WO2011061206A1 - Polyruréthane polyurées anioniques stables à la lumière - Google Patents

Polyruréthane polyurées anioniques stables à la lumière Download PDF

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Publication number
WO2011061206A1
WO2011061206A1 PCT/EP2010/067631 EP2010067631W WO2011061206A1 WO 2011061206 A1 WO2011061206 A1 WO 2011061206A1 EP 2010067631 W EP2010067631 W EP 2010067631W WO 2011061206 A1 WO2011061206 A1 WO 2011061206A1
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Prior art keywords
polyurethane
polyurea
range
polymer according
acid
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PCT/EP2010/067631
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English (en)
Inventor
Rolf Gertzmann
Henricus Peerlings
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Bayer Materialscience Ag
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Priority claimed from EP10001665A external-priority patent/EP2361938A1/fr
Application filed by Bayer Materialscience Ag filed Critical Bayer Materialscience Ag
Publication of WO2011061206A1 publication Critical patent/WO2011061206A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—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
    • C08G18/08—Processes
    • C08G18/0804—Manufacture of polymers containing ionic or ionogenic groups
    • C08G18/0819—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—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
    • C08G18/0828—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups containing sulfonate groups or groups forming them
    • 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
    • C09D175/06—Polyurethanes from polyesters
    • 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
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/20—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes for coatings strippable as coherent films, e.g. temporary coatings strippable as coherent films

Definitions

  • the present invention relates to new peelable coatings based on cosolvent-free water-based light-stable anionic polyurethane polyureas, methods for the manufacture thereof and the use thereof as a coating, preferably as a peelable coating for temporarily protecting motor vehicles, aeroplanes, steel and aluminium profiles, panes of glass and plastics and any other substrates, and methods for the re-use of the used peeled-off coating films.
  • Anionic polyurethane polyurea dispersions are in principle known.
  • Cosolvent-free water-based anionic polyurethane dispersions, methods for the manufacture thereof and the use thereof as coatings, coating compounds, adhesives and peelable coatings are also known from the prior art. An assessment of the relevant prior art is given in this regard in DE-A 19 653 585.
  • DE-A 19 653 585 describes polyurea dispersions which after physical drying at 20 to 100°C
  • transparent high-gloss UV-resistant heat-resistant (-30 to 80°C) coatings which are resistant to precipitation (of an organic or inorganic nature) and on the one hand adhere well and on the other can easily be removed by peeling.
  • the tear resistance and elongation behaviour of the coating films are reasonably high, as described for example in DE- A 19 653 585.
  • WO 98/23692 describes mixtures of polyolefins which are used as peelable coatings for motor cars. These mixtures do not contain any PU components, however. Nor are the peelable coatings described here recyclable. DE-A 10311420 describes polyether-based peelable coatings which do not, however, have the required light stability.
  • EP-B 1 072652 and EP-A 1132413 describe complex methods for the manufacture of polyurethane dispersions, in which a mixture of two polyurethane dispersions having different glass transition temperatures or an additional grafting of acrylic monomers is carried out on the polyurethane dispersion.
  • EP-A 1338634 and DE-A 10311420 describe in principle the fact that a mixture of hyrophilising agents that contain both carboxylate groups and sulfonate groups can be used.
  • the users of coatings of this kind now seek coating compounds which, after they have been used in coatings, in addition to the conventional advantageous properties such as light stability and acid resistance display better water resistance and peelability.
  • the desired application-engineering properties are obtained if there is used as the hydrophilising agent a mixture of substances containing carboxyl groups and sulfonyl groups in a certain ratio and a certain quantity in relation to all the components of the polyurethane polymer.
  • the invention therefore relates to new peelable coatings based on containing a water-based anionic polyurethane polyurea which contains a mixture of substances containing carboxyl groups and sulfonyl groups.
  • the invention further relates to light-stable coatings which are manufactured therefrom, in which these coatings may be applied to any substrates and dried at temperatures of up to 150°C.
