WO2019183300A1 - Composition aqueuse durcissable comprenant un prépolymère d'urétdione dispersé, un réactif et un azolate - Google Patents

Composition aqueuse durcissable comprenant un prépolymère d'urétdione dispersé, un réactif et un azolate Download PDF

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Publication number
WO2019183300A1
WO2019183300A1 PCT/US2019/023286 US2019023286W WO2019183300A1 WO 2019183300 A1 WO2019183300 A1 WO 2019183300A1 US 2019023286 W US2019023286 W US 2019023286W WO 2019183300 A1 WO2019183300 A1 WO 2019183300A1
Authority
WO
WIPO (PCT)
Prior art keywords
aqueous
curable composition
uretdione
composition according
compound
Prior art date
Application number
PCT/US2019/023286
Other languages
English (en)
Inventor
Alan Ekin
Sebastian Dörr
Saskia BEUCK
Hans-Josef Laas
Dorata GRETSZTA-FRANZ
Nusret Yuva
Ralph-Georg BORN
Original Assignee
Covestro Llc
Covestro Deutschland 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
Priority claimed from EP18163625.9A external-priority patent/EP3543271A1/fr
Priority claimed from US15/933,500 external-priority patent/US10696775B2/en
Priority claimed from EP18163621.8A external-priority patent/EP3543270A1/fr
Priority claimed from US15/933,553 external-priority patent/US10633477B2/en
Priority claimed from US15/933,475 external-priority patent/US11008416B2/en
Priority claimed from US15/933,507 external-priority patent/US20190292294A1/en
Priority claimed from EP18163620.0A external-priority patent/EP3543269A1/fr
Priority claimed from US15/933,570 external-priority patent/US10731051B2/en
Priority claimed from US15/933,487 external-priority patent/US20190292305A1/en
Priority claimed from US15/933,470 external-priority patent/US11292864B2/en
Priority claimed from US15/933,527 external-priority patent/US20190292296A1/en
Priority claimed from US15/933,495 external-priority patent/US11312881B2/en
Priority claimed from US15/933,511 external-priority patent/US11440988B2/en
Priority claimed from EP18181877.4A external-priority patent/EP3590988A1/fr
Priority claimed from EP18181876.6A external-priority patent/EP3590987A1/fr
Priority to CN201980021447.8A priority Critical patent/CN111886271A/zh
Priority to EP19713663.3A priority patent/EP3768747A1/fr
Application filed by Covestro Llc, Covestro Deutschland Ag filed Critical Covestro Llc
Publication of WO2019183300A1 publication Critical patent/WO2019183300A1/fr

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    • 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
    • C08G18/798—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing urethdione groups
    • C—CHEMISTRY; METALLURGY
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    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
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    • C08G18/12—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step using two or more compounds having active hydrogen in the first polymerisation step
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08G18/2036—Heterocyclic amines; Salts thereof containing one heterocyclic ring having at least three nitrogen atoms in the ring
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    • C08G18/2063—Heterocyclic amines; Salts thereof containing condensed heterocyclic rings having two nitrogen atoms in the condensed ring system
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    • C08G18/2825—Alkanols, cycloalkanols or arylalkanols including terpenealcohols having at least 6 carbon atoms
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    • 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
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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
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    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
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    • C08G18/3225—Polyamines
    • C08G18/325—Polyamines containing secondary or tertiary amino 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
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    • C08G18/3225—Polyamines
    • C08G18/3253—Polyamines being in latent form
    • 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
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    • C08G18/3256—Reaction products of polyamines with aldehydes or ketones
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C—CHEMISTRY; METALLURGY
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • 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
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    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
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    • C08G2190/00—Compositions for sealing or packing joints

Definitions

  • the invention relates to aqueous, curable compositions, which require low curing temperatures and can provide coatings on substrates upon curing.
  • the invention also relates to a curing process of the aqueous, curable composition of the invention and the use of the compositions for coatings, adhesives and/or sealants.
  • polyaddition compounds comprising uretdione groups function as crosslinkers for the preparation of polyurethane-based coatings.
  • the crosslinking principle utilized in these crosslinkers is the thermal cleavage of the uretdione structures back into free isocyanate groups and the subsequent reaction thereof with a hydroxy-functional binder. A temperature of at least about 130°C is required for said thermal cleavage.
  • polyaddition compounds containing uretdione groups obtainable by reacting uretdione polyisocyanates formed from diisocyanates having exclusively secondary- and/or tertiary-attached isocyanate groups with a molar fraction of isocyanurate structures, based on the sum of uretdione groups and isocyanurate groups, of not more than 10%, with compounds reactive towards isocyanates.
  • Said uretdione polyisocyanates are prepared from diisocyanates, wherein the formation of the uretdione group is facilitated by oligomerization catalysts containing 1,2,3- or 1,2,4-triazolate structures in the anion.
  • Shaffer et al. (c.f. WO 2011/115669 A2) have successfully developed uretdione- based curing compositions capable of curing at low temperature of 20°C to 70°C. The temperature was lowered by introducing an amine derived catalyst into the curing composition. It was found, that if the curing compositions of Shaffer were applied as solutions or dispersions in a solvent, the solvent used should be inert. Selected organic solvents were suggested by Shaffer et al. being appropriate solvents for said low temperature curing method.
  • aqueous, curable composition which cures faster and/or cures at low temperature.
  • Coatings based on said aqueous, curable composition should have excellent mechanical and optical properties.
  • the coatings should be resistant against solvents, especially against water.
  • the coatings can be applied on different kind of substrates, for example on textiles, plastic, glass, metal, wood, etc.
  • the curable composition of this invention can also function as a base composition for an adhesive.
  • the resulting coatings are preferably transparent.
  • the present invention relates to aqueous, curable composition, comprising or consisting of
  • At least one uretdione prepolymer which comprises at least one uretdione group, and which is obtainable by reacting
  • At least one reactant which comprises at least one Zerewitinoff-active group and being different from A2 or which is 3 ⁇ 40,
  • the prepolymer has an acid number of at most 4 mg KOH/g, preferably determined according to DIN EN ISO 2114:2002-06 as 37 wt.% aqueous dispersion;
  • the present invention pertains to a process for curing the composition of the present invention on a substrate and a cured article obtained by this process. Moreover, the invention relates to the use of the compositions of the present invention for coatings, adhesives and/or sealants.
  • any numerical range recited herein is intended to include all sub-ranges subsumed therein.
  • a range of "1 to 10" is intended to include all sub-ranges between (and including) the recited minimum value of 1 and the recited maximum value of 10, that is, having a minimum value equal to or greater than 1 and a maximum value of equal to or less than 10.
  • a "monomer” is a low-molecular weight compound comprising functional moieties, wherein said monomer functions as a building block for polymers and has a defined molecular weight.
  • a polymer refers to a compound, formed during a chemical reaction by linking several monomers (i.e. more than two monomers) of the same or different kind together via covalent bonding, wherein the resulting polymer can differ in its degree of polymerization, molecular weight distribution and chain length respectively.
  • a polymer according to the present invention is a compound, comprising in its molecular structure at least one repeating unit, which was integrated in the polymer structure during polymer synthesis by repeatedly linking monomers together via covalent bonds to form said polymer structure.
  • the number average molecular weight is preferably at least 250 g/mol, more preferably at least 1,000 g/mol.
  • polymer includes homopolymers, copolymers, block-copolymers and oligomers.
  • a "prepolymer” is a polymer with reactive groups.
  • the molecular structure of a prepolymer is formed by repeatedly linking more than two monomers of the same or different kind together.
  • the prepolymer can participate in a subsequent formation of a polymer, which has a higher molecular weight than said prepolymer.
