EP1558660A1 - Use of hyperbranched polymers comprising urethane and/or urea groups for modifying surfaces - Google Patents

Use of hyperbranched polymers comprising urethane and/or urea groups for modifying surfaces

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Publication number
EP1558660A1
EP1558660A1 EP03782180A EP03782180A EP1558660A1 EP 1558660 A1 EP1558660 A1 EP 1558660A1 EP 03782180 A EP03782180 A EP 03782180A EP 03782180 A EP03782180 A EP 03782180A EP 1558660 A1 EP1558660 A1 EP 1558660A1
Authority
EP
European Patent Office
Prior art keywords
groups
polymers
hyperbranched
urethane
copolymers
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Withdrawn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
EP03782180A
Other languages
German (de)
French (fr)
Inventor
Bernd Bruchmann
Helmut Meffert
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.)
BASF SE
Original Assignee
BASF SE
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Filing date
Publication date
Application filed by BASF SE filed Critical BASF SE
Publication of EP1558660A1 publication Critical patent/EP1558660A1/en
Withdrawn legal-status Critical Current

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Classifications

    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/564—Polyureas, polyurethanes or other polymers having ureide or urethane links; Precondensation products forming them
    • 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
    • C08G18/0804—Manufacture of polymers containing ionic or ionogenic groups
    • C08G18/0819—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups
    • C08G18/0823—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups containing carboxylate salt groups or groups forming them
    • 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
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
    • C08G18/3203—Polyhydroxy compounds
    • C08G18/3206—Polyhydroxy compounds aliphatic
    • 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
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
    • C08G18/3225—Polyamines
    • C08G18/3228—Polyamines acyclic
    • 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
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/34—Carboxylic acids; Esters thereof with monohydroxyl compounds
    • C08G18/348—Hydroxycarboxylic acids
    • 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
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/80—Masked polyisocyanates
    • C08G18/8061—Masked polyisocyanates masked with compounds having only one group containing active hydrogen
    • C08G18/8064—Masked polyisocyanates masked with compounds having only one group containing active hydrogen with monohydroxy compounds
    • 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
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/80—Masked polyisocyanates
    • C08G18/8061—Masked polyisocyanates masked with compounds having only one group containing active hydrogen
    • C08G18/807—Masked polyisocyanates masked with compounds having only one group containing active hydrogen with nitrogen containing compounds
    • C08G18/808—Monoamines
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/0427—Coating with only one layer of a composition containing a polymer binder
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/044—Forming conductive coatings; Forming coatings having anti-static properties
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/054—Forming anti-misting or drip-proofing coatings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/056—Forming hydrophilic coatings
    • 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
    • C09D201/005—Dendritic macromolecules
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2323/10—Homopolymers or copolymers of propene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2400/00—Characterised by the use of unspecified polymers
    • C08J2400/14—Water soluble or water swellable polymers, e.g. aqueous gels
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
    • D06M2200/10—Repellency against liquids
    • D06M2200/12—Hydrophobic properties
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31551—Of polyamidoester [polyurethane, polyisocyanate, polycarbamate, etc.]

Definitions

  • hyperbranched polymers which have urethane and / or urea groups to modify surfaces
  • the present invention relates to substrates which have on their surface an amount of a hyperbranched polymer which is suitable for modifying the surface properties and which has urethane and / or urea groups.
  • the invention further relates to a method for modifying the surface properties of substrates.
  • hydrophilic materials are characterized by a pronounced interaction with water and usually other polar solvents, whereas predominantly hydrophobic materials are not or only slightly wetted by water and aqueous liquids.
  • the surface properties of a material often limit its application and treatment options in such a way that a modification seems desirable.
  • a modification to increase water affinity (hydrophilicity) is referred to as hydrophilizing, while an improvement in water-repellent properties is referred to as hydrophobizing.
  • Objects made of various synthetic materials have hydrophobic surface properties.
  • hydrophobic properties are undesirable if the objects are to be glued, coated, printed, colored or lacquered, since most adhesives, coating agents or paints show insufficient adhesion to hydrophobic surfaces.
  • Hydrophobic properties are also undesirable in the case of flat textile structures, such as in particular nonwovens.
  • Nonwovens are e.g. B. used as cleaning and wiping cloths, dishcloths and serviettes. In these applications it is important that e.g. B. spilled liquids, such as milk, coffee, etc., quickly and completely absorbed when wiping and damp surfaces are dried as completely as possible.
  • a cleaning cloth absorbs liquids the faster the faster they are transported on the fiber surface, whereby fibers with a hydrophilic surface are easily and quickly wetted by aqueous liquids.
  • Various methods are customary for hydrophilizing the surfaces of foils or moldings.
  • the surfaces of plastic articles can be activated by gaseous fluorine.
  • this process requires working with the highly toxic gas fluorine with an increased outlay on equipment.
  • corona or plasma treatments are used to increase the hydrophilicity of the surface of various materials such as plastics or metals.
  • Nonwovens such as emulsifiers, surfactants or wetting agents are also used to improve the water absorption properties of nonwovens, for example. Excellent initial hydrophilicity is achieved in this way.
  • these nonwovens have the disadvantage that the hydrophilic agents are gradually washed out by water or other aqueous media. After repeated contact with water, the product becomes increasingly hydrophobic.
  • Another disadvantage of the known surface-active agents is the strong reduction in the interfacial tension of water, so that in many applications, in particular in the case of hygiene and diaper nonwovens, the
  • Permeability and the wetting capacity of the absorbed liquid is undesirably increased.
  • Examples of a modification of surface properties with regard to hydrophobization are natural surfaces or surfaces which are produced from natural sources, such as wood, leather, paper, plaster or concrete, in order to protect them against the ingress of water. Wood can be prevented from rotting by specifically adjusting the water intake. Leather for clothing is equipped in such a way that water rolls off the surface in order to increase comfort. Furthermore, the surfaces of hydrophilic synthetic materials can also be made hydrophobic.
  • WO 98/27263 continuously discloses hydrophilic polymer coatings for polyester, polypropylene and similar fibers.
  • the coating contains certain polyoxypropylamines or polypropylene oxide polymers and hydrophilic polyester copolymers containing ethylene terephthalate units.
  • WO 97/00351 describes permanently hydrophilic polymer coatings for polyester, polyethylene or polypropylene fibers and fabrics which contain hydrophilic copolyesters and polypropylene oxide polymers.
  • PCT / EP01 / 06719 describes the use of polymers which have urethane and / or urea groups and ammonium groups for modifying the surface properties of particle, line, sheet or three-dimensional structures.
  • PCT / EP02 / 02201 describes the use of polymers which have urethane and / or urea groups and anionic groups, the content of urethane and / or urea groups being at least 2 mol / kg of polymer for modifying the surface properties of particles -, linear, flat or three-dimensional structures.
  • polyurethanes and / or polyureas used according to the last two documents mentioned are not hyperbranched polymers.
  • WO 97/02304 describes highly functionalized polyurethanes and a process for their production.
  • One possible use is described as a highly functional crosslinker for polyurethane paints and coatings or for polyurethane foams.
  • No. 5,936,055 describes acid-functionalized polyurethane adducts with a branched structure. These are suitable for the production of crosslinked aqueous polymer latices, which are suitable for paints.
  • DE-A-199 04 444 describes a process for the production of dendrimers or highly branched polyurethanes which can be used as phase mediators, rheology aids, thixotropic agents, nucleating agents. or are suitable as active ingredient or catalyst carriers.
  • DE-A-100 13 187 describes a process for the production of highly functional polyisocyanates which are suitable as a component for the production of polyurethane, the resulting polyurethanes e.g. B. can be used for the production of paints, coatings, adhesives, sealants, cast elastomers or foams.
  • the use of the highly functional polyisocyanates per se for modifying the surface properties of substrates is not described.
  • DE-A-100 30 869 describes a process for the production of polyfunctional polyisocyanate polyaddition products which are suitable as a component for the production of polyurethane.
  • the resulting polyurethanes can be used for the production of paints, coatings, adhesives, sealants, cast elastomers or foams. be set.
  • the use of the polyisocyanate polyaddition products per se to modify the surface properties of substrates is also not described in this document.
  • the unpublished German patent application P 102 04 979.3 describes a process for the production of highly functional highly branched polyureas. These are suitable, for example, as adhesion promoters, thixotropic agents or as components for the production of lacquers, coatings, adhesives, sealing compounds, cast elastomers or foams.
  • the object of the present invention is to provide substrates with specifically modified surface properties.
  • the modified substrates should have the desired profile of properties with regard to their affinity for water and water-containing liquids (hydrophilic or hydrophobic finish).
  • the invention is also based on the object of providing a method for increasing the surface hydrophilicity or hydrophobicity of substrates.
  • this object is achieved by a substrate containing on its surface at least one hyperbranched polymer which has urethane and / or urea groups.
  • Suitable substrates generally comprise particulate, linear, flat or three-dimensional structures.
  • particle structures encompasses the range from fine pigments to macroscopic particles. These include, for example, those with a particle size of 1 nm to 10 mm, such as 10 nm to 1 mm, especially 1 ⁇ m to 0.1 mm, which are preferably are dispersible or dispersed in a medium, examples being pigments, mineral or metallic fillers or inanimate organic materials.
  • Line-like structures mean in particular fibers, filaments, yarns, threads and the like.
  • “Sheet-like structures” are, in particular, woven fabrics, knitted fabrics, felts, nonwovens or nonwovens, the latter being preferred.
  • a structure of fibers is deposited, which is then solidified into nonwovens using different methods treated with an aqueous binder, for example a polymer latex, and then dried, if appropriate after removal of excess binder, and optionally hardened.
  • shaped structures are also foils, paper and comparable two-dimensional structures.
  • sheet-like textile structures are also understood to mean textile composite materials, such as carpets, laminated and laminated textiles, etc.
  • Three-dimensional structures are generally shaped bodies of various dimensions. These include, in particular, shaped bodies made of wood, paper, metals, plastics, ceramic supports, fabrics made of natural or synthetic fibers in the form of fluffs, tissues etc.
  • Preferred configurations of the structure according to the invention are linear or flat textile structures.
  • Other preferred configurations of the structure according to the invention are plastic films or molded plastic bodies.
  • the structures used according to the invention preferably comprise at least one natural or synthetic polymeric material.
  • Polymers of mono- and diolefins for example polypropylene, polyisobutylene, polybutene-1, poly-4-methyl-pentene-1, polyisoprene or polybutadiene and polymers of cycloolefins, such as, for. B. of cyclopentene or norbornene; also polyethylene (which may or may not be crosslinked), e.g. B.
  • HDPE High Density Polyethylene
  • HDPE-HMW High Density and High Molecular Weight Polyethylene
  • HDPE-UHMW Medium Density Polyethylene
  • MDPE Low Density Polyethylene
  • LDPE Low Density Polyethylene
  • LLDPE linear low density polyethylene
  • VLDPE branched low density polyethylene
  • Polyolefins ie polymers of monoolefins, as mentioned by way of example in the preceding paragraph, in particular polyethylene. and polypropylene can be produced by various processes, in particular by free radicals or by means of a catalyst, the catalyst usually containing one or more metals from group IVb, Vb, VIb or VIII. These catalyst systems are commonly referred to as Phillips, Standard Oil Indiana, Ziegler (-Natta), TNZ (DuPont), Metal Locen or Single Site Catalysts (SSC). 2nd Mixtures of the polymers mentioned under 1., for. B. Mixtures of polypropylene with polyisobutylene, polypropylene with polyethylene (e.g. PP / HDPE, PP / LDPE) and mixtures of different types of polyethylene (e.g. LDPE / HDPE).
  • Copolymers of mono- and diolefins with one another or with other vinyl monomers such as.
  • Hydrocarbon resins including hydrogenated modifications thereof (eg tackifier resins) and mixtures of polyalkylenes and starch.
  • Polystyrene poly- (p-methylstyrene), poly- ( ⁇ -methylstyrene).
  • Copolymers of styrene or ⁇ -methylstyrene with dienes or acrylic derivatives such as.
  • styrene on polybutadiene styrene on polybutadiene-styrene or polybutadiene-acrylonitrile copolymers, styrene and acrylonitrile (or methacrylonitrile) on polybutadiene; Styrene, acrylonitrile
  • Halogen-containing polymers such as. B. polychloroprene, chlorinated rubber, chlorinated and brominated copolymer of isobutylene-isoprene (halobutyl rubber), chlorinated or chlorosulfo-
  • polyethylene copolymers of ethylene and chlorinated ethylene, epichlorohydrin homo- and copolymers, in particular polymers of halogen-containing vinyl compounds, such as.
  • Polymers derived from unsaturated alcohols and amines or their acyl derivatives or acetals such as polyvinyl alcohol, polyvinyl acetate, stearate, benzoate, maleate, polyvinyl butyral, polyallyl phthalate, polyallyl melamine; and their copolymers with olefins mentioned in point 1.
  • Homopolymers and copolymers of cyclic ethers such as polyalkylene glycols, polyethylene oxide, polypropylene oxide, or their copolymers with bisglycidyl ethers.
  • Polyacetals such as polyoxymethylene, and also such polyoxymethylene, the comonomers, such as. B. ethylene oxide; Polyacetals modified with thermoplastic polyurethanes, acrylates or MBS.
  • Polyurethanes which are derived from polyethers, polyesters and polybutadienes with terminal hydroxyl groups on the one hand and ali-
  • Polyamides and copolyamides which are derived from diamines and dicarboxylic acids and / or from aminocarboxylic acids or the corresponding lactams, such as polyamide 4, polyamide 6, polyamide 6/6, 6/10, 6/9, 6 / 12, 4/6, 12/12, polyamide 11, polyamide 12, aromatic polyamides, e.g. B. starting from p-phenylenediamine and adipic acid; Polyamides made from hexamethylene diamine and iso- and / or terephthalic acid and optionally an elastomer as a modifier, e.g. B. poly-2,4,4-trimethyl-hexamethylene terephthalamide or poly-m-phenylene-isophthalamide.
  • Block copolymers of the abovementioned polyamides with polyolefins, olefin copolymers, ionomers or chemically bonded or grafted elastomers are also suitable; 0 or with polyethers, such as. B. with polyethylene glycol, polypropylene glycol or polytetramethylene glycol. Also suitable are polyamides or copolyamides modified with EPDM or ABS and polyamides condensed during processing (“RIM polyamide systems”). 5
  • Polyureas Polyureas, polyimides, polyamideimides, polyetherimides, polyesterimides, polyhydantoins and polybenzimidazoles.
  • Polyesters which are derived from dicarboxylic acids and dialcohols and / or from hydroxycarboxylic acids or the corresponding lactones, such as polyethylene terephthalate, polybutylene terephthalate, poly-1, 4-dimethylolcyclohexane terephthalate, polyhydroxybenzoates and block polyether esters which differ from polyethers Derive hydroxyl end groups; furthermore polyesters modified with polycarbonates 5 or MBS. 19. Polycarbonates and polyester carbonates.
  • phenols, urea or melamine on the other hand, such as phenol-formaldehyde, urea-formaldehyde and melamine-formaldehyde resins.
  • Unsaturated polyester resins derived from copolyesters of saturated and unsaturated dicarboxylic acids with polyhydric alcohols and vinyl compounds as crosslinking agents.
  • Crosslinkable acrylic resins which are derived from substituted acrylic acid esters, such as, for. B. of epoxy acrylates, urethane acrylic
  • crosslinked epoxy resins derived from aliphatic, cycloaliphatic, heterocyclic or aromatic glycidyl compounds, eg. B. Products of bisphenol A diglycidyl ethers, bisphenol F diglycidyl ethers, which by means of conventional 0 hardeners, such as. B. anhydrides or amines with or without accelerators.
  • Natural polymers such as cellulose (for example wood or cotton), natural rubber, gelatin, and their polymer-homologously chemically modified derivatives, such as cellulose acetates, propionates and butyrates, or the cellulose ethers, such as methyl cellulose; as well as rosins and derivatives.
  • binary and polynary mixtures 0 (polyblends) of the aforementioned polymers, such as, for. B. PP / EPDM,
  • Polya id / EPDM or ABS Polya id / EPDM or ABS, PVC / EVA, PVC / ABS, PVC / MBS, PC / ABS, PC / ASA, PC / PBT, PVC / CPE, PVC / Acrylate, POM / thermoplastic PUR, PC / thermoplastic PUR, POM / Acrylate, POM / MBS, PPO / HIPS, PPO / PA 6.6 and copolymers, PA / HDPE, PA / PP, PA / PPO, PBT / 5 PC / ABS or PBT / PET / PC.
  • Particulate, linear, sheet-like or three-dimensional structures are preferred which comprise at least one polymeric material which is selected from polyolefins, polyesters, polyamides, polyacrylonitrile, polyaromatics, styrene-acrylonitrile copolymers (SAN), acrylonitrile-butadiene-styrene copolymers (ABS), polyurethanes and mixtures (polyblends) of the aforementioned polymers.
  • polymeric material which is selected from polyolefins, polyesters, polyamides, polyacrylonitrile, polyaromatics, styrene-acrylonitrile copolymers (SAN), acrylonitrile-butadiene-styrene copolymers (ABS), polyurethanes and mixtures (polyblends) of the aforementioned polymers.
  • the structures used according to the invention are plastic fibers, in particular made of polyolefins, such as, for. As polyethylene and polypropylene, polyesters, polyacrylonitrile and polyamides, such as. B. Polyamide 6 and Polyamide 66.
  • polyolefins such as, for. As polyethylene and polypropylene, polyesters, polyacrylonitrile and polyamides, such as. B. Polyamide 6 and Polyamide 66.
  • the structures used according to the invention are preferably sheet-like structures and in particular films or foils. These preferably contain a polymer which is selected from polyolefins, such as polyethylene and / or polypropylene, polymers of halogenated monomers, such as, for. B. polyvinyl chloride and / or polytetrafluoroethylene, polyesters and mixtures thereof.
  • the structure used according to the invention is preferably still a shaped body.
  • This preferably comprises at least one polymeric material which is selected from polyolefins, such as. B. polyethylene and / or polypropylene, polyaromatics, such as polystyrene, polymers of halogenated monomers, such as polyvinyl chloride and / or polytetrafluoroethylene, polyesters, polyacrylonitrile, styrene-acrylonitrile copolymers, acrylonitrile-butadiene-styrene copolymers, polyamides, such as polyamide 6 and / or polyamide 66, polyurethanes and mixtures thereof.
  • polyolefins such as. B. polyethylene and / or polypropylene
  • polyaromatics such as polystyrene
  • polymers of halogenated monomers such as polyvinyl chloride and / or polytetrafluoroethylene
  • polyesters polyacrylonitrile
  • At least one polyurethane polymer is used to modify the surface properties of the substrates.
  • polyurethanes includes not only those polymers whose repeating units are connected to one another by urethane groups, but very generally polymers that can be obtained by reacting at least one di- and / or poly-isocyanate with at least one compound which has at least one has a group reactive toward isocyanate groups.
  • polyurethanes include polymers, the repeating units of which, in addition to urethane groups, are also linked by urea, allophanate, biuret, carbodiimide, amide, uretonimine, uretdione, isocyanurate or oxazolidone (oxazolidinone) groups (see for example Plastic pocket book, Saechtling, 26th edition, p. 491ff, Carl-Hanser-Verlag, Kunststoff 1995).
  • polyurethanes includes in particular polymers which have urethane and / or urea groups. Polyurethanes which have a weight-average molecular weight in the range from about 500 to 100,000, preferably 1000 to 50,000, are preferred.
  • Their content of urethane and / or urea groups is preferably in a range from 0.5 to 10 mol / kg, particularly preferably 1 to 10 mol / kg, in particular 2 to 8 mol / kg.
  • hyperbranched polymers generally encompasses polymers which are distinguished by a branched structure and high functionality.
  • the hyperbranched polymers preferably have at least four further functional groups.
  • the proportion of functional groups is preferably 4 to 100, particularly preferably 5 to 30 and in particular 6 to 20.
  • the "hyperbranched polymers" in the sense of the invention also include star polymers, dendrimers (dendritic polymers) and various high molecular weight polymers, such as, for. B. comb polymers.
  • Star polymers are polymers in which three or more chains start from a center.
  • the center can be a single atom or a group of atoms.
  • “Dendrimers” dendritic polymers, cascade polymers, arborols, isotropically branched polymers, iso-branched polymers, starburst polymers
  • the dimers derive from the star polymers, the individual chains each being branched in a star shape. They arise from small molecules through a constantly repeating sequence of reactions, resulting in ever higher branches, at the ends of which there are functional groups, which in turn are the starting point for further branches.
  • dendrimers The number of monomer end groups increases exponentially with each reaction step, resulting in a spherical tree structure at the end.
  • a characteristic feature of the dendrimers is the number of reaction stages (generations) carried out to build them up. Due to their uniform structure, dendrimers generally have a defined molar mass. Also suitable are both molecularly and structurally non-uniform "hyperbranched polymers" which have side chains of different lengths and branches as well as a molecular weight distribution.
  • So-called AB x monomers are particularly suitable for the synthesis of these hyperbranched polymers. These have two different functional groups A and B, which can react with one another to form a link. The functional group A is only contained once per molecule and the functional group B twice or more. The reaction of the AB x monomers with one another produces uncrosslinked polymers with regularly arranged branching points. The polymers have almost exclusively B groups at the chain ends. Further details are, for example, in the Journal of Molecular Science, Rev. Macromol. Chem. Phys., C37 (3), 555-579 (1997).
  • Hyperbranched polymers suitable according to the invention are described in WO 97/02304, US Pat. No. 5,936,055, DE-A-100 13 187, DE-A-100 30 869, DE-A-199 04 444 and German patent application P 102 04 979.3, whereupon here is fully referred to.
  • the hyperbranched polymers used according to the invention preferably have a degree of branching (DB) corresponding to an average number of dendritic linkages and terminal units per molecule of 10 to 100%, preferably 10 to 90% and in particular 10 to 80%.
  • DB degree of branching
  • Hyperbranched polymers i.e. H.
  • Molecularly and structurally non-uniform polymers are preferably used. These are generally simpler and therefore more economical to produce than dendrimers.
  • structurally and molecularly uniform dendrimeric polymers and star polymers can also be used.
  • hyperbranched polyurethanes and polyureas which can be used according to the invention can be carried out, for example, as described below.
  • AB x monomers which have both isocyanate groups and groups which can react with isocyanate groups to form a link.
  • X is a natural number between 2 and 8. It is preferably x 2 or 3. Either A is the isocyanate groups and B is reactive with these groups, or the reverse may be the case.
  • the groups reactive with the isocyanate groups are preferably OH, NH 2 , NH, SH or COOH groups.
  • the AB x monomers can be prepared in a known manner using various techniques.
  • AB x monomers can be synthesized, for example, by the method disclosed by WO 97/02304 using protective group techniques. This technique is exemplified by the preparation of an AB 2 monomer from 2,4-tolylene diisocyanate (TDI) and trimethylol propane. First, one of the TDI isocyanate groups is blocked in a known manner, for example by reaction with an oxime. The remaining free NCO group is reacted with trimethylolpropane, one of the three OH groups reacting with the isocyanate group. After the protective group has been removed, a molecule with an isocyanate group and 2 OH groups is obtained.
  • TDI 2,4-tolylene diisocyanate
  • trimethylol propane trimethylol propane
  • DE-A 199 04 444 disclosed method can be synthesized in which no protective groups are required.
  • di- or polyisocyanates are used and reacted with compounds which have at least two groups reactive with isocyanate groups.
  • At least one of the reactants has groups with different reactivity than the other reactant.
  • Both reactants preferably have groups with different reactivities than the other reactants.
  • the reaction conditions are chosen so that only certain reactive groups can react with each other.
  • AB x molecules can also be produced as described in German patent application P 102 04 979.3. Here isocyanate groups protected by capping agents are reacted with polyamines to form polyureas.
  • Suitable di- or polyisocyanates are the aliphatic, cycloaliphatic, araliphatic and aromatic di- or polyisocyanates known from the prior art and exemplified below.
  • 4,4'-diphenylmethane diisocyanate the mixtures of monomeric diphenylethane diisocyanates and oligomeric diphenylmethane diisocyanates (polymer MDI), tetramethylene diisocyanate, tetramethylene diisocyanate trimers, hexamethylene diisocyanate, hexamethylene diisocyanate tri mere, isophorone diisocyanate tri, 4,4'-methylenebis (cyclohexyl) diisocyanate, xylylene diisocyanate, tetramethylxylylene diisocyanate, dodecyl diisocyanate, lysine alkyl ester diisocyanate, where alkyl is C 1 -
  • Di- or polyisocyanates which have NCO groups of different reactivity are particularly preferred for the construction of the polyurethanes and polyureas.
  • Examples include 2,4-tolylene diisocyanate (2,4-TDI), 2,4'-diphenylmethane diisocyanate (2,4'-MDI), triisocyanatotoluene, isophorone diisocyanate (IPDI), 2-butyl-2-ethylpentamethylene diisocyanate, 2, 2,4- or 2,4,4-trimethyl-1, 6-hexamethylene diisocyanate, 2-isocyanatopropylcyclohexyl isocyanate, 3 (4) -isocyanatomethyl-1-methylcyclohexyl isocyanate, 1,4-diisocyanato-4- methyl pentane, 2,4'-methylenebiscyclohexyl) diisocyanate and 4-methyl-cyclohexane-1,3-diiso
  • isocyanates are suitable for the construction of the polyurethanes and polyureas, the NCO groups of which are initially equally reactive, but in which a drop in reactivity in the second NCO group can be induced by the first addition of a reactant to an NCO group.