  • Suitable dispersions for the light-stable coating compounds according to the invention which are based on low-cosolvent or cosolvent-free water-based anionic dispersions of polyurethane polyureas whereof the solids contain the reaction product at least partly in salt form, comprising a) at least one NCO prepolymer, including i) 20 to 60 wt.% of at least one diisocyanate, ii) 20-80 wt.%) of at least one macrodiol having a number average molecular weight of from 500 to 10 000, iii) 2 to 12 wt.%) of at least one 2,2-bis-(hydroxymethyl)-alkane-monocarboxylic acid, iv) 0 to 15 wt.%) of at least one short-chain diol having a number average molecular weight of from 62 to 400, v) 0 to 10 wt.%) of at least one monofunctional alcohol having a number average molecular weight of from 32 to 350, bl
  • the NCO content is adjusted to from 75 to 80% of the calculated NCO content.
  • the sum of aiii) and bl) lies in the range of from 3 to 10 wt.%, particularly preferably in the range of from 3 to 8 wt.%.
  • the ratio of aiii) to b 1 ) lies in the range of from 5:1 to 1 :1.
  • the acid value of the prepolymer lies in the range of from 5 to 20 mg KOH/g, particularly preferably in the range of from 8 to 18 mg KOH/g.
  • the polyurethane dispersions used according to the invention are low in cosolvents.
  • the polyurethane dispersions used according to the invention preferably contain 0.0 to 0.9 wt.%>, particularly preferably 0.0 to 0.5 wt.%>, most particularly preferably 0.0 to 0.4 wt.%>, of cosolvents in relation to the total polyurethane dispersion.
  • the polymer mixtures according to the invention are low in cosolvents.
  • the polyurethane dispersions used according to the invention preferably contain 0.0 to 0.9 wt.%>, particularly preferably 0.0 to 0.5 wt.%>, most particularly preferably 0.0 to 0.4 wt.%>, of cosolvents in relation to the total polyurethane dispersion.
  • cosolvents are polar organic solvents.
  • cosolvents are organic solvents having a Hansen parameter in the range of from 7.2 to 16.0 (cal/cm 3 ) 0 ' 5 , as published in "Polymer Handbooks", Eds. Brandrup, J.; Immergut, E.H.; Grulke, E.A., 4th Edition, John Wiley, New York, 1999, VH/pages 675-711.
  • preferred cosolvents are polar organic solvents selected from the group comprising acetone, methyl ethyl ketone, butyl diglycol, dimethyl sulfoxide, n- ethyl pyrrolidone, dimethyl formamide, dimethyl acetamide and dipropylene glycol dimethyl ether.
  • the coating compound according to the invention preferably has a solids content in the range of from 20 - 60 wt.%>, particularly preferably in the range of from 30 - 40 wt.%>, in water determined according to DIN EN ISO 3251.
  • component a)i) there are preferably used aliphatic and/or cycloaliphatic diisocyanates such as diisocyanates selected from the group comprising isophorone diisocyanate (IPDI), 4,4'- dicyclohexylmethane diisocyanate, l-methyl-2,4-diisocyanato-cyclohexane, l-methyl-2,6- diisocyanato-cyclohexane, 1 ,6-hexamethylene diisocyanate and 1,3-cyclohexane diisocyanate.
  • IPDI isophorone diisocyanate
  • 4'- dicyclohexylmethane diisocyanate 4,4'- dicycl
  • aromatic diisocyanates such as 2,4- and 2,6- toluene diisocyanate or 2,4'- and 4,4'-diphenylmethane diisocyanate is also possible.
  • component a)ii) there are preferably used macrodiols having a molecular weight of from 500 to 10 000.
  • Suitable dicarboxylic acids or their anhydrides are adipic acid, succinic acid (anhydride), maleic acid (anhydride), sebacic acid, azelaic acids, dimer fatty acids (in hydrogenated and unhydrogenated form), phthalic acid (anhydride), isophthalic acid, tetrahydrophthalic acid (anhydride), 1 ,4-cyclohexane dicarboxylic acid and hexahydrophthalic acid (anhydride).
  • Diols which may be used are the industrially available diols such as ethylene glycol, 1,2- and 1 ,3-propanediol, 1,3- and 1 ,4-butanediol, 1,6-hexanediol, diethylene glycol, dipropylene glycol, neopentyl glycol or mixtures of such diols.
