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WO2025168572A1 - Composition réticulable non aqueuse - Google Patents

Composition réticulable non aqueuse

Info

Publication number
WO2025168572A1
WO2025168572A1 PCT/EP2025/052835 EP2025052835W WO2025168572A1 WO 2025168572 A1 WO2025168572 A1 WO 2025168572A1 EP 2025052835 W EP2025052835 W EP 2025052835W WO 2025168572 A1 WO2025168572 A1 WO 2025168572A1
Authority
WO
WIPO (PCT)
Prior art keywords
acid
carboxylic acid
weight
isocyanate
group
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
PCT/EP2025/052835
Other languages
English (en)
Inventor
Elwin Aloysius Cornelius Adrianus DE WOLF
Jack KOEVOETS
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Allnex Netherlands BV
Original Assignee
Allnex Netherlands BV
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Allnex Netherlands BV filed Critical Allnex Netherlands BV
Publication of WO2025168572A1 publication Critical patent/WO2025168572A1/fr
Pending legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • 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
    • 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
    • C08G18/16—Catalysts
    • C08G18/22—Catalysts containing metal compounds
    • C08G18/24—Catalysts containing metal compounds of tin
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/2805—Compounds having only one group containing active hydrogen
    • C08G18/281—Monocarboxylic acid compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
    • C08G18/4063—Mixtures of compounds of group C08G18/62 with other macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/62—Polymers of compounds having carbon-to-carbon double bonds
    • C08G18/6216—Polymers of alpha-beta ethylenically unsaturated carboxylic acids or of derivatives thereof
    • C08G18/622—Polymers of esters of alpha-beta ethylenically unsaturated carboxylic acids
    • C08G18/6225—Polymers of esters of acrylic or methacrylic acid
    • C08G18/6229—Polymers of hydroxy groups containing esters of acrylic or methacrylic acid with aliphatic polyalcohols

Definitions

  • the invention relates a crosslinkable composition
  • a crosslinkable composition comprising an isocyanate-reactive compound having free reactive groups, a polyisocyanate crosslinker, and a particular catalyst, and its use in coatings.
  • Two component polyurethane coatings are well-known in the art. Usually, they are formulated as two-pack systems, the first pack normally containing a polyol resin and the second pack comprising a crosslinking agent, often a polyisocyanate.
  • Two component crosslinkable compositions especially those that comprise a polyol and a polyisocyanate, are widely used in Automotive OEM coatings, especially clearcoats. These compositions are usually appreciated for their good flexibility, hardness, chemical resistance and appearance. In Automotive OEM, these two-component crosslinkable compositions are in general cured at 140 °C for 24 minutes, after which they display good resistance to chemicals and have good hardness.
  • Formulations comprising polyols, polyisocyanates, a catalyst and an acid have been known since long and are for example disclosed in US 3808162, WO 2005/019362, WO 2007/020270 and WO 2013/131835.
  • US10815330 provides a two-component system comprising:
  • the present invention aims to provide a non-aqueous crosslinkable composition for coating compositions that do not present the limitations of the current state of the art coating systems.
  • the present invention discloses a crosslinkable composition
  • a crosslinkable composition comprising: a) at least one isocyanate-reactive compound, b) at least one polyisocyanate crosslinker having free isocyanate groups, c) at least one thermolatent metal-based catalyst for catalysing the reaction between the isocyanate-reactive groups of the isocyanate-reactive compound a) and the isocyanate groups of said polyisocyanate crosslinker b), said thermolatent metal-based catalyst comprising cyclic metal compounds, d) at least one aromatic carboxylic acid, and/or at least one tertiary carboxylic acid of formula RR'R"CCOOH wherein each R, R' and R" group, independently, is an alkyl, alkenyl, aryl or aralkyl group containing at least one carbon atom, wherein the total number of carbon atoms in the R, R' and R" groups is in the range of from 3 to 40, and wherein two
  • the carboxylic acid d) is a tertiary carboxylic acid with general formula RR'R"CCOOH wherein the total number of carbon atoms in the R, R' and R" groups is in the range of from 3 to 30;
  • the isocyanate-reactive compound a) is a polyol, comprising:
  • the polyisocyanate crosslinker b) is selected from the group consisting of aliphatic polyisocyanates, cycloaliphatic polyisocyanate, the adducts of aliphatic isocyanates, the adducts of cycloaliphatic polyisocyanates, and mixtures thereof, the adducts being selected from the group consisting of biurets, isocyanurates, imino-oxadiazinediones, allophanates, uretdiones, homopolymers of polyisocyanates, and mixtures thereof;
  • crosslinkable composition comprises:
  • thermolatent metal-based catalyst c • from 0,01 to 10 % of weight of at least one thermolatent metal-based catalyst c
  • the one or more additives and auxiliaries are selected from the group consisting of pigments, dyes, surfactants, pigment dispersion aids, levelling agents, wetting agents, anticratering agents, antifoaming agents, matting agents, sag control agents, other rheology control agents, heat stabilizers, light stabilizers, UV absorbers, antioxidants, radical inhibitors, and fillers, and mixtures thereof;
  • the sag control agent is a polyurea-based sag control agent.
