EP1910440A1 - Nouveaux agents d'hydrophilisation / produit de remplacement de hps - Google Patents

Nouveaux agents d'hydrophilisation / produit de remplacement de hps

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Publication number
EP1910440A1
EP1910440A1 EP06754444A EP06754444A EP1910440A1 EP 1910440 A1 EP1910440 A1 EP 1910440A1 EP 06754444 A EP06754444 A EP 06754444A EP 06754444 A EP06754444 A EP 06754444A EP 1910440 A1 EP1910440 A1 EP 1910440A1
Authority
EP
European Patent Office
Prior art keywords
polyisocyanates
polyurethanes
free
acid
silicon
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP06754444A
Other languages
German (de)
English (en)
Inventor
Jan Mazanek
Sebastian Dörr
Olaf Fleck
Heino Müller
Harald Blum
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Covestro Deutschland AG
Original Assignee
Bayer MaterialScience AG
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Bayer MaterialScience AG filed Critical Bayer MaterialScience AG
Publication of EP1910440A1 publication Critical patent/EP1910440A1/fr
Withdrawn legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/60—Polyamides or polyester-amides
    • 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
    • C08G18/2805—Compounds having only one group containing active hydrogen
    • C08G18/2815—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
    • C08G18/28—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
    • C08G18/3271—Hydroxyamines
    • 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
    • C08G18/3823—Low-molecular-weight compounds having heteroatoms other than oxygen having nitrogen containing -N-C=O groups
    • C08G18/3825—Low-molecular-weight compounds having heteroatoms other than oxygen having nitrogen containing -N-C=O groups containing amide groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • 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
    • C08G18/703—Isocyanates or isothiocyanates transformed in a latent form by physical means
    • C08G18/705—Dispersions of isocyanates or isothiocyanates in a liquid medium
    • C08G18/706—Dispersions of isocyanates or isothiocyanates in a liquid medium the liquid medium being water
    • 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
    • C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
    • C08G18/78—Nitrogen
    • C08G18/79—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates
    • C08G18/791—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups
    • C08G18/792—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups formed by oligomerisation of aliphatic and/or cycloaliphatic isocyanates or isothiocyanates
    • 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
    • C08G18/8077—Oximes
    • 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
    • C08G18/82—Post-polymerisation treatment
    • 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
    • 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
    • C08G2150/00—Compositions for coatings
    • C08G2150/90—Compositions for anticorrosive coatings