  • Preferable as component a)ii) are polyester diols of adipic acid, hexanediol and neopentyl glycol.
  • component a)ii) are polycarbonate diols, polycaprolactone diols, hydroxypolytetrahydrofurans or hydroxypolyethers based on propylene oxide.
  • Suitable polycarbonate diols are obtained for example by reacting carbonic acid derivatives such as diphenyl carbonate or phosgene with alcohols, preferably diols of the type mentioned above.
  • the average molar mass of the polyols of component a)ii) lies between 500 and 10 000, preferably between 700 and 4 000, and macrodiols having a molar mass of between 1 000 and 2 500 are particularly preferred.
  • the starting components a)iii) are preferably 2,2-bis-(hydroxymethyl)-alkane-monocarboxylic acids having a total of 5 - 8 carbon atoms, that is to say compounds of the general formula (I),
  • R represents an alkyl radical having 1 - 4 carbon atoms.
  • R represents an unsubstituted alkyl radical having 1 - 4 carbon atoms.
  • the component a)iii) is 2,2-dimethylolpropionic acid.
  • the starting component a)iv) are short-chain diols having a molecular weight in the range of from 62 - 400. Particularly preferred as the component a)iv) is 1 ,4-butanediol.
  • Possible as the starting component a)v) are alcohols having a molecular weight in the range of from 32 to 350.
  • alcohols selected from the group comprising methanol, ethanol, butanol, hexanol, 2-ethylhexanol, octanol and dodecanol are used.
  • R 1 and R 2 independently of one another represent a Ci to C6-alkanediyl group, preferably ethylene, and R 3 represents H or alkali, preferably Na.
  • the component b2) it is possible to use any aliphatic and/or cycloaliphatic compounds which have at least two amino groups that are reactive with isocyanates and have a molecular weight in the range of from 60 to 300. Possible for this are in particular ethylenediamine, propylenediamine, hexamethylenediamine, isophoronediamine, p-xylylenediamine, 4,4'-di- amino-dicyclohexylmethane and 4,4'-diamino-3,3'-dimethyldicyclohexylmethane.
  • the component c) there are, as well as ammonia and alkanolamines, also monofunctional amines such as primary amines from the group comprising methylamine, ethylamine, n-propylamine, n-butylamine, n-octylamine, laurylamine, stearylamine, isopropylamine and cyclohexylamine, as well as secondary amines such as dimethylamine, diethylamine, diisopropylamine, dibutylamine and piperidine. Particularly preferred are secondary amines such as dibutylamine. It goes without saying that mixtures of these may be used.
  • Suitable as the neutralising agent e) are for example ammonia, N-methylmorpholine, dimethylisopropanolamine, triethylamine, dimethylethanolamine, methyldiethanolamine, triethanolamine, morpholine, tripropylamine, ethanolamine, diethanolamine, triisopropanolamine, n-ethyl-diisopropylamine and mixtures thereof.
  • Light-stable coating compounds including a) at least one NCO prepolymer, including i) 20 to 60 wt.% of at least one diisocyanate, ii) 20-80 wt.% of at least one macrodiol having a molecular weight of from 500 to 10 000, iii) 2 to 12 wt.% of dimethylolpropionic acid, iv) 0 to 15 wt.%) of at least one short-chain diol having a molecular weight of from 62 to 400, v) 0 to 10 wt.%) of at least one monofunctional alcohol having a molecular weight of from 32 to 350, bl) 0,5 to 10 wt.% of the sodium salt of N-(2-aminoethane)-2-aminoethanesulfonic acid, b2) 0 to 15 wt.% of at least one diamine having a molecular weight of from 60 to 300, c) 0 to 10 wt.
  • the present invention further relates to a method for manufacturing water-based polyurethane dispersions.
  • the components a)i), ii) and iii) are placed in a reactor and reacted in anhydrous conditions in a temperature range of from 50 - 150°C, preferably 50 - 110°C, and the batch is then cooled and has added to it industrially conventional acetone and optionally the short-chain diol (iv) and optionally monofunctional alcohols (v), and the mixture is heated until the NCO content thereof has fallen to a value of from 65 to 85% of the calculated NCO content. In this way, the NCO prepolymer is obtained.
