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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• Chemical & Material Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Organic Chemistry (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Health & Medical Sciences (AREA)
• Engineering & Computer Science (AREA)
• Materials Engineering (AREA)
• Life Sciences & Earth Sciences (AREA)
• Wood Science & Technology (AREA)
• Manufacturing & Machinery (AREA)
• Textile Engineering (AREA)
• Compositions Of Macromolecular Compounds (AREA)
• Polyurethanes Or Polyureas (AREA)
• Coating Of Shaped Articles Made Of Macromolecular Substances (AREA)
• Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)

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• 2002
  • 2002-10-25 DE DE2002149841 patent/DE10249841A1/de not_active Withdrawn
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