a no-sort detergent, that is, a detergent with the colorful and white washes can be used.
  • the polyether polyol used is a 6-arm random poly (ethylene oxide-co-propylene oxide) having an EO / PO ratio of 80/20 and with a molecular weight of 12000 g / mol, which is prepared by anionic ring-opening polymerization of ethylene oxide and propylene oxide Use of sorbitol as initiator was made. Before the reaction, the polyol was heated in vacuo with stirring for 1 h at 80 0 C.
  • Example 2 Six-Arm Triethoxysilyl-Hydroxy-Terminated Polvether (PP2): Analogously to Example 1, a solution of polyether-polyol (10 g, 0.83 mmol), triethylenediamine (30 mg, 0.27 mmol) and dibutyltin dilaureate (30 mg , 0.048 mmol) in 50 ml of anhydrous toluene, to which a solution of (3-isocyanatopropyl) triethoxysilane (0.65 ml, 2.49 mmol) in 15 ml of anhydrous toluene was added dropwise. The solution was further stirred at 50 ° C overnight.
  • Example 3 Six-Arm Triethoxysilyl-Hydroxy-Terminated Polvether (PP3): Analogously to Example 1, a solution of polyether-polyol (10 g, 0.83 mmol), triethylenediamine (30 mg, 0.27 mmol) and dibutyltin dilaureate (30 mg , 0.048 mmol) in 50 ml of anhydrous toluene. To this was added dropwise a solution of (3-isocyanatopropyl) triethoxysilane (0.22 ml, 0.84 mmol) in 15 ml of anhydrous toluene. The solution was further stirred overnight at 50 ° C.
  • Example 7 Six-Armed Triethoxysilyl Isocvanate-Terminated Polvether (PP7): A mixture of the product of Example 2 (4 g, 0.32 mmol), isophorone diisocyanate, (IPDI, 3.2 mL, 15.1 mmol) and 7 mL Anhydrous toluene was stirred at 50 0 C for 48 hours. After removing the toluene under vacuum, the crude product was repeatedly washed with anhydrous ether. After vacuum drying, the product containing triethoxylsilyl and isocyanate groups having a statistical ratio of 3/3 at the free ends of the polymer arms of the star-shaped prepolymers was obtained as a colorless viscous liquid.
  • IPDI isophorone diisocyanate
  • Example 8 Six-Arm Triethoxysilyl Isocvanate-Terminated Polvether (PP8): A mixture of the product of Example 3 (4.7 g, 0.38 mmol), isophorone diisocyanate, (IPDI, 5.65 mL, 26.7 mmol) and 5 Anhydrous toluene was stirred at 50 ° C. for 48 hours. After removing the toluene under vacuum, the crude product was repeatedly washed with anhydrous ether. After vacuum drying, the product containing triethoxylsilyl and isocyanate groups with a statistical ratio of 1/5 at the free ends of the polymer arms of the star-shaped prepolymers was obtained as a colorless viscous liquid.
  • IPDI isophorone diisocyanate
  • the substrates used were glass slides and silicon wafers (Si [100]).
  • the substrates were coated for 1 h at 60 ° C. in a mixture of concentrated aqueous ammonia,
  • Hydrogen peroxide 25 wt .-%) and water in a volume ratio of 1: 1: 5 stored and then rinsed several times with water. After drying, they were used for coating.
  • a hydrogel coating of a six-armed isocyanate-terminated polyether prepolymer (PP12, comparative prepolymer) is prepared analogously to the literature (J. Groll et al., Biomacromolecules 2005, 6, 956-962) directly on the substrate purified as in Example 12.
  • the hydrogel coatings PP12 (comparative prepolymer), PP2 and PP7 prepared in Example 13 were stored in water and taken out after a certain period of time in order to evaluate the coatings in terms of their release behavior. After about 2 days, it was observed that the coating PP12 had completely detached from the surface, while the coatings PP2 and PP7 remain unchanged. This result was also confirmed by ellipsometric layer thickness measurement.