  • isocyanates the NCO groups of which are coupled via a delocalized ⁇ -electron system, e.g. B. 1,3- and 1,4-phenylene diisocyanate, 1,5-naphthylene diisocyanate, diphenyl diisocyanate, tolidine diisocyanate or 2,6-tolylene diisocyanate.
  • oligo- or polyisocyanates which are obtained from the above-mentioned di- or polyisocyanates or their mixtures by linking using urethane, allophanate, urea, biuret, uretdione, amide, iso- Have cyanurate, carbodiimide, uretonimine, oxadiazinetrione or iminoxadiazinedione structures produced.
  • Preferred for the production of polyurethanes and polyurea polyurethanes are compounds with at least one primary and at least one secondary hydroxyl group, at least one hydroxyl group and at least one mercapto group, particularly preferably with at least one hydroxyl group and at least one amino group in the molecule, in particular amino alcohols, aminodiols and Aminotriole, because the reactivity of the amino group towards Hydroxyl group in the reaction with isocyanate is significantly higher.
  • Examples of the compounds mentioned with at least two groups reactive with isocyanates are propylene glycol, glycerol, mercaptoethanol, ethanolamine, N-methylethanolamine, diethanolamine, ethanolpropanolamine, dipropanolamine, diisopropanolamine, 2-amino-1, 3-propanediol, 2-amino-2 -methyl-l, 3-propanediol or tris (hydroxymethyl) aminomethane. Mixtures of the compounds mentioned can also be used.
  • Isocyanate-reactive products which have at least two amino groups in the molecule are preferably used for the production of polyureas.
  • ethylenediamine N-alkylethylenediamine, propylenediamine, N-alkylpropylenediamine, hexamethylenediamine, N-alkylhexamethylenediamine, diaminodicyclohexylmethane, phenylenediamine, isophoronediamine, amine-terminated polyoxyalkylene polyols (so-called Jeffethylamine), bis (so-called Jeffethylamine) amine bis (aminopropyl) amine,
  • an AB x molecule for the production of a polyurethane from a diisocyanate and an aminodiol is explained here by way of example.
  • one mole of a diisocyanate is first reacted with one mole of an aminodiol at low temperatures, preferably in the range between -10 to 30 ° C. In this temperature range, the urethane formation reaction is virtually completely suppressed and the NCO groups of the isocyanate react exclusively with the amino group of the aminodiol.
  • the AB x molecule formed, here an AB 2 type has one free NCO group and two free OH groups and can be used to synthesize a hyperbranched polyurethane.
  • this AB 2 molecule can react intermolecularly to form a hyperbranched polyurethane.
  • the hyperbranched polyurethane can advantageously be synthesized in a further reaction step at elevated temperature, preferably in the range between 30 and 80 ° C., without prior isolation of the AB 2 molecule.
  • a hyperbranched polymer is formed which contains one free NCO group per molecule and - depending on the degree of polymerization - one more or less ger has a large number of OH groups.
  • the reaction can be carried out up to ⁇ high turnover, resulting in very high molecular weight structures are obtained.
  • an AB 2 molecule can also be produced from 1 mol of glycerol and 2 mol of 2,4-TDI.
  • the primary alcohol groups and the isocyanate group preferably react in the 4-position, and an adduct is formed which has one OH group and two isocyanate groups and which, as described, are converted to a hyperbranched polyurethane at higher temperatures can.
  • a hyperbranched polymer is formed which has a free OH group and - depending on the degree of polymerization - a more or less large number of NCO groups.
  • the hyperbranched polyurethanes and polyureas can in principle be prepared without a solvent, but preferably in solution. In principle, all solvents which are liquid at the reaction temperature and which are suitable as solvents are suitable. Monomers and polymers inert compounds.
  • AB 3 molecules can be obtained, for example, by reacting diisocyanates with compounds having at least 4 groups that are reactive toward isocyanates.
  • the reaction of tolylene diisocyanate with tris (hydroxymethyl) aminomethane may be mentioned as an example.
  • Hyperbranched polyurethanes and polyureas with chain-extended branches can be obtained, for example, by using a diisocyanate and a compound which has two groups reactive with isocyanate groups in addition to the AB x molecules in addition to the AB x molecules in a molar ratio of 1: 1.
  • These additional AA or BB connections can also be made via have other functional groups, which, however, must not be reactive towards the A or B groups under the reaction conditions. In this way, further functionalities can be introduced into the hyperbranched polymer.
  • urethane and / or urea group-containing hyperbranched polymers can generally already be used as such for modifying the surface properties of substrates. Their surface-modifying properties depend on the functional groups introduced with the synthesis.
  • the hyperbranched polymers described above are preferably subjected to a polymer-analogous reaction before they are used to modify substrate surfaces.
  • the polymer properties can thus be specifically adapted to the respective application, depending on the type and amount of the compounds used for the polymer-analogous reaction.
  • Substrates as described above are therefore preferred, the hyperbranched polymer being obtainable on the substrate surface by polymer-analogous reaction of a hyperbranched polymer which carries urethane and / or urea groups and / or further functional groups which are capable of a condensation or addition reaction, with at least one compound selected from
  • complementary functional groups is understood to mean a pair of functional groups which can react with one another in a condensation or addition reaction.
  • “Complementary connections” are pairs of Compounds that have complementary functional groups.
  • Preferred complementary functional groups of the hyperbranched polymers and components a) and b) are selected from the complementary functional groups in the overview below.
  • R and R ' are preferably selected independently from hydrogen, alkyl, particularly preferably C 1 -C 20 -alkyl, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, the isomeric pentylene, hexylene, heptylene, Octylene etc., cycloalkyl, particularly preferably C 5 -C 8 cycloalkyl, such as cyclopentyl and cyclohexyl, aryl, particularly preferably phenyl, heteryl etc.
  • Preferred complementary compounds are e.g. B. on the one hand compounds with active hydrogen atoms, the z. B. are selected from compounds with alcohol, primary and secondary amine and thiol groups and on the other hand compounds with groups that are reactive towards it, preferably isocyanate groups. It is generally not critical which functional group the polymer component and which the compound a) and / or b) carries.
  • Suitable hydrophilic groups of the compounds a) are selected from ionogenic, ionic and non-ionic hydrophilic groups.
  • the ionogenic or ionic groups are preferably carboxylic acid groups and / or sulfonic acid groups and / or nitrogen-containing groups (amines) or carboxylate groups and / or sulfonate groups and / or quaternized or protonated groups.
  • Compounds a) which contain acid groups can be converted into the corresponding salts by partial or complete neutralization.
  • Suitable bases for the neutralization are, for example, alkali metal bases, such as sodium hydroxide solution, potassium hydroxide solution, sodium carbonate, sodium hydrogen carbonate, potassium carbonate or potassium hydrogen carbonate and alkaline earth metal bases, such as Calcium hydroxide, calcium oxide, magnesium hydroxide or magnesium carbonate as well as ammonia and amines, such as trimethylamine, triethylamine etc.
  • alkali metal bases such as sodium hydroxide solution, potassium hydroxide solution, sodium carbonate, sodium hydrogen carbonate, potassium carbonate or potassium hydrogen carbonate
  • alkaline earth metal bases such as Calcium hydroxide, calcium oxide, magnesium hydroxide or magnesium carbonate as well as ammonia and amines, such as trimethylamine, triethylamine etc.
  • charged cationic groups can be obtained either by protonation, eg by B. with carboxylic acids, such as acetic acid, or by quaternization, z.
  • alkylating agents such as -CC 4 alkyl halides or
  • Hyperbranched polymers with ionic hydrophilic groups obtainable by polymer-analogous reaction are generally water-soluble or water-dispersible.
  • Hydroxycarboxylic acids such as hydroxyacetic acid (glycolic acid), hydroxypropionic acid (lactic acid), hydroxysuccinic acid (malic acid), hydroxypivalic acid, 4-hydroxybenzoic acid, 12-hydroxydodecanoic acid, dimethylolpropionic acid, etc., are preferably used as component a).
  • component a) are hydroxysulfonic acids, such as hydroxymethanesulfonic acid or 2-hydroxyethanesulfonic acid.
  • component a) are mercaptocarboxylic acids, such as mercaptoacetic acid.
  • component a) are aminosulfonic acids of the formula:
  • Y represents o-, m- or p-phenylene or straight-chain or branched C 2 -C 6 alkylene, which is optionally substituted by 1, 2 or 3 hydroxyl groups, and
  • R 1 represents a hydrogen atom, a C 1 -C 2 -alkyl group (preferably C 1 -C 8 and in particular C 1 -C 6 -alkyl group) or a Cs-C ß -cycloalkyl group, the alkyl group or the cycloalkyl group optionally being represented by 1 , 2 or 3 hydroxyl groups, carboxyl groups or sulfonic acid groups can be substituted.
  • the aminosulfonic acids of the above formula are preferably taurine, N- (l, l-dimethyl-2-hydroxyethyl) -3-amino-2-hydroxypropanesulfonic acid or 2-aminoethylaminoethanesulfonic acid.
  • component a) are ⁇ -, ⁇ - or ⁇ -amino acids, for example glycine, alanine, valine, leucine, isoleucine, phenylalanine, thyrosine, proline, hydroxyproline, serine, threonine, methionine, cysteine , Tryptophan, ß-alanine, aspartic acid or glutamic acid, used.
  • ⁇ -, ⁇ - or ⁇ -amino acids for example glycine, alanine, valine, leucine, isoleucine, phenylalanine, thyrosine, proline, hydroxyproline, serine, threonine, methionine, cysteine , Tryptophan, ß-alanine, aspartic acid or glutamic acid, used.
  • Polyetherols are also preferably used as component a).
  • Suitable polyetherols are linear or branched terminal hydroxyl-containing substances which contain ether bonds and have a molecular weight in the range of, for. B. have about 300 to 10,000.
  • These include, for example, polyalkylene glycols, e.g. B. polyethylene glycols, polypropylene glycols, polytetrahydrofurans, copolymers of ethylene oxide, propylene oxide and / or butylene oxide, which contain the alkylene oxide units randomly distributed or copolymerized in the form of blocks.
  • ⁇ , ⁇ -diamino polyethers which can be prepared by aminating polyetherols with ammonia. Such compounds are commercially available under the name Jeffamine®.
  • Component a) is furthermore preferably selected from diamines, polyamines and mixtures thereof.
  • Suitable amines a) are straight-chain and branched, aliphatic and cycloaliphatic amines with generally about 2 to 30, preferably about 2 to 20, carbon atoms. These include e.g. B. ethylenediamine, 1,2-diaminopropane, 1,3-diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane, 1,6-diaminohexane, 1,7-diaminoheptane, 1,8-diaminooctane, 1, 9-diaminononane, 1,10-diaminodecane, 1,11-diaminodecane, 1, 12-diaminododecane, diethylene triamine, triethylene tetraamine, 4-azaheptamethylene diamine, N, N'-bis (3-aminopropyl) butane -l, 4-diamine, and mixtures thereof.
  • Suitable polyamines a) generally have a number average molecular weight of about 400 to 10,000, preferably about 500 to 8000.
  • These include e.g. B. polyamides with terminal, primary or secondary amino groups, Polyalkylenijnine, preferably polyethyleneimines and by hydrolysis of poly-N-vinylamides, such as. B. Poly-N-vinyl acetamide, vinyl amines obtained.
  • Component a) is furthermore preferably selected from polyols.
  • polyols include e.g. B. diols having 2 to 18 carbon atoms, preferably 2 to 10 carbon atoms, such as 1,2-ethanediol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, 1,5-pentanediol, 1,10-decanediol, 2-methyl-l, 3-propanediol, 2-methyl-2-butyl-l, 3- propanediol, 2,2-dimethyl-l, 3-propanediol, 2,2-dimethyl-l, 4-butanediol, 2-ethyl-2-butyl-l, 3-propanediol, hydroxypivalic acid neopentylglycol ester, diethylene glycol and triethylene glycol.
  • Suitable triols and higher polyols are compounds having 3 to 25, preferably 3 to 18, particularly preferably 3 to 6 carbon atoms.
  • Examples of useful triols are glycerol or trimethylolpropane.
  • erythritol, pentaerythritol and sorbitol can be used as higher polyols.
  • amino alcohols are preferably used as component a). These preferably have 2 to 16, particularly preferably 3 to 12 carbon atoms, such as.
  • Suitable hydrophobic groups of the compounds b) are selected from saturated or unsaturated hydrocarbon radicals having 8 to 40, preferably 9 to 35, in particular 10 to 30 carbon atoms. They are preferably alkyl, alkenyl, cycloalkyl or aryl radicals.
  • the cycloalkyl or aryl radicals can have 1, 2 or 3 substituents, preferably alkyl or alkenyl substituents.
  • alkenyl radicals are radicals which have one, two or more carbon-carbon double bonds.
  • C 8 -C 0 alkyl includes straight-chain and branched alkyl groups. These are preferably straight-chain and branched C 9 -C 35 alkyl, particularly preferably C 0 -C 30 - and especially C ⁇ 2 -C 26 alkyl groups. These are preferably predominantly linear alkyl radicals, as they also occur in natural or synthetic fatty acids and fatty alcohols and oxo alcohols.
  • C 8 -C 4 o-alkenyl preferably represents straight-chain and branched alkenyl groups which can be mono-, di- or poly-unsaturated. It is preferably C 9 -C 35 -, in particular C 10 -C 30 - and especially C 12 -C 6 alkenyl groups.
  • octenyl nonenyl, decenyl, undecenyl, dodecenyl, tridecenyl, tetradecenyl, pentadecenyl, hexadecenyl, heptadecenyl, octa- decenyl, nonadecenyl, linolylyl, linolenylyl, eleostearyl etc. and in particular oleyl (9-octadecenyl).
  • the compound of the formula b) then preferably represents alkylamines, such as 1-octylamine, 1-nonylamine, 1-decylamine, 1-undecylamine, 1-un-dec-10-enylamine, 1-tridecylamine, 1-tetradecylamine, 1-pentad - Cylamine, 1-hexadecylamine, 1-heptadecylamine, 1-octadecylamine, l-octadeca-9,12-dienylamine, 1-nonadecylamine, 1-eicosylamine, 1-egg-cos-9-enylamine, 1-heneicosylamine, 1-docosylamine and especially for oleylamine and 1-hexadecylamine (cetylamine) or for amine mixtures made from naturally occurring fatty acids, such as.
  • alkylamines such as 1-octylamine, 1-nonylamine, 1-decyl
  • B. tallow fatty amines which contain predominantly saturated and unsaturated C ⁇ 4 -, Ci 6 -Ci 8 alkylamines or coconut amines, which contain saturated, mono- and di-unsaturated C8-C 22 -f preferably C ⁇ 2 -Ci 4 alkylamines.
  • the compound b) is preferably selected from monohydric alcohols which have one of the aforementioned hydrophobic radicals.
  • Such alcohols and alcohol mixtures b) are, for. B. obtainable by hydrogenation of fatty acids from natural fats and oils or of synthetic fatty acids, for. B. from the catalytic oxidation of paraffins.
  • Suitable alcohols and alcohol mixtures b) can also be obtained by hydroformylation of olefins with simultaneous hydrogenation of the aldehydes, which generally results in mixtures of straight-chain and branched primary alcohols (oxo alcohols).
  • Suitable alcohols and alcohol mixtures b) are also obtainable by partial oxidation of n-paraffins by known processes, predominantly linear secondary alcohols being obtained.
  • the essentially primary, straight-chain and even-numbered Ziegler alcohols obtainable by organoaluminum synthesis.
  • Suitable monohydric alcohols b) are e.g. B. octanol, nonanol, decanol, undecanol, dodecanol, tridecanol, tetradecanol, pentadecanol, hexadecanol, heptadecanol, octadecanol, etc. and mixtures thereof.
  • Suitable monoisocyanates b) are e.g. B. C 8 -C 40 alkyl isocyanates, which are available from the aforementioned amines and amine mixtures by phosgenation or from natural or synthetic fatty acids and fatty acid mixtures by Hofmann, Curtius or Lossen degradation.
  • the aforementioned compounds a) and b) can each be used individually, as mixtures of exclusively hydrophilic compounds a) or exclusively hydrophobic compounds b) and as Mixtures of hydrophilic compounds a) with hydrophobic compounds b) are used.
  • the surface-modifying properties of the hyperbranched polymers can be varied within a wide range by polymer-analogous reaction of urethane and / or urea group-bearing hyperbranched polymers with individual compounds a) or b) or with mixtures thereof. This allows the substrates modified with these polymers to be given surface properties which range from a strong affinity for water and aqueous liquids (hydrophilicity) to a very low affinity for water and aqueous liquids (hydrophobicity).
  • hyperbranched polyurethanes By reacting with compounds containing acrylate groups, such as, for example, alcohols containing acrylate groups, such as 2-hydroxyethyl acrylate or 2-hydroxyethyl methacrylate, hyperbranched polyurethanes can be obtained which have polymerizable olefinic groups and which are used to produce radiation-crosslinking, in particular UV, wetting polymers can be used.
  • acrylate groups such as, for example, alcohols containing acrylate groups, such as 2-hydroxyethyl acrylate or 2-hydroxyethyl methacrylate
  • hyperbranched polyurethanes By reaction with appropriately substituted alcohols, epoxy or vinyl ether groups can also be introduced, which can be used for cationically crosslinking polymers.
  • Oxidatively drying hyperbranched polyurethanes or polyureas can be obtained by combining polymers containing NCO or urethane groups with mono- or polyunsaturated fatty acid esters which have at least one OH group, or with mono- or polyunsaturated fatty alcohols or fatty amines, in particular with 3 to 40 carbon atoms. implements.
  • esters of linoleic acid, linolenic acid or eleostearic acid containing OH groups can be reacted with NCO groups.
  • NCO or urethane groups can also be reacted directly with alcohols or amines containing vinyl or allyl groups.
  • hyperbranched polyurethanes or polyureas which have different functionalities
  • 2 moles of 2,4-TDI can be reacted with a mixture of 1 mole of trimethylolpropane and 1 mole of dimethylolpropionic acid.
  • a product is obtained which has both carboxylic acid groups and OH groups.
  • such products can also be obtained by polymerizing with an AB x molecule, terminating the polymerization at the desired degree of conversion and then only part of the functional groups originally present, for example only part of the OH or NCO groups, implements.
  • some of the NCO groups can be reacted with ethanolamine and the remaining NCO groups with mercaptoacetic acid.
  • an OH-terminated polymer composed of isophorone diisocyanate and diethanolamine can subsequently be made hydrophobic by, for example, reacting some of the OH groups with dodecyl isocyanate or with dodecanoic acid.
  • the functionalization of a hyperbranched polyurethane or the adaptation of the polymer properties to the application problem can advantageously be carried out immediately after the polymerization reaction, without the NCO-terminated polyurethane being isolated beforehand. However, the functionalization can also take place in a separate reaction.
  • the hyperbranched polymers used according to the invention can be used in mixtures or in combination with other surface-active substances. These include conventional anionic, non-ionic or cationic surfactants or wetting agents. If desired, the hyperbranched polymers used according to the invention can also be used in combination with other polymers, as are customary for modifying the surface properties of substrates. Such a combination makes it possible in individual cases to achieve an enhancement of the surface-modifying effect.
  • the hyperbranched polyurethanes used according to the invention with urethane and / or urea groups are advantageously suitable for modifying the surface properties of substrates. These can generally be in the form of particulate, linear, sheet-like or three-dimensional structures.
  • modification of the surface properties is widely understood in the context of the present invention. Above all, this includes changing the affinity of the surface for water and water-containing liquids compared to an unmodified surface.
  • the hyperbranched polymers used according to the invention on the one hand comprise polymers which improve the affinity of a surface treated therewith for water (hydrophilize) and on the other hand those which reduce the affinity of a surface treated therewith with water (hydrophobize).
  • a suitable measure for assessing the hydrophilicity / hydrophobicity of the surface of a substrate is the measurement the contact angle of water on the respective surface (see, for example, Römpp, Chemielexikon, 9th edition, p. 372 "Wettung”, Georg-Thieme-Verlag (1995)).
  • a “hydrophobic surface” is understood to mean a surface whose contact angle of water is> 90 °.
  • a “hydrophilic surface” is understood to mean a surface whose contact angle of water is 90 90 °. Hydrophilizing hyperbranched polymers bring about a decrease in the contact angle compared to the unmodified surface on surfaces treated with them.
  • a hydrophilically acting hyperbranched polymer preferably brings about a decrease in the contact angle by at least 10 °, preferably by at least 30 °, with respect to the unmodified surface.
  • Hyperbranched polymers with a hydrophobic effect bring about an increase in the contact angle compared to the unmodified surface on surfaces treated with them.
  • Hyperbranched polymers which have a hydrophobizing action preferably cause the contact angle to increase by at least 10 °, particularly preferably by at least 30 °, compared to the unmodified surface.
  • the substrates according to the invention which have a hyperbranched polymer with a hydrophilizing effect on their surface generally show a substantially smaller decrease in the interfacial tension of water than when using commercially available surfactants.
  • the hyperbranched polymers used according to the invention remain on the treated surfaces even when rinsed with water and aqueous liquids and thus enable long-lasting hydrophilic modification.
  • the decrease in the interfacial tension with respect to water in the case of surfaces modified with hydrophilizing hyperbranched polymers is generally at most 30%, particularly preferably at most 20% and in particular at most 10% compared to the unmodified surface.
  • the substrates according to the invention modified with hydrophilizing hyperbranched polymers generally have a faster and / or increased fluid absorption and / or an improved fluid retention, generally also under pressure.
  • the hydrophilically modified substrates according to the invention are generally advantageous for all areas of application in which water or aqueous liquids come into contact with materials which are essentially hydrophobic in the unmodified state. This includes, in particular, the rapid absorption and / or the rapid transport of water in hydrophobic materials per se.
  • the structures according to the invention can furthermore generally be used advantageously where, by modifying surfaces in the sense of hydrophilization, improved adhesive properties, improved antistatic properties, improved anti-fog properties, an improved grip and / or improved wearing comfort can be achieved.
  • hydrophilically modified substrates according to the invention are advantageously suitable in or as synthetic fibers, fabrics, knitted fabrics, nonwovens, felts, textile composites, such as. B. carpets, laminated and laminated textiles etc. They are furthermore advantageously suitable for use in diapers, hygiene liners, cleaning and wiping cloths, dishcloths, serviettes,
  • hydrophilic, hyperbranched polymers used according to the invention are suitable as hydrophilizing agents for the above-mentioned materials, in particular for synthetic fibers, for example those made of polyethylene, polypropylene, polyesters, polyacrylonitrile and polyamides.
  • the polymers are also suitable for improving the printability and adhesiveness of films and foils, for example those made of polyethylene, polypropylene, polyvinyl chloride, polytetrafluoroethylene and polyesters.
  • the antistatic properties of films and foils can be improved by using the hydrophilic, hyperbranched polymers.
  • Typical moldings are, for example, made of polyethylene, polypropylene, polystyrene, polyvinyl chloride, polytetrafluoroethylene, polyesters, polyacrylonitrile, styrene-acrylonitrile copolymers (SAN), acrylonitrile-butadiene-styrene terpolymers (ABS), polyamides, such as polyamide 6 or polyamide 6, 6, polyurethanes and / or mixtures of the aforementioned plastics.
  • hydrophilic, hyperbranched polymers with urethane and / or urea groups leads to an improvement in the surface conductivity of hydrophobic, non-conductive materials, in particular the aforementioned plastics, and thus improves their antistatic properties.
  • hydrophilic, hyperbranched polymers are suitable for reducing the tendency of plastic films to fog up.
  • the substrates according to the invention in the form of particulate, linear, sheet-like or three-dimensional structures with the hyperbranched polymers can be carried out according to the methods normally used for hydrophilizing or hydrophobicizing the aforementioned structures with hydrophilizing agents or hydrophobicizing agents of the prior art applies.
  • the structure is usually treated with a dilute, preferably aqueous solution of the polymer in a manner customary for the type of structure, eg. B. by rinsing, dipping, spraying, splashing or similar methods, as are usually used in the finishing of textile fabrics or films.
  • the polymer content of the solutions is generally in the range from at least 0.01 to 20% by weight and preferably 0.1 to 10% by weight, based on the weight of the solution.
  • Aqueous solutions of the polymers are preferably used for the treatment.
  • the amount of polymer required for hydrophilization or hydrophobization is absorbed or adsorbed by the surface and remains adhering to it after drying. To achieve effective.
  • the amounts required for hydrophilization or hydrophobization are automatically established and are extremely low. For structures with a smooth surface such as foils and similar structures, 0.1 mg / m 2 of polymer is sufficient.
  • the polymer in another embodiment of the method according to the invention for hydrophilizing or hydrophobicizing surfaces, can also be added to the material from which the structure is made and then the structure can be produced therefrom.
  • the polymer when finishing thermoplastic materials, can be compounded as a solid with the plastic material.
  • the plastic material equipped in this way is then further processed by the usual methods to give films, for example by extrusion, or to fiber materials, for example by a melt spinning process.
  • the simple applicability of the polymers according to the invention and used according to the invention permits use in many areas of application, for example as a hydrophilizing agent for nonwovens which, for. B. in diapers, hygiene pads, textiles, agricultural or geotextiles or filter systems.
  • the plastic fibers finished with the polymers can in turn be further processed into textiles.