  • the present invention further discloses a kit of parts for preparing a coating composition according to the present invention, said kit of parts comprising:
  • a binder module i) comprising at least one isocyanate-reactive compound a), at least one carboxylic acid compound d), optionally at least one thermolatent catalyst c), optionally one or more additives and auxiliaries, and optionally water-free volatile organic solvents,
  • a crosslinker module ii) comprising at least one polyisocyanate crosslinker b) optionally at least one thermolatent catalyst c), optionally one or more additives and auxiliaries, and optionally water-free volatile organic solvents, wherein
  • thermolatent metal-based catalyst is present in at least binder module i) and/or crosslinker module ii); and o in a preferred embodiment the carboxylic acid d) of binder module i) is a tertiary carboxylic acid d), o in another preferred embodiment binder module i) comprises sag control agents;
  • the present invention also discloses a method of providing a coating layer, said method comprising the steps of applying a coating composition according to the present invention to at least a part of an object, preferably the (exterior) surface of a transportation vehicle, and curing the applied coating composition, preferably in a temperature range of 5 to 180 °C.
  • a coating composition according to the present invention to at least a part of an object, preferably the (exterior) surface of a transportation vehicle, and curing the applied coating composition, preferably in a temperature range of 5 to 180 °C.
  • a crosslinkable composition comprising at least one isocyanate-reactive compound a), at least one isocyanate crosslinker b), at least one thermolatent metal-based catalyst c), and at least one aromatic carboxylic acid and/or at least one tertiary carboxylic acid d) provides a coating composition, which upon curing results in a coating having an improved chemical resistance and hardness, said coating composition being characterized by an increased potlife while being curable at low temperature, and an improved film hardness build-up.
  • the crosslinkable composition according to the present invention comprises a) at least one isocyanate-reactive compound, b) at least one polyisocyanate crosslinker having free isocyanate groups, c) at least one thermolatent metal-based catalyst for catalyzing the reaction between the isocyanate-reactive groups of the isocyanate-reactive compound a) and the isocyanate groups of said polyisocyanate crosslinker b), said thermolatent metal-based catalyst comprising cyclic metal compounds, wherein the metal atom is part of one or more ring structure(s), said ring structures being at least five-membered, d) at least one aromatic carboxylic acid, and/or at least one tertiary carboxylic acid of formula RR'R"CCOOH, wherein each R, R' and R" group, independently, is an alkyl, alkenyl, aryl or aralkyl group containing at least one carbon atom, wherein the total number of carbon atoms in the
  • the crosslinkable composition according to the invention is a non-aqueous composition, though water may be present in one or more of its constituents, as they are technical grade constituents which, as generally known by the one skilled in the art, may contain up to 0.2% of water.
  • non-aqueous crosslinkable composition in the present invention is meant a crosslinkable composition containing at most 0.2% by weight of water, based on the total of crosslinkable composition (a), b), c), d)) and water, if present, being 100% by weight.
  • the water content is determined by Karl Fischer titration as a volumetric method according to DIN 53715 (DIN 53715 was based on DIN 51777 part 1 (1973 edition)).
  • the measurement range of the water content is 0.01% to less than 99% by weight.
  • the isocyanate-reactive compound a) of the crosslinkable composition according to the present invention comprises one or more functional groups selected from the group consisting of the hydroxyl-group, the thiol-group, the amine-group, the carboxylic acid-group, and combinations thereof.
  • the isocyanate-reactive compound a) comprises one or more hydroxyl groups.