  • Example 15 Fluorescence Microscopic Investigation of Protein Adsorption on Hvdrooel Surfaces:
  • the hydrogel coating was prepared as described in Example 12 with prepolymer PP7 on a silicon wafer. Protein adsorption experiments were carried out analogously to the literature (J. Groll et al., Biomacromolecules 2005, 6, 956-962). One half of the hydrogel coated substrates were dip coated with polystyrene (from a 2% solution of polystyrene in toluene and at a rate of 10 mm / min). The sample was then incubated in a solution of streptavidin-rhodamine red conjugate (5 ⁇ g / ml) in PBS buffer (pH 7.4) for 20 min.
  • the sample was examined by fluorescence microscopy.
  • the result showed that the hydrogel coating was protein repellent because the fluorescently labeled proteins adsorbed only on the polystyrene-treated surface but not on the hydrogel-coated side of the substrate.
  • the hydrogel coatings were prepared as described in Example 12 with the prepolymers PP7 and PP8 on a silicon wafer, protein adsorption experiments were carried out analogously to the literature (J. Groll et al., Biomacromolecules 2005, 6, 956-962).
  • the samples were incubated in a solution of lysozyme or insulin (1 mg / ml) in 0.1 M carbonate buffer (pH 8.3) at 37 ° C for 1 h. After thorough rinsing with buffer and demineralized water, the samples were examined with a surface-sensitive MALDI-ToF mass spectrometer set up for this purpose.
  • the characteristic peaks for lysozyme or insulin can be easily identified in the reference spectra measured on purified silicon wafers. The results showed that no adsorption of lysozyme or insulin on the hydrogel surfaces according to the invention was detectable.
  • Example 17 Array of stripe-shaped regions of a biotin-streptavidin system
  • the hydrogel coating was prepared as described in Example 12 with prepolymer PP7 on a silicon wafer.
  • biotinamidocaproic acid N-hydroxysuccinimide ester Molecular Probes
  • the thus-obtained stamper was contacted with the above-mentioned hydrogel coating for 5 minutes. After releasing the stamp, the surface thus obtained was extensively washed with water to remove unbound ester and dried in a filtered stream of argon. In this way, a surface with striped areas of immobilized biotin was obtained.
  • the result shows a red glowing strip with a dark background.
  • Example 18 Stability of a Coating Produced by Spraying in Water
  • PP1 Prepolymer of the Invention
  • Water 1.6% by Weight
  • Acetic Acid 1.6% by Weight
  • ethanol a Mixture of the Prepolymer of the Invention (PP1, 3.1% by Weight), Water (1.6% by Weight) and Acetic Acid (1.6% by Weight) in ethanol was stirred at room temperature for 2 days. It was then diluted tenfold with water and sprayed onto cleaned tile surfaces. After drying (about 10 minutes), a coating was obtained which is hydrophilic (water contact angle 40 °) and at the same time water-repellent (the water droplets rapidly run off at a tilt angle of about 10 °). The coated tile was then immersed in water and evaluated for its temporal change. After one week, no change in the water drainage behavior on the surface could be detected, indicating that the coating is stable under the specified conditions.
  • Example 19 Water contact angle and hysteresis of a coating produced by a spray process
  • a mixture of the prepolymer (PP1, 3.0% by weight) according to the invention, TEOS (6.0% by weight), water (1, 5% by weight) and acetic acid (1, 5% by weight) in Ethanol was stirred at room temperature for 2 days. It was then diluted twice with water and sprayed onto a cleaned glass surface. After rinsing with water, a coating was obtained whose water contact angle was determined by means of a Wilhelmy balance and was 39 ° (advancing) or 34 ° (receding). The water contact angle hysteresis is thus 5 °.