  • the term“prepolymer” encompasses polymers, which are able to chemically react via at least one of its reactive groups, forming a repeating unit of a (preferably crosslinked) polymer. Therefore the term“prepolymer” encompasses as well self-crosslinking polymers with at least two different kinds of reactive groups, wherein said groups are able to chemically react among themselves, so that the prepolymer molecules are able to crosslink.
  • the average molecular weight is defined as the number average molecular weight Mn.
  • Mn is determined via gel permeation chromatography (GPC at 23 °C) in tetrahydrofurane as the solvent.
  • low-molecular“ is defined to encompass a molecular weight up to 800 g/mol.
  • high-molecular“ is defined to encompass a molecular weight above 800 g/mol.
  • An“organic compound 11 contains at least one moiety, comprising a carbon- hydrogen covalent bond.
  • aliphatic is defined as non-aromatic hydrocarbyl groups being saturated or unsaturated.
  • aromatic is defined as hydrocarbyl moieties composed of a non-aromatic, as well as saturated or unsaturated hydrocarbyl group, which is directly bonded to an aromatic moiety.
  • alicyclic or “cycloaliphatic” are optionally substituted, carbocyclic or heterocyclic compounds or moieties, which are non-aromatic (like for example cycloalkanes, cycloalkenes or oxa-, thia-, aza- or thiazacycloalkanes).
  • Particular examples are cyclohexyl groups, cyclopentyl groups, and their N- or O-heterocyclic derivatives like for example pyrimidine, pyrazine, tetrahydropyrane or tetrahydrofurane.
  • Ci- 6 -Alkoxy especially methoxy and ethoxy
  • hydroxy, trifluoromethyl and trifluoromethoxy respectively functioning as a substitute for a carbon bound hydrogen atom of the molecule in question.
  • a covalent bond of said formula marked with a * defines the covalent bond, which connects said illustrated moiety to the rest of a more complex molecular structure.
  • Transparent preferably means that the coating (with a thickness of 45 pm) is capable of transmitting rays of visible light so bodies situated beyond or behind can be distinctly seen.
  • Transparent coatings according to this invention exhibit a Haze-value ⁇ 20 (Haze measurement instrument: DIN EN ISO 2813 (the DIN-version used at the application date (or at the priority date if applicable) of the present invention at the latest version).
  • the present invention in particular pertains to:
  • An aqueous, curable composition comprising or consisting of
  • At least one uretdione prepolymer which comprises at least one uretdione group, and which is obtainable by reacting
  • At least one reactant which comprises at least one Zerewitinof -active group and being different from A2 or which is H2O,
  • the prepolymer has an acid number of at most 4 mg KOH/g, preferably determined according to DIN EN ISO 2114:2002-06 as 37 wt.% aqueous dispersion;
  • aqueous, curable composition according to aspect 1, characterized in that
  • the at least one uretdione polyisocyanate Al is reacted, preferably in the presence of a catalyst, with the at least one compound A2 wherein after the first step the resulting intermediate product has preferably an isocyanate content of 0.5 to 10 wt-%, preferably 1 to 6 wt.-%, more preferably 2 to 4 wt.-%, measured according to DIN EN ISO 11909:2007- 05;
  • aqueous, curable composition according to aspect 1, characterized in that
  • aqueous, curable composition according to aspect 1, characterized in that
  • the at least one uretdione polyisocyanate Al is reacted with the at least one reactant A3 and in a second step the polymer obtained in the first step is reacted in a second step with the at least one compound A2, preferably in the presence of a catalyst.
  • the aqueous, curable composition according to any one of the above aspects characterized in that said uretdione prepolymer is a nonionic prepolymer.
  • uretdione prepolymer A comprises at least one *-0-(CH2CH 2 0) n -R moiety, in which R is a hydrogen atom or a (Ci- C 4 )-alkyl group and n is a number from 3 to 100.
  • uretdione polyisocyanate A1 is obtained from at least one cycloaliphatic polyisocyanate.
  • said uretdione polyisocyanate A1 is obtained from isophorone diisocyanate (IPDI), 1,6-hexylene diisocyanate or mixtures thereof.
  • uretdione polyisocyanate A1 is prepared from at least 20 mol% isophorone diisocyanate (IPDI) based on the total amount of polyisocyanates used.
  • IPDI isophorone diisocyanate
  • said uretdione polyisocyanate A1 is prepared from isophorone diisocyanate as the only polyisocyanate used.
  • uretdione polyisocyanate A1 contains from 1 to 10 uretdione moieties.
  • compound A2 is at least one polyol, preferably at least one polyalkoxy ether derivative comprising at least two -OH groups, which are present on two different non-neighbouring atoms of the molecule; and is more preferably selected from compounds of formula (I):
  • X is H or alkyl, preferably H or Ci-20-alkyl, more preferably H or C2-io-alkyl;
  • R is a CM alkylene group
  • p is an integer of 2 to 50;
  • n is independently 0 or 1 and
  • n is independently 0 or 1 ,
  • X is H, methyl, ethyl, or propyl, preferably ethyl;
  • R is methyl
  • p is an integer of 5 to 25;
  • n is independently 0 or 1 and
  • n is independently 0 or 1
  • n or m in each unit p is 1 and the total amount of n > m, preferably the total amount of n is at least 2*m, more preferably n is at least 3*m, most preferably only n is present.
  • compound A3 is selected from at least one polyol which is different from A2, preferably selected from polyester polyols, polyether polyols, polyurethane polyols, polyacrylate polyols, polymethacrylate polyols, polycarbonate polyols or mixtures thereof, preferably A3 is selected from polyester polyols, polyether polyols, polycarbonate polyols, polyurethane polyols, polyacrylate polyols, polymethacrylate polyols, C2-Cio-hydrocarbons with at least two hydroxyl groups, or mixtures thereof, most preferably A3 is a polyester polyol.
  • aqueous, curable composition according to any one of the above aspects, characterized in that said compound Al is used in an amount of 3.0 to 50.0 wt.% based on the total weight of compounds Al to A3. 16. The aqueous, curable composition according to any one of the above aspects, characterized in that said compound A 2 is used in amount of 50 to 97 wt.-% based on the total weight of compounds Al to A3.
  • aqueous, curable composition according to any one of the above aspects, characterized in that the weight ratio of Al to A2 is from 1 : 1 to 1 : 32.3.
  • uretdione prepolymer is a dispersed uretdione prepolymer, preferably characterized in that the uretdione prepolymer is suspended in the aqueous liquid.
  • aqueous, curable composition according to any one of the above aspects, characterized in that said uretdione prepolymer A is contained in a total amount of 3 to 40 wt.% based on the total weight of the composition. 0.
  • R 1 , R 2 , R 3 and R 4 are independently selected from a hydrogen atom, a halogen atom, a nitro group, a saturated or unsaturated, aliphatic or cycloaliphatic radical, an optionally substituted aromatic group comprising up to 20 carbon atoms and optionally up to 3 heteroatoms selected from oxygen, sulphur, nitrogen, an optionally substituted araliphatic group comprising up to 20 carbon atoms and optionally up to 3 heteroatoms selected from oxygen, sulphur, nitrogen,
  • the aqueous, curable composition according to any one of the above aspects characterized in that said at least one compound B, which comprises at least one Zerewitinoff-active group is selected from polyester polyols, polyether polyols, polyurethane polyols, polyacrylate polyols, polymethacrylate polyols, or polycarbonate polyols and mixtures thereof.
  • said uretdione prepolymer A is contained in an amount of 1 to 50 wt.% and
  • said at least one compound B which comprises at least one Zerewitinoff- active group is contained in an amount of 0 to 80 wt.-% and
  • said triazolate-compound C is contained in an amount of 0.1 to 10 wt.%, based on the total weight of the composition, respectively.
  • the aqueous, curable composition according to any one of the above aspects characterized in that the composition comprises water in an amount of 10 to 85 wt.%, based on the total weight of the composition.
