Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • 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
  • C08G18/2805—Compounds having only one group containing active hydrogen
  • C08G18/2815—Monohydroxy compounds
  • C08G18/283—Compounds containing ether groups, e.g. oxyalkylated 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
  • C08G18/08—Processes
  • C08G18/0838—Manufacture of polymers in the presence of non-reactive compounds
  • C08G18/0842—Manufacture of polymers in the presence of non-reactive compounds in the presence of liquid diluents
  • C08G18/0861—Manufacture of polymers in the presence of non-reactive compounds in the presence of liquid diluents in the presence of a dispersing phase for the polymers or a phase dispersed in the polymers
  • C08G18/0866—Manufacture of polymers in the presence of non-reactive compounds in the presence of liquid diluents in the presence of a dispersing phase for the polymers or a phase dispersed in the polymers the dispersing or dispersed phase being an aqueous medium
• • 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
  • C08G18/73—Polyisocyanates or polyisothiocyanates acyclic
• • 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
  • C09D175/12—Polyurethanes from compounds containing nitrogen and active hydrogen, the nitrogen atom not being part of an isocyanate group

Definitions

• Non-ionic hydrophilized binder dispersions are non-ionic hydrophilized binder dispersions
• Coating agents based on polyurethanes because of their outstanding properties, e.g. high scratch resistance and cold flexibility, a big role. Due to increasing environmental and other legal regulations, the solvent-free, aqueous polyurethanes are of particular importance. Coatings based on polyurethane dispersions come in different applications, e.g. textile coating, plastic and automotive painting. For certain applications, e.g. In electronics it is necessary for coatings to have the lowest possible conductivity in order to ensure high electrical insulation. At the same time, it is desirable for the aqueous coating compositions to be stable to coagulation over a broad temperature range for use in the various processes, e.g. Spraying or doctoring at variable conditions as possible to apply.
• the stabilization of the polyurethane particles in an aqueous phase can be effected by two mechanisms, either by charges on the surface leading to repulsion of the particles (ionic stabilization) or by surface-adsorbed or covalently bonded, water-soluble or partially water-soluble oligomer or polymer chains Van der Waals interactions prevent agglomeration (non-ionic stabilization).
• Non-ionic polyurethane dispersions in which PEG chains are attached to the side of the polyurethane dispersion are described in US Pat. No. 3,905,929.
• the resulting binders are characterized by relatively good mechanical properties.
• the PEG groups are not terminally anchored and can By-products are created during the process
• EP-A 0 792 900 describes polyurethane dispersions for use in glass fiber guns. These may be ionically and / or non-ionically hydrophilic, wherein the polyisocyanate consists of at least 50% of l-methyl-2,4- and / or 2,6-dinocyanatocyclohexane
• Non-ionic polyurethane dispersions are described in US Pat. No. 5,066,732, in which a monofunctional polyethylene glycol component is intermediately reacted with a dinocyanate and the reaction product is subsequently reacted with a dihydroxyamine to give a hydrophobic component. Accordingly, the polyethylene oxide is also anchored to the side in the polyurethane
• the present invention relates to aqueous polyurethaneurea dispersions containing the synthesis components
• Suitable polyisocyanates of component A) are the aromatic, araliphatic, aliphatic or cycloaliphatic polyisocyanates known to the person skilled in the art.
• Suitable polyisocyanates are e.g. 1, 4-Butylendiisocyanat, 1, 6-hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI), 2,2,4- and / or 2,4,4-trimethylhexamethylene diisocyanate, the isomeric bis (4,4'-isocyanatocyclohexyl ) methanes or mixtures thereof of any isomer content, 1,4-cyclohexylene diisocyanate, 1,4-phenylene diisocyanate, 2,4- and / or 2,6-toluene diisocyanate, 1,5-naphthylene diisocyanate, 2,4'- or 4,4'-diisocyanate Diphenylmethane diisocyanate
• Proportionally also polyisocyanates with a functionality> 2 can be used. These include modified diisocyanates having uretdione, isocyanurate, urethane, allophanate, biuret, iminoxadiazinedione and / or oxadiazinetrione structures, as well as unmodified polyisocyanates having more than 2 NCO groups per molecule, e.g. 4-isocyanatomethyl-l, 8-octane diisocyanate (nonantriisocyanate) or triphenylmethane-4,4 ', 4 "-triisocyanate.