  • preferred polymeric polyols are the polyester polyols and polyacrylic polyols and mixtures and hybrids thereof wherein by mixtures a physical blend of polyester polyols and polyacrylate polyols is meant whereas hybrids comprise the chemical reaction product of polyacrylate and polyester, wherein polyester segments and polyacrylate segments are linked through covalent bonds and wherein the polyester segments and/or the polyacrylate segments comprise -OH groups, the resulting polyester-polyacrylate hybrid comprising at least two -OH groups.
  • Suitable polyester polyols can be obtained, for instance, by the polycondensation of one or more di- and/or higher functional hydroxyl compounds with one or more di- and/or higher functional carboxylic acids, optionally in combination with one or more monofunctional carboxylic acids and/or mono-hydroxyl functional compounds.
  • di- and/or higher functional hydroxyl compounds can be one or more alcohols selected from ethylene glycol, neopentyl glycol, trimethylol propane and pentaerythritol.
  • the di- and/or higher functional carboxylic acids are one or more carboxylic acids selected from the group consisting of adipic acid, 1 ,4-cyclohexyl dicarboxylic acid, hexahydrophthalic acid, succinic acid, and functional equivalents thereof.
  • polyester polyols can be prepared from di- and/or higher functional hydroxyl compounds and from carboxylic acid anhydrides and/or C1-C4 alkyl esters of the carboxylic acids.
  • Suitable (meth)acrylic polyols can be obtained, for instance, by the (co)polymerization of one or more hydroxyl- functional (meth)acrylic monomers such as for example 2- hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 3-hydroxybutyl (meth)acrylate, 4- hydroxybutyl (meth)acrylate, 2,3-dihydroxypropyl (meth)acrylate, polyethylene glycol esters of (meth)acrylic acid, polypropylene glycol esters of (meth)acrylic acid, and mixed polyethylene glycol and polypropylene glycol esters of (meth)acrylic acid, and one or more alpha, beta-ethylenically unsaturated monomers selected from the group consisting of alpha, beta-ethylenically unsaturated monoacids, such as (meth)acrylic acid, alky
  • the polymeric polyol used in the crosslinkable composition according to the present invention preferably has a hydroxyl value of at least 20 mg KOH/g, more preferably of at least 50 mg KOH/g, most preferably of at least 100 mg KOH/g; preferably the polymeric polyol a) has a hydroxyl value of at most 1 ,000 mg KOH/g, more preferably of at most 500 mg KOH/g, most preferably of at most 250 mg KOH/g, the hydroxyl value being measured according to the method ASTM E222 - 17.
  • the polymeric polyol used in the crosslinkable composition according to the present invention preferably has an acid value of at most 15 mg KOH/g, more preferably of at most 10 mg KOH/g, even more preferably of at most 6 mg KOH/g, most preferably of at most 4 mg KOH/g; preferably the polymeric polyol a) has an acid value higher than 0 mg KOH/g ), more preferably higher than 1 mg KOH/g, most preferably higher than 2 mg KOH/g, the acid value being measured according to ISO 3682-1996.
  • the polymeric polyol used in the crosslinkable composition according to the invention further is characterized by: a number average molecular weight (Mn) of less than 10,000 Dalton, preferably less than 5,000, more preferably less than 3,000, most preferably less than 2,000 Dalton and of at least 600 Dalton, preferably at least 700 Dalton, more preferably at least 900 Dalton, most preferably at least 1 ,000 Dalton and/or a weight average molecular weight (Mw) of less than 15,000 Dalton, preferably less than 10,000, more preferably less than 8,000, most preferably less than 6,000, even less than 4,000 Dalton and of at least 900 Dalton, preferably at least 1 ,100 Dalton, more preferably at least 1 ,300 Dalton, most preferably at least 1 ,500 Dalton and/or a polydispersity Mw/Mn of higher than 1 , more preferably of from 1.1 to 6.6, most preferably of from 1 .4 to 4, as determined according to ASTM D 3593 by Gel Permeation
  • the polymeric polyol used in the crosslinkable composition according to the invention further is characterized by: a number average molecular weight (Mn) of less than 10,000 Dalton, preferably less than 5,000, more preferably less than 3,000, most preferably less than 2,000 Dalton and of at least 600 Dalton, preferably at least 700 Dalton, more preferably at least 900 Dalton, most preferably at least 1 ,000 Dalton, and a weight average molecular weight (Mw) of less than 15,000 Dalton, preferably less than 10,000, more preferably less than 8,000, most preferably less than 6,000, even less than 4,000 Dalton and of at least 900 Dalton, preferably at least 1 ,100 Dalton, more preferably at least 1 ,300 Dalton, most preferably at least 1 ,500 Dalton and a polydispersity Mw/Mn of higher than 1 , more preferably of from 1.1 to 6.6, most preferably of from 1 .4 to 4, as determined according to ASTM D 3593 by Gel Permeation Chr
  • the polymeric polyol used in the crosslinkable composition according to the invention further is characterized by a glass transition temperature (Tg), as determined by Differential Scanning Calorimetry (DSC) according to DIN EN ISO 16805 and ISO 11357, of more than -80 °C, preferably of more than -40 °C, more preferably of more than -10 °C, and most preferably of more than 10 °C.