  • the aqueous, curable composition according to any one of the above aspects characterized in that the pH-value at 20°C is from pH 5 to pH 13.
  • a cured article obtainable by the process according to any one of aspects 26 to 30.
  • composition according to any one of aspects 1 to 25 for coatings, adhesives and/or sealants.
  • aqueous, curable compositions cure at low temperature, especially from 60°C to l60°C, preferably from 60 to l20°C, most preferably 80 to l00°C.
  • Said aqueous, curable composition comprises less organic solvents compared to conventional curing compositions.
  • water is used in the composition as a component (preferably as the main component) of the liquid continuous phase of the dispersion. Replacement of organic solvents, especially of low-VOC compounds, by water leads to more ecologically friendly compositions.
  • Preferred compositions according to the invention are characterized in that they comprise water in an amount of 10 to 85 wt.%, particularly preferred in an amount of 30 to 75 wt.%, most preferred in an amount of 50 to 70 wt.%, also preferred in an amount from 40 to 70 wt.%, most preferred in an amount of 60 to 70 wt.%, based on the weight of the composition respectively.
  • the aqueous, curable compositions of the invention have a preferred pH-value (20°C) of from pH 5 to pH 13, more preferred from pH 6 to pH 12, even more preferred from pH 7 to pH 9.
  • Said reactant B of the composition comprises on average at least one Zerewitinoff-active group and can be optionally present. Zerewitinoff-active groups are able to react with uretdione groups. It is also possible that the uretdione prepolymer A reacts with itself, i.e., forms a self-curable composition when B is absent.
  • an aqueous, curable composition comprises or consists of
  • At least one uretdione prepolymer which comprises at least one uretdione group, and which is obtainable by reacting
  • At least one reactant which comprises at least one Zerewitinoff- active group and being different from A2 or which is H2O, preferably in the presence of at least one catalyst, to obtain the uretdione prepolymer;
  • the prepolymer has an acid number of at most 4 mg KOH/g, preferably determined according to DIN EN ISO 2114:2002-06 as 37 wt.% aqueous dispersion;
  • the least one uretdione prepolymer comprising on average at least one uretdione group (and preferably at least one Zerewitinoff-active group), is preferably dispersed in said aqueous, liquid continuous phase. It is more preferred, when the dispersed uretdione prepolymer is suspended in the aqueous liquid.
  • the composition of the invention is preferably substantially free of compounds comprising at least one isocyanate group. Due to the water present in the composition, the majority up to all isocyanate groups will hydrolyze. Preferably the content of the isocyanates groups (expressed as NCO, M.G. 42g/mol) is below 0.05 wt.-%. Particularly preferred, the composition of the invention is free of compounds comprising at least one isocyanate moiety. Unless expressly mentioned otherwise, NCO contents were determined volumetrically in accordance with DIN-EN ISO 11909 (the DIN- version used at the application date (or at the priority date if applicable) of the present invention at the latest version).
  • the composition comprises said uretdione prepolymer in a total amount of 1 to 50 wt.%, preferably 3 to 40 wt.% and most preferred 30 to 40 wt.%, based on the weight of the composition.
  • the mean weight average molecular weight M w of the uretdione prepolymers is preferably in the range of 20,000 to 800,000 g/mol, particular preferred in the range of 100,000 to 500,000 g/mol.
  • the curing time is significantly reduced, if said uretdione prepolymer exhibits an acid number of at most 4 mg KOH/g, preferably at most 3.5 mg KOH/g, more preferably 3.0 mg KOH/g, most preferably at most 2.5 mg KOH/g (each determined according to DIN EN ISO 2114:2002-06), based on the total weight of the sample prepared to be used as initial compound to be tested in the determination according to DIN EN ISO 2114:2002-06.
  • the unit of the acid number according to said DIN EN ISO 2114:2002-06 is the used amount of KOH in mg per g of said sample.
  • the sample essentially consists (or consists) of 37 wt.% uretdione prepolymer and water.
  • the acid number of the respective uretdione prepolymer sample was always determined according to DIN EN ISO 2114:2002-06. Instead of a mixture of toluene and ethanol as described in DIN EN ISO 2114:2002-06, a mixture of acetone and ethanol in a weight ratio of 2: 1 was used.
  • the acid number according to this invention is preferably at most 10.8 mg KOH/g, more preferred at most 9.5 mg KOH/g, particularly preferred 8.1 mg KOH/g, most preferred at most 6.8 mg KOH/g.
  • the unit of the acid number is the calculated used amount of KOH in mg per g of uretdione prepolymer. The determination is still performed by using above mentioned sample as initial compound for determination of the acid number ( vide supra).
  • a preferred composition comprises at least one uretdione prepolymer, which exhibits a zeta potential of -20 mV or higher.
  • the zeta potential of the uretdione prepolymer is determined from a dispersion of uretdione prepolymer in water as the sample.
  • One drop of a preformed dispersion of the uretdione prepolymer is highly diluted with 20 ml of demineralized water and homogenized by stirring, leading to the sample.
  • the zeta potential is determined at 23°C in the Malvern Nanosizer ZS90 instrument (Malvern Instruments,dorfberg, Germany).
  • the given values of the zeta potential are always related to said sample of the dispersed uretdione polymer.
  • said uretdione prepolymer is a nonionic prepolymer.
  • a preferred uretdione prepolymer comprises grafts with at least one hydrophilic group selected from polyoxyalkylene ether capped with methyl, ethyl, propyl or butyl, polyethylene oxide capped with one methyl group, polyethylene oxide capped with one ethyl, propyl, or butyl group.
  • Particularly preferred uretdione prepolymers comprise additionally on average at least one *-0-(CH 2 CH 2 0) n -R moiety, in which R denotes a (Ci-C 4 )-alkyl group and n denotes a number from 3 to 100, n denotes preferably a number from 5 to 70, more preferably from 7 to 55. R is preferably a methyl group.
  • Said hydrophilic groups can be introduced into the structure of said uretdione prepolymer by compound A2, which is preferably a hydrophylizing agent, more preferably a nonionic one.
  • Suitable nonionically hydrophilizing agents are, for example, polyoxyalkylene ethers which have isocyanate-reactive groups, such as hydroxy, amino or thiol groups.
  • Suitable examples are monohydroxy-functional polyalkylene oxide polyether alcohols having, on statistical average, 5 to 70, preferably 7 to 55, ethylene oxide units per molecule, as are accessible in a manner known per se by alkoxylation of suitable starter molecules (e.g.
  • Suitable starter molecules for such nonionic hydrophilizing agents are in particular saturated monoalcohols, such as methanol, ethanol, n-propanol, isopropanol, n- butanol, isobutanol, sec-butanol, the isomeric pentanols, hexanols, octanols and nonanols, n-decanol, n-dodecanol, n-tetradecanol, n-hexadecanol, n-octadecanol, cyclohexanol, the isomeric methylcyclohexanols or hydroxymethylcyclohexane, 3 -ethyl-3 -hydroxymethyloxetane or tetrahydrofurfuryl alcohol, diethylene glycol monoalkyl ethers, such as, for example, diethylene glycol monobutyl ether, unsaturated alcohols,
  • Preferred starter molecules are saturated monoalcohols of the type specified above. Particular preference is given to using diethylene glycol monobutyl ether or n-butanol as starter molecules.
  • Alkylene oxides suitable for the alkoxylation reaction are in particular ethylene oxide and propylene oxide, which can be used in the alkoxylation reaction in any desired order or else in a mixture.
  • Another preferred group of hydrophilization agents are polymers with two OH groups and a polyalkylene oxide side group, e.g. polyether-1, 3-Diols. Commercially available examples are, YmerTM N120 (CAS number: 131483-27- 7) by Perstorp Holding AB, Malmo, Sweden and Tegomer® D 3403 (Evonik Industries AG, Essen, DE).