Definitions

  • the present invention relates to novel hydrophilicizing agents, their use for the preparation of aqueous and / or water-dilutable blocked polyisocyanates, and the preparation of these blocked polyisocyanates and their use in optionally self-crosslinking stoving systems with improved corrosion protection properties.
  • hydrophilicizing agents are used in order to be able to convert the polymers into the aqueous phase after the synthesis or to stabilize the solutions and / or dispersions against sedimentation.
  • hydrophilicizing agents used are various cationic, anionic and / or nonionic compounds, such as mono- and / or dihydroxycarboxylic acids or monofunctional alkyl ethoxylates, which are also used in mixtures with one another.
  • Hydroxyl-containing alkylamidocarboxylic acids which can be easily prepared, for example, from alkylamines and carboxylic anhydrides, have hitherto been used only sporadically in the preparation of dispersions.
  • hydroxy-functional amides of at least difunctional carboxylic acids are well suited for the hydrophilization of polyisocyanates or polyurethanes.
  • the hydrophilicized polyisocyanates or polyurethanes according to the invention have in addition to the hydrophilic Groups also blocked NCO groups. Such compounds are particularly suitable for the preparation of self-crosslinking aqueous stoving coating compositions.
  • the invention therefore provides silicon-free polyisocyanates or polyurethanes which have at least one structural unit of the formula (1),
  • n 0 to 8
  • R 1 , R 2 independently of one another are hydrogen or an OH-group-free, optionally substituted C 1 to C 8 alkyl or cycloalkyl radical,
  • R 4 is the radical of a difunctional aliphatic dicarboxylic acid having at least 2 C atoms, a cycloaliphatic dicarboxylic acid having at least 6 C atoms or aromatic dicarboxylic acid having at least 6 C atoms and
  • R 3 is R 1 or R 2 or a radical according to formula (2)
  • R 1 and R 2 have the above meaning and R 6 is a derived from a di- or polyisocyanate with optionally blocked NCO groups alkyl or aryl radical.
  • R 3 corresponds to the definition of the radicals R 1 , R 2 .
  • polyurethanes are preferably based on aliphatic and / or cycloaliphatic polyisocyanates, more preferably HDI and / or IPDI.
  • an object of the present invention is a process for producing such silicon-free polyisocyanates or polyurethanes, in which A) polyisocyanates with
  • R 5 is the same as R 1 , R 2 or is of the formula (6)
  • the polyisocyanates used for this purpose in A) are the NCO-functional compounds known per se to a person skilled in the art having a functionality of preferably 2 or more. These are typically aliphatic, cycloaliphatic, araliphatic and / or aromatic di- or triisocyanates and their higher molecular weight derivatives with urethane, allophanate, biuret, uretdione and / or isocyanurate groups which have two or more free NCO groups.
  • Preferred di- or triisocyanates are tetramethylene diisocyanate, cyclohexane-1,3- and 1,4-diisocyanate, hexamethylene diisocyanate (HDI), 1-isocyanato-S 1 -S-trimethyl-S-isocyanato-methylcyclohexane (isophorone diisocyanate, IPDI), methylene bis (4-isocyanatocyclohexane), tetramethyl xylylene diisocyanate (TMXDI), triisocyanatononane, tolylene diisocyanate (TDI), di-phenylmethan- 2,4'- and / or 4,4 ⁇ -diisocyanate (MDI), triphenylmethane-4,4 'Diisocyanate, naphthylene-l, 5-diisocyanate and their mixtures with each other.
  • HDI hexamethylene diisocyanate
  • Such polyisocyanates typically have isocyanate contents of 0.5 to 50 wt .-%, preferably 3 to 30 wt .-%, particularly preferably 5 to 25 wt .-%.
  • Preferred polyisocyanates A) for the preparation of the polyisocyanates or polyurethanes according to the invention are of the abovementioned type and have biuret, isocyanurate and / or Uretdione on and are based preferably on hexamethylene diisocyanate or isophorone diisocyanate.
  • the monoamides used in B) are obtainable by reacting hydroxylamines with one or two free OH groups and a primary or secondary amino group with compounds which have at least two carboxylic acid groups or instead at least one anhydride group per molecule. It is preferable to use 0.5 equivalents of the hydroxylamine per free COOH or COO * function or 1 equivalent of the hydroxylamine per anhydride function.
  • R 4 is the radical of a difunctional aliphatic dicarboxylic acid having at least 2 C atoms, a cycloaliphatic dicarboxylic acid having at least 6 C atoms or aromatic dicarboxylic acid having at least 6 C atoms.
  • Preferred anhydrides of formula (4) are phthalic, succinic, trimellitic, hexa- and tetrahydrophthalic and maleic anhydrides. Particularly preferred anhydrides are phthalic, trimellitic and hexahydrophthalic anhydride.
  • hydroxylamines used correspond to the general formula (5)
  • R 1 , R 2 are independently hydrogen or an OH group-free, optionally substituted Q to C 8 alkyl or cycloalkyl radical and
  • R 5 is the same as R 1 , R 2 or is of the formula (6)
  • R 1 and R 2 have the significance given above.
