WO2002070578A1 - Verwendung von anionischen polymeren, die urethan- und/oder harnstoffgruppen aufweisen, zur modifizierung von oberflächen - Google Patents
Verwendung von anionischen polymeren, die urethan- und/oder harnstoffgruppen aufweisen, zur modifizierung von oberflächen Download PDFInfo
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- WO2002070578A1 WO2002070578A1 PCT/EP2002/002201 EP0202201W WO02070578A1 WO 2002070578 A1 WO2002070578 A1 WO 2002070578A1 EP 0202201 W EP0202201 W EP 0202201W WO 02070578 A1 WO02070578 A1 WO 02070578A1
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- 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
-
- 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
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
-
- 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
-
- 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
- C08G18/28—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
- C08G18/38—Low-molecular-weight compounds having heteroatoms other than oxygen
- C08G18/3819—Low-molecular-weight compounds having heteroatoms other than oxygen having nitrogen
- C08G18/3821—Carboxylic acids; Esters thereof with monohydroxyl compounds
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- 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
- C08G18/38—Low-molecular-weight compounds having heteroatoms other than oxygen
- C08G18/3855—Low-molecular-weight compounds having heteroatoms other than oxygen having sulfur
- C08G18/3857—Low-molecular-weight compounds having heteroatoms other than oxygen having sulfur having nitrogen in addition to sulfur
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- 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
-
- 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
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- 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
- Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
- Y10T428/2913—Rod, strand, filament or fiber
- Y10T428/2933—Coated or with bond, impregnation or core
-
- 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
- Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
- Y10T428/2982—Particulate matter [e.g., sphere, flake, etc.]
- Y10T428/2991—Coated
- Y10T428/2998—Coated including synthetic resin or polymer
-
- 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]
- Y10T428/31547—Of polyisocyanurate
Definitions
- the present invention relates to particulate, linear, sheet-like or three-dimensional structures which, at least on their surface, have a hydrophilizing amount of a polymer which has urethane and / or urea groups and anionic groups.
- the invention further relates to a polymer obtained from at least one polyisocyanate and at least one compound having at least one group which is reactive toward isocyanate groups and at least one anionic group or group which can be converted into an anionic group, and also a process for modifying the surface properties of particles, lines and , flat or three-dimensional structures.
- Objects made of synthetic materials such as thermosetting or thermoplastic plastics, generally 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 wipes, dishcloths and napkins. 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 should be dried as completely as possible.
- a cleaning cloth absorbs liquids the faster the faster they are transported on the surface of the fibers, whereby fibers with a hydrophilic surface are easily and quickly wetted by aqueous liquids.
- hydrophilizing agents such as emulsifiers, surfactants or wetting agents are also used to improve the water absorption properties of nonwovens. 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.
- WO 98/27263 continuously discloses hydrophilic polymer coatings for polyester, polypropylene and similar fibers.
- the coating contains certain polyoxyproylamines 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.
- the present invention has for its object to provide hydrophilic particle, line, sheet or three-dimensional structures and a method for increasing the surface hydrophilicity of such structures.
- this object is achieved by a particle, line, sheet-like or three-dimensional structure containing, at least on its surface, a hydrophilizing amount of at least one polymer which has urethane and / or urea groups and anionic groups, the urethane content - And / or urea groups is at least 2 mol / kg polymer.
- Preferred configurations of the structure according to the invention are linear or planar textile structures.
- Other preferred configurations of the structure according to the invention are plastic films or plastic molded bodies.
- particle structures encompasses the range from fine pigments to macroscopic particles. These include in particular those with a particle size of 1 nm to 10 mm, in particular 10 nm to 1 mm, which are preferably dispersible or dispersed in a medium. Examples include pigments, mineral or metallic fillers or inanimate organic materials.
- Line-shaped structures are understood in particular to mean 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 (fleece) is deposited, which is then consolidated into nonwovens using different processes.
- the fleece is coated with an aqueous binder, e.g. B. treated with a polymer latex and then, optionally after removing excess binder, dried and optionally hardened.
- Sheet-like structures are also foils, paper and comparable two-dimensional structures.
- textile composites such as, for. B. carpets, laminated and laminated textiles etc. understood.
- Three-dimensional structures are generally shaped bodies of various dimensions. These include, in particular, moldings 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 planar textile structures.
- Other preferred configurations of the structure according to the invention are plastic films or plastic moldings.
