EP1497385A1 - Dispersions de polyurethanne autoreticulantes - Google Patents

Dispersions de polyurethanne autoreticulantes

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Publication number
EP1497385A1
EP1497385A1 EP03717273A EP03717273A EP1497385A1 EP 1497385 A1 EP1497385 A1 EP 1497385A1 EP 03717273 A EP03717273 A EP 03717273A EP 03717273 A EP03717273 A EP 03717273A EP 1497385 A1 EP1497385 A1 EP 1497385A1
Authority
EP
European Patent Office
Prior art keywords
acid
component
added
mol
polyol
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Withdrawn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
EP03717273A
Other languages
German (de)
English (en)
Inventor
Jan Mazanek
Dieter Mager
Joachim Petzoldt
Heino Müller
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 EP1497385A1 publication Critical patent/EP1497385A1/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Withdrawn legal-status Critical Current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
    • C08G18/70—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
    • C08G18/8003—Masked polyisocyanates masked with compounds having at least two groups containing active hydrogen
    • C08G18/8048—Masked polyisocyanates masked with compounds having at least two groups containing active hydrogen with compounds of C08G18/34
    • 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
    • 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
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
    • C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
    • C08G18/6633—Compounds of group C08G18/42
    • C08G18/6637—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38
    • C08G18/664—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
    • C08G18/6644—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203 having at least three hydroxy 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
    • C08G18/70—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
    • 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