  • Example 20 incorporation as an additive in cleaning agent
  • a mixture of the inventive prepolymer (PP1, 3.1% by weight), water (1.6% by weight) and acetic acid (1.6% by weight) in ethanol was stirred at room temperature for 2 days. Then it was tenfold diluted with a commercial liquid bath cleaner and sprayed on tile or glass surfaces. After wiping with a soft cloth, the surface was rinsed with water. In this way, a coating was obtained which behaves exactly like the coating in Example 18.
  • a coating having the same properties and effects can also be prepared directly from the prepolymer according to the invention, for example as described below:
  • a solution of the prepolymer (PP1, 0.3% by weight) according to the invention in a commercial liquid bath cleaner was heated at room temperature for two days touched. Then it was sprayed on tile or glass surfaces. After this Wiping with a soft cloth, the surface was rinsed with water. In this way, a coating was obtained which behaves as described above.
  • Dynamic contact angles were determined using a Wilhelmy balance (computer-controlled contact angle measuring instrument from Lemke & Partner, Kaarst, with evaluation software "contact angle", version 3.60) as indicated above.
  • the actual surface tension of the double-distilled water used for this was determined before the measurements using a platinum standard (Krüss). Thereafter, the coated substrate was measured (20 mm wide, 1 mm thick) and slowly dipped with the Wilhelmy balance over a period of 90 min at a constant speed 0.5 cm in this water and pulled out again. The forces occurring in connection with the geometry of the substrate, the surface tension of the water and the train speed lead to the values for advancing and receding contact angle.
  • a coating having similar properties and effects can also be prepared from the above-mentioned mixture, but without the addition of TEOS.
  • TEOS a coating having similar properties and effects
  • a coating for example, a mixture of prepolymer (PP1, 1, 0 wt .-%), water (0.5 wt .-%) and acetic acid (0.5 wt .-%) in ethanol at room temperature for 2 days. It is then diluted tenfold with water and sprayed on cleaned tile surfaces. After drying (about 10 minutes), a coating was obtained which behaves like the coating described above.
  • a coating PP1 prepared according to Example 22 on a glass surface was overcoated with IKW ballast dirt, prepared according to S ⁇ FW-Journal, 1998, 124, 1029 and dried overnight at room temperature, using a non-treated glass surface as reference. After drying, the surfaces were washed off with running water. Under identical washing conditions, it was found that the IKW ballast dirt on PP1 coating is completely removed, while a white greasy layer remains on uncoated glass surfaces. The eased cleaning effect on the coating is widely confirmed by an Edding® test: writing on the above-mentioned coating and on the reference using a waterproof Edding® pen. After drying, the surfaces were washed off with running water. After only a short time (less than 1 min.), The Edding® fonts on PP1 coating were completely removed, while on uncoated glass surfaces they remained unchanged even after a longer time (more than 10 min.).
  • a coating prepared according to Example 23 on a tile surface was overcoated with IKW ballast dirt, prepared according to S ⁇ FW-Journal, 1998, 124, 1029 and dried overnight at room temperature, using as reference an untreated tile surface. After drying, the surfaces were washed off with running water. Under identical washing conditions it was found that the IKW ballast dirt on the coating is completely removed, while on uncoated tile surfaces a white greasy layer remains.
  • a coating prepared according to Example 23 on a tile surface was placed on a slightly tilted (about 30 °) test apparatus. Tap water was applied dropwise and continuously to the tile surface using an untreated tile surface as reference. Due to the low contact angle hysteresis, the water droplets on the coating with a barely changed shape run off quickly, while leaving a long water nose on the untreated tile surfaces. After one week, it can be clearly determined that lime accumulates on the untreated surfaces, but not on the treated surfaces.

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EP07722790A 2006-02-23 2007-02-08 Multifunktionelle sternförmige präpolymere, deren herstellung und verwendung Withdrawn EP1987080A1 (de)

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CN101389690A (zh) 2009-03-18
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