- the structures used according to the invention preferably comprise at least one natural or synthetic polymeric material.
- Suitable polymeric materials are e.g. B. Polymers with essentially hydrophobic surface properties, which are obtainable by radical polymerization of monomers with at least one ethylenically unsaturated double bond. Suitable monomers are e.g. B.
- esters selected from esters, ß-ethylenically unsaturated mono- and dicarboxylic acids with monohydric alcohols, amides ⁇ , ß-ethylenically unsaturated mono- and / or dicarboxylic acids with N-alkyl and N, N-dialkylamines, esters of vinyl alcohol or allyl alcohol with monocarboxylic acids , Vinyl ethers, vinyl aromatics, vinyl halides, vinylidene halides, (meth) acrylonitrile, mono- and diolefins and mixtures thereof.
- Suitable polymeric materials are also polyamides, polyesters, aldehyde resins, epoxy resins and polyurethanes. The polymeric materials can be used individually or in the form of mixtures.
- Preferred polymeric materials are:
- Polymers of mono- and diolefins for example polyethylene, polypropylene, polyisobutylene, polybutene-1, poly-4-methylpentene-1, polyisoprene or polybutadiene, and polymers of cycloolefins, such as, for. B. of cyclopentene or norborne;
- vinyl aromatics in particular polystyrene, poly- (p-methylstyrene) and poly- (-methylstyrene); ,
- Copolymers of vinyl aromatics such as styrene or ⁇ -methylstyrene, e.g. B. with dienes or acrylic derivatives such as styrene-butadiene, styrene-acrylonitrile, styrene-alkyl (meth) acrylate, styrene-butadiene-alkyl (meth) acrylate, styrene-maleic anhydride, styrene-acrylonitrile-methyl (meth) acrylate;
- graft copolymers of vinyl aromatics such as styrene or ⁇ -methylstyrene, such as.
- Halogen-containing homopolymers and copolymers e.g. B. of vinyl halides and vinylidene halides;
- Polyamides and copolyamides the z. B. derived from diamines and 5 dicarboxylic acids and / or from amino carboxylic 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, etc .;
- Phenol-formaldehyde, urea-formaldehyde and melamine-formaldehyde resins Phenol-formaldehyde, urea-formaldehyde and melamine-formaldehyde resins
- Crosslinkable acrylic resins which are derived from substituted acrylic acid esters, such as. B. of epoxy acrylates, urethane acrylates or polyester acrylates;
- Epoxy resins which are derived, for example, from aliphatic, cycloaliphatic, heterocyclic or aromatic glycine
- Derive 30 dyl compounds e.g. B. Products of bisphenol A diglycidyl ethers;
- 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 acrylonitrile-butadiene-styrene copolymers
- polyurethanes polyurethanes and mixtures (polyblends) of the aforementioned polymers.
- the structures used according to the invention are preferably plastic fibers, in particular made of polyolefins, such as 45.
- polyolefins such as 45.
- 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. B. polyvinyl chloride and / or polytetrafluoroethylene, polyesters and mixtures thereof.
- the structure used according to the invention is preferably also 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 6,6, 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 polymer which has urethane and / or urea groups and anionic groups is used to modify the surface properties.
- the polymer always contains a proportion of anionic (negatively charged) groups. Charged anionic groups can be generated from the (uncharged) groups of the compounds of component b) and / or of the polymer which can be converted into anionic groups by deprotonation. The polymer then contains at least some of the groups that can previously be converted into anionic groups in the form of its reaction products with at least one neutralizing (deprotonating) agent.
- the polyisocyanates a) are preferably selected from compounds with 2 to 5 isocyanate groups, isocyanate prepolymers with an average number of 2 to 5 isocyanate groups, oligomers of di- and polyisocyanates with free NCO groups, such as isocyanate, biuret and / or allophanate groups containing compounds and mixtures thereof. Also suitable are compounds which, in addition to or instead of free isocyanate groups, have functional groups which release isocyanate groups or react like isocyanate groups. These include e.g. B. capped isocyanate groups and uretdione compounds.
- the compounds containing isocyanurate groups are in particular simple triisocyanatoisocyanurates, ie cyclic trimers of diisocyanates, or mixtures with their higher homologues containing more than one isocyanurate ring.