• polyisocyanates or polyisocyanate mixtures of the abovementioned type with exclusively aliphatically and / or cycloaliphatically bonded isocyanate groups having an average functionality of 2 to 4, preferably 2 to 2.6 and more preferably 2 to 2.4.
• isophorone diisocyanate the isomers of bis (4,4'-isocyanatocyclohexyl) methane and mixtures thereof.
• Polymeric polyols which can be used as compounds B) have a molecular weight M n of from 400 to 8000 g / mol, preferably from 400 to 6000 g / mol and more preferably from 400 to 3000 g / mol.
• Their hydroxyl number is 22 to 400 mg KOH / g, preferably 30 to 300 mg KOH / g and more preferably 40 to 250 mg KOH / g and have an OH functionality of 1, 5 to 6, preferably from 1, 8 to 3 and more preferably from 1.9 to 2.1.
• Polyols in the context of the present invention are the organic polyhydroxyl compounds known in polyurethane coating technology, such as the customary polyester polyols, polyacrylate polyols, polyurethane polyols, polycarbonate polyols, polyether polyols, polyester polyacrylate polyols and polyurethane polyacrylate polyols, polyurethane polyester polyols, polyurethane polyether polyols, polyurethane polycarbonate polyols, polyester polycarbonate polyols, phenol.
• the customary polyester polyols such as the customary polyester polyols, polyacrylate polyols, polyurethane polyols, polycarbonate polyols, polyether polyols, polyester polyacrylate polyols and polyurethane polyacrylate polyols, polyurethane polyester polyols, polyurethane polyether polyols, polyurethane polycarbonate polyols, polyester polycarbonate polyols, phenol
• Formaldehyde resins alone or in mixtures. Polyester polyols, polyether polyols or polycarbonate polyols are preferred, polyester polyols are particularly preferred.
• polyether polyols e.g. the polyaddition of the styrene oxides, ethylene oxide, propylene oxide, tetrahydrofuran, butylene oxide, epichlorohydrin, and their Mischadditions- and graft products, as well as by condensation of polyhydric alcohols or mixtures thereof and obtained by alkoxylation of polyhydric alcohols, amines and amino alcohols polyether polyols called.
• Suitable hydroxy-functional polyethers B) have OH functionalities of 1.8 to 6.0, preferably 2.0 to 4.0, OH numbers of 50 to 700, preferably 100 to 600 mg KOH / g solids and molecular weights M n of 106 to 4,000 g / mol, preferably from 200 to 3,500, such as alkoxylation products of hydroxy-functional starter molecules such as ethylene glycol, propylene glycol, butanediol, hexanediol, trimethylolpropane, glycerol, pentaerythritol, sorbitol or mixtures of these and other hydroxy-functional compounds with propylene oxide or butylene oxide.
• hydroxy-functional starter molecules such as ethylene glycol, propylene glycol, butanediol, hexanediol, trimethylolpropane, glycerol, pentaerythritol, sorbitol or mixtures of these and other
• polyether component B are polypropylene oxide polyols having a molecular weight of 300 to 4000 g / mol.
• the particularly low molecular weight polyether polyols can be water-soluble at correspondingly high OH contents.
• water-insoluble polypropylene oxide polyols and polytetramethylene oxide polyols and mixtures thereof are particularly preferred.
• polyester polyols are those of the known polycondensates of di- and optionally tri- and tetraols and di- and optionally tri- and tetracarboxylic acids or hydroxycarboxylic acids or lactones.
• the corresponding polycarboxylic anhydrides or corresponding polycarboxylic acid esters of lower alcohols can also be used to prepare the polyesters.
• diols examples include ethylene glycol, butylene glycol, diethylene glycol, triethylene glycol, polyalkylene glycols such as polyethylene glycol, furthermore 1,2-propanediol, 1,3-propanediol, butanediol (1,3), butanediol (1,4), hexanediol ( 1, 6) and isomers, neopentyl glycol or hydroxypivalic acid neopentyl glycol esters, the latter three compounds being preferred.
• polyalkylene glycols such as polyethylene glycol, furthermore 1,2-propanediol, 1,3-propanediol, butanediol (1,3), butanediol (1,4), hexanediol ( 1, 6) and isomers, neopentyl glycol or hydroxypivalic acid neopentyl glycol esters, the latter three compounds being preferred.