  • Preferred hydroxylamines are those of the formula (5) wherein R 5 corresponds to the definition of the radicals R 1 , R 2 and the hydroxylamine is therefore monohydroxyfunktionell.
  • Particularly preferred hydroxylamines are 1-amino-propanol, alkylethanolamines or alkylisopropanolamines having 1 to 5 C atoms in the alkyl radical. Very particular preference is given to N-methylethanolamine, N-methylisopropanolamine or 1-amino-propanol.
  • OH and COOH-containing monoamides are carried out in a manner known per se by reacting carboxylic acid or anhydride with the hydroxylamine, for example at temperatures of 10 to 80 0 C, preferably from 25 to 60 0 C, preferably in solvents such as N-methylpyrrolidone, acetone, methyl ethyl ketone or methoxypropyl acetate.
  • polyols in component C for example, relatively high molecular weight compounds from the classes of polyester, polyesteramide, polyurethane, polyacrylate, polycarbonate, polyacetal and polyether polyols having number average molecular weights of at least 500 g / mol, preferably 500 to 8000 g / mol , particularly preferably 800 to 5000 g / mol used.
  • Suitable polyester polyols are, in particular, linear polyester diols or also branched polyester polyols, such as those known from aliphatic, cycloaliphatic or aromatic di- or polycarboxylic acids or their anhydrides, such as succinic, glutaric, adipic, pimelinic, cork -, azelaic, sebacic, nonanedicarboxylic, decanedicarboxylic, terephthalic, isophthalic, o-phthalic, tetrahydrophthalic, hexahydrophthalic or trimellitic acid and acid anhydrides such as o-phthalic, trimellitic or succinic anhydride or mixtures thereof with polyhydric alcohols such as ethanediol, di-, tri-, tetraethylene glycol, 1, 2-propanediol, di-, tri-, tetrapropylene glycol, 1,3-propanediol, 1,4-butan
  • cycloaliphatic and / or aromatic di- and polyhydroxyl compounds are also suitable as polyhydric alcohols for the preparation of the polyesterpolyols.
  • the free polycarboxylic acid it is also possible to use the corresponding polycarboxylic acid anhydrides or corresponding polycarboxylic acid esters of lower alcohols or mixtures thereof to prepare the polyesters.
  • the polyester polyols may also be homopolymers or copolymers of lactones, which are preferably prepared by addition of lactones or lactone mixtures such as butyrolactone, ⁇ -caprolactone and / or methyl- ⁇ -caprolactone to suitable di- and / or higher-functional Starter molecules, such as the above-mentioned as structural components for polyester polyols low molecular weight, polyhydric alcohols, can be obtained.
  • the corresponding polymers of ⁇ -caprolactone are particularly preferred.
  • hydroxyl group-containing polycarbonates come into consideration as polyhydroxyl components, e.g. those obtained by reacting diols such as 1,4-butanediol and / or 1,6-hexanediol with diaryl carbonates, e.g. Diphenyl carbonate, or phosgene can be prepared.
  • 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.
  • low molecular weight polyhydroxyl compounds preferably diols of the molecular weight range from 62 to 499 g / mol.
  • they include, for example, the polyhydric, in particular dihydric, alcohols mentioned for the preparation of the polyester polyols, and also low molecular weight polyester diols, such as, for example, Adipic acid bis (hydroxyethyl) ester or short-chain initiated on aromatic diols homo- and Mischadditions occur of ethylene oxide or propylene oxide in question.
  • aromatic diols which can be used as starters for short-chain homopolymers and copolymers of ethylene oxide or of propylene oxide are, for example, 1,4-, 1,3-, 1, 2-dihydroxybenzene or 2,2-bis- (4-hydroxyphenyl) -propane (bisphenol A).
  • the blocking agents known per se to the person skilled in the art can be used.
  • examples are ⁇ -caprolactam, diethyl malonate, ethyl acetoacetate, oximes such as butanone oxime, amines such as N-tert-butylbenzylamine or diisopropylamine, dimethylpyrazole, triazole or mixtures thereof.
  • oximes such as butanone oxime
  • amines such as N-tert-butylbenzylamine or diisopropylamine, dimethylpyrazole, triazole or mixtures thereof.
  • suitable hydrophilizing agents are further hydrophilizing agents.
  • Suitable hydrophilicizing agents in D) in addition to the hydrophilicizing agents of B) according to the invention are all cationic, anionic and / or nonionic compounds suitable for this purpose, such as mono- and / or dihydroxycarboxylic acids or monofunctional alkylethoxylates. Of course, mixtures of different hydrophilic
  • A) is first reacted with B) in such a way that free NCO groups are still present in the reaction product.
  • the NCO / OH ratio is preferably 20: 1 to 1.5: 1, more preferably 15: 1 to 2: 1.
  • this hydrophilized NCO group-containing polymer is reacted with polyols of component C) of the type defined above in such a ratio that an OH-functional NCO group-free polymer is obtained.
  • polymers can deblock and crosslink with free OH groups.
  • these polymers can also be used as the OH component which is crosslinked with further polyisocyanates which have blocked or free NCO groups.