- Compounds containing biotroups can e.g. B. are obtained by adding three molecules of diisocyanate to one molecule of water. Capped isocyanate groups are formed in the reaction with a blocking agent, which releases the isocyanate groups again when the blocked isocyanate groups are heated to a temperature which corresponds at least to the so-called deblocking temperature.
- Compounds that block (block or protect) isocyanate groups are the usual ones known to those skilled in the art. These include e.g. B. phenols, caprolactam, imidazoles, pyrazoles, pyrazolines, 1,2,4-triazoles, diketopiperazines, malonic esters and oximes.
- Aliphatic, cycloaliphatic and aromatic diisocyanates are preferably used as component a). Suitable aliphatic diisocyanates then preferably have a hydrocarbon radical with 4 to 12 carbon atoms. Suitable cycloaliphatic and aromatic diisocyanates preferably have a cycloaliphatic or aromatic hydrocarbon radical with 6 to 15 carbon atoms or an araliphatic hydrocarbon radical with 7 to 15 carbon atoms. Suitable diisocyanates are e.g. B.
- tetramethylene diisocyanate hexamethylene diisocyanate, 2,3, 3-trimethylhexamethylene diisocyanate, dodecamethylene diisocyanate, 1,4-cyclohexylene diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, 2,2-bis (4-isocyanatocyclohexyl) propane -Phenylene diisocyanate, 2,4- and 2,6-tolylene diisocyanate and their isomer mixtures (e.g.
- Diisocyanate mixtures used with preference are the isomer mixtures of tolylene diisocyanate and diphenylmethane diisocyanate and in particular a tolylene diisocyanate isomer mixture. mix of about 80% 2,4- and about 20% 2,6-isomer. Mixtures which comprise at least one aromatic and at least one aliphatic and / or cycloaliphatic diisocyanate are also preferred. The mixing ratio of aliphatic and / or cycloaliphatic to aromatic diisocyanates is preferably in a range from about 4: 1 to 1: 4.
- a suitable triisocyanate is e.g. B. triphenylmethane-4,4 ', 4''triisocyanate.
- isocyanate prepolymers and polyisocyanates which can be obtained by adding the aforementioned diisocyanates to polyfunctional compounds containing hydroxyl or amine groups. These include e.g. B. the low molecular weight adducts of 3 moles of diisocyanate, such as hexamethylene diisocyanate, isophorone diisocyanate etc.
- trihydric alcohols such as. B. Trimethylolpropane with a molecular weight of usually at most 400 g / mol. Hexamethylene diisocyanate, isophorone diisocyanate and mixtures thereof are preferably used.
- the groups of the compounds of component b) which are reactive toward isocyanate groups are preferably selected from hydroxyl groups, primary and secondary amino groups and thiol groups. Depending on these groups, polymers result which have urethane groups, urea groups and / or thiocarbamate groups.
- the anionic groups or groups which can be converted into an anionic group are preferably carboxylic acid groups, phosphonic acid groups, phosphoric acid groups and / or sulfonic acid groups and their reaction products with at least one neutralizing agent.
- Hydroxyalkylcarboxylic acids and dihydroxyalkylcarboxylic acids are preferred, the alkyl radicals preferably having 1 to 10 carbon atoms.
- Suitable hydroxycarboxylic acids are e.g. B. hydroxyacetic acid (glycolic acid), hydroxypropionic acid (lactic acid), hydroxy succinic acid (malic acid) and the salts thereof.
- Preferred dihydroxyalkyl carboxylic acids are 2,2-di (hydroxymethyl) alkyl carboxylic acids of the formula
- R is hydroxymethyl, hydrogen or -CC 20 alkyl.
- Suitable compounds b) which have at least one sulfonic acid group or a sulfonate as a polar functional group are, for.
- dicarboxylic acids z.
- sulfosuccinic acid 4-sulfophthalic acid, 5-sulfoisophthalic acid, sulfoterephthalic acid, 4-sulfonaphthalene-2, 7-dicarboxylic acid, 5- (4-sulfophenoxy) terephthalic acid or the corresponding metal sulfonates can be used.
- Further suitable compounds b) which have at least one sulfonic acid or sulfonate group are appropriately substituted straight-chain or branched aliphatic, cycloaliphatic or aromatic diols. These include e.g. B. 2-sulfo-l, 4-butanediol, 2, 5-dimethyl-3-sulfo-2, 5-hexanediol and their sodium and potassium salts.