• Suitable dicarboxylic acids are, for example, phthalic acid, isophthalic acid, terephthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, cyclohexanedicarboxylic acid, adipic acid, azelaic acid, sebacic acid, glutaric acid, tetrachlorophthalic acid, maleic acid, fumaric acid, itaconic acid, malonic acid, suberic acid, 2-methylsuccinic acid, 3,3-diethylglutaric acid, 2, 2-Dimethylbemstein- acid.
• Anhydrides of these acids are also useful, as far as they exist.
• anhydrides are encompassed by the term "acid”.
• Monocarboxylic acids such as benzoic acid and hexanecarboxylic acid can also be used, provided that the average functionality of the polyol is> 2.
• Saturated aliphatic or aromatic acids are preferred, such as adipic acid or isophthalic acid.
• trimellitic acid may be mentioned here.
• Hydroxycarboxylic acids which may be used as reactants in the preparation of a hydroxyl-terminated polyester polyol include hydroxycaproic acid, hydroxybutyric acid, hydroxydecanoic acid, hydroxystearic acid and the like.
• Useful lactones are i.a. Caprolactone, butyrolactone and homologs.
• the candidate polycarbonate polyols are prepared by reaction of carbonic acid derivatives, e.g. Diphenyl carbonate, dimethyl carbonate or phosgene with diols available.
• diols come e.g. Ethylene glycol, 1, 2 and 1, 3-propanediol, 1, 3- and 1, 4-butanediol, 1, 6-hexanediol, 1, 8-octanediol, neopentyl glycol, 1, 4-bishydroxymethylcyclohexane, 2-methyl-l, 3 Propanediol, 2,2,4-trimethylpentanediol-1, 3, dipropylene glycol, polypropylene glycols, dibutylene glycol, polybutylene glycols, bisphenol A, tetrabromobisphenol A, but also lactone-modified diols in question.
• the diol component contains from 40 to 100% by weight of 1,6-hexaned
• Derivatives preferably those which in addition to terminal OH groups ether or ester groups, for example products by reacting 1 mol of hexanediol with at least 1 mol, preferably 1 to 2 moles of ⁇ -caprolactone or by etherification of hexanediol with itself to the diester Trihexylenglykol be obtained.
• Polyether-polycarbonate polyols can also be used. Preference is given to polycarbonate polyols B) based on dimethyl carbonate and hexanediol and / or butanediol and / or caprolactone. Very particular preference is given to polycarbonate polyols B) based on dimethyl carbonate and hexanediol and / or caprolactone.
• Suitable nonionic hydrophilicizing monofunctional compounds corresponding to the definition of component C) are e.g. Polyoxyalkylene ethers containing only one hydroxy or amino group. These polyethers contain from 50% by weight to 100% by weight of building blocks derived from ethylene oxide, preferably from 70% by weight to 100% by weight and more preferably from 80% by weight to 100% by weight. % as they are accessible in a conventional manner by alkoxylation of the starter molecules mentioned under B).
• Alkylene oxides which are suitable for the alkoxylation reaction are, in particular, ethylene oxide and propylene oxide, which can be used in any desired order or even as a mixture in the alkoxylation reaction.
• the molecular weight M n of these building blocks is from 1200 g / mol to 3000 g / mol, preferably from 1500 g / mol to 3000 g / mol and more preferably from 2000 g / mol to 3000 g / mol.
• Suitable such nonionically hydrophilicizing, monofunctional compounds are, for example, monofunctional alkoxypolyethylene glycols, e.g. Methoxypolyethylene glycols (MPEG).
• MPEG Methoxypolyethylene glycols
• monofunctional polyether monoalkyl ethers such as e.g. LB 25 built from butanol and
• MPEG Carbowax ® 2000, LB 25 or Jeffamine w M 2070 Preferably used as C) MPEG Carbowax ® 2000, LB 25 or Jeffamine w M 2070. Particularly preferred are MPEG Carbowax 00 2000 or LB 25.
• alkanolamines such as N-aminoethylethanolamine, ethanolamine, 3-aminopropanol or neopentanolamine.
• Diethanolamine and / or hydrazine and / or isophoronediamine (EPDA) and / or ethylenediamine are preferred.
• Hydrazine and / or isophoronediamine and / or ethylenediamine are particularly preferred.