  • the batch is diluted with further acetone and the calculated quantity of a mixture of diamine and chain terminator (components bl), b2) and c)) is added, dissolved in water.
  • a mixture of diamine and chain terminator components bl), b2) and c)
  • 90%> of the NCO groups are reacted with the chain extender, the diamine and the chain terminator.
  • the remaining isocyanate is reacted with the water that is present to give the polyurethane polyurea according to the invention.
  • the reaction that creates the polymer structure is preferably carried out without the use of catalysts, but it also possible to use catalysts that are known in isocyanate chemistry (for example tertiary amines such as triethylamine, tin compounds such as tin(II) octoate, dibutyl tin dilaurate and similar commonly available catalysts).
  • catalysts that are known in isocyanate chemistry (for example tertiary amines such as triethylamine, tin compounds such as tin(II) octoate, dibutyl tin dilaurate and similar commonly available catalysts).
  • the calculated quantity of neutralising agent preferably ammonia solution
  • is added to the batch such that 50 - 100% of the carboxyl groups present are neutralised by the neutralising agent, or ammonia.
  • Polyurethane polyurea dispersions which are obtained by the method according to the invention preferably have a solids content in the range of from 20 - 60 wt.%, particularly preferably in the range of from 30 - 40 wt.%, in water determined according to DIN EN ISO 3251.
  • the polyurethane dispersion includes particles having an average particle diameter in the range of from 20 - 1 000 nm, particularly preferably in the range of from 50 - 500 nm, as measured by the method of dynamic light scattering according to ISO 13320-1.
  • pH values of the polyurethane polyurea dispersions used according to the invention lie within the range of from 6 - 9.
  • the dispersion can be blended with other anionic or non-ionic dispersions such as polyvinyl acetate, polyethylene, polystyrene, polybutadiene, polyvinylchloride, polyacrylate and copolymer plastics dispersions.
  • anionic or non-ionic dispersions such as polyvinyl acetate, polyethylene, polystyrene, polybutadiene, polyvinylchloride, polyacrylate and copolymer plastics dispersions.
  • Any desired adjustment of the pH value of the mixtures may be made using organic or inorganic bases, such as ammonia, alkali carbonates, amines or aminoalcohols, in which organic bases are preferred. Most particularly preferred is 2-amino-2-methyl-l-propanol.
  • the invention further also relates to the use of the polyurethane polyurea in coating compounds in order to manufacture high-gloss, light-stable, weathering-resistant, solvent- free coatings and finishes.
  • These coatings and finishes serve to protect motor vehicles, steel, aluminium and metal articles of all kinds, glass and plastics articles of all kinds, mineral substrates, masonry or natural stone, and to prevent corrosion in ships, bridges, aeroplanes or railways, and to protect articles of wood and natural materials and any other substrates.
  • the coating compounds are applied by dipping, knife coating, pouring, brush application or spraying and are then dried at 120 to 150°C.
  • the invention further also relates to the use of the polyurethane polyurea in coating compounds in order to manufacture recyclable peelable coatings.
  • These peelable coatings serve to temporarily protect motor vehicles, railways, ships, furniture, metal articles, mineral articles, glass and plastics articles and any other substrates.
  • the coating compounds are applied by dipping, knife coating, pouring, spraying or brush application and are then dried at 20 to 100°C, preferably 20 to 80°C, by heat or infrared light, microwave irradiation or ultrasonic treatment.
  • the finishes according to the invention are coatings which are water-resistant, transparent, tear-resistant, UV-resistant, heat-resistant, resistant to precipitation (of an organic or inorganic nature) and optionally pigmented and which on the one hand adhere well to the substrates and on the other can easily be removed by peeling.
  • the aids which are conventional in coatings chemistry, such as pigments, light stabilisers, anti-sedimentation agents, thickeners, surface-active compounds, defoaming agents, etc. can be used.