  • the uretdione prepolymers exhibit an acid number of at most 4 mg KOH/g (preferably at most 3.5 mg KOH/g, particularly preferred 3.0 mg KOH/g, most preferred 2.5 mg KOH/g) and comprising at least one uretdione group: additionally on average at least one Zerewitinoff-active group, particularly preferred at least two hydroxyl groups and at least one *-0-(CH 2 CH 2 0) n -R moiety, in which R denotes a hydrogen atom or a (Ci-C 4 )-alkyl group and n denotes a number from 3 to 100, n denotes preferably a number from 5 to 70, more preferably from 7 to 55. R is preferably a methyl group.
  • the uretdione prepolymer comprises at least one uretdione group. It is preferred, that the uretdione prepolymer comprises at least two uretdione groups.
  • Preferred uretdione prepolymers of this invention are self-curing prepolymers. During heat induced curing, the uretdione prepolymer will (self-)crosslink via reaction of said uretdione groups with said Zerewitinoff-active groups. The more uretdione groups and Zerewitinoff-active groups are on average comprised in said uretdione prepolymer (or said reactant), the better.
  • A“Zerewitinoff-active group” is defined as a functional group, comprising at least one Zerewitinoff-active hydrogen atom, being an acidic hydrogen atom or active hydrogen atom.
  • the abundance of such an active hydrogen atom is determined by a known reaction of the compound in question with a Grignard reagent.
  • the amount of Zerewitinoff-active hydrogen atoms is typically determined by measuring the amount of released methane gas, and subsequently calculated in consideration of the stoichiometry of the following reaction equation, wherein for each mole of active hydrogen atoms of the compound in question (R-XH) one mole of methyl magnesium bromide (CH3-MgBr) is used and one mole of methane is released:
  • Zerewitinoff-active groups are in particular C-H active organic groups, -OH, -SH, -NH2 or -NHR' wherein R' denotes an organic moiety.
  • Zerewitinoff- active groups are selected from -OH, -SH, -NH2 or -NHR' wherein R' denotes an organic moiety.
  • the Zerewitinoff-active groups according to the invention are selected from -OH.
  • a particularly preferred uretdione prepolymer comprises as Zerewitinoff-active groups at least two hydroxyl groups.
  • the preparation of said uretdione prepolymer is typically achieved by reacting an uretdione polyisocyanate with at least one compound, comprising at least two Zerewitinoff-active groups using standard reaction techniques. It was found, that it was even possible to cure uretdione prepolymers at low temperature, which were prepared from at least one aliphatic uretdione polyisocyanate (especially cycloaliphatic uretdione polyisocyanate), preferably from at least 20 mol% aliphatic uretdione polyisocyanate based on the total amount of polyisocyanates used, particularly preferred only from aliphatic uretdione polyisocyanates.
  • the uretdione polyisocyanate A1 is used in an amount of 3 to 50 wt.-% based on the total amount of reactants used for preparation of said dispersed uretdione prepolymer.
  • the compound with at least one Zerewitinoff-active group A2 is preferably used in an amount of 50 to 97 wt.-% based on the total amount of reactants used for preparation of said dispersed uretdione prepolymer.
  • uretdione polyisocyanate A1 for preparation of said dispersed uretdione prepolymer it is particularly preferred to use the uretdione polyisocyanate A1 in relation to said compound A2 in a weight ratio from 1 : 1 to 1 : 32.3.
  • the uretdione polyisocyanates A1 are typically obtained by catalytic dimerization of polyisocyanates by methods, which are known in the art.
  • suitable polyisocyanates include diisocyanates such as linear aliphatic polyisocyanates, cycloaliphatic polyisocyanates and alkaryl polyisocyanates.
  • 1,4-diisocyanatobutane 1,5-diisocyanatopentane (PDI)
  • PDI 1,5-diisocyanatopentane
  • HDI 1,6- diisocyanatohexane
  • HDI 1,6-hexylene diisocyanate
  • HMD1 2,4’- and 4,4 '-diisocyanatodicyclohexylmethane
  • IPDI isophorone diisocyanate
  • XDI 1,3- and 1,4-bisisocyanatomethylcyclohexane
  • XDI 1,3- and 1,4-xylylene diisocyanates
  • dimerization catalysts are: trialkylphosphines, aminophosphines and aminopyridines such as dimethylaminopyridines, and tris(dimethylamino)phosphine, as well as any other dimerization catalyst known to those skilled in the art.
  • the result of the dimerization reaction depends, in a manner known to the skilled person, on the catalyst used, on the process conditions and on the polyisocyanates employed.
  • products which contain on average more than one uretdione group per molecule, the number of uretdione groups being subject to a distribution.
  • Preferred uretdione compounds are prepared from the catalytic dimerization of HDI and/or IPDI.
  • the uretdione polyisocyanate A1 preferably on average contains from 1 to 10 uretdione moieties.
  • Said uretdione polyisocyanate A1 is preferably prepared from isophorone diisocyanate (IPDI), 1,6-diisocyanatohexane (also referred to as HDI or 1,6- hexylene diisocyanate) or mixtures thereof.
  • IPDI isophorone diisocyanate
  • HDI 1,6-diisocyanatohexane
  • 1,6- hexylene diisocyanate 1,6-diisocyanatohexane
  • said uretdione polyisocyanate A1 is prepared from at least one cycloaliphatic polyisocyanate. In another preferred embodiment, said uretdione polyisocyanate A1 is prepared from at least 20 mol% isophorone diisocyanate (IPDI) based on the total amount of polyisocyanates used. Said uretdione polyisocyanate A1 is most particularly preferred prepared from isophorone diisocyanate as the only polyisocyanate used.
  • IPDI isophorone diisocyanate
  • Preferred uretdione polyisocyanates are for example commercially available as Desmodur N3400 from Covestro GmbH AG, Leverkusen, Germany.
  • the polyuretdione prepolymer is prepared from at least one uretdione polyisocyanate A1 with at least one compound A2.
  • a preferred curable composition according to this invention comprises at least one uretdione prepolymer, which is prepared by the reaction of at least one uretdione polyisocyanate A1 as defined above with a compound A2 selected from at least one polyol.
  • polyol is meant to include materials having an average of two or more primary hydroxyl groups per molecule.
  • the polyols useful in the practice can be either low or high molecular weight materials and in general will have average hydroxyl values as determined by ASTM designation E-222-67, Method B, between about 1000 and 2, and preferably between about 500 and 2.
  • the polyols include low molecular weight diols, triols and higher alcohols and polymeric polyols such as polyester polyols, polyether polyols, polyurethane polyols and hydroxy-containing (meth)acrylic polymers.
  • Said at least one polyol as compound A2 is preferably selected from polyester polyol, polyether polyol, polyurethane polyol, polycarbonate polyol, polyacrylate polyol, polymethacrylate polyol, C2-Cio-hydrocarbon with at least two hydroxyl groups, or mixtures thereof.
  • the low molecular weight diols, triols and higher alcohols useful in the instant invention are known in the art. For the most part they are monomeric and have hydroxy values of 200 and above, usually within the range of 1500 to 200.
  • Such materials include aliphatic polyols, particularly alkylene polyols containing from 2 to 18 carbon atoms. Examples include ethylene glycol, 1 ,4-butanediol, 1 ,6- hexanediol; cycloaliphatic polyols such as cyclohexane dimethanol.
  • triols and higher alcohols include trimethylol propane and pentaerythritol. Also useful are polyols containing either linkages such as diethylene glycol and triethylene glycol.
  • polymeric polyols are those having hydroxyl values less than 200, such as 10 to 180.
  • polymeric polyols include polyalkylene ether polyols, polyester polyols including hydroxyl-containing polycaprolactones, hydroxy-containing (meth)acrylic polymers, polycarbonate polyols and polyurethane polyols.