• Very particularly preferred is a mixture of hydrazine hydrate and IPDA.
• the low molecular weight polyols E) used to build up the polyurethane resins generally cause stiffening and / or branching of the polymer chain.
• the molecular weight is preferably between 62 and 200.
• Suitable polyols may include aliphatic, alicyclic or aromatic groups. Mention may be made, for example, of the low molecular weight polyols having up to about 20 carbon atoms per molecule, such as e.g.
• Ethylene glycol diethylene glycol, triethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 1,3-butylene glycol, cyclohexanediol, 1,4-cyclohexanedimethanol, 1,6-hexanediol, hydroquinone dihydroxyethyl ether, bisphenol A (2,2-bis (4-hydroxyphenyl) propane), hydrogenated bisphenol A (2,2-bis (4-hydroxycyclohexyl) propane) and mixtures thereof, and trimethylolpropane, glycerol or pentaerythritol.
• ester diols such as e.g. ⁇ -hydroxybutyl- ⁇ -hydroxy-caproic acid ester, ⁇ -hydroxyhexyl- ⁇ -hydroxybutyric acid ester,
• Adipic acid ( ⁇ -hydroxyethyl) ester or terephthalic acid bis ( ⁇ -hydroxyethyl) ester may be used. Preference is given to hexanediol and / or trimethylolpropane and / or butanediol. Particularly preferred are trimethylolpropane and / or butanediol.
• auxiliaries or additives F can also be used by dissolving them in the aqueous, continuous phase following preparation of the aqueous polyurethane dispersion or adding them by dispersion in the organic phase prior to dispersion and thus codispersing them.
• Suitable adjuvants or additives are e.g. Anti-oxidants, UV stabilizers, leveling agents, biocides, antistatic agents or adhesion promoters.
• the PU dispersions is preferably prepared by the acetone process.
• the components A), B), C), E) and optionally F which may have no primary or secondary amino groups no disability
• the polyisocyanate component A) for the preparation of a isocyanate-functional polyurethane prepolymer completely or partially and optionally diluted with a water-miscible but isocyanate-inert solvent and heated to temperatures in the range of 50 to 120 0 C.
• a water-miscible but isocyanate-inert solvent can be used. Preference is given to dibutyltin dilaurate.
• the molar ratio of isocyanate groups to isocyanate-reactive groups is 1.0 to 3.5, preferably 1.1 to 3.0, particularly preferably 1.1 to 2.5.
• chain extension / termination can be carried out either in a solvent before dispersing, during dispersion or in water after dispersion.
• the chain extension is preferably carried out in water prior to dispersion. If compounds corresponding to the definition of D) with NH 2 or NH groups are used for chain extension, the chain extension of the prepolymers preferably takes place before the dispersion.
• the degree of chain extension ie the equivalent ratio of NCO-reactive groups of the compounds used for chain extension to free NCO groups of the prepolymer, is between 40 and 100%, preferably between 60 and 100%, particularly preferably between 70 and 100%.
• the aminic components D) can optionally be used individually or in mixtures in water- or solvent-diluted form in the process according to the invention, wherein basically any order of addition is possible.
• the content of the diluent is preferably 70 to 95% by weight.
• the solvent still present in the dispersions after the dispersion step is then usually removed by distillation. Removal during the dispersion is also possible.
• the solids content of the polyurethane-polyurea dispersion according to the invention is between 20 to 70 wt .-%, preferably 30 to 65 wt .-% and particularly preferably between 35 to 62 wt .-%.
• Another object of the invention is the use of polyurethane dispersions of the invention for the preparation of coating compositions, preferably for the production of glass fiber sizes.
• Suitable substrates include plastics, metals, and glass.
• the polyurethane-polyurea dispersions according to the invention can also be used in combination with crosslinking, aqueous, blocked polyisocyanates and processed into glass fiber sizes.
• aqueous coating compositions comprising the polyurethane-polyurea dispersion of the invention and a crosslinker selected from the group of water-dispersible or water-soluble blocked polyisocyanates.
• the isocyanate groups of the polyisocyanates of the water-dispersible or water-soluble blocked polyisocyanates are present in blocked form in at least 50%, preferably at least 60% and particularly preferably at least 70%.