Definitions

  • the present invention relates to aqueous self-crosslinking PUR dispersions, stoving lacquers produced therefrom and their use in lacquers and paints, in particular in the automotive OEM coating.
  • DE-A 40 01 783 deals with special anionically modified aliphatic polyisocyanates
  • DE-A 28 14 815 and EP-A 0 012 348 and EP-A 0 424 697 which describe aqueous stoving enamel binders based on blocked polyisocyanates and organic polyhydroxyl compounds.
  • Isocyanate groups an aminoplast and other components are disclosed.
  • a disadvantage of these one-component systems is that the previously produced components are then formulated into paints and therefore require an additional mixing step.
  • the lacquers described in the prior art do not meet all practical requirements, not even with regard to the solids content and the stability of the lacquers, and also the surface quality of the coatings produced therefrom, such as surface smoothness and gloss.
  • the object of the present invention was to provide improved IC stoving systems, the paints, in particular, having a high solids content and the coatings having a high gloss.
  • the present invention relates to a process for producing self-crosslinking polyurethane polymers, characterized in that in one step an isocyanate component (A) with an isocyanate group functionality greater than or equal to 2 with an at least difunctional polyol component (B1) with an average molecular weight of 62 to 2500 , which contains at least one acid-functional compound (C), is converted to an isocyanate group-containing or hydroxyl group-containing prepolymer,.
  • an isocyanate component (A) with an isocyanate group functionality greater than or equal to 2 with an at least difunctional polyol component (B1) with an average molecular weight of 62 to 2500 , which contains at least one acid-functional compound (C), is converted to an isocyanate group-containing or hydroxyl group-containing prepolymer,.
  • polyol component (B2) with an OH functionality greater than or equal to 2 and optionally an isocyanate component (A '), which may be the same or different from (A), are added, the resulting NCO-functional product is mixed with a blocking agent (D) and, in a further step, a polyol component
  • an acid-functional compound (C), which can be the same or different from (C), and an isocyanate component (A "), the same or different from ( A) and (A ') can be added.
  • the ratio of the isocyanate groups, including the blocked groups, to all groups which are reactive toward isocyanates is from 0.5 to 3.0 to 1, preferably 0.6 to 2.0 to 1, particularly preferably 0.8 to 1.5 to 1 chosen.
  • the present invention also relates to self-crosslinking polyurethane polymers obtainable by the process according to the invention.
  • Suitable isocyanate components (A), (A '), (A ") are aliphatic, cycloaliphatic, araliphatic and / or aromatic isocyanates with an average functionality of 2 to 5, preferably 2 and with an isocyanate content of 0.5 to 60% .-%, preferably from 3 to 40% by weight, particularly preferably from 5 to 30% by weight, such as, for example, tetramethylene diisocyanate, cyclohexane-1,3- and 1,4-diisocyanate, hexamethylene diisocyanate (HDI) , l-Isocyanato-3,3,5-Mmethyl-5-isocyanato-methylcyclohexane (isophorone diisocyanate, IPDI), methylene-bis- (4-isocyanato-cyclohexane), tetramethylxylylene diisocyanate (TMXDI), triisocyanatononane, tolylene diisocyan
  • component (A), (A '), (A ") are polyisocyanates which are particularly suitable as component (A), (A '), (A ") are polyisocyanates which are particularly suitable as component (A), (A '), (A ") are polyisocyanates which are particularly suitable as component (A), (A '), (A ") are polyisocyanates which are particularly suitable as component (A), (A '), (A ") are polyisocyanates which
  • Contain heteroatoms in the radical containing the isocyanate groups include carbodiimide groups, allophanate groups, isocyanurate groups, urethane groups and polyisocyanates containing biuret groups.
  • Particularly preferred Polyisocyanates are those which are mainly used in the production of lacquers, for example modification products containing biuret, isocyanurate or uretdione groups of the simple polyisocyanates mentioned above, in particular hexamethylene diisocyanate or isophorone diisocyanate.
  • low molecular weight polyisocyanates containing urethane groups are also suitable, as can be obtained by reacting excess IPDI or TDI with simple polyhydric alcohols in the molecular weight range 62 to 300, in particular with trimethylolpropane or glycerol.
  • Suitable polyisocyanates are furthermore the known prepolymers containing terminal isocyanate groups, as are accessible in particular by reacting the simple polyisocyanates mentioned above, especially diisocyanates, with inadequate amounts of organic compounds having at least two functional groups which are reactive toward isocyanates.
  • the ratio of isocyanate groups to hydrogen atoms reactive towards NCO corresponds to 1.05: 1 to 10: 1, preferably 1.5: 1 to 4: 1, the hydrogen atoms preferably originating from hydroxyl groups.
  • NCO prepolymers The type and proportions of the starting materials used in the production of NCO prepolymers are chosen such that the NCO prepolymers preferably have an average NCO functionality of 2 to 3 and a number average molecular weight of 500 to 10,000, preferably 800 to 4000.
  • polyisocyanates in the context of the invention, such polymers containing free isocyanate groups on polyurethane, polyester and / or polyacrylate are
  • Heating to suitable stoving temperatures without adding further isocyanate groups reactive groups networked self-crosslinking one-component baking systems.