  • polyether polyols examples include poly(oxytetramethylene) glycols, poly(oxyethylene) glycols, poly(oxypropylene) glycols, and the reaction product of ethylene glycol with a mixture of propylene oxide and ethylene oxide.
  • polyether polyols formed from the oxyalkylation of various polyols, for example, glycols such as ethylene glycol, 1,4-butane glycol, 1,6- hexanediol, and the like, or higher polyols, such as trimethylol propane, pentaerythritol and the like.
  • glycols such as ethylene glycol, 1,4-butane glycol, 1,6- hexanediol, and the like
  • polyols such as trimethylol propane, pentaerythritol and the like.
  • One commonly utilized oxyalkylation method is reacting a polyol with an alkylene oxide, for example, ethylene oxide in the presence of an acidic or basic catalyst.
  • Polyester polyols can also be used as a polymeric polyol component in the practice of the invention.
  • the polyester polyols can be prepared by the polyesterification of organic polycarboxylic acids or anhydrides thereof with organic polyols.
  • the polycarboxylic acids and polyols are aliphatic or aromatic dibasic acids and diols.
  • the diols which are usually employed in making the polyester include alkylene glycols, such as ethylene glycol and butylene glycol, neopentyl glycol and other glycols such as cyclohexane dimethanol, caprolactone diol (for example, the reaction product of caprolactone and ethylene glycol), polyether glycols, for example, poly(oxytetramethylene) glycol and the like.
  • alkylene glycols such as ethylene glycol and butylene glycol
  • neopentyl glycol and other glycols such as cyclohexane dimethanol
  • caprolactone diol for example, the reaction product of caprolactone and ethylene glycol
  • polyether glycols for example, poly(oxytetramethylene) glycol and the like.
  • other diols of various types and, as indicated, polyols of higher functionality can also be utilized.
  • Such higher polyols preferably include, for example, trimethylol propane, trimethylol ethane, pentaerythritol, and the like, as well as higher molecular weight polyols such as those produced by oxyalkylating low molecular weight polyols.
  • a particularly preferred example of such high molecular weight polyol is the reaction product of 20 moles of ethylene oxide per mole of trimethylol propane.
  • the acid component of the polyester polyols consists primarily of monomeric carboxylic acids or anhydrides having 2 to 18 carbon atoms per molecule.
  • acids which are useful are phthalic acid, isophthalic acid, terephthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, adipic acid, azelaic acid, sebacic acid, maleic acid, glutaric acid, chlorendic acid, tetrachlorophthalic acid and other dicarboxylic acids of varying types.
  • polycarboxylic acids such as trimellitic acid and tricarballylic acid (where acids are referred to above, it is understood that the anhydrides of those acids which form anhydrides can be used in place of the acid).
  • lower alkyl esters of acids such as dimethyl glutarate can be used.
  • polyester polyols formed from polybasic acids and polyols polycaprolactone-type polyesters can also be employed. These products are formed from the reaction of a cyclic lactone such as e-caprolactone with a polyol with primary hydroxyls such as those mentioned above. Such products are described in U.S. Pat. No. 3,169,945 to Hostettler.
  • hydroxy-containing (meth)acrylic polymers or (meth)acrylic polyols can be used as the polyol component.
  • the (meth)acrylic polymers are polymers of about 2 to 20 percent by weight primary hydroxy-containing vinyl monomers such as hydroxyalkyl acrylate and methacrylate having 2 to 6 carbon atoms in the alkyl group and 80 to 98 percent by weight of other ethylenically unsaturated copolymerizable materials such as alkyl (meth)acrylates; the percentages by weight being based on the total weight of the monomeric charge.
  • Suitable hydroxy alkyl (meth)acrylates are hydroxyl ethyl and hydroxy butyl (meth)acrylate.
  • suitable alkyl acrylates and (meth)acrylates are lauryl methacrylate, 2-ethylhexyl methacrylate and n-butyl acrylate.
  • ethylenically unsaturated materials such as monoolefmic and diolefmic hydrocarbons, halogenated monoolefmic and diolefmic hydrocarbons, unsaturated esters of organic and inorganic acids, amides and esters of unsaturated acids, nitriles and unsaturated acids and the like.
  • Examples of such monomers include styrene, 1,3- butadiene, acrylamide, acrylonitrile, a-methyl styrene, a-methyl chlorostyrene, vinyl butyrate, vinyl acetate, alkyl chloride, divinyl benzene, diallyl itaconate, triallyl cyanurate and mixtures thereof.
  • styrene 1,3- butadiene
  • acrylamide acrylonitrile
  • a-methyl styrene 1,3- butadiene
  • acrylamide acrylonitrile
  • vinyl butyrate vinyl acetate
  • alkyl chloride divinyl benzene
  • diallyl itaconate diallyl itaconate
  • triallyl cyanurate and mixtures thereof.
  • these other ethylenically unsaturated materials are used in admixture with the above-mentioned acrylates and methacrylates.
  • said compound A2 is selected from polyester polyol, polyether polyol, polycarbonate polyol, polyurethane polyol, polyacrylate polyol, polymethacrylate polyol, C2-C10- hydrocarbon with at least two hydroxyl groups, or mixtures thereof, wherein said compound A2 comprises at least one *-0-(CH 2 CH 2 0) n -R moiety, in which R denotes a (Ci-C4)-alkyl group and n denotes a number from 3 to 100, n denotes preferably a number from 5 to 70, more preferably from 7 to 55. R is preferably a methyl group.
  • a further suitable compound A2 is selected from a compound of formula (I) X-0-(CH 2 CH 2 0) consult-R (I)
  • X denotes a linear dihydroxy (C3-Cio)-alkyl group, a branched dihydroxy (C3- Cio)-alkyl group or a monohydroxy (C2-C6)-alkyl group,
  • R is a hydrogen atom or a (Ci-C4)-alkyl group
  • n is a number from 3 to 100.
  • X denotes preferably a di(hydroxymethyl)-(Ci-C 8 )-alkyl group or a branched di(hydroxymethyl)-(Ci-Cg)-alkyl group.
  • Particular preferred X of formula (I) denotes a di(hydroxymethyl)-(Ci-Cg)-alkyl group or a branched di(hydroxymethyl)-(Ci-Cg)-alkyl group, with the proviso, that both hydroxymethyl groups bind to the same carbon atom respectively.
  • n denotes preferably a number from 5 to 70, more preferably from 7 to 55.
  • R denotes preferably a methyl group.
  • said dispersed uretdione prepolymer is prepared from compound A2, which is a combination of at least one polyoxyalkylene ether, which have isocyanate-reactive groups, such as hydroxy, amino or thiol groups (preferably at least one compound of above mentioned formula (I)) and at least one polyol polymer.
  • compound A2 is a combination of at least one polyoxyalkylene ether, which have isocyanate-reactive groups, such as hydroxy, amino or thiol groups (preferably at least one compound of above mentioned formula (I)) and at least one polyol polymer.
  • said dispersed uretdione prepolymer it is again preferably prepared from a combination of A2-1) at least one compound of formula (I)
  • X denotes a hydrogen atom, a linear dihydroxy (C3-Cio)-alkyl group or a branched dihydroxy (C3-Cio)-alkyl group,
  • R is a (Ci-C4)-alkyl group, preferably methyl and
  • n is a number from 3 to 100, preferably 8 to 30,
  • compound A2-1 is used in a total amount of 1 to 25 wt-%, preferably 5 to 20 wt.-% and compound A3 is used in a total amount of 20 to 70 wt.-%, preferably 35 to 65 wt.-%, based on the total amount of reactants used for preparation of said dispersed uretdione prepolymer.
  • a fraction of the isocyanate groups of the uretdione polyisocyanate A1 are reacted first with compound A2-1, yielding an uretdione polyisocyanate with at least one *-0-(CH2CH20) n -R moiety and second the remaining isocyanate groups of the previous reaction product are reacted with compound A3, leading to the final uretdione prepolymer.