  • the hydrophilization or hydrophobization generally also improves the water vapor permeability and the capillary transport of sweat and the soiling behavior compared to many hydrophobic substances. Dirt types reduced above. In addition, the releasability of dirt is positively influenced.
  • the polymers can also be used as antistatic equipment for plastic films or silicon wafers.
  • polyurea was modified hydrophilically by means of OH groups, in example 2 with alkyl chains hydrophobically.
  • Example 3 Polyurea According to the Invention:
  • Example 4 Polyurethane According to the Invention:
  • a 50% strength solution of the hyperbranched polyurea from Example 2 in ethanol is applied onto a non-treated PP film in a layer thickness of 30 ⁇ m. After drying at 50 ° C, the contact angle of a drop of water is determined. Contact angle 1: 27 °
  • a 50% solution of the hyperbranched polyurea from Example 1 in ethanol is applied onto a non-treated PP film in a layer thickness of 30 ⁇ m. After drying at 50 ° C, the contact angle of a drop of water is determined.
  • a 50% solution of the hyperbranched polyurea from Example 3 in ethanol was applied onto a non-treated PP film in a layer thickness of 30 ⁇ m. After drying at 20 50 ° C, the contact angle of a drop of water was determined. The film could no longer be washed off with water
  • a 10% aqueous solution of the hyperbranched polyurethane from Example 4 was applied onto a non-treated PP film in a 30 layer thickness of 30 ⁇ m. After drying at 50 ° C, the contact angle of a drop of water was determined. The film could no longer be washed off with water.
  • Hydrophilic suction cardboard pieces from Schleicher & Schuell (grade 40 2282) are immersed in a 5% solution of the hyperbranched polyurea from Example 1 in ethanol. The pieces of cardboard are then left to air dry at room temperature. The sinking behavior of attached water drops is monitored by the KW measuring device dataphysics 0CA15 +. It is shown in Figure 1. 45 An untreated piece of cardboard soaks up a drop of water within a second.
  • the hyperbranched polymer of Example 2 is content to 20% polymer ⁇ diluted with ethanol. Cotton pieces were soaked in this solution and pressed on the laboratory press. After drying, the occupancy was determined. The occupancy was 24%, based on the weight of the fabric. Then the sinking behavior of water on the tissue was observed. The tissue was stored in daylight at room temperature for 10 days. Then the sinking behavior was checked with the KW measuring device dataphysics 0CA15 +. It is shown in Figure 2.
  • An untreated piece of cotton fabric soaks up a drop of water within a second.

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Abstract

The invention relates to substrates comprising a suitable amount of a hyperbranched polymer on the surface thereof for modifying the properties of the surface. Said polymer comprises urethane and/or urea groups. The invention also relates to a method for modifying the properties of the surface of substrates.

Description

Verwendung von hyperverzweigten Polymeren, die ürethan- und/oder Harnstoffgruppen aufweisen, zur Modifizierung von OberflächenUse of hyperbranched polymers which have urethane and / or urea groups to modify surfaces
Beschreibungdescription
Die vorliegende Erfindung betrifft Substrate, die auf ihrer Oberfläche eine zur Modifizierung der Oberflächeneigenschaften geeignete Menge eines hyperverzweigten Polymers aufweisen, das üre- than- und/oder Harnstoffgruppen aufweist. Die Erfindung betrifft weiterhin ein Verfahren zur Modifizierung der Oberflächeneigenschaften von Substraten.The present invention relates to substrates which have on their surface an amount of a hyperbranched polymer which is suitable for modifying the surface properties and which has urethane and / or urea groups. The invention further relates to a method for modifying the surface properties of substrates.
Die Oberflächeneigenschaften von natürlichen und synthetischen Materialien werden wesentlich bestimmt von der Affinität gegenüber Wasser. Überwiegend hydrophile Materialien zeichnen sich durch eine ausgeprägte Wechselwirkung mit Wasser und in der Regel weiteren polaren Lösungsmitteln aus, wohingegen überwiegend hydrophobe Materialien von Wasser und wässrigen Flüssigkeiten nicht oder nur in geringem Maße benetzt werden. Häufig schränken die Oberflächeneigenschaften eines Materials dessen Einsatz- und Behandlungsmöglichkeiten derart ein, dass eine Modifizierung wünschenswert erscheint. Eine Modifizierung zur Erhöhung der Wasseraffinität (Hydrophilie) bezeichnet man dabei als Hydrophilie- ren, während eine Verbesserung der wasserabweisenden Eigenschaften als Hydrophobieren bezeichnet wird.The surface properties of natural and synthetic materials are largely determined by their affinity for water. Mainly hydrophilic materials are characterized by a pronounced interaction with water and usually other polar solvents, whereas predominantly hydrophobic materials are not or only slightly wetted by water and aqueous liquids. The surface properties of a material often limit its application and treatment options in such a way that a modification seems desirable. A modification to increase water affinity (hydrophilicity) is referred to as hydrophilizing, while an improvement in water-repellent properties is referred to as hydrophobizing.
Gegenstände aus verschiedenen synthetischen Materialien, wie duroplastische oder thermoplastische Kunststoffe, weisen hydrophobe Oberflächeneigenschaften auf. Vielfach sind hydrophobe Eigenschaften jedoch unerwünscht, wenn die Gegenstände beklebt, beschichtet, bedruckt, gefärbt oder lackiert werden sollen, da die meisten Klebstoffe, Beschichtungsmittel oder Anstrichmittel auf hydrophoben Oberflächen nur unzureichende Haftung zeigen. Hydro- phobe Eigenschaften sind auch bei flächenförmigen textilen Gebilden, wie insbesondere Vliesstoffen, unerwünscht. Vliesstoffe werden z. B. als Putz- und Wischtücher, Spültücher und Servietten verwendet. Bei diesen Anwendungen ist es wichtig, dass z. B. verschüttete Flüssigkeiten, wie Milch, Kaffee usw., beim Aufwischen rasch und vollständig aufgesaugt und feuchte Oberflächen möglichst vollständig getrocknet werden. Ein Putztuch saugt Flüssigkeiten umso rascher auf, je schneller deren Transport auf der Faseroberfläche erfolgt, wobei Fasern mit hydrophiler Oberfläche von wässrigen Flüssigkeiten leicht und rasch benetzt werden. Um die Oberflächen von Folien oder Formkörpern zu hydrophilieren sind verschiedene Verfahren üblich. Z. B. können die Oberflächen von Kunststoffartikeln durch gasförmiges Fluor aktiviert werden. Dieses Verfahren erfordert allerdings das Arbeiten mit dem hoch- giftigen Gas Fluor unter einem erhöhten apparativen Aufwand. Daneben werden Korona- oder Plasmabehandlungen angewandt, um die Hydrophilie der Oberfläche verschiedener Materialien wie Kunststoffen oder Metallen zu erhöhen.Objects made of various synthetic materials, such as thermosetting or thermoplastic plastics, have hydrophobic surface properties. In many cases, however, hydrophobic properties are undesirable if the objects are to be glued, coated, printed, colored or lacquered, since most adhesives, coating agents or paints show insufficient adhesion to hydrophobic surfaces. Hydrophobic properties are also undesirable in the case of flat textile structures, such as in particular nonwovens. Nonwovens are e.g. B. used as cleaning and wiping cloths, dishcloths and serviettes. In these applications it is important that e.g. B. spilled liquids, such as milk, coffee, etc., quickly and completely absorbed when wiping and damp surfaces are dried as completely as possible. A cleaning cloth absorbs liquids the faster the faster they are transported on the fiber surface, whereby fibers with a hydrophilic surface are easily and quickly wetted by aqueous liquids. Various methods are customary for hydrophilizing the surfaces of foils or moldings. For example, the surfaces of plastic articles can be activated by gaseous fluorine. However, this process requires working with the highly toxic gas fluorine with an increased outlay on equipment. In addition, corona or plasma treatments are used to increase the hydrophilicity of the surface of various materials such as plastics or metals.
Zur Verbesserung der Wasseraufnahmeeigenschaften beispielsweise von Vliesstoffen werden auch oberflächenaktive hydrophilierende Agenzien, wie Emulgatoren, Tenside oder Netzmittel, eingesetzt. Hierdurch wird eine ausgezeichnete Anfangshydrophilie erreicht. Diese Vliesstoffe weisen aber den Nachteil auf, dass die hydro- philen Agenzien durch Wasser oder andere wässrige Medien allmählich ausgewaschen werden. Nach mehrmaligem Wasserkontakt wird das Erzeugnis zunehmend hydrophober. Ein weiterer Nachteil der bekannten oberflächenaktiven Agenzien besteht in der starken Herabsetzung der Grenzflächenspannung von Wasser, so dass in vielen Anwendungen, insbesondere bei Hygiene- und Windelvliesen, dieSurface-active hydrophilizing agents such as emulsifiers, surfactants or wetting agents are also used to improve the water absorption properties of nonwovens, for example. Excellent initial hydrophilicity is achieved in this way. However, these nonwovens have the disadvantage that the hydrophilic agents are gradually washed out by water or other aqueous media. After repeated contact with water, the product becomes increasingly hydrophobic. Another disadvantage of the known surface-active agents is the strong reduction in the interfacial tension of water, so that in many applications, in particular in the case of hygiene and diaper nonwovens, the
Permeationsneigung und das Netzvermögen der aufgesaugten Flüssigkeit unerwünscht erhöht ist.Permeability and the wetting capacity of the absorbed liquid is undesirably increased.
Beispiele für eine Modifizierung von Oberflächeneigenschaften hinsichtlich einer Hydrophobierung sind natürliche Oberflächen oder Oberflächen, die aus natürlichen Quellen hergestellt werden, wie beispielsweise Holz, Leder, Papier, Gips oder Beton, um sie gegen das Eindringen von Wasser zu schützen. Holz kann durch gezielte Einstellung der Wasseraufnähme vor Fäulnis bewahrt werden. Leder für Bekleidung wird so ausgerüstet, dass Wasser von der Oberfläche abperlt, um so den Tragekomfort zu erhöhen. Des Weiteren können auch die Oberflächen von hydrophilen synthetischen Materialien hydrophobiert werden.Examples of a modification of surface properties with regard to hydrophobization are natural surfaces or surfaces which are produced from natural sources, such as wood, leather, paper, plaster or concrete, in order to protect them against the ingress of water. Wood can be prevented from rotting by specifically adjusting the water intake. Leather for clothing is equipped in such a way that water rolls off the surface in order to increase comfort. Furthermore, the surfaces of hydrophilic synthetic materials can also be made hydrophobic.
Die WO 98/27263 offenbart beständig hydrophile Polymerbeschich- tungen für Polyester-, Polypropylen- und ähnliche Fasern. Die Beschichtung enthält bestimmte Polyoxypropylamine oder Polypropylenoxidpolymere und Ethylentherephthalateinheiten enthaltende hydrophile Polyestercopolymere .WO 98/27263 continuously discloses hydrophilic polymer coatings for polyester, polypropylene and similar fibers. The coating contains certain polyoxypropylamines or polypropylene oxide polymers and hydrophilic polyester copolymers containing ethylene terephthalate units.
Die WO 97/00351 beschreibt dauerhaft hydrophile Polymerbeschich- tungen für Polyester-, Polyethylen- oder Polypropylenfasern und -gewebe, die hydrophile Copolyester sowie Polypropylenoxidpolymere enthalten. Die PCT/EP01/06719 beschreibt die Verwendung von Polymeren, die Urethan- und/oder Harnstoffgruppen sowie Ammoniumgruppen aufweisen zur Modifizierung der Oberflächeneigenschaften teilchen-, li- nien-, flächenförmiger oder dreidimensionaler Gebilde.WO 97/00351 describes permanently hydrophilic polymer coatings for polyester, polyethylene or polypropylene fibers and fabrics which contain hydrophilic copolyesters and polypropylene oxide polymers. PCT / EP01 / 06719 describes the use of polymers which have urethane and / or urea groups and ammonium groups for modifying the surface properties of particle, line, sheet or three-dimensional structures.
Die PCT/EP02/02201 beschreibt die Verwendung von Polymeren, die Urethan- und/oder Harnstoffgruppen sowie anionische Gruppen aufweisen, wobei der Gehalt an Urethan- und/oder Harnstoffgruppen mindestens 2 mol/kg Polymer beträgt, zur Modifizierung deir Ober- flächeneigenschaften von teilchen-, linien-, flächenförmigen oder dreidimensionalen Gebilden.PCT / EP02 / 02201 describes the use of polymers which have urethane and / or urea groups and anionic groups, the content of urethane and / or urea groups being at least 2 mol / kg of polymer for modifying the surface properties of particles -, linear, flat or three-dimensional structures.
Bei den gemäß den beiden zuletzt genannten Dokumenten eingesetzten Polyurethanen und/oder Polyharnstoffen handelt es sich nicht um hyperverzweigte Polymere.The polyurethanes and / or polyureas used according to the last two documents mentioned are not hyperbranched polymers.
Die WO 97/02304 beschreibt hochfunktionalisierte Polyurethane und ein Verfahren zu ihrer Herstellung. Als Einsatzmöglichkeit wird eine Verwendung als hochfunktionelle Vernetzer für Polyurethan- lacke und -beschichtungen oder für Polyurethanschäume beschrieben.WO 97/02304 describes highly functionalized polyurethanes and a process for their production. One possible use is described as a highly functional crosslinker for polyurethane paints and coatings or for polyurethane foams.
Die US 5,936,055 beschreibt säurefunktionalisierte Polyurethanad- dukte mit verzweigter Struktur. Diese eignen sich zur Herstellung vernetzter wässriger Polymerlatices, die sich für Anstrichfarben eignen.No. 5,936,055 describes acid-functionalized polyurethane adducts with a branched structure. These are suitable for the production of crosslinked aqueous polymer latices, which are suitable for paints.
Die DE-A-199 04 444 beschreibt ein Verfahren zur Herstellung von Dendrimeren oder hochverzweigten Polyurethanen, die sich als Pha- senvermittler, Rheologiehilfsmittel, Thixotropiermittel, Nukleie- rungsreagenzien. oder als Wirkstoff- oder Katalysatorträger eignen.DE-A-199 04 444 describes a process for the production of dendrimers or highly branched polyurethanes which can be used as phase mediators, rheology aids, thixotropic agents, nucleating agents. or are suitable as active ingredient or catalyst carriers.
Die DE-A-100 13 187 beschreibt ein Verfahren zur Herstellung von hochfunktionellen Polyisocyanaten, die sich als Komponente zur Polyurethanherstellung eignen, wobei die resultierenden Polyurethane z. B. zur Herstellung von Lacken, Überzügen, Klebstoffen, Dichtmassen, Gießelastomeren oder Schaumstoffen eingesetzt werden können. Eine Verwendung der hochfunktionellen Polyisocyanate per se zur Modifizierung der Oberflächeneigenschaften von Substraten wird nicht beschrieben.DE-A-100 13 187 describes a process for the production of highly functional polyisocyanates which are suitable as a component for the production of polyurethane, the resulting polyurethanes e.g. B. can be used for the production of paints, coatings, adhesives, sealants, cast elastomers or foams. The use of the highly functional polyisocyanates per se for modifying the surface properties of substrates is not described.
Die DE-A-100 30 869 beschreibt ein Verfahren zur Herstellung von mehrfunktionellen Polyisocyanat-Polyadditionsprodukten, die sich als Komponente zur Polyurethanherstellung eignen. Die resultierenden Polyurethane können zur Herstellung von Lacken, Überzügen, Klebstoffen, Dichtmassen, Gießelastomeren oder Schaumstoffen ein- gesetzt werden. Eine Verwendung der Polyisocyanat-Polyadditions- produkte per se zur Modifizierung der Oberflächeneigenschaften von Substraten ist auch in diesem Dokument nicht beschrieben.DE-A-100 30 869 describes a process for the production of polyfunctional polyisocyanate polyaddition products which are suitable as a component for the production of polyurethane. The resulting polyurethanes can be used for the production of paints, coatings, adhesives, sealants, cast elastomers or foams. be set. The use of the polyisocyanate polyaddition products per se to modify the surface properties of substrates is also not described in this document.
Die unveröffentlichte deutsche Patentanmeldung P 102 04 979.3 beschreibt ein Verfahren zur Herstellung von hochfunktionellen hochverzweigten Polyharnstoffen. Diese eignen sich beispielsweise als Haftvermittler, Thixotropiermittel oder als Komponenten zur Herstellung von Lacken, Überzügen, Klebstoffen, Dichtmassen, Gießelastomeren oder Schaumstoffen.The unpublished German patent application P 102 04 979.3 describes a process for the production of highly functional highly branched polyureas. These are suitable, for example, as adhesion promoters, thixotropic agents or as components for the production of lacquers, coatings, adhesives, sealing compounds, cast elastomers or foams.
Der vorliegenden Erfindung liegt die Aufgabe zu Grunde, Substrate mit gezielt modifizierten Oberflächeneigenschaften zur Verfügung zu stellen. Die modifizierten Substrate sollen dabei das ge- wünschte Eigenschaftsprofil bezüglich ihrer Affinität gegenüber Wasser und wasserhaltigen Flüssigkeiten (hydrophile bzw. hydrophobe Ausrüstung) aufweisen. Der Erfindung liegt weiterhin die Aufgabe zu Grunde, ein Verfahren zur Erhöhung der Oberflächenhy- drophilie bzw. -hydrophobie von Substraten bereitzustellen.The object of the present invention is to provide substrates with specifically modified surface properties. The modified substrates should have the desired profile of properties with regard to their affinity for water and water-containing liquids (hydrophilic or hydrophobic finish). The invention is also based on the object of providing a method for increasing the surface hydrophilicity or hydrophobicity of substrates.
Erfindungsgemäß wird diese Aufgabe gelöst durch ein Substrat, enthaltend auf seiner Oberfläche wenigstens ein hyperverzweigtes Polymer, das Urethan- und/oder Harnstoffgruppen aufweist.According to the invention, this object is achieved by a substrate containing on its surface at least one hyperbranched polymer which has urethane and / or urea groups.
Geeignete Substrate umfassen allgemein teilchen-, linien-, flä- chenför ige oder dreidimensionale Gebilde.Suitable substrates generally comprise particulate, linear, flat or three-dimensional structures.
Der Begriff „teilchenförmige Gebilde" umfasst den Bereich der feinen Pigmente bis hin zu makroskopischen Partikeln. Dazu zählen beispielsweise solche mit einer Teilchengröße von 1 nm bis 10 mm, wie 10 nm bis 1 mm, speziell 1 μm bis 0,1 mm, die vorzugsweise in einem Medium dispergierbar oder dispergiert sind. Als Beispiele lassen sich Pigmente, mineralische oder metallische Füllstoffe oder unbelebte organische Materialien nennen.The term “particulate structures” encompasses the range from fine pigments to macroscopic particles. These include, for example, those with a particle size of 1 nm to 10 mm, such as 10 nm to 1 mm, especially 1 μm to 0.1 mm, which are preferably are dispersible or dispersed in a medium, examples being pigments, mineral or metallic fillers or inanimate organic materials.
Unter „linienförmigen Gebilden" werden insbesondere Fasern, Fila- mente, Garne, Fäden und dergleichen verstanden.“Line-like structures” mean in particular fibers, filaments, yarns, threads and the like.
„Flächenförmige Gebilde" sind insbesondere Gewebe, Gewirke, Filze, Vliese oder Vliesstoffe, wobei Letztere bevorzugt sind. Zur Herstellung eines Vliesstoffs wird ein Gefüge von Fasern (Vlies) abgelegt, das anschließend nach unterschiedlichen Verfahren zu Vliesstoffen verfestigt wird. Z. B. wird das Vlies mit einem wässrigen Bindemittel, z. B. einem Polymerlatex, behandelt und anschließend, gegebenenfalls nach Entfernung von überschüssigem Bindemittel, getrocknet und gegebenenfalls gehärtet. Flächen- förmige Gebilde sind auch Folien, Papier und vergleichbare zwei- dimensionale Gebilde.“Sheet-like structures” are, in particular, woven fabrics, knitted fabrics, felts, nonwovens or nonwovens, the latter being preferred. To produce a nonwoven, a structure of fibers (nonwoven) is deposited, which is then solidified into nonwovens using different methods treated with an aqueous binder, for example a polymer latex, and then dried, if appropriate after removal of excess binder, and optionally hardened. shaped structures are also foils, paper and comparable two-dimensional structures.
Unter „flächenförmigen textilen Gebilden" werden im Rahmen der vorliegenden Anmeldung auch TextilVerbundstoffe, wie z. B. Teppiche, kaschierte und laminierte Textilien etc., verstanden.In the context of the present application, “sheet-like textile structures” are also understood to mean textile composite materials, such as carpets, laminated and laminated textiles, etc.
„Dreidimensionale Gebilde" sind allgemein Formkörper unterschiedlichster Dimensionen. Dazu zählen insbesondere Formkörper aus Holz, Papier, Metallen, Kunststoffen, keramischen Trägern, Geweben aus natürlichen oder synthetischen Fasern in Form von Fluffs, Tissues etc."Three-dimensional structures" are generally shaped bodies of various dimensions. These include, in particular, shaped bodies made of wood, paper, metals, plastics, ceramic supports, fabrics made of natural or synthetic fibers in the form of fluffs, tissues etc.
Bevorzugte Ausgestaltungen des erfindungsgemäßen Gebildes sind linien- oder flächenförmige textile Gebilde. Andere bevorzugte Ausgestaltungen des erfindungsgemäßen Gebildes sind Kunststofffolien oder Kunststoffformkörper.Preferred configurations of the structure according to the invention are linear or flat textile structures. Other preferred configurations of the structure according to the invention are plastic films or molded plastic bodies.
Vorzugsweise umfassen die erfindungsgemäß eingesetzten Gebilde wenigstens ein natürliches oder synthetisches polymeres Material.The structures used according to the invention preferably comprise at least one natural or synthetic polymeric material.
Beispiele für derartige Materialien sind:Examples of such materials are:
1. Polymere von Mono- und Diolefinen, beispielsweise Polypropy- len, Polyisobutylen, Polybuten-1, Poly-4-methyl-penten-l, Po- lyisopren oder Polybutadien sowie Polymerisate von Cycloole- finen, wie z. B. von Cyclopenten oder Norbornen; ferner Poly- ethylen (das gegebenenfalls vernetzt sein kann), z. B. Poly- ethylen hoher Dichte (HDPE) , Polyethylen hoher Dichte und ho- her Molmasse (HDPE-HMW), Polyethylen hoher Dichte und ultrahoher Molmasse (HDPE-UHMW), Polyethylen mittlerer Dichte (MDPE), Polyethylen niederer Dichte (LDPE), lineares Polyethylen niederer Dichte (LLDPE), verzweigtes Polyethylen niederer Dichte (VLDPE).1. Polymers of mono- and diolefins, for example polypropylene, polyisobutylene, polybutene-1, poly-4-methyl-pentene-1, polyisoprene or polybutadiene and polymers of cycloolefins, such as, for. B. of cyclopentene or norbornene; also polyethylene (which may or may not be crosslinked), e.g. B. High Density Polyethylene (HDPE), High Density and High Molecular Weight Polyethylene (HDPE-HMW), High Density and Ultra High Molecular Weight Polyethylene (HDPE-UHMW), Medium Density Polyethylene (MDPE), Low Density Polyethylene (LDPE) , linear low density polyethylene (LLDPE), branched low density polyethylene (VLDPE).
Polyolefine, d. h. Polymere von Monoolefinen, wie sie beispielhaft im vorstehenden Absatz erwähnt sind, insbesondere Polyethylen. und Polypropylen, können nach verschiedenen Verfahren hergestellt werden, insbesondere radikalisch oder mit- tels Katalysator, wobei der Katalysator gewöhnlich ein oder mehrere Metalle der Gruppe IVb, Vb, VIb oder VIII enthält. Diese Katalysatorsysteme werden gewöhnlich als Phillips, Standard Oil Indiana, Ziegler (-Natta), TNZ (DuPont), Metal- locen oder Single Site Katalysatoren (SSC) bezeichnet. 2 . Mischungen der unter 1. genannten Polymeren, z. B. Mischungen von Polypropylen mit Polyisobutylen, Polypropylen mit Polyethylen (z. B. PP/HDPE, PP/LDPE) und Mischungen verschiedener Polyethylentypen (z. B. LDPE/HDPE) .Polyolefins, ie polymers of monoolefins, as mentioned by way of example in the preceding paragraph, in particular polyethylene. and polypropylene can be produced by various processes, in particular by free radicals or by means of a catalyst, the catalyst usually containing one or more metals from group IVb, Vb, VIb or VIII. These catalyst systems are commonly referred to as Phillips, Standard Oil Indiana, Ziegler (-Natta), TNZ (DuPont), Metal Locen or Single Site Catalysts (SSC). 2nd Mixtures of the polymers mentioned under 1., for. B. Mixtures of polypropylene with polyisobutylene, polypropylene with polyethylene (e.g. PP / HDPE, PP / LDPE) and mixtures of different types of polyethylene (e.g. LDPE / HDPE).