  • the polyol component (B1) contains 2- to 6-valent polyol components with a molecular weight of 62 to 2500, preferably 62 to 1000, particularly preferably 62 to 500, at least one of these components being an acid-functional compound (C).
  • Preferred polyol components are, for example, 1,4- and / or 1-3-butanediol, 1,6-hexanediol, 2,2,4-trimethyl-1,3-pentanediol, trimethylolpropane, polyester and / or polyether polyols of average molecular weight of less or equal to 1000.
  • the polyol component (B1) preferably contains more than 50% by volume of an acid-functional compound (C), particularly preferably the component (B1) contains exclusively compound (C), very particularly preferably only dimethylol propionic acid.
  • Suitable acid-functional compounds (C) / (C) are hydroxy-functional carboxylic acids and / or sulfonic acids, preferably mono- and dihydroxy-carboxylic acids, such as e.g. 2-hydroxyacetic acid, 3-hydroxypropanoic acid and 12-hydroxy-9-octadecanoic acid (ricinoleic acid).
  • Particularly preferred carboxylic acids (C) / (C) are those in which the carboxyl group is prevented from reacting due to steric effects, e.g. Lactic acid.
  • 3-Hydroxy-2,2-dimethylpropanoic acid (hydroxypivalic acid) and dimethylolpropionic acid are very particularly preferred.
  • the polyol component (B2) is selected from the group of
  • Suitable polyol components (bl) are 2- to 6-valent alcohols and / or mixtures thereof which have no ester groups. Typical examples are ethanediol-1,2, propanediol-1,2 and -1,3, butanediol-1,4, -1,2 or -2,3, hexanediol-1,6, 1,4-dihydroxycyclohexane, glycerol, Trimethylolethane, trimethylolpropane, pentaerythritol and sorbitol. Of course, alcohols with ionic groups or groups which can be converted into ionic groups can also be used as component bl).
  • 1,4- or 1,3-butanediol, 1,6-hexanediol and / or trimethylolpropane are preferred.
  • Suitable linear difunctional polyols (b2) are selected from the group of polyethers, polyesters and / or polycarbonates.
  • the polyol component (b2) preferably contains at least one diol containing ester groups in the molecular weight range from 350 to 4000, preferably from 350 to 2000, particularly preferably from 350 to 1000. This is the average molecular weight which can be calculated from the hydroxyl number.
  • the ester diols are mixtures in which individual constituents which have a molecular weight below or above these limits can also be present in minor amounts. These are the polyester diols known per se, which are composed of diols and dicarboxylic acids.
  • Suitable diols are, for example, 1,4-dimethylol-cyclohexane, 1,4- or 1,3-butanediol, 1,6-hexanediol, neopentyl glycol, 2,2,4-trimethyl-1,3-pentanediol, trimethylolpropane and pentaerythritol respectively.
  • Suitable dicarboxylic acids are, for example, aromatic dicarboxylic acids such as phthalic acid, isophthalic acid and terephthalic acid, cycloaliphatic dicarboxylic acids such as hexahydrophthalic acid, tetrahydrophthalic acid, endomethylene tetrahydrophthalic acid or its anhydrides and ahphatic dicarboxylic acids, which are preferably used, such as Bernutar
  • Adipic acid, suberic acid, azelaic acid and sebacic acid or their anhydrides Adipic acid, suberic acid, azelaic acid and sebacic acid or their anhydrides. Polyester diols based on adipic acid, phthalic acid, isophthalic acid and tetrahydrophthalic acid are preferably used as component (b2).
  • component (b2) are polycaprolactone diols in the average molecular weight range from 350 to 4000, preferably from 350 to 2000, particularly preferably from 350 to 1000, which in a manner known per se from a diol or diol mixture of the type mentioned above as starters and ⁇ -caprolactone have been produced.
  • the preferred starter molecule is 1,6-hexanediol.
  • Those polycaprolactone diols which have been prepared by polymerizing ⁇ -caprolactone using 1,6-hexanediol as starters are very particularly preferred.
  • polyethers of ethylene oxide, propylene oxide and / or tetrahydrofuran can also be used as the linear polyol component (b2).
  • hydroxyl-containing polycarbonates preferably an average molecular weight of 400 to 2000, such as Hexane diol.
  • Suitable monofunctional linear polyethers (b3) are e.g. (Co) polyether from ethylene oxide and / or propylene oxide. Monoalcohol-started polyalkylene oxide polyethers with an average molecular weight of 350 to 2500 and at least 70% ethylene oxide units are preferred. (Co) polymers with more than 75% ethylene oxide units and a molecular weight of 300 to 2500, preferably 500 to 1000, are particularly preferred. Monofunctional alcohols having 1 to 6 carbon atoms are preferably used as starter molecules in the preparation of these polyethers.
  • Suitable polyols (B3) are polyols with an OH functionality greater than 2 and with average molecular weights from 300 to 5000, preferably from 300 to 3000, particularly preferably from 300 to 2000.
  • Preferred polyols (B3) are, for example, polyethers with an average molecular weight of 300 to 2000 and an average functionality of 2.5 to 4 OH groups / molecule.
  • Polyesters with average OH functionality of 2.5 to 4.0 are also preferred.
  • Suitable diols and dicarboxylic acids for the polyesters are those mentioned under component (b2), but they additionally contain tri- to hexafunctional short-chain polyols, such as trimethylolpropane, pentaerythritol or sorbitol. It is preferred to use polyester polyols based on adipic acid, phthalic acid, isophthalic acid and tetrahydrophthalic acid.
  • component (B3) are (co) polyethers of ethylene oxide, propylene oxide and or tetrahydrofuran with an average functionality of greater than 2, as well as branched polycarbonates.