- R is in each case a C 2 -C 8 -alkylene group and Me is Na or K.
- Suitable compounds b) with at least one thiol group are those compounds which are derived from the abovementioned compounds b) with at least one hydroxyl group by (formal) replacement of one or, if possible, some or all of the OH groups by an SH group.
- Suitable compounds b) with at least one primary and / or secondary amino group reactive towards isocyanate groups are e.g. B. aminocarboxylic acids such as lysine, alanine, valine, etc., aminosulfonic acids etc.
- Suitable compounds b) are also those in the
- DE-A-20 34 479 described adducts of aliphatic diamines with two primary amino groups on ⁇ , ⁇ -unsaturated carboxylic acids. This mainly results in N-aminoalkyl-aminoalkane carboxylic acids, such as. B. N- (2-aminoethyl) -2-aminoethane carboxylic acids. The alkanediyl units preferably have 2 to 6 carbon atoms.
- DE-A-20 34 479 is referred to here in full.
- the amount used is preferably selected so that polymers with a molecular weight of at least 1000 g / mol result.
- Suitable compounds b) with a group reactive towards isocyanate groups are the aforementioned monohydroxycarboxylic acids and monothio- and monoamino acids.
- the anionic groups are preferably in the form of the alkali metal or ammonium salts.
- Suitable neutralizing agents are alkali metal bases, such as sodium hydroxide solution, potassium hydroxide solution, sodium carbonate, sodium hydrogen carbonate, potassium carbonate or potassium hydrogen carbonate, and also ammonia and amines.
- Suitable amines are e.g. B.
- Ci-C ⁇ -alkylamines such as n-propylamine and n-butylamine, dialkylamines, trialkylamines, such as diethylpropylamine, dipropylmethylamine and triethylamine etc.
- the polymers used according to the invention can contain further components, as are customary for the production of polyurethanes or polyureas. These include e.g. B. Compounds different from component b) with at least two groups reactive toward isocyanate groups, as are usually used as chain extenders.
- the additional components of the polymers are preferably diols, diamines, amino alcohols and mixtures thereof.
- the molecular weight of these compounds is preferably in a range from about 56 to 500.
- Diols are preferably used as an additional component.
- Useful diols are e.g. B. ethylene glycol, propylene glycol, butylene glycol, neopentyl glycol, cyclohexanedimethylol, di-, tri-, tetra-, penta- or hexaethylene glycol and mixtures thereof.
- Suitable additional amino alcohols are e.g. B. 2-aminoethanol, 2- (N-methylamino) ethanol, 3-aminopropanol, 4-aminobutanol, l-ethylaminobutan-2-ol, 2-amino-2-methyl-l-propanol, 4-methyl-4 -aminopentan-2-ol etc.
- Suitable additional diamines are e.g. B. ethylenediamine, propylene diamine, 1,4-diaminobutane, 1,5-diaminopentane and 1, 6-diaminohexane.
- Suitable diamines are also diamines of the formula R a -NH- (CH 2 ) 2 _ 3 -NH 2 , where R a is Cs to C 22 alkyl or Cs to C 2 alkenyl, the alkenyl radical 1, 2 or 3 can have non-adjacent double bonds.
- the molecular weight of these diamines is preferably in a range from about 160 to 400.
- diamines which are usually used as chain extenders, are e.g. B. hexamethylene diamine, piperazine, 1,2-diaminocyclohexane, 1,3-diaminocyclohexane, 1,4-diaminocyclohexane, neopentane diamine, 4, 4 '-diaminodicyclohexylmethane etc.
- the aforementioned additional components can be used individually or as mixtures. Preferably no chain extenders are used.
- the polymers used according to the invention can additionally contain at least one further compound having a group which is reactive toward isocyanate groups (stoppers).
- This group is preferably a hydroxyl or a primary or secondary amino group.
- Suitable compounds with a group reactive toward isocyanate groups are e.g. B. monofunctional alcohols, such as methanol, ethanol, n-propanol, isopropanol etc.
- amines with a primary or secondary amino group such as. As methylamine, ethylamine, n-propyl laminate, isopropylamine, dimethylamine, diethylamine, di-n-propylamine, diisopropylamine, etc.
- stoppers which have a group which is reactive toward isocyanate groups and at least one tertiary amino and / or ammonium group. Examples of this are e.g. B. N, N-dialkylamino alcohols or amines.