  • Tg glass transition temperature
  • the glass transition temperature of the polymeric polyol preferably is lower than 90 °C, more preferably lower than 75 °C, even more preferably lower than 60 °C, most preferably lower than 50 °C.
  • the polymeric polyol used in the crosslinkable composition according to the invention further is characterized by:
  • Mn number average molecular weight
  • Mw weight average molecular weight
  • Tg glass transition temperature
  • the polymeric polyol a) has a hydroxyl value of at most 500 mg KOH/g, more preferably of at most 250 mg KOH/g.
  • the isocyanate-reactive compound a) of the crosslinkable composition according to the present invention further may comprise one or more reactive diluents selected from the group consisting of monomeric compounds having 2 to 5 hydroxyl groups, aliphatic mono-alcohols, oligomeric compounds having on average 1 to 5 hydroxyl groups, and mixtures thereof.
  • Suitable monomeric compounds include, for instance, 1 ,2-ethylene glycol, 1 ,2-propylene glycol 1 ,3-propylene glycol, 1 ,4-butanediol, and 1 ,6 hexanediol.
  • Suitable aliphatic mono-alcohols include, for instance, n-butanol, 2-butanol, 2- ethylhexylalcohol, 1- or 2-octanol, nonylalcohol, 3,3,5-trimethylhexanol, decyl and lauryl alcohols, cyclopentanol, cyclohexylalcohol, and benzylalcohol.
  • Suitable oligomeric compounds include, for instance, low molecular weight hydroxyl functional polyesters, hydroxyl functional (meth)acrylic (co)polymers and polyether polyols, said oligomeric compounds being characterized by a degree of polymerization of at most 15.
  • the isocyanate-reactive compound a) of the crosslinkable composition according to the present invention preferably comprises at least 70% by weight, more preferably at least 80% by weight, most preferably at least 90% by weight of polymeric polyol, and preferably comprises at most 30% by weight, more preferably at most 20% by weight, most preferably at most 10% by weight of reactive diluent, based on the total amount of isocyanate-reactive compound a) being 100% by weight.
  • the isocyanate-reactive compound a) is present in the crosslinkable composition according to the present invention preferably in an amount of from 9 to 90% by weight, more preferably of from 19 to 80% by weight, most preferably of from 29 to 70% by weight, based on the total amount of the isocyanate-reactive compound a), the polyisocyanate crosslinker b), the thermolatent metal-based catalyst c), the carboxylic acid d), the total amount being 100% by weight.
  • the polyisocyanate crosslinker b) of the crosslinkable composition according to the present invention preferably is a polyisocyanate crosslinker having at least 2 free isocyanate groups.
  • the polyisocyanate crosslinker b) is preferably selected from the group consisting of hexamethylene diisocyanate, 2,4,4-trimethyl hexamethylene diisocyanate, 1 ,2-cyclohexylene diisocyanate, 1 ,4-cyclohexylene diisocyanate, 4,4'-dicyclohexylene diisocyanate methane, 3, 3'-dimethyl-4,4'-dicyclohexylene diisocyanate methane, norbornane diisocyanate, m- and p- phenylene diisocyanate, 1 ,3- and 1 ,4-bis (isocyanate methyl) benzene, xylylene diisocyanate, a,a,a',a'-tetramethyl xylylene diisocyanate (TMXDI), 1 ,5-dimethyl-2,4-bis (isocyanate methyl) benzene, 2,4-
  • isocyanate crosslinkers are the adducts of polyisocyanates, e.g., biurets, isocyanurates, imino-oxadiazinediones, allophanates, uretdiones, homopolymers of polyisocyanates, and mixtures thereof.