3. Copolymere von Mono- und Diolefinen untereinander oder mit anderen Vinylmonomeren, wie z. B. Ethylen-Propylen-Copoly- mere, lineares Polyethylen niederer Dichte (LLDPE) und Mischungen desselben mit Polyethylen niederer Dichte (LDPE), Propylen-Buten-1-Copolymere, Propylen-Isobutylen-Copolymere, Ethylen-Buten-1-Copolymere, Ethylen-Hexen-Copolymere, Ethy- len-Methylpenten-Copolymere, Ethylen-Hepten-Copolymere, Ethy- len-Octen-Copolymere, Propylen-Butadien-Copolymere, Isobuty- len-Isopren-Copolymere, Ethylen-Alkylacrylat-Copolymere, Ethylen-Alkylmethacrylat-Copolymere, Ethylen-Vinylacetat-Co- polymere und deren Copolymere mit Kohlenstoffmonoxid, oder Ethylen-Acrylsäure-Copolyere und deren Salze (Ionomere), sowie Terpolymere von Ethylen mit Propylen und einem Dien, wie Hexandien, Dicyclopentadien oder Ethylidennorbornen; ferner Mischungen solcher Copolymere untereinander und mit unter 1. genannten Polymeren, z. B. Polypropylen/Ethylen-Propylen-Co- polymere, LDPE/Ethylen-Vinylacetat-Copolymere, LDPE/Ethylen- Acrylsäure-Copolymere, LLDPE/Ethylen-Vinylacetat-Copolymere, LLDPE/Ethylen-Acrylsäure-Copolymere und alternierend oder statistisch aufgebaute Polyalkylen/Kohlenstoffmonoxid-Copoly- mere und deren Mischungen mit anderen Polymeren, wie z . B. Polyamiden.3. Copolymers of mono- and diolefins with one another or with other vinyl monomers, such as. B. ethylene-propylene copolymers, linear low-density polyethylene (LLDPE) and mixtures thereof with low-density polyethylene (LDPE), propylene-butene-1 copolymers, propylene-isobutylene copolymers, ethylene-butene-1 copolymers, Ethylene-hexene copolymers, ethylene-methylpentene copolymers, ethylene-heptene copolymers, ethylene-octene copolymers, propylene-butadiene copolymers, isobutylene-isoprene copolymers, ethylene-alkyl acrylate copolymers, ethylene Alkyl methacrylate copolymers, ethylene-vinyl acetate copolymers and their copolymers with carbon monoxide, or ethylene-acrylic acid copolymers and their salts (ionomers), and also terpolymers of ethylene with propylene and a diene, such as hexanediene, dicyclopentadiene or ethylidene norbornene; furthermore mixtures of such copolymers with one another and with polymers mentioned under 1., for. B. polypropylene / ethylene-propylene copolymers, LDPE / ethylene-vinyl acetate copolymers, LDPE / ethylene-acrylic acid copolymers, LLDPE / ethylene-vinyl acetate copolymers, LLDPE / ethylene-acrylic acid copolymers and alternating or randomly constructed polyalkylene / Carbon monoxide copolymers and their mixtures with other polymers, such as. B. polyamides.
4. Kohlenwasserstoffharze, inklusive hydrierte Modifikationen davon (z. B. Klebrigmacherharze) und Mischungen von Polyalky- lenen und Stärke.4. Hydrocarbon resins, including hydrogenated modifications thereof (eg tackifier resins) and mixtures of polyalkylenes and starch.
5. Polystyrol, Poly-(p-methylstyrol) , Poly-(α-methylstyrol) .5. Polystyrene, poly- (p-methylstyrene), poly- (α-methylstyrene).
6. Copolymere von Styrol oder α-Methylstyrol mit Dienen oder Acrylderivaten, wie z. B. Styrol-Butadien, Styrol-Acrylni- tril, Styrol-Alkylmethacrylat, Styrol-Butadien-Alkylacrylat und -methacrylat, Styrol-Maleinsäureanhydrid, Styrol-Acrylni- tril-Methylacrylat; Mischungen von hoher Schlagzähigkeit aus Styrol-Copolymeren und einem anderen Polymer, wie z. B. einem Polyacrylat, einem Dien-Polymeren oder einem Ethylen-Propy- len-Dien-Terpolymeren; sowie Block-Copolymere des Styrols, wie z. B. Styrol-Butadien-Styrol, Styrol-Isopren-Styrol, Sty- rol-Ethylen/Butylen-Styrol oder Styrol-Ethylen/Propylen-Sty- rol. 7. Pfropfcopolymere von Styrol oder α-Methylstyrol, wie z. B. Styrol auf Polybutadien, Styrol auf Polybutadien-Styrol- oder Polybutadien-Acrylnitril-Copolymere, Styrol und Acrylnitril (bzw. Methacrylnitril) auf Polybutadien; Styrol, Acrylnitril6. Copolymers of styrene or α-methylstyrene with dienes or acrylic derivatives, such as. B. styrene-butadiene, styrene-acrylonitrile, styrene-alkyl methacrylate, styrene-butadiene-alkyl acrylate and methacrylate, styrene-maleic anhydride, styrene-acrylonitrile-methyl acrylate; Mixtures of high impact strength from styrene copolymers and another polymer, such as. B. a polyacrylate, a diene polymer or an ethylene-propylene-diene terpolymer; and block copolymers of styrene, such as. B. styrene-butadiene-styrene, styrene-isoprene-styrene, styrene-ethylene / butylene-styrene or styrene-ethylene / propylene-styrene. 7. graft copolymers of styrene or α-methylstyrene, such as. B. styrene on polybutadiene, styrene on polybutadiene-styrene or polybutadiene-acrylonitrile copolymers, styrene and acrylonitrile (or methacrylonitrile) on polybutadiene; Styrene, acrylonitrile
5 und Methylmethacrylat auf Polybutadien; Styrol und Maleinsäureanhydrid auf Polybutadien; Styrol, Acrylnitril und Maleinsäureanhydrid oder Maleinsäureimid auf Polybutadien; Styrol und Maleinsäureimid auf Polybutadien, Styrol und Alkylacry- late bzw. Alkylmethacrylate auf Polybutadien, Styrol und5 and methyl methacrylate on polybutadiene; Styrene and maleic anhydride on polybutadiene; Styrene, acrylonitrile and maleic anhydride or maleimide on polybutadiene; Styrene and maleimide on polybutadiene, styrene and alkyl acrylates or alkyl methacrylates on polybutadiene, styrene and
10 Acrylnitril auf Ethylen-Propylen-Dien-Terpolymeren, Styrol und Acrylnitril auf Polyalkylacrylaten oder Polyalkylmetha- crylaten, Styrol und Acrylnitril auf Acrylat-Butadien-Copoly- meren, sowie deren Mischungen mit den unter 6. genannten Co- polymeren, wie sie z. B. als so genannte ABS-, MBS-, ASA-10 acrylonitrile on ethylene-propylene-diene terpolymers, styrene and acrylonitrile on polyalkyl acrylates or polyalkyl methacrylates, styrene and acrylonitrile on acrylate-butadiene copolymers, and their mixtures with the copolymers mentioned under 6, as described, for. B. as so-called ABS, MBS, ASA
15 oder AES-Polymere bekannt sind.15 or AES polymers are known.
8. Halogenhaltige Polymere, wie z. B. Polychloropren, Chlorkautschuk, chloriertes und bromiertes Copolymer aus Isobutylen- Isopren (Halobutylkautschuk) , chloriertes oder chlorsulfo-8. Halogen-containing polymers, such as. B. polychloroprene, chlorinated rubber, chlorinated and brominated copolymer of isobutylene-isoprene (halobutyl rubber), chlorinated or chlorosulfo-
20 niertes Polyethylen, Copolymere von Ethylen und chloriertem Ethylen, Epichlorhydrinhomo- und -copolymere, insbesondere Polymere aus halogenhaltigen Vinylverbindungen, wie z. B. Polyvinylchlorid, Polyvinylidenchlorid, Polyvinylfluorid, Poly- vinylidenfluorid; sowie deren Copolymere, wie Vinylchlorid-20 nierte polyethylene, copolymers of ethylene and chlorinated ethylene, epichlorohydrin homo- and copolymers, in particular polymers of halogen-containing vinyl compounds, such as. B. polyvinyl chloride, polyvinylidene chloride, polyvinyl fluoride, polyvinylidene fluoride; and their copolymers, such as vinyl chloride
25 Vinylidenchlorid, Vinylchlorid-Vinylacetat oder Vinylidench- lorid-Vinylaceta .25 vinylidene chloride, vinyl chloride-vinyl acetate or vinylidene chloride-vinyl acetate.
9. Polymere, die sich von α,ß-ungesättigten Säuren und deren Derivaten ableiten, wie Polyacrylate und Polymethacrylate, mit9. Polymers derived from α, β-unsaturated acids and their derivatives, such as polyacrylates and polymethacrylates
30 Butylacrylat schlagzäh modifizierte Polymethylmethacrylate, Polyacrylamide und Polyacrylnitrile.30 butyl acrylate impact modified polymethyl methacrylates, polyacrylamides and polyacrylonitriles.
10. Copolymere der unter 9. genannten Monomeren untereinander oder mit anderen ungesättigten Monomeren, wie z. B. Acrylni-10. Copolymers of the monomers mentioned under 9 with each other or with other unsaturated monomers, such as. B. Acrylic
35 tril-Butadien-Copolymere, Acrylnitril-Alkylacrylat-Copoly- mere, Acrylnitril-Alkoxyalkylacrylat-Copolymere, Acrylnitril- Vinylhalogenid-Copolymere oder Acrylnitril-Alkylmethacrylat- Butadien-Terpolymere.35 tril-butadiene copolymers, acrylonitrile-alkyl acrylate copolymers, acrylonitrile-alkoxyalkyl acrylate copolymers, acrylonitrile-vinyl halide copolymers or acrylonitrile-alkyl methacrylate-butadiene terpolymers.
40 11. Polymere, die sich von ungesättigten Alkoholen und Aminen bzw. deren Acylderivaten oder Acetalen ableiten, wie Polyvi- nylalkohol, Polyvinylacetat, -stearat, -benzoat, -maleat, Po- lyvinylbutyral, Polyallylphthalat, Polyallylmelamin; sowie deren Copolymere mit in Punkt 1 genannten Olefinen.40 11. Polymers derived from unsaturated alcohols and amines or their acyl derivatives or acetals, such as polyvinyl alcohol, polyvinyl acetate, stearate, benzoate, maleate, polyvinyl butyral, polyallyl phthalate, polyallyl melamine; and their copolymers with olefins mentioned in point 1.
45 12. Homo- und Copolymere von cyclischen Ethern, wie Polyalkylen- glykole, Polyethylenoxid, Polypropylenoxid, oder deren Copolymere mit Bisglycidylethern.45 12. Homopolymers and copolymers of cyclic ethers, such as polyalkylene glycols, polyethylene oxide, polypropylene oxide, or their copolymers with bisglycidyl ethers.
5 13. Polyacetale, wie Polyoxymethylen, sowie solche Polyoxymethy- lene, die Comonomere, wie z. B. Ethylenoxid, enthalten; Polyacetale, die mit thermoplastischen Polyurethanen, Acrylaten oder MBS modifiziert sind.5 13. Polyacetals, such as polyoxymethylene, and also such polyoxymethylene, the comonomers, such as. B. ethylene oxide; Polyacetals modified with thermoplastic polyurethanes, acrylates or MBS.
10 14. Polyphenylenoxide und -sulfide und deren Mischungen mit Sty- rolpolymeren oder Polyamiden.10 14. Polyphenylene oxides and sulfides and their mixtures with styrene polymers or polyamides.
15. Polyurethane, die sich von Polyethern, Polyestern und Polybu- tadienen mit endständigen Hydroxylgruppen einerseits und ali-15. Polyurethanes, which are derived from polyethers, polyesters and polybutadienes with terminal hydroxyl groups on the one hand and ali-
15 phatischen oder aromatischen Polyisocyanaten andererseits ableiten, sowie deren Vorprodukte.Derive 15 phatic or aromatic polyisocyanates, on the other hand, and their precursors.
16. Polyamide und Copolyamide, die sich von Diaminen und Dicar- bonsäuren und/oder von Aminocarbonsäuren oder den entspre- 0 chenden Lactamen ableiten, wie Polyamid 4, Polyamid 6, Polyamid 6/6, 6/10, 6/9, 6/12, 4/6, 12/12, Polyamid 11, Polyamid 12, aromatische Polyamide, z. B. ausgehend von p-Phenylendia- min und Adipinsäure; Polyamide, hergestellt aus Hexamethylen- diamin und Iso- und/oder Terephthalsäure und gegebenenfalls 5 einem Elastomer als Modifikator, z. B. Poly-2,4,4-trimethyl- hexamethylenterephthalamid oder Poly-m-phenylen-isophthala- mid. Geeignet sind auch Block-Copolymere der vorstehend genannten Polyamide mit Polyolefinen, Olefin-Copolymeren, Iono- meren oder chemisch gebundenen oder gepfropften Elastomeren; 0 oder mit Polyethern, wie z. B. mit Polyethylenglykol, Poly- propylenglykol oder Polytetramethylenglykol. Geeignet sind ferner mit EPDM oder ABS modifizierte Polyamide oder Copolyamide sowie während der Verarbeitung kondensierte Polyamide ( "RIM-Polyamidsysteme" ) . 516. Polyamides and copolyamides which are derived from diamines and dicarboxylic acids and / or from aminocarboxylic acids or the corresponding lactams, such as polyamide 4, polyamide 6, polyamide 6/6, 6/10, 6/9, 6 / 12, 4/6, 12/12, polyamide 11, polyamide 12, aromatic polyamides, e.g. B. starting from p-phenylenediamine and adipic acid; Polyamides made from hexamethylene diamine and iso- and / or terephthalic acid and optionally an elastomer as a modifier, e.g. B. poly-2,4,4-trimethyl-hexamethylene terephthalamide or poly-m-phenylene-isophthalamide. Block copolymers of the abovementioned polyamides with polyolefins, olefin copolymers, ionomers or chemically bonded or grafted elastomers are also suitable; 0 or with polyethers, such as. B. with polyethylene glycol, polypropylene glycol or polytetramethylene glycol. Also suitable are polyamides or copolyamides modified with EPDM or ABS and polyamides condensed during processing (“RIM polyamide systems”). 5
17. Polyharnstoffe, Polyimide, Polyamidimide, Polyetherimide, Po- lyesterimide, Polyhydantoine und Polybenzimidazole.17. Polyureas, polyimides, polyamideimides, polyetherimides, polyesterimides, polyhydantoins and polybenzimidazoles.
18. Polyester, die sich von Dicarbonsäuren und Dialkoholen und/ 0 oder von Hydroxycarbonsäuren oder den entsprechenden Lactonen ableiten, wie Polyethylenterephthalat, Polybutylenterephtha- lat, Poly-l,4-dimethylolcyclohexanterephthalat, Polyhydroxy- benzoate sowie Block-Polyetherester, die sich von Polyethern mit Hydroxylendgruppen ableiten; ferner mit Polycarbonaten 5 oder MBS modifizierte Polyester. 19. Polycarbonate und Polyestercarbonate.18. Polyesters which are derived from dicarboxylic acids and dialcohols and / or from hydroxycarboxylic acids or the corresponding lactones, such as polyethylene terephthalate, polybutylene terephthalate, poly-1, 4-dimethylolcyclohexane terephthalate, polyhydroxybenzoates and block polyether esters which differ from polyethers Derive hydroxyl end groups; furthermore polyesters modified with polycarbonates 5 or MBS. 19. Polycarbonates and polyester carbonates.
20. Polysulfone, Polyethersulfone und Polyetherketone.20. Polysulfones, polyether sulfones and polyether ketones.
5 21. Vernetzte Polymere, die sich von Aldehyden einerseits und5 21. Cross-linked polymers that differ from aldehydes on the one hand and
Phenolen, Harnstoff oder Melamin andererseits ableiten, wie Phenol-Formaldehyd-, Harnstoff-Formaldehyd- und Melamin-For- maldehydharze.Derive phenols, urea or melamine, on the other hand, such as phenol-formaldehyde, urea-formaldehyde and melamine-formaldehyde resins.
10 22. Trocknende und nicht-trocknende Alkydharze.10 22. Drying and non-drying alkyd resins.
23. Ungesättigte Polyesterharze, die sich von Copolyestern gesättigter und ungesättigter Dicarbonsäuren mit mehrwertigen Alkoholen, sowie Vinylverbindungen als Vernetzungsmittel ablei-23. Unsaturated polyester resins derived from copolyesters of saturated and unsaturated dicarboxylic acids with polyhydric alcohols and vinyl compounds as crosslinking agents.
15 ten, wie auch deren halogenhaltige, schwerbrennbare Modifikationen.15 th, as well as their halogen-containing, flame-retardant modifications.
24. Vernetzbare Acrylharze, die sich von substituierten Acrylsäu- reestern ableiten, wie z. B. von Epoxyacrylaten, Urethanacry-24. Crosslinkable acrylic resins which are derived from substituted acrylic acid esters, such as, for. B. of epoxy acrylates, urethane acrylic
20 laten oder Polyesteracrylaten.20 latates or polyester acrylates.
25. Alkydharze, Polyesterharze und Acrylatharze, die mit Melamin- harzen, Harnstoffharzen, Isocyanaten, Isocyanuraten, Polyiso- cyanaten oder Epoxidharzen vernetzt sind. 525. Alkyd resins, polyester resins and acrylate resins which are crosslinked with melamine resins, urea resins, isocyanates, isocyanurates, polyisocyanates or epoxy resins. 5
26. Vernetzte Epoxidharze, die sich von aliphatischen, cycloali- phatischen, heterocyclischen oder aromatischen Glycidylver- bindungen ableiten, z. B. Produkte von Bisphenol-A-diglyci- dylethern, Bisphenol-F-diglycidylethern, die mittels üblichen 0 Härtern, wie z . B. Anhydriden oder Aminen mit oder ohne Beschleunigern vernetzt werden.26. Crosslinked epoxy resins derived from aliphatic, cycloaliphatic, heterocyclic or aromatic glycidyl compounds, eg. B. Products of bisphenol A diglycidyl ethers, bisphenol F diglycidyl ethers, which by means of conventional 0 hardeners, such as. B. anhydrides or amines with or without accelerators.
27. Natürliche Polymere, wie Cellulose (beispielsweise Holz oder Baumwolle), Naturkautschuk, Gelatine, sowie deren polymerho- 5 molog chemisch abgewandelte Derivate, wie Celluloseacetate, -propionate und -butyrate, bzw. die Celluloseether, wie Me- thylcellulose; sowie Kolophoniumharze und Derivate.27. Natural polymers, such as cellulose (for example wood or cotton), natural rubber, gelatin, and their polymer-homologously chemically modified derivatives, such as cellulose acetates, propionates and butyrates, or the cellulose ethers, such as methyl cellulose; as well as rosins and derivatives.
28. Geeignet sind ganz allgemein binäre und polynäre Mischungen 0 (Polyblends) der vorgenannten Polymeren, wie z. B. PP/EPDM,28. Generally suitable are binary and polynary mixtures 0 (polyblends) of the aforementioned polymers, such as, for. B. PP / EPDM,
Polya id/EPDM oder ABS, PVC/EVA, PVC/ABS, PVC/MBS, PC/ABS, PC/ASA, PC/PBT, PVC/CPE, PVC/Acrylate, POM/thermoplastisches PUR, PC/thermoplastisches PUR, POM/Acrylat, POM/MBS, PPO/ HIPS, PPO/PA 6.6 und Copolymere, PA/HDPE, PA/PP, PA/PPO, PBT/ 5 PC/ABS oder PBT/PET/PC. Bevorzugt sind teilchen-, linien-, flächenförmige oder dreidimensionale Gebilde, die wenigstens ein polymeres Material umfassen, das ausgewählt ist unter Polyolefinen, Polyestern, Polyamiden, Polyacrylnitril, Polyaromaten, Styrol-Acrylnitril-Copolymeren (SAN), Acrylnitril-Butadien-Styrol-Copolymeren (ABS), Polyurethanen und Mischungen (Polyblends) der vorgenannten Polymeren.Polya id / EPDM or ABS, PVC / EVA, PVC / ABS, PVC / MBS, PC / ABS, PC / ASA, PC / PBT, PVC / CPE, PVC / Acrylate, POM / thermoplastic PUR, PC / thermoplastic PUR, POM / Acrylate, POM / MBS, PPO / HIPS, PPO / PA 6.6 and copolymers, PA / HDPE, PA / PP, PA / PPO, PBT / 5 PC / ABS or PBT / PET / PC. Particulate, linear, sheet-like or three-dimensional structures are preferred which comprise at least one polymeric material which is selected from polyolefins, polyesters, polyamides, polyacrylonitrile, polyaromatics, styrene-acrylonitrile copolymers (SAN), acrylonitrile-butadiene-styrene copolymers (ABS), polyurethanes and mixtures (polyblends) of the aforementioned polymers.
Vorzugsweise handelt es sich bei den erfindungsgemäß eingesetzten Gebilden um Kunststofffasern insbesondere aus Polyolefinen, wie z. B. Polyethylen und Polypropylen, Polyestern, Polyacrylnitril und Polyamiden, wie z. B. Polyamid 6 und Polyamid 66.Preferably, the structures used according to the invention are plastic fibers, in particular made of polyolefins, such as, for. As polyethylene and polypropylene, polyesters, polyacrylonitrile and polyamides, such as. B. Polyamide 6 and Polyamide 66.
Vorzugsweise handelt es sich bei den erfindungsgemäß eingesetzten Gebilden weiterhin um flächenförmige Gebilde und insbesondere um Filme oder Folien. Diese enthalten vorzugsweise ein Polymer, das ausgewählt ist unter Polyolefinen, wie Polyethylen und/oder Polypropylen, Polymeren halogenierter Monomerer, wie z. B. Polyvinylchlorid und/oder Polytetrafluorethylen, Polyestern und Mischungen davon.The structures used according to the invention are preferably sheet-like structures and in particular films or foils. These preferably contain a polymer which is selected from polyolefins, such as polyethylene and / or polypropylene, polymers of halogenated monomers, such as, for. B. polyvinyl chloride and / or polytetrafluoroethylene, polyesters and mixtures thereof.
Vorzugsweise handelt es sich bei dem erfindungsgemäß eingesetzten Gebilde weiterhin um einen Formkörper. Dieser umfasst vorzugsweise wenigstens ein polymeres Material, das ausgewählt ist unter Polyolefinen, wie z. B. Polyethylen und/oder Polypropylen, Poly- aromaten, wie Polystyrol, Polymeren halogenierter Monomerer, wie Polyvinylchlorid und/oder Polytetrafluorethylen, Polyestern, Polyacrylnitril, Styrol-Acrylnitril-Copolymeren, Acrylnitril-Buta- dien-Styrol-Copolymeren, Polyamiden, wie Polyamid 6 und/oder Polyamid 66, Polyurethanen und Mischungen davon.The structure used according to the invention is preferably still a shaped body. This preferably comprises at least one polymeric material which is selected from polyolefins, such as. B. polyethylene and / or polypropylene, polyaromatics, such as polystyrene, polymers of halogenated monomers, such as polyvinyl chloride and / or polytetrafluoroethylene, polyesters, polyacrylonitrile, styrene-acrylonitrile copolymers, acrylonitrile-butadiene-styrene copolymers, polyamides, such as polyamide 6 and / or polyamide 66, polyurethanes and mixtures thereof.
Erfindungsgemäß wird zur Modifizierung der Oberflächeneigenschaften der Substrate wenigstens ein Polyurethan-Polymer eingesetzt. Der Begriff "Polyurethane" umfasst im Rahmen dieser Erfindung nicht nur solche Polymere, deren Wiederholungseinheiten durch Urethangruppen miteinander verbunden sind, sondern ganz allgemein Polymere, die durch Umsetzung wenigstens eines Di- und/oder Poly- isocyanats mit wenigstens einer Verbindung erhältlich sind, die mindestens eine gegenüber Isocyanatgruppen reaktive Gruppe aufweist. Dazu zählen Polymere, deren Wiederholungseinheiten neben Urethangruppen auch durch Harnstoff-, Allophanat-, Biuret-, Car- bodiimid-, Amid-, Uretonimin-, Uretdion-, Isocyanurat- oder Oxa- zolidon-(Oxazolidinon-)Gruppen verbunden sind (siehe beispielsweise Kunststofftaschenbuch, Saechtling, 26. Aufl., S. 491ff, Carl-Hanser-Verlag, München 1995). Der Begriff "Polyurethane" um- fasst insbesondere Polymere, die Urethan- und/oder Harnstoffgruppen aufweisen. Bevorzugt sind Polyurethane, die ein gewichtsmittleres Molekulargewicht im Bereich von etwa 500 bis 100000, bevorzugt 1000 bis 50000, aufweisen.According to the invention, at least one polyurethane polymer is used to modify the surface properties of the substrates. In the context of this invention, the term “polyurethanes” includes not only those polymers whose repeating units are connected to one another by urethane groups, but very generally polymers that can be obtained by reacting at least one di- and / or poly-isocyanate with at least one compound which has at least one has a group reactive toward isocyanate groups. These include polymers, the repeating units of which, in addition to urethane groups, are also linked by urea, allophanate, biuret, carbodiimide, amide, uretonimine, uretdione, isocyanurate or oxazolidone (oxazolidinone) groups (see for example Plastic pocket book, Saechtling, 26th edition, p. 491ff, Carl-Hanser-Verlag, Munich 1995). The term "polyurethanes" includes in particular polymers which have urethane and / or urea groups. Polyurethanes which have a weight-average molecular weight in the range from about 500 to 100,000, preferably 1000 to 50,000, are preferred.