- Polymers are preferably used which have a number average molecular weight in the range from about 1000 to 50,000, preferably 2,000 to 20,000.
- the polymers preferably have an anionic group content of 0.1 to 5 mol / kg, preferably 0.5 to 3 mol / kg, in particular 1 to 3 mol / kg. Groups which can be converted into anionic groups in the polymer are not taken into account here.
- the content of urethane and / or urea groups is preferably at least 2.5 mol / kg, particularly preferably at least 3 mol / kg, in particular at least 4 mol / kg.
- the maximum content of urethane and / or urea groups is rather uncritical and is z. B. 10 mol / kg, preferably 8 mol / kg.
- Another object of the invention is a polymer obtained from
- component b) having at least one compound with at least one anionic group or in the polymer with at least some of the groups which can be converted into anionic groups in the form of their reaction products at least one neutralizing agent is present and the content of urethane and / or urea groups of the polymer is at least 2 mol / kg of polymer.
- Polymers which are composed only of compounds of components a) and b) are preferred.
- the polymers used according to the invention and the polymers according to the invention are prepared by reacting at least one polyisocyanate a) with at least one compound of component b) and, if appropriate, additional compounds having groups which are reactive toward isocyanate groups.
- the ratio of NCO equivalent of component a) to equivalent active hydrogen atom of component b) and, if appropriate, additional compounds is generally in a range from about 0.6: 1 to 1.4: 1, preferably 0.9: 1 to 1.1: 1, in particular 0.9: 1 to 1: 1.
- the reaction can be carried out without a solvent or in a suitable inert solvent or solvent mixture. Solvents which are infinitely miscible with water are preferred.
- solvents which have a boiling point at normal pressure in the range from about 40 to 100 ° C.
- Aprotic polar solvents e.g. B. tetrahydrofuran, ethyl acetate, N-methylpyrrolidone, dimethylformamide, dimethylacetamide and preferably ketones such as acetone and methyl ethyl ketone.
- the reaction can be carried out under an inert gas atmosphere, such as. B. under nitrogen.
- the reaction is preferably carried out at ambient pressure or under elevated pressure, in particular the internal pressure of the reactants under the reaction conditions.
- the reaction temperature is preferably in a range from about 20 to 180 ° C., in particular 50 to 150 ° C.
- the reaction can, if desired, take place in a solvent or solvent mixture which can have active hydrogen atoms.
- alcohols such as methanol and ethanol, mixtures of alcohols and water, mixtures of ketones and water and mixtures of alcohols and the aforementioned ketones are then preferably used. If the resulting polymers still have free isocyanate groups, they can then be deactivated.
- the response time can range from a few minutes to a few hours.
- the reaction can in the presence of conventional catalysts, such as. B.
- dibutyltin dilaurate, tin (II) octoate or diazabicyclo [2.2.2] octane can be carried out.
- Suitable polymerization apparatuses are known to the person skilled in the art. These include e.g. B. stirred kettle, which are optionally equipped with devices for removing the heat of reaction. Is used in the tion of the polymers used an organic solvent, this can then be carried out by conventional methods known to those skilled in the art, e.g. B. by distillation under reduced pressure. Before the solvent is separated off, water can also be added to the polymer. If desired, high-boiling solvents can also remain in the solution, but their proportion should preferably not be more than 10% by weight, based on the weight of the polymer.
- the polymers can be used in mixtures or in combination with surface-active substances, such as. B. anionic, nonionic or cationic surfactants or wetting agents. They can also be used in a mixture with other polymers, whereby under certain circumstances the surface-modifying effect can be enhanced.
- surface-active substances such as. B. anionic, nonionic or cationic surfactants or wetting agents. They can also be used in a mixture with other polymers, whereby under certain circumstances the surface-modifying effect can be enhanced.
- the polymers according to the invention and used according to the invention with urethane and / or urea groups and anionic groups are advantageously suitable for modifying the surface properties of particles, lines, sheets or three-dimensional structures.
- modification of the surface properties is widely understood in the context of the present invention. This includes above all hydrophilization, which is generally understood to mean an improvement in wettability with water or an aqueous liquid. Improved wettability is usually associated with faster and / or increased fluid absorption and / or improved fluid retention, generally also under pressure.
- the "modification of surfaces” also includes an improvement in the adhesive effect, an improved antistatic effect, an anti-fog effect, improved wearing properties, e.g. B. in hygiene products, and / or an improved grip.