  • the coatings are applied by the conventional methods of coating technology, by dipping, knife coating, pouring, spraying, brush application or roller application. They serve as a peelable coating for temporarily protecting motor vehicles, steel and aluminium profiles, or panes or articles of glass and plastics. After application the coated parts are dried at room temperature or at an elevated temperature of up to 100°C.
  • the polyurethane polyurea dispersions according to the invention are dried for 30 minutes at 140-150°C, such that finishes which adhere well to the substrates are produced. It goes without saying that drying temperatures above 150°C are also possible, but the use of such high temperatures is generally uneconomic. Examples
  • the solids content was determined according to DIN EN ISO 3251 (thick- layer method: lid, 1 g sample, 1 h 125°C, convection oven).
  • the OH number was determined according to DIN
  • UV mass-average molar weight
  • the particle size was measured by the method of dynamic light scattering according to ISO 13320-1.
  • Example 1 (not according to the invention):
  • 170 g (0.1 mol) of a polyester comprising adipic acid, 1,6-hexanediol and neopentyl glycol having an average molecular weight of 1 700 g/mol and 2 % OH was dewatered for 30 minutes in a reaction vessel at 120°C and 10 mbar with stirring.
  • 10.5 g (0.078 mol) of dimethylolpropionic acid and 111 g (0.5 mol) of isophorone diisocyanate were introduced under nitrogen. After a reaction time of 1 hour at 1 10°C, the batch was cooled to 60°C and dissolved in 100 g of acetone.
  • the acid value of the prepolymer was 14 mg KOH/g and the total quantity of hydrophilising agent was 3.12 wt.% in relation to the quantity of solid resin.
  • 170 g (0.1 mol) of a polyester comprising adipic acid, 1,6-hexanediol and neopentyl glycol having an average molecular weight of 1 700 g/mol and 2 % OH was dewatered for 30 minutes in a reaction vessel at 120°C and 10 mbar with stirring.
  • 1 1 1 g (0.5 mol) of isophorone diisocyanate was introduced under nitrogen. After a reaction time of 1 hour at 110°C, the batch was cooled to 60°C and dissolved in 100 g of acetone. 23 g (0.26 mol) of 1,4-butanediol was added and the batch was stirred for another 22 hours at 50°C.
  • the NCO content was 2.38% (calculated: 2.95%).
  • the batch was diluted with 600 g of acetone. The following were added to the NCO prepolymer at 50°C : first 2.5 g (0.01 9 mol) of dibutylamine, then an aqueous mixture comprising 10.6 g (0.062 mol) of isophorone diamine and 18.4 g of a 45 wt.% solution of AAS in 1 16 g of water. Then the batch was stirred at 50°C for a further 5 hours. It was dispersed using 405 g of water.
  • the acetone was removed at 50°C and 150 mbar, and a white dispersion with a solids content of 33.5% and an average particle size of 149 nm and a pH value (10% solids) of 6.93 was obtained.
  • the acid value of the prepolymer was 0 mg KOH/g and the total quantity of hydrophilising agent was 2.55 wt.%) in relation to the quantity of solid resin.
  • 170 g (0.1 mol) of a polyester comprising adipic acid, 1 ,6-hexanediol and neopentyl glycol having an average molecular weight of 1 700 g/mol and 2 % OH was dewatered for 30 minutes in a reaction vessel at 120°C and 10 mbar with stirring.
  • 7 g (0.052 mol) of dimethylolpropionic acid and 1 1 1 g (0.5 mol) of isophorone diisocyanate were introduced under nitrogen. After a reaction time of 1 hour at 110°C, the batch was cooled to 60°C and dissolved in 100 g of acetone.
  • the acetone was removed at 50°C and 150 mbar, and in this way a white dispersion with a solids content of 39.4%> and an average particle size of 164 nm and a pH value (10%> solids) of 6.80 was obtained.
  • the acid value of the prepolymer was 9.5 mg KOH/g and the total quantity of hydrophilising agent was 3.65 wt.%) in relation to the quantity of solid resin.
  • 170 g (0.1 mol) of a polyester comprising adipic acid, 1,6-hexanediol and neopentyl glycol having an average molecular weight of 1 700 g/mol and 2 %> OH was dewatered for 30 minutes in a reaction vessel at 120°C and 10 mbar with stirring.