  • the catalysts, additives, auxiliaries and solvents known to those skilled in polyurethane chemistry can also be used. If catalysts are used, they are used in amounts of from 0.01 to 5% by weight, preferably from 0.05 to 4% by weight, particularly preferably from 0.07 to 1.5% by weight.
  • Another object is dispersions containing the polyurethanes according to the invention.
  • Aqueous dispersions can be prepared from the inventive silicon-free blocked polyisocyanates or polyurethanes by neutralizing all or part of the free carboxyl groups by base addition before, during or after the polyisocyanates are mixed with water.
  • the neutralization can be carried out for example with any amines such as triethyl, dimethylcyclohexyl, methyl and ethyl diisopropyl or dimethylethanolamine. Also ammonia is suitable.
  • Preferred for neutralization are triethylamine, ethyldiisopropylamine and dimethylethanolamine.
  • the neutralization is generally carried out between room temperature and 1 10 0 C.
  • the amount of bases is usually between 50 and 150%, preferably between 60 and 100% of the molar amount of the anionic groups.
  • a solids mass fraction in the dispersion of from 20% to 70%, preferably from 25% to 50%, is thus obtained.
  • the polyurethanes according to the invention can be used as self-crosslinking polymers or else in combination with polyols and other auxiliaries and additives customary in coating technology. Substances are used for the production of coating compositions, adhesives and elastomers.
  • coating compositions are a further object of the invention, at least containing the polyurethanes according to the invention and optionally polyols.
  • Suitable polyols are the above-mentioned higher molecular weight compounds from the classes of polyester, polyesteramide, polyurethane, polyacrylate, polycarbonate, polyacetal and polyether polyols having number average molecular weights of at least 500 g / mol, preferably 500 to 8000 g / mol , more preferably 800 to 5000 g / mol.
  • coating compositions are suitable for coating substrates, preferably metals, mineral substances, wood, plastics, for example for industrial coating, in textile coating and in automotive finishing.
  • the coating compositions can be applied by doctoring, dipping, spray application such as compressed air or airless spraying, as well as by electrostatic application, for example, high-rotation bell application.
  • the dry film layer thickness can be, for example, 10-120 ⁇ m.
  • the curing of the dried films is carried out by baking in the temperature range of 90 to 16O 0 C, preferably 110 to 140 ° C, particularly preferably 120 to 130 0 C.
  • the paints, dyes and other formulations of the polyisocyanates or polyurethanes according to the invention are prepared by methods known per se.
  • customary additives and other auxiliaries such as pigments, fillers, leveling agents, defoamers, dispersing aids and catalysts, can be added to the formulations in amounts which can be easily determined by the person skilled in the art.
  • the indicated viscosities were determined by means of rotational viscometry according to DIN 53019 with a rotational viscometer from Anton Paar Germany GmbH, Ostfildern, DE.
  • NCO contents were determined volumetrically in accordance with DIN-EN ISO 11909, unless expressly stated otherwise.
  • the indicated particle sizes were determined by means of laser correlation spectroscopy (device: Malvern Zetasizer 1000, Malver Inst. Limited).
  • Desmodur ® N 3300 isocyanurate based on hexamethylene diisocyanate, Bayer MaterialScience AG, Leverkusen, DE
  • Additol XW 395 flow control agent / defoamer, UCB Chemicals, St. Louis, USA
  • Surfvnol 104 flow control agent / defoamer, 50% in NMP, Air Products, Hattingen, DE
  • Example 4 The procedure was as in Example 4 except that submitted the compound of Example 3 and 1,6-hexanediol, and were then mixed with Desmodur ® N 3300th Subsequently, the mixture was further stirred at 35 ° C until reaching an NCO value of 2.91%.
  • the dispersion had the following properties:
  • the dispersion had the following properties:
  • Example 9 The procedure was as described in Example 9, except that in addition to the compound from Example 2 16.00 g (0.032 VaI OH) of a methanol-started polyethylene oxide average molecular weight of 500 was added and only 108.73 g (1.248 VaI) butanone oxime used.
  • the dispersion had the following properties: Solids content 39.0% pH 8.58
  • Solubility exposure time 1 minute, order of solvents: xylene / methoxypropyl acetate / ethyl acetate / acetone rating: 0 very good to 5 poor
  • the paints were sprayed onto steel sheets by means of a flow cup gun and baked.
  • the salt spray test was carried out in accordance with DIN 53 167.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Dispersion Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Polyurethanes Or Polyureas (AREA)
  • Paints Or Removers (AREA)
  • Adhesives Or Adhesive Processes (AREA)