  • compound A3 is water.
  • reactant B is present and may be selected from at least one compound, which comprises on average at least one Zerewitinoff- active group.
  • reactant B is selected from at least one polyol, particularly preferred from at least one polymeric polyol, most preferred from at least one of the preferred polymeric polyols as previously defined for A2 (vide supra).
  • compositions of the invention alternatively comprise at least one reactant B wherein said reactant is selected from polyester polyol, polyether polyol, polycarbonate polyol, polyurethane polyol, polyacrylate polyol, polymethacrylate polyol, C2-Cio-hydrocarbon with at least two hydroxyl groups, or mixtures thereof.
  • the curable composition of this invention comprises as component C at least one azolate-compound.
  • an azole is the generic term for unsaturated five- membered heterocyclic compounds, comprising in the cycle one nitrogen atom and in addition to that optionally at least one or more further hetero atoms including nitrogen atom.
  • An azolate-compound according to this invention includes the corresponding salts thereof as well (azolate).
  • Preferred azolate compound comprise a five-membered N-heterocycle.
  • the five membered ring of said N-heterocycle comprises two endocyclic double bonds. Said endocyclic double bonds are preferably conjugated double bonds.
  • the five- membered N-heterocycle is negatively charged. Said negative charge is delocalized. Preferably the endocyclic double bonds contribute to the delocalization of the negative charge.
  • compositions comprise at least one azolate-compound of formula (II)
  • one, two or three moieties of X 1 , X 2 , X 3 and X 4 independently of one another represent the moiety
  • the cycle of formula (II) represents a p-system, comprising the two endocyclic double bonds and the delocalized charge.
  • the azolate compounds are usually prepared by deprotonation of a neutral azole compound. Deprotonation is achieved preferably with a base, preferably with alkaline alkoxides like sodium methanolate, alkaline earth alkoxides, alkaline hydroxides or alkaline earth hydroxides.
  • the azolate compound of formula (II) is prepared by deprotonization of neutral compounds of formula (II-l) with a base, preferably with at least one of the above mentioned preferred bases,
  • Suitable neutral compounds for preparation of the azolate compound according to the invention include pyrrole, substituted pyrroles and carbocyclic and/or heterocyclic annellated derivatives of pyrrole.
  • Suitable neutral compounds for preparation of the azolate compound according to the invention include pyrazole and/or imidazole, substituted pyrazoles and/or imidazoles and carbocyclically and/or heterocyclically annellated derivatives of pyrazole and/or imidazole.
  • Suitable neutral compounds for preparation of the azolate compound according to the invention include triazole, preferably selected from 1,2,3- and 1,2,4-triazoles, substituted species of 1,2,3- and 1,2,4-triazoles and carbocyclically and/or heterocyclically annellated species of 1,2,3- and 1 ,2,4-triazoles.
  • N-heterocycles which carry at least one hydrogen atom bound to a ring nitrogen atom.
  • examples of these include pyrrole, indole, carbazole and substituted derivatives such as 5-nitroindole or 5-methoxyindole, pyrazole, indazole and substituted derivatives such as 5-nitroindazole, imidazole and substituted derivatives such as 4-nitroimidazole or 4-methoxyimidazole, benzimidazole or substituted benzimidazoles, for example 5-nitrobenzimidazole, 5- methoxybenzimidazole, 2-trifluoromethylbenzimidazole, hetero-aromatic annellated imidazoles such as pyridinoimidazole or purine, 1,2, 3-triazole and substituted derivatives such as 4-chloro-5-carbomethoxy-l, 2, 3-triazole or 4- chloro-5-cyano-l, 2, 3-triazole
  • the composition comprises at least one triazolate-compound as component C).
  • Said triazolate-compound is most preferably selected from at least one triazolate- compound of the group comprised of formula (III) and formula (IV)
  • R 1 , R 2 , R 3 and R 4 independent from one another denote a hydrogen atom, a halogen atom, a nitro group, a saturated or unsaturated, aliphatic or cycloaliphatic radical, an optionally substituted aromatic group comprising up to 20 carbon atoms and optionally up to 3 heteroatoms selected from oxygen, sulphur, nitrogen, an optionally substituted araliphatic group comprising up to 20 carbon atoms and optionally up to 3 heteroatoms selected from oxygen, sulphur, nitrogen, and where R 3 and R 4 of formula (IV) together with the carbon atoms of the 1,2,3-triazolate five-membered ring form fused rings with 3 to 6 carbon atoms.
  • Said triazolate-compound is particularly preferred selected from alkaline metal- 1, 2, 4-triazolate, alkaline metal-1, 2, 3-triazolate, alkaline metal-benzotriazolate, alkaline earth metal- 1,2, 4-triazolate, alkaline earth metal-1, 2, 3-triazolate, alkaline earth metal-benzotriazolate.
  • the triazolate-compound is selected from alkaline metal- 1,2, 4-triazolate, alkaline metal-1, 2, 3-triazolate, alkaline metal-benzotriazolate.
  • Sodium 1,2, 4-triazolate, potassium 1,2, 4-triazolate, sodium 1,2, 3-triazolate, potassium 1,2,3-triazolate, sodium benzotriazolate, potassium benzotriazolate and mixtures thereof are the most preferred triazolate- compounds.
  • curable compositions which comprise said azolate-compound, preferably said triazolate-compound, in an amount of 0,1 to 10,0 wt.%, particularly preferred of 0,3 to 3 wt.%, based on the weight of the composition respectively.
  • Particularly preferred curable compositions of the invention comprise said dispersed uretdione prepolymer in an amount of 1 to 50 wt.%, preferably 3 to 40 wt.% and most preferred 30 to 40 wt.% and said azolate-compound, preferably said triazolate-compound, in an amount of 0,1 to 10,0 wt.%, preferably 0,3 to 3 wt.-%, based on the weight of the composition respectively.
  • compositions may contain various optional ingredients.
  • these are dyes, pigments, fillers and reinforcing agents, for example calcium carbonate, silicates, talc, kaolin, mica and barium sulfate.
  • Other additives for example plasticizers, lubricants and rheological additives and solvent or diluent may be included in the compositions.
  • these optional ingredients may constitute up to 50% by weight of the composition based on the total weight of the composition.
  • these optional ingredients may constitute up to 50% by weight of the composition based on the total weight of the composition.
  • the compositions of the invention for preparing coatings on substrates of all kinds.
  • Such coatings are preferably protective and decorative coatings such as exterior coatings on substrates of all kinds, for example buildings, fences, chipboard panels, and as a coating on stone, concrete or metal, for the coating of vehicles, for example, such as cars, railways or aircraft.
  • the compositions may likewise be used in automotive OEM finishing and automotive refinish, and also for the finishing of car bodies, plastic parts for cars and body-mounted car parts.
  • compositions of the invention can also be used as sealants or adhesives.
  • Another object of the present invention is a Process for curing a liquid composition on a substrate, comprising
  • the aqueous, curable composition may be applied uniformly to a substrate, for example by spin coating, dip coating, knife coating, curtain coating, brushing, spraying—especially electrostatic spraying— and reverse roll coating.
  • Said coating compositions can be used as a primer, color coat or as a clearcoat.
  • the aqueous, curable composition of step a) is prepared from an aqueous, curable concentrate, comprising i) 25 to 50 wt.-%, preferably 32 to 45 wt-%, of at least one uretdione prepolymer A,
  • step a) comprising, related to the weight of said aqueous, curable composition of step a) i) 12.5 to 42.2 wt.-%, preferably 27 to 38 wt.-%, of at least one uretdione prepolymer A,
  • the choice of diluent and the concentration depend predominantly on the choice of coating ingredients and the coating process.