  • 1 1.9 g (0.089 mol) of dimethylolpropionic acid and 1 1 1 g (0.5 mol) of isophorone diisocyanate were introduced under nitrogen. After a reaction time of 1 hour at 1 10°C, the batch was cooled to 60°C and dissolved in 100 g of acetone.
  • the acid value of the prepolymer was 16 mg KOH/g and the total quantity of hydrophilising agent was 4.43 wt.%) in relation to the quantity of solid resin.
  • 170 g (0.1 mol) of a polyester comprising adipic acid, 1,6-hexanediol and neopentyl glycol having an average molecular weight of 1 700 g/mol and 2 % OH was dewatered for 30 minutes in a reaction vessel at 120°C and 10 mbar with stirring.
  • 1 1.9 g (0.89 mol) of dimethylolpropionic acid and 1 1 1 g (0.5 mol) of isophorone diisocyanate were introduced under nitrogen. After a reaction time of 1 hour at 110°C, the batch was cooled to 60°C and dissolved in 100 g of acetone.
  • the acid value of the prepolymer was 16 mg KOH/g and the total quantity of hydrophilising agent was 4.42 wt.%) in relation to the quantity of solid resin.
  • 170 g (0.1 mol) of a polyester comprising adipic acid, 1,6-hexanediol and neopentyl glycol having an average molecular weight of 1 700 g/mol and 2 % OH was dewatered for 30 minutes in a reaction vessel at 120°C and 10 mbar with stirring. 6.9 g (0.052 mol) of dimethylolpropionic acid and 1 1 1 g (0.5 mol) of isophorone diisocyanate were introduced under nitrogen. After a reaction time of 1 hour at 110°C, the batch was cooled to 60°C and dissolved in 100 g of acetone.
  • the acid value of the prepolymer was 9.5 mg KOH/g and the total quantity of hydrophilising agent was 2.9 wt.%) in relation to the quantity of solid resin.
  • a film of both dispersions was applied, without the aid of a cosolvent, using a knifing applicator frame (150 ⁇ ) and was stored in a water bath for 24 hours. Then the peelability and the cloudiness of the film were subjected to qualitative assessment. In addition, the stability on storage was tested by continuous pumping of the dispersion at 40°C. After 24 h, a qualitative assessment was made of whether agglomeration had taken place.
  • Comparison Example 1 describes a polyurethane dispersion in which only DMPA was used as the hydrophilising agent. Although the peelability is good, the pumping test shows agglomeration, which results in undesirable specks forming in the film when it is applied.
  • Comparison Example 2 describes a polyurethane dispersion in which only AAS was used for hydrophilisation. Although the dispersion is stable in the pumping test, the film comes away from the substrate too easily when stored in water, which can lead to its becoming detached when the vehicles in question are transported in wet weather conditions.

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Abstract

La présente invention concerne de nouveaux revêtements pelables et recyclables à base de polyuréthane-polyurées anioniques stables à la lumière à base d'eau et sans cosolvant, leurs procédés de fabrication et leur utilisation en tant que revêtement, de préférence en tant que revêtement pelable assurant la protection temporaire de véhicules à moteur, d'avions, de profilés en acier et en aluminium, de panneaux de verre et de plastiques, et de tout autre substrat, ainsi que des procédés de réutilisation des films de revêtement déjà utilisés et décollés.
PCT/EP2010/067631 2009-11-19 2010-11-17 Polyruréthane polyurées anioniques stables à la lumière WO2011061206A1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
EP09014439.5 2009-11-19
EP09014439 2009-11-19
EP10001665A EP2361938A1 (fr) 2010-02-18 2010-02-18 Revêtement stable à la lumière
EP10001665.8 2010-02-18

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Cited By (1)

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Publication number Priority date Publication date Assignee Title
CN112250818A (zh) * 2020-09-27 2021-01-22 长春一汽富维东阳汽车塑料零部件有限公司 一种可重复利用水性聚氨酯遮蔽材料及其制备方法

Citations (19)

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