- the structures according to the invention are generally advantageously suitable for all areas of use 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.
- the structures 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, dish cloths, serviettes, agricultural and / or geotextiles and for filter applications.
- the polymers according to the invention and 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, copolymers of monoolefins with one another or with at least one further radically polymerizable monomer, polyesters, polyacrylonitrile and polyamides.
- the polymers are 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 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.
- SAN styrene-acrylonitrile copolymers
- ABS acrylonitrile-butadiene-styrene terpolymers
- polyamides such as polyamide 6 or polyamide 6 / 6, polyurethanes and / or mixtures of the aforementioned plastics.
- polymers with urethane and / or urea groups and anionic 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.
- the polymers are also suitable for reducing the tendency to fogging of plastic films.
- the advantage of the agents according to the invention over known hydrophilizing agents also lies in the fact that they do not lead to a significant reduction in the surface tension of water.
- the particle-shaped, line-shaped, sheet-like or three-dimensional structures according to the invention can be finished with the polymers by the methods normally used to hydrophilize the aforementioned structures with hydrophilizing agents of the prior art.
- the structure is treated with a dilute, preferably aqueous solution of the polymer in a manner customary for the type of structure, e.g. 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 is absorbed by the surface and remains on it after drying. The amounts required to achieve effective hydrophilization are automatically established and are extremely low. In the case of structures with a smooth surface such as foils and similar structures, 0.1 mg / m 2 of polymer is already sufficient.
- the polymer in another embodiment of the method according to the invention for hydrophilizing 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 method.
- the simple applicability of the polymers according to the invention and used according to the invention allows 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 also improves the water vapor permeability and the capillary transport of sweat and reduces the soiling behavior in relation to many types of hydrophobic dirt.
- the removability of dirt is also positively influenced.
- the polymers can also be used as antistatic equipment for plastic films or silicon wafers.
- a suitable measure for assessing the hydrophilicity / hydrophobicity of the surface of a particle-shaped, line-shaped, sheet-like or three-dimensional structure is the measurement of the contact angle of water on the respective surface (see, for example, Römpp, Chemielexikon, 9th edition, p 372 "Wetting", Georg Thieme Verlag
- hydrophobic surfaces when the contact angle of water is greater than 90 °.
- the use of at least one polymer with urethane and / or urea groups and ammonium groups preferably results in a decrease in the contact angle by at least 10 °, preferably by at least 30 °, compared to the unmodified hydrophobic surface.
- the disadvantageous effects on the interfacial tension of aqueous solutions known from the prior art and an increased tendency to migrate are generally not observed.
- the polymers used according to the invention are distinguished by particularly good compatibility with polymer melts. As a rule, they are therefore also suitable as additives for a melt of polymeric fiber or molded article raw materials.
- the polymers can also be used as aftertreatment agents for modifying the structures.
- the respective substrate is treated with a 0.5% by weight solution of the polymer for 30 minutes at 21 ° C. with stirring.
- the sample is dried immediately after the treatment and the contact angle is determined with distilled water at room temperature.
- the measurement was carried out on a polypropylene fleece.
- the fleece is treated with an aqueous, 0.5% by weight solution of the polymer and then dried.
- a drop of water is placed on the substrate to be measured.
- the wetting of the fleece by the water is visualized using a scale from 1 to 10 judged. 0 points mean no wetting and 10 points mean the drop drips immediately.
- a 0.01% by weight solution of the polymer is adjusted to a pH of 7.
- a polypropylene film applied to a silicon wafer is flowed vertically at room temperature with this solution at a flow rate of 0.7 ml per minute.
- a change in the detection signal compared to a polymer-free solution is observed.
- Computer-aided modeling of the beam path gives an assignment from this change.
- Example 1 Polyurea from isophorone diisocyanate and the Michael adduct from ethylenediamine and sodium acrylate
- Example 2 Polyurea from isophorone diisocyanate and sodium salt of 2-aminoethyl-2-aminoethanesulfonic acid
- a polyurea was prepared from 84.0 g (0.2 mol) of sodium salt of 2-aminoethyl-2-aminoethanesulfonic acid and 44.4 g (0.2 mol) of isophorone diisocyanate.
- a polyurea solution with a solids content of 29.3% by weight, a calculated content of urea groups of 4.63 mol / kg and a content of anionic groups of 2.31 mol / kg was obtained.