  • the diluent should be inert. In other words, it should not undergo any chemical reaction with the components and should be capable of being removed after the coating operation in the curing process. Surprisingly it was found, that especially water is an appropriate diluent.
  • Suitable diluents are water, ketones, ethers and esters, such as methyl ethyl ketone, isobutyl methyl ketone, cyclopentanone, cyclohexanone, N- methylpyrrolidone, dioxane, tetrahydrofuran, 2-methoxyethanol, 2-ethoxyethanol, l-methoxy-2 -propanol, 1,2-dimethoxyethane, ethyl acetate, n-butyl acetate and ethyl 3-ethoxypropionate. It is particularly preferred to use water as the most abundant diluent.
  • the deposited aqueous curable composition coalesces to form a coating.
  • the coating thickness upon drying is typically from 0.5 to 46 pm. If the coating is a base coat, the coating thickness upon drying is preferably 15 to 20 pm. If the coating is a top coat, the coating thickness upon drying is preferably 45 to 50 pm.
  • the deposited aqueous, curable composition is preferably exposed to a temperature of 60 to 120°C, preferably 80 to l00°C, to cure said deposited curing composition.
  • the deposited aqueous, curable composition is preferably exposed to said temperature for a period of 20 to 45 minutes to cure said deposited curing composition. It is particularly preferred to expose the deposited aqueous, curable composition to a temperature of 60 to 120°C, preferably 80 to 100°C, for a period of 20 to 45 minutes.
  • the preheating step is advantageous, since the amount of water is reduced in the deposited, curable composition prior to curing. The subsequent curing reaction at 60°C to 160°C is thereby enhanced.
  • the cured aqueous curable composition forms a crosslinked film on the substrate that shows excellent mechanical and optical properties and a high resistance against chemicals and solvents.
  • the pendulum hardness by the Konig method was measured on a glass plate according to DIN EN ISO 1522:2007-04.
  • the cured coating were tested for resistance to xylene, l-methoxy-2-propyl acetate, ethyl acetate, acetone and water.
  • a piece of cotton wool soaked in the test substance was placed on the coating surface and covered with a watch glass. After the indicated exposure time, the cotton was removed, the exposed area was dried and examined immediately.
  • the evaluation of the softening or discoloration of the coating surface was carried out according to DIN EN ISO 4628-1 : 2016-07.
  • the uretdione ring opening was characterized by an FT-IR spectrometer (tensor II with Platinum ATR unit (diamond crystal) from Broker). The spectra were recorded in a wave number range of (4000-400) cm 1 . The maximum of the uretdione peak (about 1760 cm ) was evaluated. Peak heights to comparative systems were compared with an initial value set to 100% (uretdione film without catalyst, dried at room temperature) and variations relative to this (ratio formation). Uretdione peak height of films cured for 30 min at 180 °C were set to 0%.
  • the intensity of the spectrum depends on the occupation of die crystal surface. Since a comparable coverage of the crystal surface cannot be ensured in the case of different measurements by the sample preparation, a correction of this effect must be made for the ratio formation by normalizing all spectra on the peak of the CH stretching vibration (wave number range (3000-2800 cm 4 ). In the case of the evaluation of peak heights as described above, a baseline correction of the spectra is additionally carried out.
  • Rheometer Rheometrics ARES. The measurements are made with the exclusion of oxygen (convection oven with nitrogen). The sample preparation takes place in Teflon-Petry dishes. From the dried films (24h room temperature in air) circular samples with a 14 mm diameter are punched out. The rheometer oven is previously heated to the measurement temperature (e.g. 160 ° C). A few seconds before the measurement, the furnace is opened, the cut-out sample inserted between the 14mm diameter circular measuring plates, the furnace closed and the measuring plates collapsed until the sample height fills the measuring gap and a clear increase in the normal force was observed. Directly thereafter, the time measurement is started and the storage module G' is determined as a function of the measurement time at a constant sample temperature. Measuring frequency: 1 Hz. 1.5 Catalysts:
  • Lupragen N 700 (or DBU or l,8-Diazabicyclo-5,4,0-undecene-7) was purchased from BASF SE, Ludwigshafen, Germany.
  • Polycat SA2LE (Cat 2) (blocked DBU) was purchased from Air Products
  • Triazolate-catalysts were purchased from Sigma-Aldrich Chemie GmbH, Kunststoff, Germany. If a triazole (amine form) was purchased, the triazolate catalyst was prepared as follows: 1 mol of catalyst (amine form) was slurried in water (10%), followed by the addition of 1 mol of NaOH (solid) or KOH, LiOH, RbOH, CsOH and stirring until a clear liquid was formed.
  • the triazolate catalyst solutions used had the following specifications:
  • Na-l,2,3-Triazolate solid content: 24.0%, pH: 11,5
  • Na-l,2,4-Triazolate solid content: 12.4%, pH: 12,3
  • Na-Benztriazolate solid content: 20.5%, pH: 10,9
  • Li-l,2,4-Triazolate solid content: 9.9%, pH: 11,7
  • the solids contents were determined by heating a weighed sample at l25°C to constant weight. At constant weight, the solid content is calculated by reweighing the sample.
  • NCO contents were determined volumetrically in accordance with DIN-EN ISO 11909:2007-05. The control on free NCO groups was carried out by means of IR spectroscopy (band at 2260 cm 1 )
  • the stated viscosities were determined by means of rotary viscometry in accordance with DIN 53019 at 23°C using a rotary viscometer with a shear rate of 40 1/s, from Anton Paar Germany GmbH, Ostfildem, Germany.
  • the average particle sizes (number-average) of the polyurethane dispersions were determined following dilution with deionized water by means of laser correlation spectroscopy (instrument: Malvern Zetasizer 1000, Malver Inst. Limited, London, UK).
  • Zeta potential was measured by diluting one drop of the sample with 20 ml demineralized water and homogenized by stirring. Subsequently the zeta potential is determined at 23°C in the Malvern Nanosizer ZS90 " (Malvern Instruments,dorfberg, Germany).
  • Acid number of the respective dispersion was determined according to DIN EN ISO 2114:2002-06. Instead of a mixture of toluene and ethanol - as described in DIN EN ISO 2114:2002-06 - a mixture of acetone and ethanol (2:1 by weight) was used as solvent. The unit of the acid number is mg KOH per g of the analyzed sample.
  • YmerN120 (CAS number: 131483-27-7, a hnear, trimethylolpropane started polyethylene glycol monomethyl ether, OH number 100-120 mg KOH/g) was acquired from Perstorp Holding AB, Malmo, Sweden polyester 1 OH-functional polyester prepared from 3039 g adipic acid, 4041 g isopthalic acid, 267 g 1, 2-propylene glycol, 4773 g neopentyl glycol and 1419 g trimethylol propane (OH number: 181 mg KOH/g, acid number ⁇ 3 mg KOH/g)
  • IPDI isophorone diisocyanate
  • DMAP 4-dimethylaminopyridine
  • the resulting white dispersion had the following properties:
  • Viscosity (viscometer, 23 °C): 118 mPas
  • the curing reaction can be monitored by observation of the ring opening of the uretdione.
  • uretdione peak almost vanishes.
  • pendulum hardness increases with the effectiveness of catalyst.
  • the required resistance to xylene 00 should be to be at least 2-3, resistance against water shall be at least 1. Both resistances can only be obtained with triazolate catalysts.