  • adducts examples include the adduct of two molecules of hexamethylene diisocyanate or isophorone diisocyanate to a diol such as ethylene glycol, the adduct of 3 molecules of hexamethylene diisocyanate to 1 molecule of water, the adduct of 1 molecule of trimethylol propane to 3 molecules of isophorone diisocyanate, the adduct of 1 molecule of pentaerythritol to 4 molecules of toluene diisocyanate, the isocyanurate of hexamethylene diisocyanate (available under the trade name DESMODUR® (E) N3390 or TOLONATETM HDT-LV, TOLONATETM HDT-90, a mixture of the uretdione and the isocyanurate of hexamethylene diisocyanate, under the trade name DESMODUR® N3400, the allophanate of hexamethylene diisocyanate,
  • (co)polymers of isocyanate-functional monomers such as a,a'-dimethyl-m-isopropenyl benzyl isocyanate are suitable for use.
  • the polyisocyanate crosslinker b) is selected from the group consisting of aliphatic polyisocyanates, cycloaliphatic polyisocyanate, the adducts of aliphatic isocyanates, the adducts of cycloaliphatic polyisocyanates, and mixtures thereof.
  • thermolatent metal-based catalyst c) is characterized by the absence of direct metal-carbon bonds.
  • thermolatent metal-based catalyst c) is especially understood to mean any catalyst that, in combination with aromatic and/or tertiary carboxylic acid d), does not accelerate or does not significantly accelerate the crosslinking reaction of the at least one polyisocyanate b) with the at least one isocyanate-reactive compound a) to form a urethane bond below 25° C, in particular below 30° C, preferably below 40° C, but significantly accelerates it above 60° C, especially above 70° C.
  • D represents — O — , — S — or — N(R1) wherein R1 represents a saturated or unsaturated, linear or branched, aliphatic or cycloaliphatic radical or an optionally substituted aromatic or araliphatic radical which has up to 20 carbon atoms and may optionally contain heteroatoms from the group of oxygen, sulfur, nitrogen, or is hydrogen or the radical or R1 and L3 together represent — Z-L5-;
  • D is preferably — N(R1)-, where the pair of lone pair electrons may be represented as forming a coordinate bond between the nitrogen and the metal atom;
  • R1 is preferably hydrogen or an alkyl, aralkyl, alkaryl or aryl radical having up to 20 carbon atoms or the radical particularly preferably hydrogen or an alkyl, aralkyl, alkaryl or aryl radical having up to 12 carbon atoms or the radical very particularly preferably hydrogen or a methyl, ethyl, propyl, butyl, hexyl or octyl radical, where propyl, butyl, hexyl and octyl are all isomeric propyl, butyl, hexyl and octyl radicals, or Ph-, CH 3 Ph- or the radical
  • D* is preferably — O — .
  • X, Y and Z are preferably the — C(R2)(R3), — C(R2)(R3)-C(R4)(R5)- or the ortho-arylene radical
  • R2 to R7 are preferably hydrogen or alkyl, aralkyl, alkaryl or aryl radicals having up to 20 carbon atoms, particularly preferably hydrogen or alkyl, aralkyl, alkaryl or aryl radicals having up to 8 carbon atoms, very particularly preferably hydrogen or alkyl radicals having up to 8 carbon atoms, yet more preferably hydrogen or methyl.
  • R8 to R11 are preferably hydrogen or aryl radicals having up to 8 carbon atoms, particularly preferably hydrogen or methyl.
  • R12 is preferably hydrogen or an alkyl, aralkyl, alkaryl or aryl radical having up to 20 carbon atoms, particularly preferably hydrogen or an alkyl, aralkyl, alkaryl or aryl radical having up to 12 carbon atoms, very particularly preferably hydrogen or a methyl, ethyl, propyl, butyl, hexyl or octyl radical, where propyl, butyl, hexyl and octyl represent all isomeric propyl, butyl, hexyl and octyl radicals.
  • L3 and L4 are particularly preferably Cl — , MeO — , EtO — , PrO — , BuO — , HexO — , OctO — , PhO — , formate, acetate, propanoate, butanoate, pentanoate, hexanoate, octanoate, laurate, lactate or benzoate, where Pr, Bu, Hex and Oct are all isomeric propyl, butyl, hexyl and octyl radicals, yet more preferably Cl — , MeO — , EtO — , PrO — , BuO — , HexO — , OctO — , PhO — , hexanoate, laurate or benzoate, where Pr, Bu, Hex and Oct represent all isomeric propyl, butyl, hexyl and octyl radicals.