  • blocking agents can be used as blocking agents (D), e.g. ⁇ -caprolactam, diethyl malonate, ethyl acetoacetate, oximes such as butanone oxime, diisopropylamine, dimethylpyrazole, triazole or mixtures thereof.
  • oximes such as butanone oxime, diisopropylamine, dimethylpyrazole, triazole or mixtures thereof.
  • e-caprolactam, butanone oxime, diisopropylamine, 3,5-dimethylpyrazole, triazole and / or mixtures thereof are preferred.
  • reaction of component (A) with (B1) to OH or NCO-functional prepolymers is of particular importance for the process according to the invention. This should be done before adding any other components. If necessary, further isocyanate (A ') or (A' ') should also be used after the preparation of the prepolymer.
  • the preparation of the prepolymer can be carried out in the same reactor as the reaction with the other components to give the dispersions according to the invention.
  • the process according to the invention should be carried out in such a way that when components (A) and (B1) are reacted in accordance with the theoretical stoichiometric trical equation, as little as possible of unreacted excess components (A) and / or (Bl) is present.
  • component (A) is reacted with component (B1), which contains at least one acid-functional compound (C), to form an NCO-functional prepolymer in one step, then the components ( bl), (b2) and (b3) and optionally the
  • Isocyanate component (A '), which may be the same or different from (A), are added, the resulting NCO-functional product is partially blocked with a blocking agent (D) and a polyol component (B3) is added in a further step.
  • a blocking agent (D) particularly preferred in a last stage is an acid-functional compound (C), which can be the same or different from (C), and an isocyanate component (A "), which can be the same or different from (A) and (A '), added.
  • aqueous dispersions containing the self-crosslinking polyurethanes according to the invention are prepared by processes of the prior art
  • At least 50%, preferably 80% to 120%, particularly preferably 95 to 105% of the carboxylic acid groups present in the polyurethanes according to the invention are neutralized with suitable neutralizing agents and then dispersed with deionized water.
  • the neutralization can take place before, during or after the dispersing or dissolving step. However, neutralization before adding water is preferred.
  • Suitable neutralizing agents are, for example, triethylunin, dimethyl
  • the present invention likewise relates to aqueous dispersions comprising the self-crosslinking polyurethanes according to the invention. These aqueous dispersions are used as aqueous one-component stoving systems.
  • 40% by weight of the OH or NCO functional prepolymer 0 to 50% by weight, preferably 5 to 40% by weight, particularly preferably 10 to 25% by weight of component (A ') or ( A "), 1 to 10% by weight, preferably 1 to 5% by weight of component (b1), 5 to 40% by weight, preferably 10 to 25% by weight of component (b2), 1 to 10% by weight, preferably 1 to 5% by weight of component (b3), 10 to 60% by weight, preferably 20 to 50% by weight of component (B3), 1 to 10% by weight, prefers
  • component (C) 1 to 5% by weight of component (C) and 1 to 20% by weight, preferably 1 to
  • component (D) 10% by weight of component (D), the sum of the components being 100%.
  • reaction mixture may also be used.
  • Solvents are added. All known paint solvents such as e.g. N-methylpyrrolidone, methoxypropylacetate or xylene. They are preferred
  • Quantities from 0 to 10% by weight, preferably 0 to 5% by weight, are used.
  • the solvent is preferably added during the polymerization.
  • the dispersions containing the polyurethanes according to the invention are classified as free
  • One-component baking systems containing hydroxyl groups are used for the production of lacquers, paints and other formulations.
  • Auxiliaries and additives of coating technology that may also be used, such as pigments, leveling agents, bubble-preventing additives or catalysts, can also be added to the aqueous dispersions containing the polyurethanes according to the invention.
  • the invention also relates to the use of the dispersions containing the polyurethanes according to the invention for the production of paints, lacquers or adhesives.
  • aqueous one-component coating compositions containing the polyurethanes according to the invention can be applied to any heat-resistant substrate in one or more layers by any methods of coating technology, such as spraying, brushing, dipping, flooding or with the aid of rollers and doctor blades.
  • the paint films generally have a dry layer thickness of 0.01 to 0.3 mm.
  • Suitable substrates are, for example, metal, plastic, wood or glass.
  • the coating film is cured at 80 to 220 ° C, preferably at 130 to 180 ° C.
  • aqueous one-component coating compositions containing the polyurethanes according to the invention are preferably suitable for the production of coatings and lacquers on sheet steel, as used, for example, for the production of vehicle bodies, machines, claddings, drums or containers Find.
  • the use of aqueous one-component coating compositions containing the polyurethanes according to the invention is particularly preferred for the production of automotive fillers and / or topcoats.
  • Viscosity (DIN cup 4): 14 s
  • Example 4 The procedure was as described in Example 4, but instead of the prepolymer from Example 3, 6.76 g (0.15 mol) of 1,4-butanediol, 26.83 g (0.4 mol) of dimethylolpropionic acid in 53, 4 g of N-methylpyrrolidone and 122.32 g (1.1 mol) of isophorone diisocyanate reacted to an NCO content of 10.97% (calculated 11.04%), then 44.48 g (0.4 mol) Isophorone diisocyanate and the polyester, Polyether, 1,4-butanediol and trimethylolpropane according to Example 4 were added.