- Example 3 Polyurethane made from isophorone diisocyanate and dimethylol propionic acid
- the application engineering examples show that it is possible with the polymers according to the invention and those used according to the invention to effectively hydrophilize polypropylene surfaces. None of the examples according to the invention shows significant foaming power, whereas the commercially available alcohol ethoxylate used as a comparative substance, like the conventional nonionic surfactants known from the prior art, shows strong to very strong foaming power. Furthermore, when the polymers are used, no significant reduction in the surface tension of an aqueous solution is observed, whereas the alcohol ethoxylate used as the reference substance, and also very generally the surfactants known from the prior art and used as hydrophilizing agents, greatly reduce the surface tension.
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Polymers & Plastics (AREA)
- Medicinal Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Wood Science & Technology (AREA)
- Materials Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Textile Engineering (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
- Polyurethanes Or Polyureas (AREA)
- Coating Of Shaped Articles Made Of Macromolecular Substances (AREA)
- Laminated Bodies (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Treatments Of Macromolecular Shaped Articles (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Paints Or Removers (AREA)
Abstract
Description
Claims
Priority Applications (6)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US10/468,407 US20040170832A1 (en) | 2001-03-01 | 2002-02-28 | Use of anionic polymers that carry urethane and/or urea groups for modifying surfaces |
DE50214814T DE50214814D1 (de) | 2001-03-01 | 2002-02-28 | Verwendung von anionischen polymeren, die urethan- und/oder harnstoffgruppen aufweisen, zur modifizierung von oberflächen |
JP2002570613A JP2004528422A (ja) | 2001-03-01 | 2002-02-28 | 表面変性のための、ウレタン基および/または尿素基を有するアニオン性ポリマーの使用 |
AT02722161T ATE491735T1 (de) | 2001-03-01 | 2002-02-28 | Verwendung von anionischen polymeren, die urethan-und/oder harnstoffgruppen aufweisen, zur modifizierung von oberflächen |
KR10-2003-7011394A KR20030080047A (ko) | 2001-03-01 | 2002-02-28 | 우레탄기 및 우레아기를 보유하는 표면 개질용 음이온중합체의 용도 |
EP20020722161 EP1373350B1 (de) | 2001-03-01 | 2002-02-28 | Verwendung von anionischen polymeren, die urethan- und/oder harnstoffgruppen aufweisen, zur modifizierung von oberflächen |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE10109803.0 | 2001-03-01 | ||
DE2001109803 DE10109803A1 (de) | 2001-03-01 | 2001-03-01 | Verwendung von anionischen Polymeren, die Urethan- und/oder Harnstoffgruppen aufweisen, zur Modifizierung von Oberflächen |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2002070578A1 true WO2002070578A1 (de) | 2002-09-12 |
Family
ID=7675894
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/EP2002/002201 WO2002070578A1 (de) | 2001-03-01 | 2002-02-28 | Verwendung von anionischen polymeren, die urethan- und/oder harnstoffgruppen aufweisen, zur modifizierung von oberflächen |
Country Status (9)
Country | Link |
---|---|
US (1) | US20040170832A1 (de) |
EP (1) | EP1373350B1 (de) |
JP (1) | JP2004528422A (de) |
KR (1) | KR20030080047A (de) |
CN (1) | CN1494560A (de) |
AT (1) | ATE491735T1 (de) |
DE (2) | DE10109803A1 (de) |
ES (1) | ES2356893T3 (de) |
WO (1) | WO2002070578A1 (de) |
Families Citing this family (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE10249841A1 (de) * | 2002-10-25 | 2004-05-13 | Basf Ag | Verwendung von hyperverzweigten Polymeren, die Urethan- und/oder Harnstoffgruppen aufweisen, zur Modifizierung von Oberflächen |