Bevorzugt liegt ihr Gehalt an Urethan- und/oder Harnstoffgruppen (und, falls vorhanden, weiteren durch Umsetzung einer Isocyanat- gruppe mit einer demgegenüber reaktiven Gruppe mit aktivem WasserStoffatom erhaltenen Gruppen) in einem Bereich von 0,5 bis 10 mol/kg, besonders bevorzugt 1 bis 10 mol/kg, insbesondere 2 bis 8 mol/kg.Their content of urethane and / or urea groups (and, if present, further groups obtained by reacting an isocyanate group with a group which is reactive toward this with an active hydrogen atom) is preferably in a range from 0.5 to 10 mol / kg, particularly preferably 1 to 10 mol / kg, in particular 2 to 8 mol / kg.
Im Rahmen der vorliegenden Erfindung umfasst der Begriff "hyperverzweigte Polymere" ganz allgemein Polymere, die sich durch eine verzweigte Struktur und eine hohe Funktionalität auszeichnen. Zur allgemeinen Definition hyperverzweigter Polymere wird auch auf P. J. Flory, J. Am. Chem. Soc. 1952, 74, 2718 und H. Frey et al., Chem. Eur. J. 2000, 6, Nr. 14, 2499 Bezug genommen. Vorzugsweise weisen die erfindungsgemäß eingesetzten hyperverzweigten Polymere neben Urethan- und/oder Harnstoffgruppen (bzw. weiteren aus der Reaktion von Isocyanatgruppen hervorgehenden Gruppen) wenigstens vier weitere funktionelle Gruppen auf. Bevorzugt beträgt der Anteil an funktioneilen Gruppen 4 bis 100, besonders bevorzugt 5 bis 30 und insbesondere 6 bis 20.In the context of the present invention, the term “hyperbranched polymers” generally encompasses polymers which are distinguished by a branched structure and high functionality. For the general definition of hyperbranched polymers, reference is also made to P. J. Flory, J. Am. Chem. Soc. 1952, 74, 2718 and H. Frey et al., Chem. Eur. J. 2000, 6, No. 14, 2499. In addition to urethane and / or urea groups (or further groups resulting from the reaction of isocyanate groups), the hyperbranched polymers preferably have at least four further functional groups. The proportion of functional groups is preferably 4 to 100, particularly preferably 5 to 30 and in particular 6 to 20.
Zu den "hyperverzweigten Polymeren" im Sinne der Erfindung zählen auch Sternpolymere, Dendrimere (dendritische Polymere) und davon verschiedene hochmolekulare Polymere, wie z. B. Kammpolymere.The "hyperbranched polymers" in the sense of the invention also include star polymers, dendrimers (dendritic polymers) and various high molecular weight polymers, such as, for. B. comb polymers.
"Sternpolymere" sind Polymere, bei denen von einem Zentrum drei oder mehr Ketten ausgehen. Das Zentrum kann dabei ein einzelnes Atom oder eine Atomgruppe sein. "Dendrimere" (dendritische Polymere, Kaskadenpolymere, Arborole, isotrop verzweigte Polymere, isoverzweigte Polymere, Starburst-Polymere) sind molekular einheitliche Makromoleküle mit einem hochsymmetrischen Aufbau. Den- drimere leiten sich strukturell ab von den Sternpolymeren, wobei die einzelnen Ketten jeweils ihrerseits sternförmig verzweigt sind. Sie entstehen ausgehend von kleinen Molekülen durch eine sich ständig wiederholende Reaktionsfolge, wobei immer höhere Verzweigungen resultieren, an deren Enden sich jeweils funktio- nelle Gruppen befinden, die wiederum Ausgangspunkt für weitere Verzweigungen sind. So wächst mit jedem Reaktionsschritt die Zahl der Monomer-Endgruppen exponentiell an, wobei am Ende eine kugelförmige Baumstruktur entsteht. Ein charakteristisches Merkmal der Dendrimere ist die Anzahl der zu ihrem Aufbau durchgeführten Re- aktionsstufen (Generationen) . Auf Grund ihres einheitlichen Auf- baus weisen Dendrimere in der Regel eine definierte Molmasse auf. Weiterhin geeignet sind sowohl molekular wie strukturell uneinheitliche "hyperverzweigte Polymere", die Seitenketten unterschiedlicher Länge und Verzweigung sowie eine Molmassenverteilung aufweisen."Star polymers" are polymers in which three or more chains start from a center. The center can be a single atom or a group of atoms. "Dendrimers" (dendritic polymers, cascade polymers, arborols, isotropically branched polymers, iso-branched polymers, starburst polymers) are molecularly uniform macromolecules with a highly symmetrical structure. Structurally, the dimers derive from the star polymers, the individual chains each being branched in a star shape. They arise from small molecules through a constantly repeating sequence of reactions, resulting in ever higher branches, at the ends of which there are functional groups, which in turn are the starting point for further branches. The number of monomer end groups increases exponentially with each reaction step, resulting in a spherical tree structure at the end. A characteristic feature of the dendrimers is the number of reaction stages (generations) carried out to build them up. Due to their uniform structure, dendrimers generally have a defined molar mass. Also suitable are both molecularly and structurally non-uniform "hyperbranched polymers" which have side chains of different lengths and branches as well as a molecular weight distribution.
Zur Synthese dieser hyperverzweigten Polymere eignen sich insbesondere so genannte ABx-Monomere. Diese weisen zwei verschiedene funktionelle Gruppen A und B auf, die unter Bildung einer Verknüpfung miteinander reagieren können. Die funktioneile Gruppe A ist dabei nur einmal pro Molekül enthalten und die funktioneile Gruppe B zweifach oder mehrfach. Durch die Reaktion der besagten ABx-Monomere miteinander entstehen unvernetzte Polymere mit regelmäßig angeordneten Verzweigungsstellen. Die Polymere weisen an den Kettenenden fast ausschließlich B-Gruppen auf. Nähere Einzel- heiten sind beispielsweise in Journal of Molecular Science, Rev. Macromol. Chem. Phys., C37(3), 555-579 (1997) zu finden.So-called AB x monomers are particularly suitable for the synthesis of these hyperbranched polymers. These have two different functional groups A and B, which can react with one another to form a link. The functional group A is only contained once per molecule and the functional group B twice or more. The reaction of the AB x monomers with one another produces uncrosslinked polymers with regularly arranged branching points. The polymers have almost exclusively B groups at the chain ends. Further details are, for example, in the Journal of Molecular Science, Rev. Macromol. Chem. Phys., C37 (3), 555-579 (1997).
Erfindungsgemäß geeignete hyperverzweigte Polymere sind in der WO 97/02304, US 5,936,055, DE-A-100 13 187, DE-A-100 30 869, DE-A-199 04 444 und der deutschen Patentanmeldung P 102 04 979.3 beschrieben, worauf hier in vollem Umfang Bezug genommen wird.Hyperbranched polymers suitable according to the invention are described in WO 97/02304, US Pat. No. 5,936,055, DE-A-100 13 187, DE-A-100 30 869, DE-A-199 04 444 and German patent application P 102 04 979.3, whereupon here is fully referred to.
Die erfindungsgemäß eingesetzten hyperverzweigten Polymere weisen vorzugsweise einen Verzweigungsgrad (Degree of Branching, DB) entsprechend einer mittleren Anzahl von dendritischen Verknüpfungen und terminalen Einheiten pro Molekül von 10 bis 100 %, bevorzugt 10 bis 90 % und insbesondere 10 bis 80 %, auf. Zur Definition des "Degree of Branching" wird auf H. Frey et al., Acta Po- lym., 1997, 48, 30 verwiesen.The hyperbranched polymers used according to the invention preferably have a degree of branching (DB) corresponding to an average number of dendritic linkages and terminal units per molecule of 10 to 100%, preferably 10 to 90% and in particular 10 to 80%. For the definition of the "degree of branching", reference is made to H. Frey et al., Acta Polym., 1997, 48, 30.
Hyperverzweigte Polymere, d. h. molekular und strukturell uneinheitliche Polymere, werden bevorzugt eingesetzt. Diese sind in der Regel einfacher und somit wirtschaftlicher herstellbar als Dendrimere. Zur Erzielung einer vorteilhaften Oberflächenmodifi- zierung können aber selbstverständlich auch strukturell und molekular einheitliche dendrimere Polymere und Sternpolymere eingesetzt werden.Hyperbranched polymers, i.e. H. Molecularly and structurally non-uniform polymers are preferably used. These are generally simpler and therefore more economical to produce than dendrimers. To achieve advantageous surface modification, of course, structurally and molecularly uniform dendrimeric polymers and star polymers can also be used.
Die Synthese von erfindungsgemäß einsetzbaren hyperverzweigten Polyurethanen und Polyharnstoffen kann beispielsweise wie im Folgenden geschildert erfolgen.The synthesis of hyperbranched polyurethanes and polyureas which can be used according to the invention can be carried out, for example, as described below.
Zur Synthese der hyperverzweigten Polyurethane und Polyharnstoffe werden bevorzugt ABx-Monomere eingesetzt, die sowohl Isocyanat- Gruppen sowie Gruppen, die mit Isocyanat-Gruppen unter Bildung einer Verknüpfung reagieren können, aufweisen. Bei x handelt es sich um eine natürliche Zahl zwischen 2 und 8. Bevorzugt beträgt x 2 oder 3. Entweder handelt es sich bei A um die Isocyanat- Gruppen und bei B um mit diesen reaktive Gruppen oder es kann der umgekehrte Fall vorliegen.For the synthesis of the hyperbranched polyurethanes and polyureas, it is preferred to use AB x monomers which have both isocyanate groups and groups which can react with isocyanate groups to form a link. X is a natural number between 2 and 8. It is preferably x 2 or 3. Either A is the isocyanate groups and B is reactive with these groups, or the reverse may be the case.
Bei den mit den Isocyanat-Gruppen reaktiven Gruppen handelt es sich bevorzugt um OH-, NH2-, NH-, SH- oder COOH—Gruppen.The groups reactive with the isocyanate groups are preferably OH, NH 2 , NH, SH or COOH groups.
Die ABx-Monomere sind in bekannter Art und Weise mittels verschiedener Techniken herstellbar.The AB x monomers can be prepared in a known manner using various techniques.
ABx-Monomere können beispielsweise nach der von WO 97/02304 offenbarten Methode unter Anwendung von Schutzgruppentechniken synthetisiert werden. Beispielhaft sei diese Technik an der Herstellung eines AB2-Monomers aus 2,4-Toluylendiisocyanat (TDI) und Trime- thylolpropan erläutert. Zunächst wird eine der Isocyanat-Gruppen des TDI in bekannter Art und Weise verkappt, beispielsweise durch Umsetzung mit einem Oxim. Die verbleibende freie NCO-Gruppe wird mit Trimethylolpropan umgesetzt, wobei eine der drei OH-Gruppen mit der Isocyanat-Gruppe reagiert. Nach Abspalten der Schutz- gruppe wird ein Molekül mit einer Isocyanat-Gruppe und 2 OH-Gruppen erhalten.AB x monomers can be synthesized, for example, by the method disclosed by WO 97/02304 using protective group techniques. This technique is exemplified by the preparation of an AB 2 monomer from 2,4-tolylene diisocyanate (TDI) and trimethylol propane. First, one of the TDI isocyanate groups is blocked in a known manner, for example by reaction with an oxime. The remaining free NCO group is reacted with trimethylolpropane, one of the three OH groups reacting with the isocyanate group. After the protective group has been removed, a molecule with an isocyanate group and 2 OH groups is obtained.
Besonders vorteilhaft können die ABx-Moleküle nach der vonThe AB x molecules according to the of
DE-A 199 04 444 offenbarten Methode synthetisiert werden, bei der keine Schutzgruppen erforderlich sind. Bei dieser Methode werden Di- oder Polyisocyanate eingesetzt und mit Verbindungen, die mindestens zwei mit Isocyanatgruppen reaktive Gruppen aufweisen, umgesetzt. Zumindest einer der Reaktionspartner weist Gruppen mit gegenüber dem anderen Reaktionspartner unterschiedlicher Reakti- vität auf. Bevorzugt weisen beide Reaktionspartner Gruppen mit gegenüber dem anderen Reaktionspartner unterschiedlicher Reaktivität auf. Die Reaktionsbedingungen werden so gewählt, dass nur bestimmte reaktive Gruppen miteinander reagieren können.DE-A 199 04 444 disclosed method can be synthesized in which no protective groups are required. In this method, di- or polyisocyanates are used and reacted with compounds which have at least two groups reactive with isocyanate groups. At least one of the reactants has groups with different reactivity than the other reactant. Both reactants preferably have groups with different reactivities than the other reactants. The reaction conditions are chosen so that only certain reactive groups can react with each other.
Weiterhin können ABx-Moleküle wie in der deutschen Patentanmeldung P 102 04 979.3 beschrieben hergestellt werden. Hier werden durch Verkappungsmittel geschützte Isocyanatgruppen mit Polyaminen zu Polyharnstoffen umgesetzt.AB x molecules can also be produced as described in German patent application P 102 04 979.3. Here isocyanate groups protected by capping agents are reacted with polyamines to form polyureas.
Als Di- oder Polyisocyanate kommen die nach dem Stand der Technik bekannten und nachfolgend beispielhaft genannten aliphatischen, cycloaliphatischen, araliphatischen und aromatischen Di- oder Polyisocyanate in Frage. Zu nennen sind hier vorzugsweise 4,4'-Di- phenylmethandiisocyanat, die Mischungen aus monomeren Diphenyl e- thandiisocyanaten und oligmeren Diphenylmethandiisocyanaten (Po- lymer-MDI) , Tetramethylendiisocyanat, Tetramethylendiisocyanat- Trimere, Hexamethylendiisocyanat, Hexamethylendiisocyanat-Tri- mere, Isophorondiisocyanat-Tri er, 4,4 '—Methylenbis(cyclohe- xyl) -diisocyanat, Xylylendiisocyanat, Tetramethylxylylendiisocya- nat, Dodecyldiisocyanat, Lysinalkylester-diisocyanat, wobei Alkyl für Cι-C10- steht, 1,4-Diisocyanatocyclohexan oder 4-Isocyanatome- thyl-1 , 8-octamethylendiisocyanat.Suitable di- or polyisocyanates are the aliphatic, cycloaliphatic, araliphatic and aromatic di- or polyisocyanates known from the prior art and exemplified below. 4,4'-diphenylmethane diisocyanate, the mixtures of monomeric diphenylethane diisocyanates and oligomeric diphenylmethane diisocyanates (polymer MDI), tetramethylene diisocyanate, tetramethylene diisocyanate trimers, hexamethylene diisocyanate, hexamethylene diisocyanate tri mere, isophorone diisocyanate tri, 4,4'-methylenebis (cyclohexyl) diisocyanate, xylylene diisocyanate, tetramethylxylylene diisocyanate, dodecyl diisocyanate, lysine alkyl ester diisocyanate, where alkyl is C 1 -C 10 -, 1,4-diisocyanatocyclo -Isocyanatome- ethyl, 8-octamethylene diisocyanate.
Besonders bevorzugt zum Aufbau der Polyurethane und Polyharnstoffe sind Di- oder Polyisocyanate geeignet, die NCO-Gruppen unterschiedlicher Reaktivität aufweisen. Genannt seien hier 2,4—To- luylendiisocyanat ( 2 , 4—TDI ) , 2,4 '—Diphenylmethandiisocyanat (2,4'-MDI ) , Triisocyanatotoluol, Isophorondiisocyanat ( IPDI ) , 2—Butyl—2—ethylpentamethylendiisocyanat, 2,2,4- oder 2,4,4-Trime- thyl-1 , 6-hexamethylen-diisocyanat, 2—Isocyanatopropylcyclohexyli- socyanat, 3(4) -Isocyanatomethyl-1-methylcyclohexyl-isocyanat, l,4-Diisocyanato-4-methylpentan, 2,4'—Methylenbisfcyclo- hexyl)diisocyanat und 4—Methyl—cyclohexan—1,3—diisocyanat (H-TDI) .Di- or polyisocyanates which have NCO groups of different reactivity are particularly preferred for the construction of the polyurethanes and polyureas. Examples include 2,4-tolylene diisocyanate (2,4-TDI), 2,4'-diphenylmethane diisocyanate (2,4'-MDI), triisocyanatotoluene, isophorone diisocyanate (IPDI), 2-butyl-2-ethylpentamethylene diisocyanate, 2, 2,4- or 2,4,4-trimethyl-1, 6-hexamethylene diisocyanate, 2-isocyanatopropylcyclohexyl isocyanate, 3 (4) -isocyanatomethyl-1-methylcyclohexyl isocyanate, 1,4-diisocyanato-4- methyl pentane, 2,4'-methylenebiscyclohexyl) diisocyanate and 4-methyl-cyclohexane-1,3-diisocyanate (H-TDI).
Weiterhin sind zum Aufbau der Polyurethane und Polyharnstoffe Isocyanate geeignet, deren NCO-Gruppen zunächst gleich reaktiv sind, bei denen sich jedoch durch Erstaddition eines Reaktanden an einer NCO-Gruppe ein Reaktivitätsabfall bei der zweiten NCO- Gruppe induzieren lässt. Beispiele dafür sind Isocyanate, deren NCO-Gruppen über ein delokalisiertes π-Elektronensystem gekoppelt sind, z. B. 1,3- und 1,4-Phenylendiisocyanat, 1,5-Naphthylendii- socyanat, Diphenyldiisocyanat, Tolidindiisocyanat oder 2,6-Toluy- lendiisocyanat.Furthermore, isocyanates are suitable for the construction of the polyurethanes and polyureas, the NCO groups of which are initially equally reactive, but in which a drop in reactivity in the second NCO group can be induced by the first addition of a reactant to an NCO group. Examples include isocyanates, the NCO groups of which are coupled via a delocalized π-electron system, e.g. B. 1,3- and 1,4-phenylene diisocyanate, 1,5-naphthylene diisocyanate, diphenyl diisocyanate, tolidine diisocyanate or 2,6-tolylene diisocyanate.
Weiterhin können beispielsweise Oligo- oder Polyisocyanate ver- wendet werden, die sich aus den oben genannten Di- oder Polyiso- cyanaten oder deren Mischungen durch Verknüpfung mittels Urethan-, Allophanat-, Harnstoff-, Biuret-, Uretdion-, Amid-, Iso- cyanurat-, Carbodiimid-, Uretonimin-, Oxadiazintrion- oder Imi- nooxadiazindion-Strukturen herstellen lassen.It is also possible, for example, to use oligo- or polyisocyanates which are obtained from the above-mentioned di- or polyisocyanates or their mixtures by linking using urethane, allophanate, urea, biuret, uretdione, amide, iso- Have cyanurate, carbodiimide, uretonimine, oxadiazinetrione or iminoxadiazinedione structures produced.
Als Verbindungen mit mindestens zwei mit Isocyanaten reaktiven Gruppen werden vorzugsweise di—, tri— oder tetrafunktionelle Verbindungen eingesetzt, deren funktionelle Gruppen gegenüber NCO- Gruppen eine unterschiedliche Reaktivität aufweisen.As compounds having at least two groups reactive with isocyanates, preference is given to using di-, tri- or tetrafunctional compounds whose functional groups have a different reactivity towards NCO groups.
Bevorzugt zur Herstellung von Polyurethanen und Polyharnstoff-Polyurethanen sind Verbindungen mit mindestens einer primären und mindestens einer sekundären Hydroxylgruppe, mindestens einer Hydroxylgruppe und mindestens einer Mercaptogruppe, besonders be- vorzugt mit mindestens einer Hydroxylgruppe und mindestens einer A inogruppe im Molekül, insbesondere Aminoalkohole, Aminodiole und Aminotriole, da die Reaktivität der Aminogruppe gegenüber der Hydroxylgruppe bei der Umsetzung mit Isocyanat deutlich höher ist.Preferred for the production of polyurethanes and polyurea polyurethanes are compounds with at least one primary and at least one secondary hydroxyl group, at least one hydroxyl group and at least one mercapto group, particularly preferably with at least one hydroxyl group and at least one amino group in the molecule, in particular amino alcohols, aminodiols and Aminotriole, because the reactivity of the amino group towards Hydroxyl group in the reaction with isocyanate is significantly higher.
Beispiele für die genannten Verbindungen mit mindestens zwei mit Isocyanaten reaktiven Gruppen sind Propylenglykol, Glycerin, Mer- captoethanol, Ethanolamin, N-Methylethanolamin, Diethanolamin, Ethanolpropanolamin, Dipropanolamin, Diisopropanolamin, 2-Amino-l,3-propandiol, 2-Amino-2-methyl-l,3-propandiol oder Tris(hydroxymethyl)—aminomethan. Weiterhin sind auch Mischungen der genannten Verbindungen einsetzbar.Examples of the compounds mentioned with at least two groups reactive with isocyanates are propylene glycol, glycerol, mercaptoethanol, ethanolamine, N-methylethanolamine, diethanolamine, ethanolpropanolamine, dipropanolamine, diisopropanolamine, 2-amino-1, 3-propanediol, 2-amino-2 -methyl-l, 3-propanediol or tris (hydroxymethyl) aminomethane. Mixtures of the compounds mentioned can also be used.
Für die Herstellung von Polyharnstoffen werden vorzugsweise Iso- cyanat-reaktive Produkte eingesetzt, die mindestens zwei Amino- gruppen im Molekül aufweisen.Isocyanate-reactive products which have at least two amino groups in the molecule are preferably used for the production of polyureas.
Dies sind zum Beispiel Ethylendiamin, N-Alkylethylendiamin, Pro- pylendiamin, N-Alkylpropylendiamin, Hexamethylendiamin, N-Alkyl- hexamethylendiami , Diaminodicyclohexylmethan, Phenylendiamin, Isophorondiamin, Amin-terminierte Polyoxyalkylenpolyole (so ge- nannte Jeffamine), Bis(aminoethyl)amin, Bis(aminopropyl)amin,These are, for example, ethylenediamine, N-alkylethylenediamine, propylenediamine, N-alkylpropylenediamine, hexamethylenediamine, N-alkylhexamethylenediamine, diaminodicyclohexylmethane, phenylenediamine, isophoronediamine, amine-terminated polyoxyalkylene polyols (so-called Jeffethylamine), bis (so-called Jeffethylamine) amine bis (aminopropyl) amine,
Bis(aminohexyl)amin, Tris(aminoethyl)amin, Tris (aminopropyl)amin, Tris(aminohexyl)amin, Trisaminohexan, 4-Aminomethyl-l,8-octame- thylendiamin, N'-( 3-Aminopropyl)-N,N-dimethyl-1,3-propandiamin, Trisaminononan oder Melamin. Weiterhin sind auch Mischungen der genannten Verbindungen einsetzbar.Bis (aminohexyl) amine, tris (aminoethyl) amine, tris (aminopropyl) amine, tris (aminohexyl) amine, trisaminohexane, 4-aminomethyl-l, 8-octamethylenediamine, N '- (3-aminopropyl) -N, N -dimethyl-1,3-propanediamine, trisaminononane or melamine. Mixtures of the compounds mentioned can also be used.
Die Herstellung eines ABx-Moleküls zur Herstellung eines Polyurethans aus einem Diisocyanat und einem Aminodiol sei hier beispielhaft erläutert. Hierbei wird zunächst ein Mol eines Diiso- cyanats mit einem Mol eines Aminodiols bei niedrigen Temperaturen, vorzugsweise im Bereich zwischen —10 bis 30 °C, umgesetzt. In diesem Temperaturbereich erfolgt eine praktisch vollständige Unterdrückung der Urethanbildungsreaktion und die NCO-Gruppen des Isocyanats reagieren ausschließlich mit der Aminogruppe des Ami- nodiols. Das gebildete ABx-Molekül, hier ein AB2-Typ, weist eine freie NCO-Gruppe sowie zwei freie OH-Gruppen auf und kann zur Synthese eines hyperverzweigten Polyurethans eingesetzt werden.The production of an AB x molecule for the production of a polyurethane from a diisocyanate and an aminodiol is explained here by way of example. Here, one mole of a diisocyanate is first reacted with one mole of an aminodiol at low temperatures, preferably in the range between -10 to 30 ° C. In this temperature range, the urethane formation reaction is virtually completely suppressed and the NCO groups of the isocyanate react exclusively with the amino group of the aminodiol. The AB x molecule formed, here an AB 2 type, has one free NCO group and two free OH groups and can be used to synthesize a hyperbranched polyurethane.
Durch Erwärmung und/oder Katalysatorzugabe kann dieses AB2-Molekül intermolekular zu einem hyperverzweigten Polyurethan reagieren. Die Synthese des hyperverzweigten Polyurethans kann vorteilhaft ohne vorherige Isolierung des AB2-Moleküls in einem weiteren Reaktionsschritt bei erhöhter Temperatur erfolgen, vorzugsweise im Bereich zwischen 30 und 80 °C. Bei Verwendung des geschilderten AB2-Moleküls mit zwei OH-Gruppen und einer NCO-Gruppe entsteht ein hyperverzweigtes Polymer, welches pro Molekül eine freie NCO- Gruppe sowie - je nach Polymerisationsgrad - eine mehr oder weni- ger große Zahl von OH-Gruppen aufweist. Die Reaktion kann bis zu ■ hohen Umsätzen durchgeführt werden, wodurch sehr hochmolekulare Strukturen erhalten werden. Sie kann aber auch beispielsweise durch Zugabe geeigneter monofunktioneller Verbindungen oder durch Zugabe einer der Ausgangsverbindungen zur Herstellung des AB-Mo- leküls beim Erreichen des gewünschten Molekulargewichts abgebrochen werden. Je nach der zum Abbruch verwendeten Ausgangsverbindung entstehen entweder vollständig NCO-terminierte oder vollständig OH-terminierte Moleküle.By heating and / or adding catalyst, this AB 2 molecule can react intermolecularly to form a hyperbranched polyurethane. The hyperbranched polyurethane can advantageously be synthesized in a further reaction step at elevated temperature, preferably in the range between 30 and 80 ° C., without prior isolation of the AB 2 molecule. When using the described AB 2 molecule with two OH groups and one NCO group, a hyperbranched polymer is formed which contains one free NCO group per molecule and - depending on the degree of polymerization - one more or less ger has a large number of OH groups. The reaction can be carried out up to ■ high turnover, resulting in very high molecular weight structures are obtained. However, it can also be terminated, for example, by adding suitable monofunctional compounds or by adding one of the starting compounds for the preparation of the AB molecule when the desired molecular weight has been reached. Depending on the starting compound used for the termination, either completely NCO-terminated or completely OH-terminated molecules are formed.