  • the dispersion obtained had the following properties:
  • Solids content 30% viscosity (DIN cup 4): 16 s
  • Example 3 first 123.9 g (0.295 mol) of the polyester from adipic acid and 1,6-hexanediol, 26.83 g (0.4 mol) of dimethylolpropionic acid in 62.85 g of N-methylpyrrolidone and 115.93 g (1, 0425 mol) of isophorone diisocyanate were reacted up to an isocyanate content of 3.85% and then 50.88 g (0.458 mol) of isophorone diisocyanate and the polyether, 1,4-butanediol and trimethylolpropane according to Example 4 were added.
  • the dispersion obtained had the following properties:
  • Viscosity (DIN cup 4): 17 s particle size (LKS): 26 ⁇ m
  • Hexanediol used.
  • the dispersion obtained had the following properties:
  • Viscosity (DIN cup 4): 14 s particle size (LKS): 28 im
  • Example 7 The procedure was as described in Example 7, but instead of the compound from Example 3 256.38 g (1.1 eq NCO) of the compound from Example 2 and instead of the polyether 2.5 g (0.005 mol) of a methanol ethoxylate were used.
  • the dispersion obtained had the following properties:
  • Viscosity (DIN cup 4): 13 s particle size (LKS): 48 nm
  • Example 8 The procedure was as described in Example 8, but instead of the compound from Example 2, a reaction product of 59.49 g (0.535 mol) of isophorone diisocyanate and 26.83 g (0.4 mol) of dimethylolpropionic acid (as a solution in 53.40 g of N. -Methylpyrrolidone) with an NCO content of 4.02% (calculated 4.06) in a mixture with 107.31 g (0.97 mol) of isophorone diisocyanate.
  • the reaction mixture had 4.92% NCO groups before the addition of butanone oxime.
  • the dispersion obtained had the following properties:
  • Viscosity (DIN cup 4): 13 s
  • Solids content 30% viscosity (DIN cup 4): 12 s
  • Viscosity (DIN cup 4): 12 s particle size (LKS): 96 nm
  • Dispersion had the following properties:
  • Viscosity (DIN cup 4): 21 s particle size (LKS): 63 nm
  • Example 13 (According to the invention)
  • Example 11 The procedure was as described in Example 11, but 11.25 g (0.025 mol) of polyether according to Example 4 and 729.32 g of water were used.
  • the dispersion had the following properties:
  • Viscosity (DIN cup 4): 18 s
  • Viscosity (DIN cup 4): 15 s pH value: 9.04 particle size (LKS): 50 nm
  • Polyether average molecular weight of 500, 6.70 g (0.1 mol) of trimethylolpropane and 4.50 g (0.1 mol) of 1,4-butanediol were added and the mixture was stirred for a further 5 hours until the isocyanate group content was 4.66% (calculated 4.79%) was reached.
  • the mixture was then cooled to 70 ° C. and 40.48 g (0.4 mol) of diisopropylamine were added at this temperature over the course of 60 minutes. The mixture was then stirred for 30 minutes; the NCO content was 0.75% (calculated 0.83%).
  • Solids content 30% viscosity (23 ° C, rotational
  • Example 14 The procedure was as described in Example 14, but instead of the short-chain polyether 11.25 g of a butanol-started monofunctional polyether consisting of ethylene oxide and propylene oxide (80:20, w / w) average molecular weight of 2250 and 15.58 g (0.175 mol) of N-dimethylethanolamine and 788.3 g of water are used.
  • the dispersion had the following properties:
  • Solids content 45% viscosity (23 ° C, rotational
  • Example 4 The procedure was as described in Example 4, but no NCO-functional prepolymer was produced, but all the starting materials which were used in Example 4 up to the blocking step with butanone oxime were allowed to react statistically in a mixture.
  • the dispersion obtained had the following properties:
  • Solids content 30% viscosity (DIN cup 4): 19 s
  • Example 17 The procedure was as described in Example 17, but the NCO-functional prepolymer was not prepared, but all the starting materials which were used in Example 17 up to the blocking step with butanone oxime were allowed to react statistically in a mixture.
  • the dispersion obtained had the following properties:
  • Viscosity 100 mPas
  • a pigment grinding paste listed below are mixed with 68.26 g of a 30% polyurethane dispersion according to Comparative Example 1 and 0.33 g of 10% aqueous dimethylethanolamine solution and 0.48 g of a 97% solution commercially available, water-dilutable melamine resin (Maprenal ® MF 904, Solutia, DE) stirred.
  • the spray viscosity is 22 s ISO-Cup 5 mm.
  • 35.39 g of the pigment grinding paste listed below are mixed with 58.59 g of a 40% polyurethane dispersion according to Example 17 and 0.38 g of 10% aqueous dimethylethanolamine solution and 0.55 g of a 97% solution commercially available water-dilutable melamine resin (Maprenal ® MF 904, Solutia, DE) stirred and diluted with distilled water to a spray viscosity of approx. 28 s ISO-Cup 5 mm.
  • a predispersed slurry consisting of 11.0 g of 70% water-thinnable polyester resin (Bayhydrol ® D 270, 2.9% by weight OH groups, Bayer AG,
  • varnishes are applied to the following substrates in a resulting dry film thickness of 25 to 35 ⁇ m using a flow cup spray gun with a nozzle diameter 1.5 mm and an atomizing pressure of 5 bar.
  • the wet paint films are flashed off at 23 ° C. for 5 minutes and then baked in a forced air oven.
  • the substrates are in the case of tests of pendulum hardness and Glossy glass plates, in the case of adhesion / cross cut, Erichsen creasing, degreased steel sheets.
  • Lacquer storage 30d 40 ° C 21E / 66E 52 E / 82 E 55 E / 84 E
  • Lacquer storage 30d 40 ° C 19E / 59E 45 E / 74 E
  • Pendulum hardness Vibration test according to König DIN 53157