TWI389975B (zh) * | 2004-09-21 | 2013-03-21 | Showa Denko Kk | Thermosetting ethylcarbamate resin composition |
DE102008014211A1 (de) * | 2008-03-14 | 2009-09-17 | Bayer Materialscience Ag | Wässrige Dispersion aus anionisch modifizierten Polyurethanharnstoffen zur Beschichtung eines textilen Flächengebildes |
SI2307612T1 (sl) * | 2008-07-24 | 2014-01-31 | Basf Se | Prožna ploščata podlaga z abrazivno površino |
JP6360764B2 (ja) * | 2014-09-30 | 2018-07-18 | 富士フイルム株式会社 | 反射防止フィルム、反射防止フィルムの製造方法、反射防止フィルムと清掃用布を含むキット |
CN113512223B (zh) * | 2021-06-28 | 2023-04-07 | 浙江中科玖源新材料有限公司 | 一种聚酰亚胺导电膜 |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3412054A (en) * | 1966-10-31 | 1968-11-19 | Union Carbide Corp | Water-dilutable polyurethanes |
US4156675A (en) * | 1977-02-25 | 1979-05-29 | Nhk Spring Co., Ltd. | Urea polymer containing a sulfonate radical and method of preparing the same by a polymerization reaction of diaminosulfonate with diisocyanate |
US5489389A (en) * | 1992-07-14 | 1996-02-06 | Henkel Kommanditgesellschaft Auf Aktien | New leather oiling preparations and their use |
US5583176A (en) * | 1994-09-23 | 1996-12-10 | Basf Aktiengesellschaft | Water-emulsifiable polyisocyanates |
DE19849891A1 (de) * | 1997-12-08 | 1999-06-10 | Basf Ag | Mit Polyurethandispersionen gebundene sterile Vliesstoffe |
Family Cites Families (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE2359606C3 (de) * | 1973-11-30 | 1980-01-17 | Bayer Ag, 5090 Leverkusen | Verfahren zur Herstellung von als kolloides Xerosol vorliegendem anorganisch-organischen Polymer-Polykieselsäuregelverbundmaterial |
JP2000256141A (ja) * | 1998-02-24 | 2000-09-19 | Sanyo Chem Ind Ltd | 毛髪処理剤及び毛髪処理方法 |
AU2001281835A1 (en) * | 2000-06-13 | 2001-12-24 | Basf Aktiengesellschaft | Use of polymers containing urethane and/or urea groups for the modification of surfaces |
-
2001
- 2001-03-01 DE DE2001109803 patent/DE10109803A1/de not_active Withdrawn
-
2002
- 2002-02-28 AT AT02722161T patent/ATE491735T1/de active
- 2002-02-28 US US10/468,407 patent/US20040170832A1/en not_active Abandoned
- 2002-02-28 DE DE50214814T patent/DE50214814D1/de not_active Expired - Lifetime
- 2002-02-28 JP JP2002570613A patent/JP2004528422A/ja active Pending
- 2002-02-28 KR KR10-2003-7011394A patent/KR20030080047A/ko not_active Application Discontinuation
- 2002-02-28 EP EP20020722161 patent/EP1373350B1/de not_active Expired - Lifetime
- 2002-02-28 CN CNA028058232A patent/CN1494560A/zh active Pending
- 2002-02-28 WO PCT/EP2002/002201 patent/WO2002070578A1/de active Application Filing
- 2002-02-28 ES ES02722161T patent/ES2356893T3/es not_active Expired - Lifetime
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3412054A (en) * | 1966-10-31 | 1968-11-19 | Union Carbide Corp | Water-dilutable polyurethanes |
US4156675A (en) * | 1977-02-25 | 1979-05-29 | Nhk Spring Co., Ltd. | Urea polymer containing a sulfonate radical and method of preparing the same by a polymerization reaction of diaminosulfonate with diisocyanate |
US5489389A (en) * | 1992-07-14 | 1996-02-06 | Henkel Kommanditgesellschaft Auf Aktien | New leather oiling preparations and their use |
US5583176A (en) * | 1994-09-23 | 1996-12-10 | Basf Aktiengesellschaft | Water-emulsifiable polyisocyanates |
DE19849891A1 (de) * | 1997-12-08 | 1999-06-10 | Basf Ag | Mit Polyurethandispersionen gebundene sterile Vliesstoffe |
Also Published As
Publication number | Publication date |
---|---|
DE10109803A1 (de) | 2002-09-05 |
ES2356893T3 (es) | 2011-04-14 |
CN1494560A (zh) | 2004-05-05 |
US20040170832A1 (en) | 2004-09-02 |
EP1373350A1 (de) | 2004-01-02 |
KR20030080047A (ko) | 2003-10-10 |
JP2004528422A (ja) | 2004-09-16 |
EP1373350B1 (de) | 2010-12-15 |
DE50214814D1 (de) | 2011-01-27 |
ATE491735T1 (de) | 2011-01-15 |
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