  • R15 to R20 are preferably hydrogen or alkyl, aralkyl, alkaryl or aryl radicals having up to 20 carbon atoms, particularly preferably hydrogen or alkyl, aralkyl, alkaryl or aryl radicals having up to 12 carbon atoms, very particularly preferably hydrogen, methyl, ethyl, propyl, butyl, hexyl or octyl radicals, where propyl, butyl, hexyl and octyl represent all isomeric propyl, butyl, hexyl and octyl radicals.
  • the units L1-X, L2-Y and L5-Z preferably represent — CH 2 CH 2 O — , — CH 2 CH(Me)O — ,
  • the unit L1-X-D-Y-L2 preferably represents: HN[CH 2 CH 2 O— ] 2 , HN[CH 2 CH(Me)O— ] 2 ,
  • thermolatent tin-based catalyst c) is characterized by the absence of direct tincarbon bonds.
  • thermolatent metal-based catalysts suitable according to the invention are described for example in: EP 2 900 716 A1 , EP 2 900 717 A1 , EP 2 772 496 A1 , EP 14182806, J. Organomet. Chem. 2009 694 3184-3189, Chem. Heterocycl. Comp. 2007 43 813-834, Indian J. Chem. 1967 5 643-645, and in the literature referenced therein, the disclosure content of which is hereby incorporated by reference in its entirety.
  • tin compounds have a propensity to oligomerize, and so there are often polynuclear tin compounds or mixtures of mono- and polynuclear tin compounds.
  • the tin atoms are preferably connected to one another via oxygen atoms (‘oxygen bridges’).
  • oxygen bridges oxygen atoms
  • Typical oligomeric complexes polynuclear tin compounds
  • thermolatent tin-based catalyst is selected from the group of mono- or polynuclear tin compounds of the type:
  • thermolatent tin-based catalyst is selected from:
  • aromatic carboxylic acids d) of the crosslinkable composition according to the present invention preferably are selected from the group consisting of aromatic monocarboxylic acids, alkyl- or alkoxy- or hydroxy- substituted aromatic monocarboxylic acids, aromatic dicarboxylic acids, monoalkyl esters of aromatic dicarboxylic acids, alkyl- or alkoxy- or hydroxy substituted aromatic dicarboxylic acids, monoalkyl esters of alkyl- or alkoxy- or hydroxy-substituted of aromatic dicarboxylic acids, aromatic tricarboxylic acids, monoalkyl esters of aromatic tricarboxylic acids, dialkyl esters of aromatic tricarboxylic acids, aromatic tetracarboxylic acids, monoalkyl esters of aromatic tetracarboxylic acids, dialkyl esters of aromatic tetracarboxylic acids, trialkyl esters of aromatic tetracarboxylic acids, and mixtures thereof.
  • aromatic carboxylic acid d) is selected from the group consisting of aromatic monocarboxylic acids, alkyl- or alkoxy- or hydroxy- substituted aromatic monocarboxylic acids, phthalic acid, isophthalic acid, terephthalic acid, trimesic acid, pyromellitic acid, and mixtures thereof.
  • aromatic carboxylic acid d) is selected from the group consisting of aromatic monocarboxylic acids, alkyl- or alkoxy- or hydroxy- substituted aromatic monocarboxylic acids, phthalic acid, isophthalic acid, and mixtures thereof.
  • aromatic carboxylic acid d) is selected from the group consisting of benzoic acid, phthalic acid, isophthalic acid, and mixtures thereof.
  • tertiary carboxylic acids d) are those of the formula RR'R"CCOOH wherein the total number of carbon atoms in the R, R' and R" groups are in the range of from 3 to 30, more preferably from 3 to 18, and most preferably from 3 to 8.
  • R, R’ and R” can be the same or can be different and include linear as well as branched groups as well as groups which are substituted with one or more functional groups such as -OH groups, primary, secondary or tertiary amine groups, carboxylic acids groups, ester groups, ether groups, -SH groups.
  • one of R’ or R” can be a carboxylic acid group.
  • Preferred tertiary carboxylic acids d) are those of the formula RR'R"CCOOH wherein R, R' and R" are a linear or branched alkyl group, more preferably a methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, n-pentyl or i-pentyl group and wherein optionally at least one R, R' or R" may comprise one or more hydroxyl group.