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Engineering & Computer Science (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 des dispersions aqueuses de polyuréthanne autoréticulantes, des vernis au four produits à partir de ces dispersions et l'utilisation de ces dernières dans des peintures et vernis, en particulier dans l'application d'une première couche de peinture en automobile.
EP03717273A 2002-04-17 2003-04-04 Dispersions de polyurethanne autoreticulantes Withdrawn EP1497385A1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE10216945 2002-04-17
DE10216945A DE10216945A1 (de) 2002-04-17 2002-04-17 Selbstvernetzende PUR-Dispersionen
PCT/EP2003/003526 WO2003087245A1 (fr) 2002-04-17 2003-04-04 Dispersions de polyurethanne autoreticulantes

Publications (1)

Publication Number Publication Date
EP1497385A1 true EP1497385A1 (fr) 2005-01-19

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EP03717273A Withdrawn EP1497385A1 (fr) 2002-04-17 2003-04-04 Dispersions de polyurethanne autoreticulantes

Country Status (9)

Country Link
US (1) US7049367B2 (fr)
EP (1) EP1497385A1 (fr)
JP (1) JP4309292B2 (fr)
CN (1) CN100347215C (fr)
AU (1) AU2003221551A1 (fr)
CA (1) CA2482661A1 (fr)
DE (1) DE10216945A1 (fr)
HK (1) HK1081982A1 (fr)
WO (1) WO2003087245A1 (fr)