Alternativ kann beispielsweise auch ein AB2-Molekül aus 1 Mol Glycerin und 2 Mol 2,4-TDI hergestellt werden. Bei tiefer Temperatur reagieren vorzugsweise die primären Alkoholgruppen sowie die Isocyanat-Gruppe in 4-Stellung, und es wird ein Addukt gebildet, welches eine OH-Gruppe und zwei Isocyanat-Gruppen aufweist, und das wie geschildert bei höheren Temperaturen zu einem hyperverzweigten Polyurethan umgesetzt werden kann. Es entsteht zunächst ein hyperverzweigtes Polymer, welches eine freie OH-Gruppe sowie - je nach Polymerisationsgrad - eine mehr oder weniger große Zahl von NCO-Gruppen aufweist.Alternatively, for example, an AB 2 molecule can also be produced from 1 mol of glycerol and 2 mol of 2,4-TDI. At low temperature, the primary alcohol groups and the isocyanate group preferably react in the 4-position, and an adduct is formed which has one OH group and two isocyanate groups and which, as described, are converted to a hyperbranched polyurethane at higher temperatures can. First, a hyperbranched polymer is formed which has a free OH group and - depending on the degree of polymerization - a more or less large number of NCO groups.
Die Herstellung der hyperverzweigten Polyurethane und Polyharnstoffe kann prinzipiell ohne Lösungsmittel, bevorzugt aber in Lösung erfolgen. Als Lösungsmittel prinzipiell geeignet sind alle bei der Umsetzungstemperatur flüssigen und gegenüber den. Monomeren und Polymeren inerten Verbindungen.The hyperbranched polyurethanes and polyureas can in principle be prepared without a solvent, but preferably in solution. In principle, all solvents which are liquid at the reaction temperature and which are suitable as solvents are suitable. Monomers and polymers inert compounds.
Andere Produkte sind durch weitere Synthesevarianten zugänglich. Beispielhaft seien an dieser Stelle genannt:Other products are accessible through further synthesis variants. Examples include:
AB3-Moleküle lassen sich beispielsweise durch Reaktion von Diiso- cyanaten mit Verbindungen mit mindestens 4 gegenüber Isocyanaten reaktiven Gruppen erhalten. Beispielhaft sei die Umsetzung von Toluylendiisocyanat mit Tris (hydroxymethyl) -aminomethan genannt.AB 3 molecules can be obtained, for example, by reacting diisocyanates with compounds having at least 4 groups that are reactive toward isocyanates. The reaction of tolylene diisocyanate with tris (hydroxymethyl) aminomethane may be mentioned as an example.
Zum Abbruch der Polymerisation können auch polyfunktionelle Verbindungen eingesetzt werden, die mit den jeweiligen A-Gruppen reagieren können. Auf diese Art und Weise können mehrere kleine hyperverzweigte Moleküle zu einem großen hyperverzweigten Molekül verknüpft werden.To terminate the polymerization it is also possible to use polyfunctional compounds which can react with the respective A groups. In this way, several small hyperbranched molecules can be linked to form one large hyperbranched molecule.
Hyperverzweigte Polyurethane und Polyharnstoffe mit kettenverlängerten Ästen lassen sich beispielsweise erhalten, indem zur Polymerisationsreaktion neben den ABx-Molekülen zusätzlich im molaren Verhältnis 1:1 ein Diisocyanat und eine Verbindung, die zwei mit Isocyanatgruppen reaktive Gruppen aufweist, eingesetzt werden. Diese zusätzlichen AA- bzw. BB-Verbindungen können auch noch über weitere funktioneile Gruppen verfügen, die bei den Reaktionsbedingungen aber nicht reaktiv gegenüber den A- oder B-Gruppen sein dürfen. Auf diese Art und Weise können weitere Funktionalitäten in das hyperverzweigte Polymer eingebracht werden.Hyperbranched polyurethanes and polyureas with chain-extended branches can be obtained, for example, by using a diisocyanate and a compound which has two groups reactive with isocyanate groups in addition to the AB x molecules in addition to the AB x molecules in a molar ratio of 1: 1. These additional AA or BB connections can also be made via have other functional groups, which, however, must not be reactive towards the A or B groups under the reaction conditions. In this way, further functionalities can be introduced into the hyperbranched polymer.
Weitere geeignete Synthesevarianten für hyperverzweigte Polymere finden sich in der DE-A-100 13 187 und DE-A-100 30 869.Further suitable synthesis variants for hyperbranched polymers can be found in DE-A-100 13 187 and DE-A-100 30 869.
Die zuvor beschriebenen Urethan- und/oder Harnstoffgruppen auf- weisenden hyperverzweigten Polymere können im Allgemeinen bereits als solche zur Modifizierung der Oberflächeneigenschaften von Substraten eingesetzt werden. Dabei richten sich ihre oberflächenmodifizierenden Eigenschaften nach den mit der Synthese eingeführten funktioneilen Gruppen.The above-described urethane and / or urea group-containing hyperbranched polymers can generally already be used as such for modifying the surface properties of substrates. Their surface-modifying properties depend on the functional groups introduced with the synthesis.
Bevorzugt werden die zuvor beschriebenen hyperverzweigten Polymere vor ihrem Einsatz zur Modifizierung von Substratoberflächen noch einer polymeranalogen Umsetzung unterzogen. So können die Polymereigenschaften in Abhängigkeit von Art und Menge der zur polymeranalogen Umsetzung eingesetzten Verbindungen gezielt für die jeweilige Anwendung angepasst werden. Bevorzugt sind daher Substrate, wie zuvor beschrieben, wobei das hyperverzweigte Polymer auf der Substratoberfläche erhältlich ist durch polymeranaloge Umsetzung eines hyperverzweigten Polymers, das Urethan- und/ oder Harnstoffgruppen und/oder weitere funktionelle Gruppen trägt, die zu einer Kondensations- oder Additionsreaktion befähigt sind, mit wenigstens einer Verbindung, die ausgewählt ist unterThe hyperbranched polymers described above are preferably subjected to a polymer-analogous reaction before they are used to modify substrate surfaces. The polymer properties can thus be specifically adapted to the respective application, depending on the type and amount of the compounds used for the polymer-analogous reaction. Substrates as described above are therefore preferred, the hyperbranched polymer being obtainable on the substrate surface by polymer-analogous reaction of a hyperbranched polymer which carries urethane and / or urea groups and / or further functional groups which are capable of a condensation or addition reaction, with at least one compound selected from
a) Verbindungen, die wenigstens eine zu den zur Kondensationsoder Additionsreaktion befähigten Gruppen des hyperverzweigten Polymers komplementäre funktioneile Gruppe und zusätzlich wenigstens eine hydrophile Gruppe tragen,a) compounds which carry at least one functional group which is complementary to the groups of the hyperbranched polymer capable of condensation or addition reaction and additionally carry at least one hydrophilic group,
b) Verbindungen, die wenigstens eine zu den zur Kondensationsoder Additionsreaktion befähigten Gruppen des hyperverzweigten Polymers komplementäre funktionelle Gruppe und zusätzlich wenigstens eine hydrophobe Gruppe tragen,b) compounds which carry at least one functional group which is complementary to the groups of the hyperbranched polymer which are capable of condensation or addition reaction and additionally carry at least one hydrophobic group,
und Mischungen davon.and mixtures thereof.
Als "komplementäre funktionelle Gruppen" wird im Rahmen der vorliegenden Erfindung ein Paar von funktionellen Gruppen verstanden, die in einer Kondensations- oder Additionsreaktion miteinan- der reagieren können. "Komplementäre Verbindungen" sind Paare von Verbindungen, die zueinander komplementäre funktionelle Gruppen aufweisen.In the context of the present invention, “complementary functional groups” is understood to mean a pair of functional groups which can react with one another in a condensation or addition reaction. "Complementary connections" are pairs of Compounds that have complementary functional groups.
Bevorzugte komplementäre funktionelle Gruppen der hyperverzweig- ten Polymere und der Komponenten a) und b) sind ausgewählt unter den komplementären funktioneilen Gruppen der nachfolgenden Übersicht.Preferred complementary functional groups of the hyperbranched polymers and components a) and b) are selected from the complementary functional groups in the overview below.
R und R' sind vorzugsweise unabhängig ausgewählt unter Wasserstoff, Alkyl, besonders bevorzugt Cι-C20-Alkyl, wie Methyl, Ethyl, n-Propyl, Isopropyl, n-Butyl, tert.-Butyl, den isomeren Pentylen, Hexylen, Heptylen, Octylen etc., Cycloalkyl, besonders bevorzugt C5-C8-Cycloalkyl, wie Cyclopentyl und Cyclohexyl, Aryl, besonders bevorzugt Phenyl, Het ryl etc.R and R 'are preferably selected independently from hydrogen, alkyl, particularly preferably C 1 -C 20 -alkyl, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, the isomeric pentylene, hexylene, heptylene, Octylene etc., cycloalkyl, particularly preferably C 5 -C 8 cycloalkyl, such as cyclopentyl and cyclohexyl, aryl, particularly preferably phenyl, heteryl etc.
Bevorzugte komplementäre Verbindungen sind z. B. einerseits Verbindungen mit aktiven Wasserstoffatomen, die z. B. ausgewählt sind unter Verbindungen mit Alkohol-, primären und sekundären Amin- und Thiolgruppen und andererseits Verbindungen mit demgegenüber reaktiven Gruppen, vorzugsweise Isocyanatgruppen. Dabei ist es in der Regel unkritisch, welche funktionelle Gruppe die Polymerkomponente und welche die Verbindung a) und/oder b) trägt.Preferred complementary compounds are e.g. B. on the one hand compounds with active hydrogen atoms, the z. B. are selected from compounds with alcohol, primary and secondary amine and thiol groups and on the other hand compounds with groups that are reactive towards it, preferably isocyanate groups. It is generally not critical which functional group the polymer component and which the compound a) and / or b) carries.
Geeignete hydrophile Gruppen der Verbindungen a) sind ausgewählt unter ionogenen, ionischen und nicht-ionischen hydrophilen Gruppen. Bei den ionogenen bzw. ionischen Gruppen handelt es sich vorzugsweise um Carbonsäuregruppen, und/oder Sulfonsäuregruppen und/oder stickstoffhaltige Gruppen (A ine) bzw. Carboxylatgruppen und/oder Sulfonatgruppen und/oder quaternisierte oder protonierte Gruppen. Verbindungen a) , die Säuregruppen enthalten, können durch teilweise oder vollständige Neutralisation in die entsprechenden Salze überführt werden. Geeignete Basen für die Neutrali- sation sind beispielsweise Alkalimetallbasen, wie Natronlauge, Kalilauge, Natriumcarbonat, Natriumhydrogencarbonat, Kaliumcarbo- nat oder Kaliumhydrogencarbonat und Erdalkalimetallbasen, wie Calciumhydroxid, Calciumoxid, Magnesiumhydroxid oder Magnesium- carbonat sowie Ammoniak und Amine, wie Trimethylamin, Triethylamin etc. Aus Verbindungen a) mit Aminstickstoffatomen lassen sich geladene kationische Gruppen entweder durch Protonie- rung, z. B. mit Carbonsäuren, wie Essigsäure, oder durch Quater- nisierung, z. B. mit Alkylierungsmitteln, wie Cι-C4-Alkylhalogeni- den oder -sulfaten, erzeugen. Beispiele solcher Alkylierungsmit- tel sind Ethylchlorid, Ethylbromid, Dimethylsulfat und Diethyl- sulfat.Suitable hydrophilic groups of the compounds a) are selected from ionogenic, ionic and non-ionic hydrophilic groups. The ionogenic or ionic groups are preferably carboxylic acid groups and / or sulfonic acid groups and / or nitrogen-containing groups (amines) or carboxylate groups and / or sulfonate groups and / or quaternized or protonated groups. Compounds a) which contain acid groups can be converted into the corresponding salts by partial or complete neutralization. Suitable bases for the neutralization are, for example, alkali metal bases, such as sodium hydroxide solution, potassium hydroxide solution, sodium carbonate, sodium hydrogen carbonate, potassium carbonate or potassium hydrogen carbonate and alkaline earth metal bases, such as Calcium hydroxide, calcium oxide, magnesium hydroxide or magnesium carbonate as well as ammonia and amines, such as trimethylamine, triethylamine etc. From compounds a) with amine nitrogen atoms, charged cationic groups can be obtained either by protonation, eg by B. with carboxylic acids, such as acetic acid, or by quaternization, z. B. with alkylating agents such as -CC 4 alkyl halides or sulfates. Examples of such alkylating agents are ethyl chloride, ethyl bromide, dimethyl sulfate and diethyl sulfate.
Durch polymeranaloge Umsetzung erhältliche hyperverzweigte Polymere mit ionischen hydrophilen Gruppen sind in der Regel wasserlöslich oder wasserdispergierbar.Hyperbranched polymers with ionic hydrophilic groups obtainable by polymer-analogous reaction are generally water-soluble or water-dispersible.
Vorzugsweise werden als Komponente a) Hydroxycarbonsäuren, wie Hydroxyessigsäure (Glykolsäure) , Hydroxypropionsäure (Milchsäure), Hydroxybernsteinsäure (Äpfelsäure), Hydroxypivalinsäure, 4-Hydroxybenzoesäure, 12-Hydroxydodecansäure, Dimethylolpro- pionsäure etc. eingesetzt.Hydroxycarboxylic acids, such as hydroxyacetic acid (glycolic acid), hydroxypropionic acid (lactic acid), hydroxysuccinic acid (malic acid), hydroxypivalic acid, 4-hydroxybenzoic acid, 12-hydroxydodecanoic acid, dimethylolpropionic acid, etc., are preferably used as component a).
Des Weiteren bevorzugt werden als Komponente a) Hydroxysulfonsäu- ren, wie Hydroxymethansulfonsäure oder 2-Hydroxyethansulfonsäure, eingesetzt.Also preferred as component a) are hydroxysulfonic acids, such as hydroxymethanesulfonic acid or 2-hydroxyethanesulfonic acid.
Des Weiteren bevorzugt werden als Komponente a) Mercaptocarbonsäuren, wie Mercaptoessigsäure, eingesetzt.Also preferred as component a) are mercaptocarboxylic acids, such as mercaptoacetic acid.
Des Weiteren bevorzugt werden als Komponente a) Aminosulfonsäuren der Formel:Also preferred as component a) are aminosulfonic acids of the formula:
RiH -Y-SOaHR i H -Y-SOaH
eingesetzt, worinused where
Y für o-, m- oder p-Phenylen oder geradkettiges oder verzweigtes C2-C6-Alkylen steht, das gegebenenfalls durch 1, 2 oder 3 Hydroxygruppen substituiert ist, undY represents o-, m- or p-phenylene or straight-chain or branched C 2 -C 6 alkylene, which is optionally substituted by 1, 2 or 3 hydroxyl groups, and
R1 für ein Wasserstoffatom, eine Cι-Cι2-Alkylgruppe (vorzugsweise Ci-Cio- und insbesondere Ci-Cß-Alkylgruppe) oder eine Cs-Cß-Cy- cloalkylgruppe steht, wobei die Alkylgruppe oder die Cycloal- kylgruppe gegebenenfalls durch 1, 2 oder 3 Hydroxygruppen, Carboxylgruppen oder Sulfonsäuregruppen substituiert sein kann. Bevorzugt handelt es sich bei den Aminosulfonsäuren der obigen Formel um Taurin, N-(l, l-Dimethyl-2-hydroxyethyl)-3-amino-2-hy- droxypropansulfonsäure oder 2-Aminoethylaminoethansulfonsäure.R 1 represents a hydrogen atom, a C 1 -C 2 -alkyl group (preferably C 1 -C 8 and in particular C 1 -C 6 -alkyl group) or a Cs-C ß -cycloalkyl group, the alkyl group or the cycloalkyl group optionally being represented by 1 , 2 or 3 hydroxyl groups, carboxyl groups or sulfonic acid groups can be substituted. The aminosulfonic acids of the above formula are preferably taurine, N- (l, l-dimethyl-2-hydroxyethyl) -3-amino-2-hydroxypropanesulfonic acid or 2-aminoethylaminoethanesulfonic acid.
Des Weiteren bevorzugt werden als Komponente a) α-, ß- oder γ-Ami- nosäuren, beispielsweise Glycin, Alanin, Valin, Leucin, Isoleu- cin, Phenylalanin, Thyrosin, Prolin, Hydroxyprolin, Serin, Threo- nin, Methionin, Cystein, Tryptophan, ß-Alanin, Asparaginsäure oder Glutaminsäure, eingesetzt.Also preferred as component a) are α-, β- or γ-amino acids, for example glycine, alanine, valine, leucine, isoleucine, phenylalanine, thyrosine, proline, hydroxyproline, serine, threonine, methionine, cysteine , Tryptophan, ß-alanine, aspartic acid or glutamic acid, used.
Des Weiteren bevorzugt werden als Komponente a) Polyetherole eingesetzt. Geeignete Polyetherole sind lineare oder verzweigte endständige Hydroxylgruppen aufweisende Substanzen, die Etherbindun- gen enthalten und ein Molekulargewicht im Bereich von z. B. etwa 300 bis 10000 aufweisen. Dazu zählen beispielsweise Polyalkylen- glykole, z. B. Polyethylenglykole, Polypropylenglykole, Polyte- trahydrofurane, Copolymerisate aus Ethylenoxid, Propylenoxid und/ oder Butylenoxid, die die Alkylenoxideinheiten statistisch verteilt oder in Form von Blöcken einpolymerisiert enthalten. Ge- eignet sind auch α,ω-Diaminopolyether, die durch Aminierung von Polyetherolen mit Ammoniak herstellbar sind. Derartige Verbindungen sind kommerziell unter der Bezeichnung Jeffamine® erhältlich.Polyetherols are also preferably used as component a). Suitable polyetherols are linear or branched terminal hydroxyl-containing substances which contain ether bonds and have a molecular weight in the range of, for. B. have about 300 to 10,000. These include, for example, polyalkylene glycols, e.g. B. polyethylene glycols, polypropylene glycols, polytetrahydrofurans, copolymers of ethylene oxide, propylene oxide and / or butylene oxide, which contain the alkylene oxide units randomly distributed or copolymerized in the form of blocks. Also suitable are α, ω-diamino polyethers which can be prepared by aminating polyetherols with ammonia. Such compounds are commercially available under the name Jeffamine®.
Des Weiteren bevorzugt ist die Komponente a) ausgewählt unter Diaminen, Polyaminen und Mischungen davon.Component a) is furthermore preferably selected from diamines, polyamines and mixtures thereof.
Geeignete Amine a) sind geradkettige und verzweigte, aliphatische und cycloaliphatische Amine mit im Allgemeinen etwa 2 bis 30, bevorzugt etwa 2 bis 20 Kohlenstoffatomen. Dazu zählen z. B. Ethy- lendiamin, 1,2-Diaminopropan, 1,3-Diaminopropan, 1,4-Diaminobu- tan, 1,5-Diaminopentan, 1,6-Diaminohexan, 1,7-Diaminoheptan, 1,8-Diaminooctan, 1, 9-Diaminononan 1,10-Diaminodecan, 1,11-Diami- noundecan, 1, 12-Diaminododecan, Diethylentriamin, Triethylente- traamin, 4-Azaheptamethylendiamin, N,N'-Bis(3-aminopropyl) -bu- tan-l,4-diamin, und Mischungen davon. Geeignete Polyamine a) weisen im Allgemeinen ein zahlenmittleres Molekulargewicht von etwa 400 bis 10000, bevorzugt etwa 500 bis 8000 auf. Dazu zählen z. B. Polyamide mit endständigen, primären oder sekundären Aminogrup- pen, Polyalkylenijnine, bevorzugt Polyethylenimine und durch Hy- drolyse von Poly-N-vinylamiden, wie z. B. Poly-N-vinylacetamid, erhaltene Vinylamine.Suitable amines a) are straight-chain and branched, aliphatic and cycloaliphatic amines with generally about 2 to 30, preferably about 2 to 20, carbon atoms. These include e.g. B. ethylenediamine, 1,2-diaminopropane, 1,3-diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane, 1,6-diaminohexane, 1,7-diaminoheptane, 1,8-diaminooctane, 1, 9-diaminononane, 1,10-diaminodecane, 1,11-diaminodecane, 1, 12-diaminododecane, diethylene triamine, triethylene tetraamine, 4-azaheptamethylene diamine, N, N'-bis (3-aminopropyl) butane -l, 4-diamine, and mixtures thereof. Suitable polyamines a) generally have a number average molecular weight of about 400 to 10,000, preferably about 500 to 8000. These include e.g. B. polyamides with terminal, primary or secondary amino groups, Polyalkylenijnine, preferably polyethyleneimines and by hydrolysis of poly-N-vinylamides, such as. B. Poly-N-vinyl acetamide, vinyl amines obtained.
Des Weiteren bevorzugt ist die Komponente a) ausgewählt unter Po- lyolen. Dazu zählen z. B. Diole mit 2 bis 18 Kohlenstoffatomen, vorzugsweise 2 bis 10 C-Atomen, wie 1,2-Ethandiol, 1,3-Propan- diol, 1,4-Butandiol, 1,6-Hexandiol, 1,5-Pentandiol, 1,10-Decan- diol, 2-Methyl-l,3-propandiol, 2-Methyl-2-butyl-l,3- propandiol, 2,2-Dimethyl-l,3-propandiol, 2,2-Dimethyl-l,4-butan- diol, 2-Ethyl-2-butyl-l,3-propandiol, Hydroxypivalinsäureneopen- tylglykolester, Diethylenglykol und Triethylenglykol. Geeignete Triole und höherwertige Polyole sind Verbindungen mit 3 bis 25, bevorzugt 3 bis 18, insbesondere bevorzugt 3 bis 6 C-Atomen. Beispiele für brauchbare Triole sind Glycerin oder Trimethylolpro- pan. Als höherwertige Polyole lassen sich beispielsweise Ery- thrit, Pentaerythrit und Sorbit einsetzen.Component a) is furthermore preferably selected from polyols. These include e.g. B. diols having 2 to 18 carbon atoms, preferably 2 to 10 carbon atoms, such as 1,2-ethanediol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, 1,5-pentanediol, 1,10-decanediol, 2-methyl-l, 3-propanediol, 2-methyl-2-butyl-l, 3- propanediol, 2,2-dimethyl-l, 3-propanediol, 2,2-dimethyl-l, 4-butanediol, 2-ethyl-2-butyl-l, 3-propanediol, hydroxypivalic acid neopentylglycol ester, diethylene glycol and triethylene glycol. Suitable triols and higher polyols are compounds having 3 to 25, preferably 3 to 18, particularly preferably 3 to 6 carbon atoms. Examples of useful triols are glycerol or trimethylolpropane. For example, erythritol, pentaerythritol and sorbitol can be used as higher polyols.
Des Weiteren bevorzugt werden als Komponente a) Aminoalkohole eingesetzt. Diese weisen vorzugsweise 2 bis 16, besonders bevorzugt 3 bis 12 Kohlenstoffatome auf, wie z. B. Monoethanolamin, Methylisopropanolamin, Ethylisopropanolamin, Methylethanolamin, 3-Aminopropanol, l-Ethylaminobutan-2-ol, Diethanolamin, Dipropa- nolamin, Dibutanolamin, Tris(hydroxymethyl)-aminomethan, Tris(hy- droxyethyl)-aminomethan, 4-Methyl-4-aminopentan-2-ol und N-(2-Hy- droxyethyl)-anilin und Mischungen davon.Furthermore, amino alcohols are preferably used as component a). These preferably have 2 to 16, particularly preferably 3 to 12 carbon atoms, such as. B. monoethanolamine, methylisopropanolamine, ethylisopropanolamine, methylethanolamine, 3-aminopropanol, l-ethylaminobutan-2-ol, diethanolamine, dipropanolamine, dibutanolamine, tris (hydroxymethyl) aminomethane, tris (hydroxyethyl) aminomethane, 4-methyl- 4-aminopentan-2-ol and N- (2-hydroxyethyl) aniline and mixtures thereof.
Geeignete hydrophobe Gruppen der Verbindungen b) sind ausgewählt unter gesättigten oder ungesättigten Kohlenwasserstoffresten mit 8 bis 40, bevorzugt 9 bis 35, insbesondere 10 bis 30 Kohlenstoff- atomen. Bevorzugt handelt es sich um Alkyl-, Alkenyl-, Cycloal- kyl- oder Arylreste. Die Cycloalkyl- oder Arylreste können 1, 2 oder 3 Substituenten, vorzugsweise Alkyl- oder Alkenylsubstituen- ten, aufweisen. Im Rahmen der vorliegenden Erfindung werden mit "Alkenylresten" Reste bezeichnet, die eine, zwei oder mehrere Kohlenstoff-Kohlenstoff-Doppelbindungen aufweisen.Suitable hydrophobic groups of the compounds b) are selected from saturated or unsaturated hydrocarbon radicals having 8 to 40, preferably 9 to 35, in particular 10 to 30 carbon atoms. They are preferably alkyl, alkenyl, cycloalkyl or aryl radicals. The cycloalkyl or aryl radicals can have 1, 2 or 3 substituents, preferably alkyl or alkenyl substituents. In the context of the present invention, "alkenyl radicals" are radicals which have one, two or more carbon-carbon double bonds.