Abstract

La présente invention concerne de nouveaux agents d'hydrophilisation, leur utilisation pour produire des polyisocyanates bloqués aqueux et/ou diluables dans l'eau, ainsi que la production de ces polyisocyanates bloqués et leur utilisation dans des systèmes à un composant éventuellement autoréticulables présentant des propriétés anticorrosion améliorées.
EP06754444A 2005-06-30 2006-06-20 Nouveaux agents d'hydrophilisation / produit de remplacement de hps Withdrawn EP1910440A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102005030523A DE102005030523A1 (de) 2005-06-30 2005-06-30 Neue Hydrophilierungsmittel / HPS-Ersatz
PCT/EP2006/005880 WO2007003268A1 (fr) 2005-06-30 2006-06-20 Nouveaux agents d'hydrophilisation / produit de remplacement de hps

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EP1910440A1 true EP1910440A1 (fr) 2008-04-16

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US (1) US20070004894A1 (fr)
EP (1) EP1910440A1 (fr)
JP (1) JP2008545052A (fr)
KR (1) KR20080038316A (fr)
CN (1) CN101213232A (fr)
BR (1) BRPI0613511A2 (fr)
DE (1) DE102005030523A1 (fr)
WO (1) WO2007003268A1 (fr)
ZA (1) ZA200711021B (fr)

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PL3404073T3 (pl) 2017-05-19 2022-01-31 Evonik Operations Gmbh Hydrofilowe izocyjanurany zawierające alkoksysilan
US11732083B2 (en) 2020-11-19 2023-08-22 Covestro Llc Polyisocyanate resins
CN113307935B (zh) * 2021-06-15 2022-08-16 广州冠志新材料科技有限公司 一种亲水剂及其制备方法与应用

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JP2008545052A (ja) 2008-12-11
DE102005030523A1 (de) 2007-01-04
BRPI0613511A2 (pt) 2011-01-11
CN101213232A (zh) 2008-07-02
ZA200711021B (en) 2009-03-25
KR20080038316A (ko) 2008-05-06
WO2007003268A1 (fr) 2007-01-11
US20070004894A1 (en) 2007-01-04

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