Families Citing this family (46)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE10346548A1 (de) * 2003-10-02 2005-05-12 Bayer Materialscience Ag Selbstvernetzende PUR-Dispersionen
US8604153B2 (en) * 2004-09-01 2013-12-10 Ppg Industries Ohio, Inc. Poly(ureaurethane)s, articles and coatings prepared therefrom and methods of making the same
US9464169B2 (en) 2004-09-01 2016-10-11 Ppg Industries Ohio, Inc. Polyurethanes, articles and coatings prepared therefrom and methods of making the same
US20070225468A1 (en) * 2004-09-01 2007-09-27 Rukavina Thomas G Polyurethanes prepared from polyester polyols and/or polycaprolactone polyols, articles and coatings prepared therefrom and methods of making the same
US8889815B2 (en) * 2004-09-01 2014-11-18 Ppg Industries Ohio, Inc. Reinforced polyurethanes and poly(ureaurethane)s, methods of making the same and articles prepared therefrom
US20070149749A1 (en) * 2004-09-01 2007-06-28 Rukavina Thomas G Polyurethanes prepared from polycarbonate polyols, articles and coatings prepared therefrom and methods of making the same
US20090280329A1 (en) 2004-09-01 2009-11-12 Ppg Industries Ohio, Inc. Polyurethanes, Articles and Coatings Prepared Therefrom and Methods of Making the Same
US11591436B2 (en) 2004-09-01 2023-02-28 Ppg Industries Ohio, Inc. Polyurethane article and methods of making the same
US20070148471A1 (en) * 2004-09-01 2007-06-28 Rukavina Thomas G Impact resistant polyurethane and poly(ureaurethane) articles and methods of making the same
US8399559B2 (en) * 2004-09-01 2013-03-19 Ppg Industries Ohio, Inc. Polyurethanes, articles and coatings prepared therefrom and methods of making the same
US8653220B2 (en) * 2004-09-01 2014-02-18 Ppg Industries Ohio, Inc. Poly(ureaurethane)s, articles and coatings prepared therefrom and methods of making the same
US8933166B2 (en) * 2004-09-01 2015-01-13 Ppg Industries Ohio, Inc. Poly(ureaurethane)s, articles and coatings prepared therefrom and methods of making the same
US11008418B2 (en) 2004-09-01 2021-05-18 Ppg Industries Ohio, Inc. Polyurethanes, articles and coatings prepared therefrom and methods of making the same
US9598527B2 (en) * 2004-09-01 2017-03-21 Ppg Industries Ohio, Inc. Polyurethanes, articles and coatings prepared therefrom and methods of making the same
US20070251421A1 (en) * 2004-09-01 2007-11-01 Rukavina Thomas G Powder coatings prepared from polyurethanes and poly(ureaurethane)s, coated articles and methods of making the same
US8734951B2 (en) * 2004-09-01 2014-05-27 Ppg Industries Ohio, Inc. Polyurethanes, articles and coatings prepared therefrom and methods of making the same
US20090280709A1 (en) 2004-09-01 2009-11-12 Ppg Industries Ohio, Inc. Polyurethanes, Articles and Coatings Prepared Therefrom and Methods of Making the Same
US8399094B2 (en) * 2004-09-01 2013-03-19 Ppg Industries Ohio, Inc. Multilayer laminated articles including polyurethane and/or poly(ureaurethane) layers and methods of making the same
US8349986B2 (en) * 2004-09-01 2013-01-08 Ppg Industries Ohio, Inc. Poly(ureaurethane)s, articles and coatings prepared therefrom and methods of making the same
US20070173601A1 (en) * 2004-09-01 2007-07-26 Rukavina Thomas G Polyurethanes, articles and coatings prepared therefrom and methods of making the same
US11248083B2 (en) 2004-09-01 2022-02-15 Ppg Industries Ohio, Inc. Aircraft windows
US11149107B2 (en) 2004-09-01 2021-10-19 Ppg Industries Ohio, Inc. Polyurethanes, articles and coatings prepared therefrom and methods of making the same
US8859680B2 (en) * 2004-09-01 2014-10-14 Ppg Industries Ohio, Inc Poly(ureaurethane)s, articles and coatings prepared therefrom and methods of making the same
US20070167600A1 (en) * 2004-09-01 2007-07-19 Rukavina Thomas G Polyurethanes prepared from polycaprolactone polyols, articles and coatings prepared therefrom and methods of making the same
US8207286B2 (en) 2004-09-01 2012-06-26 Ppg Industries Ohio, Inc Methods for preparing polyurethanes
US20070167601A1 (en) * 2004-09-01 2007-07-19 Rukavina Thomas G Polyurethanes prepared from polycarbonate polyols, articles and coatings prepared therefrom and methods of making the same
US8927675B2 (en) 2004-09-01 2015-01-06 Ppg Industries Ohio, Inc. Poly(ureaurethane)s, articles and coatings prepared therefrom and methods of making the same
US20060122357A1 (en) * 2004-12-08 2006-06-08 Thomas Faecke Continuous method for manufacturing an acid functional blocked solid isocyanate
DE102005019430A1 (de) * 2005-04-25 2006-10-26 Bayer Materialscience Ag N-Methylpyrrolidon-freie Polyurethan-Dispersionen auf Basis von Dimethylolpropionsäure
DE102005030225A1 (de) * 2005-06-29 2007-01-04 Bayer Materialscience Ag Selbstvernetzende PUR-Dispersionen
US8124169B2 (en) * 2005-12-14 2012-02-28 3M Innovative Properties Company Antimicrobial coating system
US9247736B2 (en) * 2005-12-14 2016-02-02 3M Innovative Properties Company Antimicrobial adhesive films
DE102006021728A1 (de) * 2006-05-09 2007-11-15 Bayer Materialscience Ag Wässrige Dispersionen mit bimodaler Teilchengrößenverteilung
JP5170499B2 (ja) * 2006-08-18 2013-03-27 日本ポリウレタン工業株式会社 ブロックイソシアネート含有エマルジョン組成物及びその製造方法並びに焼付け型塗料用又は接着剤用組成物
CN100410345C (zh) * 2006-10-23 2008-08-13 金小凤 二氯丙烷作为聚氨酯胶粘剂生产中的稀释剂的应用
DE102006059680A1 (de) * 2006-12-18 2008-06-19 Bayer Materialscience Ag Colöserfreie, selbstvernetzende PUR-Dispersionen
WO2008157323A1 (fr) * 2007-06-13 2008-12-24 3M Innovative Properties Company Composition filmogène antimicrobienne, film antimicrobien, et procédé de vérification de la présence d'un film antimicrobien
EP2011808A1 (fr) * 2007-07-03 2009-01-07 Bayer MaterialScience AG Colle médicale pour la chirurgie
US20090030146A1 (en) * 2007-07-24 2009-01-29 Yuliya Berezkin Polyurethane dispersions for sealants
CN101130598B (zh) * 2007-08-15 2010-05-26 黑龙江省化工研究院有限责任公司 液态阻尼减振膨胀胶及其制备方法
BRPI0820705A2 (pt) * 2007-12-12 2014-10-07 3M Innovative Properties Co Filme antimicrobiano microestruturado
JP2011509422A (ja) * 2007-12-21 2011-03-24 スリーエム イノベイティブ プロパティズ カンパニー 再帰反射安全物品
CN101946192B (zh) 2007-12-21 2012-09-05 3M创新有限公司 回射制品以及包括球芯和两个同心光学干涉层的回射元件
JP2011509421A (ja) * 2007-12-21 2011-03-24 スリーエム イノベイティブ プロパティズ カンパニー 衣類、繊維及びフィラメント形態の再帰反射物品
JP5757959B2 (ja) * 2010-01-22 2015-08-05 ルブリゾル アドバンスド マテリアルズ， インコーポレイテッド 架橋可能な熱可塑性ポリウレタン
JP6805826B2 (ja) * 2014-06-20 2020-12-23 宇部興産株式会社 水性ポリウレタン樹脂分散体