Im Rahmen der vorliegenden Erfindung umfasst der Ausdruck C8-C0-Alkyl geradkettige und verzweigte Alkylgruppen. Vorzugsweise handelt es sich dabei um geradkettige und verzweigte C9-C35-Alkyl-, besonders bevorzugt um Cι0-C30- und speziell Cχ2-C26-Alkylgruppen. Bevorzugt handelt es sich dabei um überwiegend lineare Alkylreste, wie sie auch in natürlichen oder synthe- tischen Fettsäuren und Fettalkoholen sowie Oxoalkoholen vorkommen. Dazu zählen insbesondere n-Octyl, Ethylhexyl, 1, 1,3,3-Tetra- methylbutyl, n-Nonyl, n-Decyl, n-Undecyl, n-Dodecyl, n-Tridecyl, Myristyl, Pentadecyl, Palmityl (=Cetyl), Heptadecyl, Octadecyl, Nonadecyl, Arrachinyl, Behenyl, Lignocerenyl, Cerotinyl, Melissi- nyl etc.In the context of the present invention, the expression C 8 -C 0 alkyl includes straight-chain and branched alkyl groups. These are preferably straight-chain and branched C 9 -C 35 alkyl, particularly preferably C 0 -C 30 - and especially Cχ 2 -C 26 alkyl groups. These are preferably predominantly linear alkyl radicals, as they also occur in natural or synthetic fatty acids and fatty alcohols and oxo alcohols. These include in particular n-octyl, ethylhexyl, 1, 1,3,3-tetramethylbutyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, myristyl, pentadecyl, palmityl (= cetyl) , Heptadecyl, octadecyl, nonadecyl, arrachinyl, behenyl, lignocerenyl, cerotinyl, melissinyl, etc.
C8-C4o-Alkenyl steht vorzugsweise für geradkettige und verzweigte Alkenylgruppen, die einfach, zweifach oder mehrfach ungesättigt sein können. Bevorzugt handelt es sich um C9-C35-, insbesondere um C10-C30- und speziell um C12-C6-Alkenylgruppen. Dazu zählen insbesondere Octenyl, Nonenyl, Decenyl, Undecenyl, Dodecenyl, Tridece- nyl, Tetradecenyl, Pentadecenyl, Hexadecenyl, Heptadecenyl, Octa- decenyl, Nonadecenyl, Linolylyl, Linolenylyl, Eleostearyl etc. und insbesondere Oleyl (9-Octadecenyl) .C 8 -C 4 o-alkenyl preferably represents straight-chain and branched alkenyl groups which can be mono-, di- or poly-unsaturated. It is preferably C 9 -C 35 -, in particular C 10 -C 30 - and especially C 12 -C 6 alkenyl groups. These include, in particular, octenyl, nonenyl, decenyl, undecenyl, dodecenyl, tridecenyl, tetradecenyl, pentadecenyl, hexadecenyl, heptadecenyl, octa- decenyl, nonadecenyl, linolylyl, linolenylyl, eleostearyl etc. and in particular oleyl (9-octadecenyl).
Die Verbindung der Formel b) steht dann bevorzugt für Alkylamine, wie 1-Octylamin, 1-Nonylamin, 1-Decylamin, 1-Undecylamin, 1-Un- dec-10-enylamin, 1-Tridecylamin, 1-Tetradecylamin, 1-Pentade- cylamin, 1-Hexadecylamin, 1-Heptadecylamin, 1-Octadecylamin, l-Octadeca-9,12-dienylamin, 1-Nonadecylamin, 1-Eicosylamin, 1-Ei- cos-9-enylamin, 1-Heneicosylamin, 1-Docosylamin und insbesondere für Oleylamin und 1-Hexadecylamin (Cetylamin) oder für aus natürlich vorkommenden Fettsäuren hergestellte Amingemische, wie z. B. Talgfettamine, die überwiegend gesättigte und ungesättigte Cι4-, Ci6-Ci8-Alkylamine enthalten oder Kokosamine, die gesättigte, einfach und zweifach ungesättigte C8-C22-f vorzugsweise Cι2-Ci4-Al- kylamine enthalten.The compound of the formula b) then preferably represents alkylamines, such as 1-octylamine, 1-nonylamine, 1-decylamine, 1-undecylamine, 1-un-dec-10-enylamine, 1-tridecylamine, 1-tetradecylamine, 1-pentad - Cylamine, 1-hexadecylamine, 1-heptadecylamine, 1-octadecylamine, l-octadeca-9,12-dienylamine, 1-nonadecylamine, 1-eicosylamine, 1-egg-cos-9-enylamine, 1-heneicosylamine, 1-docosylamine and especially for oleylamine and 1-hexadecylamine (cetylamine) or for amine mixtures made from naturally occurring fatty acids, such as. B. tallow fatty amines, which contain predominantly saturated and unsaturated Cι 4 -, Ci 6 -Ci 8 alkylamines or coconut amines, which contain saturated, mono- and di-unsaturated C8-C 22 -f preferably Cι 2 -Ci 4 alkylamines.
Des Weiteren bevorzugt ist die Verbindung b) ausgewählt unter einwertigen Alkoholen, die einen der zuvor genannten hydrophoben Reste aufweisen. Solche Alkohole und Alkoholgemische b) sind z. B. erhältlich durch Hydrierung von Fettsäuren aus natürlichen Fetten und Ölen oder von synthetischen Fettsäuren, z. B. aus der katalytischen Oxidation von Paraffinen. Geeignete Alkohole und Alkoholgemische b) sind weiterhin erhältlich durch Hydrofor ylie- rung von Olefinen mit gleichzeitiger Hydrierung der Aldehyde, wo- bei im Allgemeinen Gemische aus geradkettigen und verzweigten primären Alkoholen (Oxo-Alkohole) resultieren. Geeignete Alkohole und Alkoholgemische b) sind weiterhin erhältlich durch partielle Oxidation von n-Paräffinen nach bekannten Verfahren, wobei überwiegend lineare sekundäre Alkohole erhalten werden. Geeignet sind weiterhin die durch aluminiumorganische Synthese erhältlichen, im Wesentlichen primären, geradkettigen und geradzahligen Ziegler- Alkohole.Furthermore, the compound b) is preferably selected from monohydric alcohols which have one of the aforementioned hydrophobic radicals. Such alcohols and alcohol mixtures b) are, for. B. obtainable by hydrogenation of fatty acids from natural fats and oils or of synthetic fatty acids, for. B. from the catalytic oxidation of paraffins. Suitable alcohols and alcohol mixtures b) can also be obtained by hydroformylation of olefins with simultaneous hydrogenation of the aldehydes, which generally results in mixtures of straight-chain and branched primary alcohols (oxo alcohols). Suitable alcohols and alcohol mixtures b) are also obtainable by partial oxidation of n-paraffins by known processes, predominantly linear secondary alcohols being obtained. Also suitable are the essentially primary, straight-chain and even-numbered Ziegler alcohols obtainable by organoaluminum synthesis.
Geeignete einwertige Alkohole b) sind z. B. Octanol, Nonanol, De- canol, Undecanol, Dodecanol, Tridecanol, Tetradecanol, Pentadeca- nol, Hexadecanol, Heptadecanol, Octadecanol, etc. und Mischungen davon.Suitable monohydric alcohols b) are e.g. B. octanol, nonanol, decanol, undecanol, dodecanol, tridecanol, tetradecanol, pentadecanol, hexadecanol, heptadecanol, octadecanol, etc. and mixtures thereof.
Geeignete Monoisocyanate b) sind z. B. C8-C40-Alkylisocyanate, die aus den zuvor genannten Aminen und Amingemischen durch Phosgenie- rung oder aus natürlichen oder synthetischen Fettsäuren und Fettsäuregemischen durch Hofmann-, Curtius- oder Lossen-Abbau erhältlich sind.Suitable monoisocyanates b) are e.g. B. C 8 -C 40 alkyl isocyanates, which are available from the aforementioned amines and amine mixtures by phosgenation or from natural or synthetic fatty acids and fatty acid mixtures by Hofmann, Curtius or Lossen degradation.
Die zuvor genannten Verbindungen a) und b) können jeweils einzeln, als Mischungen aus ausschließlich hydrophilen Verbindungen a) oder aus ausschließlich hydrophoben Verbindungen b) sowie als Mischungen von hydrophilen Verbindungen a) mit hydrophoben Verbindungen b) eingesetzt werden. Durch polymeranaloge Umsetzung von Urethan- und/oder Harnstoffgruppen tragenden hyperverzweigten Polymeren mit einzelnen Verbindungen a) oder b) oder mit Gemi- sehen davon lassen sich die oberflächenmodifizierenden Eigenschaften der hyperverzweigten Polymere in einem weiten Bereich variieren. Dadurch lassen sich den mit diesen Polymeren modifizierten Substraten Oberflächeneigenschaften verleihen, die von einer starken Affinität gegenüber Wasser und wässrigen Flüssig- keiten (Hydrophilie) bis zu einer sehr geringen Affinität gegenüber Wasser und wässrigen Flüssigkeiten (Hydrophobie) reichen.The aforementioned compounds a) and b) can each be used individually, as mixtures of exclusively hydrophilic compounds a) or exclusively hydrophobic compounds b) and as Mixtures of hydrophilic compounds a) with hydrophobic compounds b) are used. The surface-modifying properties of the hyperbranched polymers can be varied within a wide range by polymer-analogous reaction of urethane and / or urea group-bearing hyperbranched polymers with individual compounds a) or b) or with mixtures thereof. This allows the substrates modified with these polymers to be given surface properties which range from a strong affinity for water and aqueous liquids (hydrophilicity) to a very low affinity for water and aqueous liquids (hydrophobicity).
Im Folgenden werden einige weitere Ausführungsformen für polymeranaloge Umsetzungen aufgezeigt:Some further embodiments for polymer-analogous reactions are shown below:
Durch Umsetzung mit Acrylatgruppen enthaltenden Verbindungen, wie beispielsweise Acrylatgruppen enthaltenden Alkoholen, wie 2-Hy- droxyethylacrylat oder 2-Hydroxyethylmethacrylat, lassen sich hyperverzweigte Polyurethane erhalten, die polymerisierbare olefi- nische Gruppen aufweisen und die zur Herstellung von strahlungs- vernetzenden, insbesondere von UV- ernetzenden Polymeren, eingesetzt werden können. Durch Umsetzung mit entsprechend substituierten Alkoholen lassen sich auch Epoxid- oder Vinylethergruppen einbringen, die für kationisch vernetzende Polymere genutzt werden können.By reacting with compounds containing acrylate groups, such as, for example, alcohols containing acrylate groups, such as 2-hydroxyethyl acrylate or 2-hydroxyethyl methacrylate, hyperbranched polyurethanes can be obtained which have polymerizable olefinic groups and which are used to produce radiation-crosslinking, in particular UV, wetting polymers can be used. By reaction with appropriately substituted alcohols, epoxy or vinyl ether groups can also be introduced, which can be used for cationically crosslinking polymers.
Oxidativ trocknende hyperverzweigte Polyurethane oder Polyharnstoffe können erhalten werden, indem man NCO- oder Urethangruppen enthaltende Polymere mit einfach oder mehrfach ungesättigten Fettsäureestern, die mindestens eine OH-Gruppe aufweisen, oder mit einfach oder mehrfach ungesättigten Fettalkoholen oder Fettaminen, insbesondere mit 3 bis 40 Kohlenstoffatomen, umsetzt. Beispielsweise können OH-Gruppen enthaltende Ester der Linol- säure, Linolensäure oder Eleostearinsäure mit NCO-Gruppen umge- setzt werden. Weiterhin können NCO- oder Urethangruppen aber auch direkt mit Vinyl- oder Allyl-Gruppen enthaltenden Alkoholen oder Aminen umgesetzt werden.Oxidatively drying hyperbranched polyurethanes or polyureas can be obtained by combining polymers containing NCO or urethane groups with mono- or polyunsaturated fatty acid esters which have at least one OH group, or with mono- or polyunsaturated fatty alcohols or fatty amines, in particular with 3 to 40 carbon atoms. implements. For example, esters of linoleic acid, linolenic acid or eleostearic acid containing OH groups can be reacted with NCO groups. Furthermore, NCO or urethane groups can also be reacted directly with alcohols or amines containing vinyl or allyl groups.
Zur Herstellung von hyperverzweigten Polyurethanen oder Polyharn- Stoffen, die verschiedenartige Funktionalitäten aufweisen, kann man beispielsweise 2 Mol 2,4-TDI mit einer Mischung aus 1 Mol Trimethylolpropan und 1 Mol Dimethylolpropionsäure reagieren lassen. Hierbei wird ein Produkt erhalten, das sowohl über Carbonsäuregruppen als auch über OH-Gruppen verfügt. Weiterhin können solche Produkte auch dadurch erhalten werden, dass man mit einem ABx-Molekül polymerisiert, die Polymerisation bei dem gewünschten Umsetzungsgrad abbricht und anschließend nur einen Teil der ursprünglich vorhandenen funktioneilen Gruppen, beispielsweise nur einen Teil der OH- oder der NCO-Gruppen, umsetzt. Beispielsweise kann man so bei einem NCO-terminierten Polymer aus 2,4-TDI und Glycerin einen Teil der NCO-Gruppen mit Ethanolamin und die übrigen NCO-Gruppen mit Mercaptoessigsäure umsetzen.For the production of hyperbranched polyurethanes or polyureas which have different functionalities, for example 2 moles of 2,4-TDI can be reacted with a mixture of 1 mole of trimethylolpropane and 1 mole of dimethylolpropionic acid. A product is obtained which has both carboxylic acid groups and OH groups. Furthermore, such products can also be obtained by polymerizing with an AB x molecule, terminating the polymerization at the desired degree of conversion and then only part of the functional groups originally present, for example only part of the OH or NCO groups, implements. For example, in the case of an NCO-terminated polymer composed of 2,4-TDI and glycerol, some of the NCO groups can be reacted with ethanolamine and the remaining NCO groups with mercaptoacetic acid.
Weiterhin kann man ein OH-terminiertes Polymerisat aus Isophoron- diisocyanat und Diethanolamin nachträglich hydrophobieren, indem man zum Beispiel einen Teil der OH-Gruppen mit Dodecylisocyanat oder mit Dodecansäure umsetzt. Die Umfunktionalisierung eines hy- perverzweigten Polyurethans oder die Anpassung der Polymereigenschaften an das Anwendungsproblem kann vorteilhaft unmittelbar im Anschluss an die Polymerisationsreaktion erfolgen, ohne dass das NCO-terminierte Polyurethan vorher isoliert wird. Die Funktiona- lisierung kann aber auch in einer separaten Reaktion erfolgen.Furthermore, an OH-terminated polymer composed of isophorone diisocyanate and diethanolamine can subsequently be made hydrophobic by, for example, reacting some of the OH groups with dodecyl isocyanate or with dodecanoic acid. The functionalization of a hyperbranched polyurethane or the adaptation of the polymer properties to the application problem can advantageously be carried out immediately after the polymerization reaction, without the NCO-terminated polyurethane being isolated beforehand. However, the functionalization can also take place in a separate reaction.
Die erfindungsgemäß eingesetzten hyperverzweigten Polymere können in Mischungen oder in Kombination mit weiteren oberflächenaktiven Substanzen eingesetzt werden. Dazu zählen übliche anionische, nicht-ionische oder kationische Tenside bzw. Netzmittel. Die er- findungsgemäß eingesetzten hyperverzweigten Polymere können ge- wünschtenfalls auch in Kombination mit weiteren Polymeren eingesetzt werden, wie sie zur Modifizierung der Oberflächeneigenschaften von Substraten üblich sind. Durch eine solche Kombination ist es im Einzelfall möglich, eine Verstärkung der oberflä- chenmodifizierenden Wirkung zu erzielen.The hyperbranched polymers used according to the invention can be used in mixtures or in combination with other surface-active substances. These include conventional anionic, non-ionic or cationic surfactants or wetting agents. If desired, the hyperbranched polymers used according to the invention can also be used in combination with other polymers, as are customary for modifying the surface properties of substrates. Such a combination makes it possible in individual cases to achieve an enhancement of the surface-modifying effect.
Die erfindungsgemäß eingesetzten hyperverzweigten Polyurethane mit Urethan- und/oder Harnstoffgruppen eignen sich in vorteilhafter Weise zur Modifizierung der Oberflächeneigenschaften von Sub- strafen. Diese können im Allgemeinen in Form von teilchen-, li- nien-, flächenförmigen oder dreidimensionalen Gebilden vorliegen. Der Begriff "Modifizierung der Oberflächeneigenschaften" wird im Rahmen der vorliegenden Erfindung weit verstanden. Dazu zählt vor allem die Veränderung der Affinität der Oberfläche gegenüber Was- ser und wasserhaltigen Flüssigkeiten im Vergleich zu einer unmo- difizierten Oberfläche. Die erfindungsgemäß eingesetzten hyperverzweigten Polymere umfassen einerseits Polymere, die die Affinität einer damit behandelten Oberfläche gegenüber Wasser verbessern (hydrophilieren) und andererseits solche, die die Affinität einer damit behandelten Oberfläche gegenüber Wasser verringern (hydrophobieren) . Ein geeignetes Maß zur Beurteilung der Hydro- philie/Hydrophobie der Oberfläche eines Substrats ist die Messung des Randwinkels von Wasser an der jeweiligen Oberfläche (siehe z. B. Römpp, Chemielexikon, 9. Aufl., S. 372 "Benetzung", Georg- Thieme-Verlag (1995)). Erfindungsgemäß wird unter einer "hydrophoben Oberfläche" eine Oberfläche verstanden, deren Kontaktwinkel von Wasser > 90° ist. Unter einer "hydrophilen Oberfläche" wird eine Oberfläche verstanden, deren Kontaktwinkel von Wasser ≤ 90° ist. Hydrophilierende hyperverzweigte Polymere bewirken bei mit ihnen behandelten Oberflächen eine Abnahme des Randwinkels gegenüber der unmodifizierten Oberfläche. Vorzugsweise bewirkt ein hy- drophilierend wirkendes hyperverzweigtes Polymer eine Abnahme des Randwinkels um mindestens 10°, bevorzugt um mindestens 30°, gegenüber der unmodifizierten Oberfläche. Hydrophobierend wirkende hyperverzweigte Polymere bewirken bei mit ihnen behandelten Oberflächen eine Zunahme des Randwinkels gegenüber der unmodifizier- ten Oberfläche. Vorzugsweise bewirken hydrophobierend wirkende hyperverzweigte Polymere eine Zunahme des Randwinkels um mindestens 10°, besonders bevorzugt um mindestens 30°, gegenüber der unmodifizierten Oberfläche.The hyperbranched polyurethanes used according to the invention with urethane and / or urea groups are advantageously suitable for modifying the surface properties of substrates. These can generally be in the form of particulate, linear, sheet-like or three-dimensional structures. The term “modification of the surface properties” is widely understood in the context of the present invention. Above all, this includes changing the affinity of the surface for water and water-containing liquids compared to an unmodified surface. The hyperbranched polymers used according to the invention on the one hand comprise polymers which improve the affinity of a surface treated therewith for water (hydrophilize) and on the other hand those which reduce the affinity of a surface treated therewith with water (hydrophobize). A suitable measure for assessing the hydrophilicity / hydrophobicity of the surface of a substrate is the measurement the contact angle of water on the respective surface (see, for example, Römpp, Chemielexikon, 9th edition, p. 372 "Wettung", Georg-Thieme-Verlag (1995)). According to the invention, a "hydrophobic surface" is understood to mean a surface whose contact angle of water is> 90 °. A "hydrophilic surface" is understood to mean a surface whose contact angle of water is 90 90 °. Hydrophilizing hyperbranched polymers bring about a decrease in the contact angle compared to the unmodified surface on surfaces treated with them. A hydrophilically acting hyperbranched polymer preferably brings about a decrease in the contact angle by at least 10 °, preferably by at least 30 °, with respect to the unmodified surface. Hyperbranched polymers with a hydrophobic effect bring about an increase in the contact angle compared to the unmodified surface on surfaces treated with them. Hyperbranched polymers which have a hydrophobizing action preferably cause the contact angle to increase by at least 10 °, particularly preferably by at least 30 °, compared to the unmodified surface.
Vorteilhafterweise zeigen die erfindungsgemäßen Substrate, die auf ihrer Oberfläche ein hydrophilierend wirkendes hyperverzweigtes Polymer tragen, eine im Allgemeinen wesentlich geringere Abnahme der Grenzflächenspannung von Wasser, als beim Einsatz handelsüblicher Tenside. Dies ist darauf zurückzuführen, dass die eingesetzten Polymere, anders als handelsübliche Polymere, kaum von der Oberfläche abgelöst werden und die Oberflächenspannung senken können. Somit werden unerwünschte Migrationsneigungen in der Regel nicht beobachtet. Die erfindungsgemäß eingesetzten hyperverzweigten Polymere verbleiben auch beim Spülen mit Wasser und wässrigen Flüssigkeiten auf den behandelten Oberflächen und ermöglichen somit eine langanhaltende hydrophile Modifizierung. Die Abnahme der Grenzflächenspannung gegenüber Wasser bei mit hydrophilierenden hyperverzweigten Polymeren modifizierten Oberflächen beträgt im Allgemeinen höchstens 30 %, besonders bevorzugt höchstens 20 % und insbesondere höchstens 10 % gegenüber der unmodifizierten Oberfläche.Advantageously, the substrates according to the invention which have a hyperbranched polymer with a hydrophilizing effect on their surface generally show a substantially smaller decrease in the interfacial tension of water than when using commercially available surfactants. This is due to the fact that, unlike commercially available polymers, the polymers used can hardly be detached from the surface and can lower the surface tension. Unwanted tendencies to migrate are therefore generally not observed. The hyperbranched polymers used according to the invention remain on the treated surfaces even when rinsed with water and aqueous liquids and thus enable long-lasting hydrophilic modification. The decrease in the interfacial tension with respect to water in the case of surfaces modified with hydrophilizing hyperbranched polymers is generally at most 30%, particularly preferably at most 20% and in particular at most 10% compared to the unmodified surface.
Die mit hydrophilierenden hyperverzweigten Polymeren modifizierten erfindungsgemäßen Substrate weisen in der Regel eine schnel- lere und/oder vermehrte Flüssigkeitsaufnahme und/oder eine verbesserte Flüssigkeitsretention, im Allgemeinen auch unter Druck auf.The substrates according to the invention modified with hydrophilizing hyperbranched polymers generally have a faster and / or increased fluid absorption and / or an improved fluid retention, generally also under pressure.
Die erfindungsgemäßen hydrophil modifizierten Substrate eignen sich im Allgemeinen vorteilhaft für alle Einsatzbereiche, bei denen Wasser oder wässrige Flüssigkeiten mit in unmodifiziertem Zustand im Wesentlichen hydrophoben Materialien in Kontakt kommen. Dazu zählt insbesondere das rasche Aufsaugen und/oder der rasche Transport von Wasser in an sich hydrophobe Materialien. Die erfindungsgemäßen Gebilde sind weiterhin im Allgemeinen dort vorteilhaft einsetzbar, wo durch Modifizierung von Oberflächen im Sinne einer Hydrophilierung verbesserte Hafteigenschaften, verbesserte antistatische Eigenschaften, verbesserte Antibeschlagei- genschaften, ein verbesserter Griff und/oder ein verbesserter Tragekomfort erreicht werden kann.The hydrophilically modified substrates according to the invention are generally advantageous for all areas of application in which water or aqueous liquids come into contact with materials which are essentially hydrophobic in the unmodified state. This includes, in particular, the rapid absorption and / or the rapid transport of water in hydrophobic materials per se. The structures according to the invention can furthermore generally be used advantageously where, by modifying surfaces in the sense of hydrophilization, improved adhesive properties, improved antistatic properties, improved anti-fog properties, an improved grip and / or improved wearing comfort can be achieved.
Die erfindungsgemäßen hydrophil modifizierten Substrate eignen sich vorteilhaft in oder als Synthesefasern, Geweben, Gewirken, Vliesstoffen, Filzen, Textilverbundstoffen, wie z. B. Teppichen, kaschierten und laminierten Textilien etc. Sie eignen sich weiterhin in vorteilhafter Weise für den Einsatz in Windeln, Hygie- neeinlagen, Putz- und Wischtüchern, Spültüchern, Servietten,The hydrophilically modified substrates according to the invention are advantageously suitable in or as synthetic fibers, fabrics, knitted fabrics, nonwovens, felts, textile composites, such as. B. carpets, laminated and laminated textiles etc. They are furthermore advantageously suitable for use in diapers, hygiene liners, cleaning and wiping cloths, dishcloths, serviettes,
Landwirtschafts- und/oder Geotextilien sowie für Filteranwendun- gen.Agricultural and / or geotextiles and for filter applications.