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  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
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  • Life Sciences & Earth Sciences (AREA)
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Abstract

La présente invention concerne une composition aqueuse durcissable, comprenant ou consistant en a) au moins un prépolymère d'urétdione, qui comprend au moins un groupe urétdione, et qui peut être obtenu par réaction A1) d'au moins un polyisocyanate d'urétdione ayant une fonctionnalité isocyanate d'au moins 2,0, ledit polyisocyanate d'urétdione étant obtenu à partir d'au moins un polyisocyanate aliphatique, A2) d'au moins un composé comprenant au moins un groupe actif Zerewtinoff, et A3) d'au moins un réactif, qui comprend au moins un groupe actif Zerewitinoff et différent d'A2 ou qui est H20, de préférence en présence d'au moins un catalyseur, pour obtenir le prépolymère d'urétdione ; le prépolymère ayant un indice d'acide d'au plus 4 mg KOH/g, de préférence déterminé selon DIN EN ISO 2114:2002-06 en tant que 37 % en poids % de dispersion aqueuse ; B) éventuellement au moins un composé, qui comprend au moins un groupe actif Zerewitinoff ; et C) au moins un composé azolate.
PCT/US2019/023286 2018-03-23 2019-03-21 Composition aqueuse durcissable comprenant un prépolymère d'urétdione dispersé, un réactif et un azolate WO2019183300A1 (fr)

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CN201980021447.8A CN111886271A (zh) 2018-03-23 2019-03-21 包含分散脲二酮预聚物、反应物和唑类的水性可固化组合物
EP19713663.3A EP3768747A1 (fr) 2018-03-23 2019-03-21 Composition aqueuse durcissable comprenant un prépolymère d'urétdione dispersé, un réactif et un azolate

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US15/933,475 US11008416B2 (en) 2018-03-23 2018-03-23 Aqueous, curable composition, comprising dispersed uretdione prepolymer, reactant and azolate
US15/933,527 2018-03-23
EP18163625.9 2018-03-23
US15/933,507 US20190292294A1 (en) 2018-03-23 2018-03-23 One component allophanate formulations through basecoat catalyst migration
US15/933,470 2018-03-23
EP18163620.0A EP3543269A1 (fr) 2018-03-23 2018-03-23 Dispersions de polyuréthane contenant de l'uretdione comprenant des groupes hydrophiles
US15/933,500 2018-03-23
US15/933,570 US10731051B2 (en) 2018-03-23 2018-03-23 Basecoat acid neutralization through inorganic salts
US15/933,475 2018-03-23
US15/933,487 2018-03-23
EP18163625.9A EP3543271A1 (fr) 2018-03-23 2018-03-23 Compositions aqueuses contenant des groupes urétdione et son procede de fabrication
EP18163621.8 2018-03-23
EP18163621.8A EP3543270A1 (fr) 2018-03-23 2018-03-23 Système catalyseur pour dispersions d'uretdions
EP18163620.0 2018-03-23
US15/933,495 US11312881B2 (en) 2018-03-23 2018-03-23 One component polyurethane/allophanate formulations with reactive reducer
US15/933,570 2018-03-23
US15/933,511 2018-03-23
US15/933,527 US20190292296A1 (en) 2018-03-23 2018-03-23 Polyol acid neutralization for low temperature uretdione curing
US15/933,511 US11440988B2 (en) 2018-03-23 2018-03-23 Polyuretdione-containing resin blend compositions
US15/933,495 2018-03-23
US15/933,553 2018-03-23
US15/933,507 2018-03-23
US15/933,500 US10696775B2 (en) 2018-03-23 2018-03-23 Curing for polyallophanate compositions through undercoat acid neutralization
US15/933,470 US11292864B2 (en) 2018-03-23 2018-03-23 Compositions using polyuretdione resins
US15/933,487 US20190292305A1 (en) 2018-03-23 2018-03-23 Uretdione based polyurethane compositions
US15/933,553 US10633477B2 (en) 2018-03-23 2018-03-23 Extended pot-life for low temperature curing polyuretdione resins
EP18181876.6 2018-07-05
EP18181877.4 2018-07-05
EP18181876.6A EP3590987A1 (fr) 2018-07-05 2018-07-05 Compositions aqueuses contenant des groupes urétdione et leur procédé de production
EP18181877.4A EP3590988A1 (fr) 2018-07-05 2018-07-05 Compositions aqueuses contenant des groupes urétdione et leur procédé de production

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PCT/EP2019/057068 WO2019180130A1 (fr) 2018-03-23 2019-03-21 Dispersions de polyuréthane contenant de l'urétdione comprenant des groupes hydrophiles
PCT/US2019/023319 WO2019183319A1 (fr) 2018-03-23 2019-03-21 Formulations d'allophanate à un composant par migration de catalyseur de couche de base
PCT/EP2019/057065 WO2019180128A1 (fr) 2018-03-23 2019-03-21 Compositions aqueuses contenant des groupes uretdione et leur procédé de préparation
PCT/US2019/023325 WO2019183323A1 (fr) 2018-03-23 2019-03-21 Formulations de polyuréthane/allophanate à un seul composant comprenant un réducteur réactif
PCT/US2019/023334 WO2019183330A1 (fr) 2018-03-23 2019-03-21 Neutralisation d'acide de couche de fond au moyen de sels inorganiques
PCT/US2019/023299 WO2019183308A1 (fr) 2018-03-23 2019-03-21 Compositions utilisant des résines polyurétdione
PCT/US2019/023312 WO2019183313A1 (fr) 2018-03-23 2019-03-21 Durée de vie en pot prolongée pour des résines polyurétdione à durcissement à basse température
PCT/US2019/023286 WO2019183300A1 (fr) 2018-03-23 2019-03-21 Composition aqueuse durcissable comprenant un prépolymère d'urétdione dispersé, un réactif et un azolate
PCT/US2019/023290 WO2019183304A1 (fr) 2018-03-23 2019-03-21 Compositions de polyuréthane à base d'uretdione
PCT/US2019/023297 WO2019183307A1 (fr) 2018-03-23 2019-03-21 Compositions de mélange de résines contenant des polyuretdione
PCT/US2019/023314 WO2019183315A1 (fr) 2018-03-23 2019-03-21 Neutralisation d'acide polyol pour durcissement d'urétdione à basse température
PCT/EP2019/057064 WO2019180127A1 (fr) 2018-03-23 2019-03-21 Compositions aqueuses contenant des groupes uretdione et leur procédé de préparation
PCT/EP2019/057069 WO2019180131A1 (fr) 2018-03-23 2019-03-21 Compositions aqueuses contenant des groupes uretdione et procédé pour leur préparation
PCT/EP2019/057066 WO2019180129A1 (fr) 2018-03-23 2019-03-21 Système catalytique pour dispersions d'uretdione
PCT/US2019/023292 WO2019183305A1 (fr) 2018-03-23 2019-03-21 Durcissement amélioré de compositions de polyallophanate par neutralisation de l'acide de sous-couche

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PCT/EP2019/057068 WO2019180130A1 (fr) 2018-03-23 2019-03-21 Dispersions de polyuréthane contenant de l'urétdione comprenant des groupes hydrophiles
PCT/US2019/023319 WO2019183319A1 (fr) 2018-03-23 2019-03-21 Formulations d'allophanate à un composant par migration de catalyseur de couche de base
PCT/EP2019/057065 WO2019180128A1 (fr) 2018-03-23 2019-03-21 Compositions aqueuses contenant des groupes uretdione et leur procédé de préparation
PCT/US2019/023325 WO2019183323A1 (fr) 2018-03-23 2019-03-21 Formulations de polyuréthane/allophanate à un seul composant comprenant un réducteur réactif
PCT/US2019/023334 WO2019183330A1 (fr) 2018-03-23 2019-03-21 Neutralisation d'acide de couche de fond au moyen de sels inorganiques
PCT/US2019/023299 WO2019183308A1 (fr) 2018-03-23 2019-03-21 Compositions utilisant des résines polyurétdione
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PCT/US2019/023314 WO2019183315A1 (fr) 2018-03-23 2019-03-21 Neutralisation d'acide polyol pour durcissement d'urétdione à basse température
PCT/EP2019/057064 WO2019180127A1 (fr) 2018-03-23 2019-03-21 Compositions aqueuses contenant des groupes uretdione et leur procédé de préparation
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