Family Cites Families (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2456469C2 (de) * 1974-11-29 1983-01-13 Bayer Ag, 5090 Leverkusen Verfahren zur Herstellung von in Wasser löslichen bzw. dispergierbaren blockierten Polyisocyanaten und ihre Verwendung als Beschichtungsmittel
US4119602A (en) * 1977-04-07 1978-10-10 W. R. Grace & Co. Aqueous urethane codispersions
DE2853937A1 (de) * 1978-12-14 1980-07-03 Bayer Ag Verfahren zur herstellung von wasserdispergierbaren oder -loeslichen blockierten polyisocyanaten, die nach dem verfahren erhaeltlichen blockierten polyisocyanate, sowie diese blockierte polyisocyanate als isocyanatkomponente enthaltende lackbindemittel
US4433017A (en) * 1981-09-17 1984-02-21 Dai-Ichi Kogyo Seiyaku Co., Ltd. Thermally reactive water-soluble blocked urethane prepolymer
DE4001783A1 (de) * 1990-01-23 1991-07-25 Bayer Ag Polyisocyanatgemische, ein verfahren zu ihrer herstellung und ihre verwendung als bindemittel fuer ueberzugsmittel oder als reaktionspartner fuer gegenueber isocyanatgruppen oder carboxylgruppen reaktionsfaehige verbindungen
DE4221924A1 (de) * 1992-07-03 1994-01-13 Bayer Ag In Wasser lösliche oder dispergierbare Polyisocyanatgemische und ihre Verwendung in Einbrennlacken
DE19914882A1 (de) * 1999-04-01 2000-10-05 Bayer Ag Selbstvernetzende Polyurethan-, Polyurethan-Polyharnstoff- bzw. Polyharnstoff-Dispersionen für Schlichten
DE19930555C1 (de) * 1999-07-02 2001-01-18 Basf Coatings Ag Wäßriger Beschichtungsstoff, insbesondere wäßriger Füller oder Steinschlagschutzgrund
DE19953445A1 (de) * 1999-11-06 2001-05-17 Basf Coatings Ag Selbstvernetzende Polyurethane und Pfropfmischpolymerisate auf Polyurethanbasis sowie ihre Verwendung zur Herstellung von Beschichtungsstoffen, Klebstoffen und Dichtungsmassen
DE10032977A1 (de) * 2000-07-06 2002-01-24 Basf Coatings Ag Beschichtungsstoff und seine Verwendung als Füller oder Steinschlagschutzgrundlack
KR100545438B1 (ko) * 2000-09-22 2006-01-24 피피지 인더스트리즈 오하이오 인코포레이티드 경화성 폴리우레탄, 그로부터 제조된 코팅물, 및 그의제조방법
US6434005B1 (en) * 2000-10-27 2002-08-13 Vlt Corporation Power converter packaging

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO03087245A1 *

Also Published As

Publication number Publication date
CN100347215C (zh) 2007-11-07
CA2482661A1 (fr) 2003-10-23
HK1081982A1 (en) 2006-05-26
AU2003221551A1 (en) 2003-10-27
JP4309292B2 (ja) 2009-08-05
DE10216945A1 (de) 2003-11-06
US7049367B2 (en) 2006-05-23
WO2003087245A1 (fr) 2003-10-23
JP2005522559A (ja) 2005-07-28
CN1662619A (zh) 2005-08-31
US20030199632A1 (en) 2003-10-23

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