• the preparation of the water-dispersible, blocked polyisocyanates II) can be carried out by known methods of the prior art (for example in DE-A 2 456 469, columns 7-8, examples 1 -5 and DE-A 2 853 937 p. 21-26). Example 1-9).
• aqueous coating compositions according to the invention can as a further component auxiliary and
• Contain additives may be adhesion promoters, lubricants, antistatic agents, but also the coating additives well known to the person skilled in the art, such as dyes, pigments, leveling agents, light and aging inhibitors and UV absorbers.
• silane coupling agents such as 3-aminopropyltrimethoxy- or triethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, 3-glycidylpropyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane or 3-methacryloxypropyltriethoxysilane.
• the coating compositions of the invention may comprise one or more nonionic and / or ionic lubricants, such as polyalkylene glycol ethers of fatty alcohols or fatty amines, polyalkylene glycol ethers and glycerol esters of fatty acids containing 12 to 18 carbon atoms,
• nonionic and / or ionic lubricants such as polyalkylene glycol ethers of fatty alcohols or fatty amines, polyalkylene glycol ethers and glycerol esters of fatty acids containing 12 to 18 carbon atoms,
• Polyalkylene glycols higher fatty acid amides having 12 to 18 carbon atoms of polyalkylene glycols and / or alkyleneamines, quaternary nitrogen compounds, e.g. ethoxylated imidazolinium salts, mineral oils or waxes
• the coating compositions of the invention may also contain one or more antistatic agents.
• antistatic agents include lithium chloride, ammonium chloride, Cr-III salts, organic titanium compounds, Arylalkylsulfate- or sulfonates, Arylpolyglykolethersulfonate or quaternary nitrogen compounds.
• the preparation of the coating agent can be carried out by the methods known per se.
• water is introduced into a suitable mixing container and the binder is added with stirring. deffen, the hardener and then added the lubricant and optionally other auxiliaries. Thereafter, the pH is adjusted to 5-7 and added a hydrolyzate of a coupling agent. After a further stirring time of 15 minutes, the coating composition is ready for use and can optionally be applied after pH adjustment.
• the coating compositions preferably used as sizing compositions, can be applied and cured by any method, for example by means of spray or roller applicators, on a suitable substrate.
• the glass fibers used are suitable both for the glass fiber types known glass types such as E, A, C, and S glass according to DIN 1259-1 as well as the other per se known products of the glass fiber manufacturer.
• the E glass fibers have the greatest importance for the reinforcement of plastics due to their alkali-free, high tensile strength and high modulus of elasticity.
• Conductivity measurement The conductivity of the dispersions is measured with a thermometer manufactured by Knick, type 703.
• Determination of the coagulation temperature For this purpose, 50 mL of the dispersion are placed in a flask equipped with stirrer and at a rate of 2 0 C / min. heated with stirring. It indicates the temperature at which it comes to a gelation of the dispersion.
• Impranir DLS anionic / nonionic, aliphatic polycarbonatepolyetherpolyurethane dispersion having a solids content of 50% (Bayer Material Science AG, DE).
• Impranil 00 DLN anionic, aliphatic polyester-polyurethane dispersion having a solids content of 50% (Bayer MaterialScience AG, DE).
• Desmodur H 1,6-hexamethylene diisocyanate (HDI), (Bayer Materialscience AG, DE)
• PEG2000 polyethylene glycol CAS no. 25322-68-3, difunctional, having a molecular weight of 2000 g mol -1 (Sigma-Aldrich)
• Tegomer D3403 Polyethylene glycol (lateral), difunctional, with a molar mass of 1200 g mol -1 (Tego Chemie Service GmbH, Essen)
• IPDA 1 -amino-3,3,5-trimethyl-5-aminomethylcyclohexane, isophoronediamine (Bayer Materialscience AG, DE)
• HyHy hydrazine, H 2 N-NH 2 (Bayer MaterialScience AG, DE)
• Example 4 (comparative example)

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• Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Health & Medical Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Dispersion Chemistry (AREA)
• Engineering & Computer Science (AREA)
• Materials Engineering (AREA)
• Wood Science & Technology (AREA)
• Life Sciences & Earth Sciences (AREA)
• Manufacturing & Machinery (AREA)
• Polyurethanes Or Polyureas (AREA)
• Paints Or Removers (AREA)
• Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
• Ceramic Products (AREA)
• Luminescent Compositions (AREA)

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