Die erfindungsgemäß eingesetzten hydrophilen, hyperverzweigten Polymere sind als Hydrophiliermittel für die oben genannten Materialien, insbesondere für Synthesefasern, beispielsweise solche aus Polyethylen, Polypropylen, Polyestern, Polyacrylnitril und Polyamiden geeignet. Außerdem eignen sich die Polymere zur Verbesserung der Bedruckbarkeit und Klebbarkeit von Filmen und Fo- lien, beispielsweise solchen aus Polyethylen, Polypropylen, Polyvinylchlorid, Polytetrafluorethylen und Polyestern.The hydrophilic, hyperbranched polymers used according to the invention are suitable as hydrophilizing agents for the above-mentioned materials, in particular for synthetic fibers, for example those made of polyethylene, polypropylene, polyesters, polyacrylonitrile and polyamides. The polymers are also suitable for improving the printability and adhesiveness of films and foils, for example those made of polyethylene, polypropylene, polyvinyl chloride, polytetrafluoroethylene and polyesters.
Außerdem lassen sich die antistatischen Eigenschaften von Filmen und Folien durch Verwendung der hydrophilen, hyperverzweigten Po- lymere verbessern.In addition, the antistatic properties of films and foils can be improved by using the hydrophilic, hyperbranched polymers.
Die Verwendung der hydrophilen, hyperverzweigten Polymere führt bei Formkörpern ebenfalls zu einer Verbesserung der Oberflächeneigenschaften, so dass diese besser bedruckbar oder beklebbar sind und bessere antistatische Eigenschaften besitzen. Typische Formkörper sind beispielsweise aus Polyethylen, Polypropylen, Polystyrol, Polyvinylchlorid, Polytetrafluorethylen, Polyestern, Polyacrylnitril, Styrol-Acrylnitril-Copolymeren (SAN), Acrylni- tril-Butadien-Styrol-Terpolymeren (ABS), Polyamiden, wie Polyamid 6 oder Polyamid 6,6, Polyurethanen und/oder Mischungen der vorgenannten Kunststoffe aufgebaut.The use of the hydrophilic, hyperbranched polymers also leads to an improvement in the surface properties of shaped articles, so that they can be better printed or pasted and have better antistatic properties. Typical moldings are, for example, made of polyethylene, polypropylene, polystyrene, polyvinyl chloride, polytetrafluoroethylene, polyesters, polyacrylonitrile, styrene-acrylonitrile copolymers (SAN), acrylonitrile-butadiene-styrene terpolymers (ABS), polyamides, such as polyamide 6 or polyamide 6, 6, polyurethanes and / or mixtures of the aforementioned plastics.
Außerdem führt die Verwendung von hydrophilen, hyperverzweigten Polymeren mit Urethan- und/oder Harnstoffgruppen zu einer Verbes- serung der Oberflächenleitfähigkeit von hydrophoben, nichtleitenden Materialien, insbesondere den vorgenannten Kunststoffen, und verbessert damit deren antistatische Eigenschaften. Ferner sind die hydrophilen, hyperverzweigten Polymere geeignet, die Beschlagsneigung von Kunststofffolien zu reduzieren.In addition, the use of hydrophilic, hyperbranched polymers with urethane and / or urea groups leads to an improvement in the surface conductivity of hydrophobic, non-conductive materials, in particular the aforementioned plastics, and thus improves their antistatic properties. Furthermore are the hydrophilic, hyperbranched polymers are suitable for reducing the tendency of plastic films to fog up.
Die Ausrüstung der erfindungsgemäßen Substrate in Form teilchen-, linien-, flächenförmiger oder dreidimensionaler Gebilde mit den hyperverzweigten Polymeren kann nach den Verfahren erfolgen, wie man sie üblicherweise zur Hydrophilierung bzw. Hydrophobierung der vorgenannten Gebilde mit Hydrophiliermitteln bzw. Hydropho- biermitteln des Stands der Technik anwendet. Üblicherweise behan- delt man hierzu das Gebilde mit einer verdünnten, vorzugsweise wässrigen Lösung des Polymers in einer für die Art des Gebildes üblichen Weise, z. B. durch Spülen, Tauchen, Besprühen, Bepflatschen oder ähnlichen Methoden, wie sie üblicherweise bei der Ausrüstung von textilen Geweben oder Folien eingesetzt werden. Der Polymergehalt der Lösungen liegt in der Regel im Bereich von wenigstens 0,01 bis 20 Gew.-% und vorzugsweise 0,1 bis 10 Gew.-%, bezogen, auf das Gewicht der Lösung. Vorzugsweise setzt man zur Behandlung wässrige Lösungen der Polymere ein. Die zur Hydrophilierung bzw. Hydrophobierung erforderliche Menge an Polymer wird von der Oberfläche absorbiert oder adsorbiert und verbleibt nach dem Trocknen auf ihr haften. Die zur Erzielung einer wirksamen. Hydrophilierung bzw. Hydrophobierung erforderlichen Mengen stellen sich dabei automatisch ein und sind äußerst gering. Bei Gebilden mit glatter Oberfläche wie Folien und ähnlichen Gebilden reichen bereits 0,1 mg/m2 Polymer aus.The substrates according to the invention in the form of particulate, linear, sheet-like or three-dimensional structures with the hyperbranched polymers can be carried out according to the methods normally used for hydrophilizing or hydrophobicizing the aforementioned structures with hydrophilizing agents or hydrophobicizing agents of the prior art applies. For this purpose, the structure is usually treated with a dilute, preferably aqueous solution of the polymer in a manner customary for the type of structure, eg. B. by rinsing, dipping, spraying, splashing or similar methods, as are usually used in the finishing of textile fabrics or films. The polymer content of the solutions is generally in the range from at least 0.01 to 20% by weight and preferably 0.1 to 10% by weight, based on the weight of the solution. Aqueous solutions of the polymers are preferably used for the treatment. The amount of polymer required for hydrophilization or hydrophobization is absorbed or adsorbed by the surface and remains adhering to it after drying. To achieve effective. The amounts required for hydrophilization or hydrophobization are automatically established and are extremely low. For structures with a smooth surface such as foils and similar structures, 0.1 mg / m 2 of polymer is sufficient.
In einer anderen Ausgestaltung des erfindungsgemäßen Verfahrens zur Hydrophilierung bzw. Hydrophobierung von Oberflächen kann man das Polymer auch dem Werkstoff, aus dem das Gebilde aufgebaut ist, zusetzen und anschließend hieraus das Gebilde herstellen. Beispielsweise kann man bei Ausrüstung von thermoplastischen Kunststoffen das Polymer als Feststoff mit dem Kunststoffmaterial kompoundieren. Das so ausgerüstete Kunststoffmaterial wird dann nach den üblichen Verfahren zu Folien, beispielsweise durch Extrusion, oder zu Fasermaterialien, beispielsweise durch ein Schmelzspinnverfahren, weiterverarbeitet.In another embodiment of the method according to the invention for hydrophilizing or hydrophobicizing surfaces, the polymer can also be added to the material from which the structure is made and then the structure can be produced therefrom. For example, when finishing thermoplastic materials, the polymer can be compounded as a solid with the plastic material. The plastic material equipped in this way is then further processed by the usual methods to give films, for example by extrusion, or to fiber materials, for example by a melt spinning process.
Die einfache Anwendbarkeit der erfindungsgemäßen und erfindungsgemäß eingesetzten Polymere erlaubt den Einsatz in vielen Anwen- dungsbereichen, beispielsweise als Hydrophiliermittel für Vliesstoffe, die z. B. in Windeln, Hygieneeinlagen, Textilien, Landwirtschafts- oder Geotextilien oder Filteranlagen eingesetzt werden. Die mit den Polymeren ausgerüsteten Kunststofffasern können ihrerseits zu Textilien weiterverarbeitet werden. Durch die Hy- drophilierung bzw. Hydrophobierung wird in der Regel auch die Wasserdampfdurchlässigkeit und der Kapillartransport von Schweiß verbessert sowie das Anschmutzverhalten gegenüber vielen hydroph- oben Schmutzarten verringert. Außerdem wird die Wiederablösbar- keit von Schmutz positiv beeinflusst. Weiterhin kann man die Polymere als Antistatikausrüstung für Kunststofffolien oder Silizi- umwafer verwenden.The simple applicability of the polymers according to the invention and used according to the invention permits use in many areas of application, for example as a hydrophilizing agent for nonwovens which, for. B. in diapers, hygiene pads, textiles, agricultural or geotextiles or filter systems. The plastic fibers finished with the polymers can in turn be further processed into textiles. The hydrophilization or hydrophobization generally also improves the water vapor permeability and the capillary transport of sweat and the soiling behavior compared to many hydrophobic substances. Dirt types reduced above. In addition, the releasability of dirt is positively influenced. The polymers can also be used as antistatic equipment for plastic films or silicon wafers.
BeispieleExamples
Beispiele 1 bis 4: erfindungsgemäße hyperverzweigte PolymereExamples 1 to 4: Hyperbranched polymers according to the invention
Herstellung der Polyharnstoffe und PolyurethaneManufacture of polyureas and polyurethanes
Beispiele 1 und 2 : erfindungsgemäße PolyharnstoffeExamples 1 and 2: polyureas according to the invention
In einem Reaktionsgefäß mit Rührer, Innenthermometer, Stickstoffeinleitrohr wurde unter Begasung mit trockenem Stickstoff 10 Mol wasserfreies Butanol vorgelegt und 1000 ppm (bezogen auf Isocyanat) Dibutylzinndilaurat zugesetzt. Anschließend wurde die Lösung auf 60 °C erwärmt und 1 Mol 2,4-Toluylendiisocyanat so zu- gegeben, dass die Temperatur der Reaktionsmischung 70 °C nicht überschritt. Nach der Zugabe des Isocyanats wurde noch 1 h bei 70 °C gerührt. Anschließend wurde die in Tabelle 1 angegebene Menge des Amins bzw. des Amingemischs zugegeben, die Temperatur auf den in Tabelle 1 angegebenen Wert erhöht und bei dieser Tem- peratur entsprechend dem in der Tabelle angegebenen Zeitraum reagieren gelassen. Danach wurde das Reaktionsprodukt am Rotationsverdampfer im Vakuum von Butanol befreit, auf Raumtemperatur abgekühlt und mittels GPC-Analytik analysiert.10 moles of anhydrous butanol were introduced into a reaction vessel with a stirrer, internal thermometer and nitrogen inlet tube while being gassed with dry nitrogen and 1000 ppm (based on isocyanate) of dibutyltin dilaurate were added. The solution was then heated to 60 ° C. and 1 mol of 2,4-tolylene diisocyanate was added so that the temperature of the reaction mixture did not exceed 70 ° C. After the isocyanate had been added, the mixture was stirred at 70 ° C. for 1 h. The amount of the amine or of the amine mixture given in Table 1 was then added, the temperature was raised to the value given in Table 1 and the mixture was left to react at the temperature given in the table. The reaction product was then freed of butanol on a rotary evaporator in vacuo, cooled to room temperature and analyzed by means of GPC analysis.
In Beispiel 1 wurde der Polyharnstoff mittels OH-Gruppen hydrophil, in Beispiel 2 mit Alkylketten hydrophob modifiziert.In example 1 the polyurea was modified hydrophilically by means of OH groups, in example 2 with alkyl chains hydrophobically.
Tabelle 1 : Erfindungsgemäße PolyharnstoffeTable 1: Polyureas according to the invention
Beispiel 3 : erfindungsgemäßer Polyharnstoff : Example 3: Polyurea According to the Invention:
In einem Reaktionsgefäß mit Rührer, Innenthermometer und Rückflusskühler wurde 1 Mol Isophorondiisocyanat vorgelegt, das Gefäß mit trockenem Stickstoff inertisiert und das Isocyanat auf 70 °C erwärmt. Dann wurden 1000 ppm (bezogen auf Isocyanat) Dibutyl- zinndilaurat zugegeben und 2,1 Mol Butanol so zugetropft, dass die Innentemperatur 80 °C nicht überstieg. Nach Zugabe des Alkohols wurde noch 1 h bei 70 °C gerührt, dann wurden 0,5 Mol Diethy- lentriamin zugegeben und die Temperatur auf 140 °C erhöht. Nach 8 h Reaktion bei 140 °C wurde das Produktgemisch am Rotationsverdampfer von Butanol befreit. Die GPC-Analytik des Produktes in Dimethylacetamid lieferte gegen PMMA-Eichung folgende Werte:1 mol of isophorone diisocyanate was placed in a reaction vessel with stirrer, internal thermometer and reflux condenser, the vessel was rendered inert with dry nitrogen and the isocyanate was heated to 70.degree. Then 1000 ppm (based on isocyanate) of dibutyltin dilaurate were added and 2.1 mol of butanol were added dropwise so that the internal temperature did not exceed 80.degree. After the alcohol had been added, the mixture was stirred at 70 ° C. for 1 h, then 0.5 mol of diethylenetriamine was added and the temperature was raised to 140 ° C. After 8 hours of reaction at 140 ° C., the product mixture was freed from butanol on a rotary evaporator. The GPC analysis of the product in dimethylacetamide gave the following values against PMMA calibration:
Mn = 1050 g/mol, Mw = 1870 g/molM n = 1050 g / mol, M w = 1870 g / mol
Beispiel 4: erfindungsgemäßes Polyurethan:Example 4: Polyurethane According to the Invention:
In einem Reaktionsgefäß mit Rührer, Innenthermometer und Rück- flusskühler wurde bei Raumtemperatur 1 Mol Isophorondiisocyanat vorgelegt und das Gefäß mit trockenem Stickstoff inertisiert. Anschließend wurde innerhalb 1 min die Mischung aus 0,5 Mol Tri e- thylolpropan und 0,5 Mol Dimethylolpropionsäure, gelöst in 356 g Dimethylacetamid, unter gutem Rühren zugegeben. Nach Zudosierung von 0,4 g Dibutylzinndilaurat wurde die Reaktionsmischung auf 60 °C erwärmt, bei dieser Temperatur gerührt und die Abnahme des Isocyanat-Gehaltes der Mischung titrimetrisch gemäß DIN 53185 verfolgt. Bei Erreichen eines NCO-Gehaltes von 0,7 Gew.% wurden der Mischung 50 g Methanol zugesetzt und noch 30 min bei 60 °C ge- rührt. Anschließend wurde das Reaktionsgemisch am Rotationsverdampfer vom Lösemittel befreit. Das Produkt wurde in Wasser aufgenommen und mit wässriger Ammoniak-Lösung neutralisiert, so dass eine 50%ige wässrige Lösung des Polymeren resultierte.1 mole of isophorone diisocyanate was placed in a reaction vessel with stirrer, internal thermometer and reflux condenser at room temperature and the vessel was rendered inert with dry nitrogen. The mixture of 0.5 mol of triethylolpropane and 0.5 mol of dimethylolpropionic acid, dissolved in 356 g of dimethylacetamide, was then added with thorough stirring within 1 minute. After 0.4 g of dibutyltin dilaurate had been metered in, the reaction mixture was heated to 60 ° C., stirred at this temperature and the decrease in the isocyanate content of the mixture was monitored titrimetrically in accordance with DIN 53185. When an NCO content of 0.7% by weight was reached, 50 g of methanol were added to the mixture and stirring was continued at 60 ° C. for 30 minutes. The reaction mixture was then freed from the solvent on a rotary evaporator. The product was taken up in water and neutralized with aqueous ammonia solution, so that a 50% aqueous solution of the polymer resulted.
Beispiele 5 bis 10:Examples 5 to 10
Modifizierung von OberflächenModification of surfaces
Beispiel 5:Example 5:
Eine 50%ige Lösung des hyperverzweigten Polyharnstoffs aus Beispiel 2 in Ethanol wird auf eine nicht behandelte PP-Folie in einer Schichtdicke von 30 um aufgeräkelt. Nach dem Trocknen bei 50 °C wird der Randwinkel eines aufgesetzten Wassertropfens bestimmt. Randwinke1: 27°A 50% strength solution of the hyperbranched polyurea from Example 2 in ethanol is applied onto a non-treated PP film in a layer thickness of 30 μm. After drying at 50 ° C, the contact angle of a drop of water is determined. Contact angle 1: 27 °
PP-Folie (z. Vgl.): 103°PP film (compare): 103 °
Beispiel 6 : 5Example 6: 5
Eine 50%ige Lösung des hyperverzweigten Polyharnstoffs aus Beispiel 1 in Ethanol wird auf eine nicht behandelte PP-Folie in einer Schichtdicke von 30 μm aufgeräkelt. Nach dem Trocknen bei 50 °C wird der Randwinkel eines aufgesetzten Wassertropfens be- 10 stimmt.A 50% solution of the hyperbranched polyurea from Example 1 in ethanol is applied onto a non-treated PP film in a layer thickness of 30 μm. After drying at 50 ° C, the contact angle of a drop of water is determined.
Randwinkel: 9°Contact angle: 9 °
PP-Folie (z. Vgl.) 103°PP film (e.g. see) 103 °
15 Beispiel 7 :15 Example 7:
Eine 50%ige Lösung des hyperverzweigten Polyharnstoffs aus Beispiel 3 in Ethanol wurde auf eine nicht behandelte PP-Folie in einer Schichtdicke von 30μm aufgeräkelt. Nach dem Trocknen bei 20 50°C wurde der Randwinkel eines aufgesetzten Wassertropfens bestimmt. Der Film ließ sich mit Wasser nicht mehr abwaschenA 50% solution of the hyperbranched polyurea from Example 3 in ethanol was applied onto a non-treated PP film in a layer thickness of 30 μm. After drying at 20 50 ° C, the contact angle of a drop of water was determined. The film could no longer be washed off with water
Randwinke1: 37°Contact angle 1: 37 °
PP-Folie (z. Vgl.) 103° 25PP film (e.g. see) 103 ° 25
Beispiel 8 :Example 8:
Eine 10%ige wässrige Lösung des hyperverzweigten Polyurethans aus Beispiel 4 wurde auf eine nicht behandelte PP-Folie in einer 30 Schichtdicke von 30 μm aufgeräkelt. Nach dem Trocknen bei 50 °C wurde der Randwinkel eines aufgesetzten Wassertropfens bestimmt. Der Film ließ sich mit Wasser nicht mehr abwaschen.A 10% aqueous solution of the hyperbranched polyurethane from Example 4 was applied onto a non-treated PP film in a 30 layer thickness of 30 μm. After drying at 50 ° C, the contact angle of a drop of water was determined. The film could no longer be washed off with water.
Randwinkel: 69Contact angle: 69
35 PP-Folie (z. vgl.) 10335 PP film (e.g. see) 103
Beispiel 9 :Example 9:
Hydrophile Saugkartonstücke der Fa. Schleicher & Schuell (Sorte 40 2282) werden in eine 5%ige Lösung des hyperverzweigten Polyharnstoffs aus Beispiel 1 in Ethanol getaucht. Anschließend lässt man die Kartonstücke bei Raumtemperatur an Luft trocknen. Das Einsinkverhalten von aufgesetzten Wassertropfen wird dem KW-Messge- rät dataphysics 0CA15+ verfolgt. Es ist in Figur 1 dargestellt. 45 Ein unbehandeltes Stück Karton saugt einen aufgesetzten Wassertropfen innerhalb einer Sekunde auf.Hydrophilic suction cardboard pieces from Schleicher & Schuell (grade 40 2282) are immersed in a 5% solution of the hyperbranched polyurea from Example 1 in ethanol. The pieces of cardboard are then left to air dry at room temperature. The sinking behavior of attached water drops is monitored by the KW measuring device dataphysics 0CA15 +. It is shown in Figure 1. 45 An untreated piece of cardboard soaks up a drop of water within a second.
Beispiel 10:Example 10:
Das hyperverzweigte Polymer aus Beispiel 2 wird auf 20 % Polymer¬ gehalt mit Ethanol verdünnt. Baumwollstücke wurden in dieser Lösung getränkt und an der Laborpresse abgepresst. Nach dem Trocknen wurde die Belegung bestimmt. Die Belegung betrug 24 %, bezo- gen auf das Gewicht des Gewebes. Dann wurde das Einsinkverhalten von Wasser auf dem Gewebe beobachtet. Das Gewebe wurde 10 Tage lang bei Raumtemperatur an Tageslicht gelagert. Anschließend wurde das Einsinkverhalten mit dem KW-Messgerät dataphysics 0CA15+ überprüft. Es ist in Figur 2 dargestellt.The hyperbranched polymer of Example 2 is content to 20% polymer ¬ diluted with ethanol. Cotton pieces were soaked in this solution and pressed on the laboratory press. After drying, the occupancy was determined. The occupancy was 24%, based on the weight of the fabric. Then the sinking behavior of water on the tissue was observed. The tissue was stored in daylight at room temperature for 10 days. Then the sinking behavior was checked with the KW measuring device dataphysics 0CA15 +. It is shown in Figure 2.
Ein unbehandeltes Stück Baumwollgewebe saugt einen aufgesetzten Wassertropfen innerhalb einer Sekunde auf. An untreated piece of cotton fabric soaks up a drop of water within a second.

Claims

Patentansprüche claims
1. Substrat, enthaltend auf seiner Oberfläche wenigstens ein hy- perverzweigtes Polymer, das Urethan- und/oder Harnstoffgruppen aufweist.1. Substrate containing on its surface at least one hyperbranched polymer which has urethane and / or urea groups.
2. Substrat nach Anspruch 1 in Form eines teilchen-, linien-, flächenförmigen oder dreidimensionalen Gebildes.2. Substrate according to claim 1 in the form of a particle, line, sheet or three-dimensional structure.
3. Substrat nach Anspruch 2 in Form eines linien- oder flächenförmigen textilen Gebildes .3. Substrate according to claim 2 in the form of a linear or sheet-like textile structure.
4. Substrat nach Anspruch 3 , worin das textile Gebilde aus Kunststofffasern aufgebaut ist.4. The substrate according to claim 3, wherein the textile structure is composed of plastic fibers.
5. Substrat nach Anspruch 2, worin das Gebilde in Form einer Kunststofffolie oder eines Kunststoffformkörpers vorliegt.5. The substrate of claim 2, wherein the structure is in the form of a plastic film or a molded plastic body.
6. Substrat nach einem der vorhergehenden Ansprüche, wobei das hyperverzweigte Polymer einen Verzweigungsgrad (DB) von 10 bis 100 % aufweist.6. Substrate according to one of the preceding claims, wherein the hyperbranched polymer has a degree of branching (DB) of 10 to 100%.
7. Substrat nach einem der vorhergehenden Ansprüche, wobei das hyperverzweigte Polymer auf der Substratoberfläche erhältlich ist durch polymeranaloge Umsetzung eines hyperverzweigten Polymers, das Urethan- und/oder Harnstoffgruppen und/oder weitere funktionelle Gruppen trägt, die zu einer Kondensations- oder Additionsreaktion befähigt sind, mit wenigstens einer Verbindung, die ausgewählt ist unter7. Substrate according to one of the preceding claims, the hyperbranched polymer being obtainable on the substrate surface by polymer-analogous reaction of a hyperbranched polymer which carries urethane and / or urea groups and / or further functional groups which are capable of a condensation or addition reaction, with at least one compound selected from
a) Verbindungen, die wenigstens eine zu den zur Kondensations- oder Additionsreaktion befähigten Gruppen des hyperverzweigten Polymers komplementäre funktionelle Gruppe und zusätzlich wenigstens eine hydrophile Gruppe tragen,a) compounds which carry at least one functional group which is complementary to the groups of the hyperbranched polymer capable of condensation or addition reaction and additionally carry at least one hydrophilic group,
b) Verbindungen, die wenigstens eine zu den zur Kondensations- oder Additionsreaktion befähigten Gruppen des hyperverzweigten Polymers komplementäre funktionelle Gruppe und zusätzlich wenigstens eine hydrophobe Gruppe tragen,b) compounds which carry at least one functional group which is complementary to the groups of the hyperbranched polymer capable of condensation or addition reaction and additionally carry at least one hydrophobic group,
und Mischungen davon. and mixtures thereof.
8. Verwendung eines hyperverzweigten Polymers, das Urethan- und/ oder Harnstoffgruppen aufweist, zur Modifizierung der Ober¬ flächeneigenschaften von Substraten.8. Use comprising a hyperbranched polymer containing urethane and / or urea groups, for modification of the upper ¬ surface properties of substrates.
5 9. Verfahren zur Modifizierung der Oberflächeneigenschaften von Substraten, bei dem man auf die Oberfläche des Substrats eine wirksame Menge eines hyperverzweigten Polymers, das Urethan- und/oder Harnstoffgruppen trägt, aufbringt.5 9. A method for modifying the surface properties of substrates, in which an effective amount of a hyperbranched polymer carrying urethane and / or urea groups is applied to the surface of the substrate.
10 10. Verfahren zur Modifizierung der Oberflächeneigenschaften von Substraten, bei dem man den Werkstoff, aus dem das Substrat besteht, mit einer wirksamen Menge eines hyperverzweigten Polymers, das Urethan- und/oder Harnstoffgruppen aufweist, versetzt und hieraus das Substrat herstellt.10 10. A method for modifying the surface properties of substrates, in which the material from which the substrate is made is mixed with an effective amount of a hyperbranched polymer which has urethane and / or urea groups, and the substrate is produced therefrom.
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US20060035091A1 (en) 2006-02-16
AU2003289852A1 (en) 2004-05-13
CA2503217A1 (en) 2004-05-06
MXPA05003910A (en) 2005-06-17
WO2004037881A1 (en) 2004-05-06
BR0315557A (en) 2005-08-23
JP2006503947A (en) 2006-02-02

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