  • Particularly preferred tertiary carboxylic acids d) are those wherein R is a methyl or ethyl group and where the total number of carbon atoms of groups R' and R" is from 2 to 17, most preferred from 2 to 12, especially from 2 to 7, and where R' and/or R" is non-substituted or substituted with only one hydroxyl group.
  • Non-limiting examples of tertiary carboxylic acids d) that can be used in the crosslinkable composition according to the invention preferably are neodecanoic acid, 3- hydroxy-2, 2- dimethylpropionic acid, 2,2-bis(hydroxymethyl)propionic acid, abietic acid, dimetylmalonic acid, ethylmethylmalonic acid, diethylmalonic acid, 2,2-dimethylsuccinic acid, 2,2- diethylsuccinic acid, 2,2-dimethylglutaric acid, 2,2-dimethylpropionic acid, 2,2-dimethylbutyric acid, 2-ethyl-2-methylbutyric acid, 2,2-diethylbutyric acid, 2,2-dimethylvaleric acid, 2-ethyl-2- methylvaleric acid, 2,2-diethylvaleric acid, 2,2-dimethylhexanoic acid, 2,2-diethylhexanoic acid, 2,2-dimethyloctanoic acid, 2-ethy
  • the tertiary carboxylic acid d) is neodecanoic acid, abietic acid, 1-methyl-1- cyclohexane carboxylic acid, 3-hydroxy-2,2-dimethylpropionic acid, 2,2-dimethylpropionic acid, or 2,2-dimethylbutyric acid, or mixtures thereof.
  • the tertiary carboxylic acid is neodecanoic acid.
  • the carboxylic acid d) of the crosslinkable composition according to the present invention is a tertiary carboxylic acid selected from the group consisting of neodecanoic acid, abietic acid, 1-methyl-1 -cyclohexane carboxylic acid, 3-hydroxy-2,2-dimethylpropionic acid, 2,2-dimethylpropionic acid, or 2,2-dimethylbutyric acid and mixtures thereof.
  • the amount of carboxylic acid d) incorporated in the crosslinkable composition according to the present invention preferably ranges from 0.005 to 0.5 mmole, per gram of isocyanatereactive compound a), viz. per gram of polyol a).
  • the amount of carboxylic acid d) ranges from 0.02 to 0.3 mmole, most preferably from 0.04 to 0.25 mmole, per gram of isocyanate-reactive compound a), viz. per gram of polyol a).
  • the carboxylic acid d) is present in the crosslinkable composition according to the present invention, preferably in an amount of from 0.001 to 10% by weight, more preferably of from 0.002 to 5% by weight, most preferably of from 0.01 to 2.5% by weight based on the total amount of the isocyanate-reactive compound a), the polyisocyanate crosslinker b), the thermolatent metal-based catalyst c), and the carboxylic acid d), the total amount being 100% by weight.
  • the crosslinkable composition according to the present invention may comprise primary and/or secondary, preferably non-polymer bonded, carboxylic acids, in addition to the carboxylic acid d).
  • the quantity of primary and/or secondary acid is preferably present in the range of from 0.01 to 1 mole, more preferably in the range of from 0.01 to 0.5 mole, most preferably in the range of from 0.01 to 0.2 mole per mole of carboxylic acid d), the total amount of the isocyanate-reactive compound a), the polyisocyanate crosslinker b), the thermolatent metal-based catalyst c), the carboxylic acid d), and primary and/or secondary acid, if present, constituting 100% by weight of crosslinkable composition.
  • Examples of primary and secondary acids are acetic acid, propionic acid, isononanoic acid, 2-ethylhexanoic acid, pentanoic acid and 3-methylbutanoic acid, 7,7-dimethyloctanoic acid, and mixtures thereof.
  • the crosslinkable composition of the present invention forms the basis for water-free coating compositions preferably comprising at least 30% by weight, more preferably at least 40% by weight, most preferably at least 50% by weight of non-volatile compounds, and preferably at most 70% by weight, more preferably at most 60% by weight, most preferably at most 50% by weight of volatile organic compounds, the sum of the weight percentages of the non-volatile compounds and the water-free volatile organic solvents not exceeding 100% by weight.
  • water-free in the present invention is meant that there is no intentional addition of water neither to the non-volatile compounds nor to the volatile organic solvents and that both, the water-free non-volatile compounds and the water-free volatile organic solvents are technical grade non-volatile compounds I volatile organic solvents, used as such without further purification and or drying.
  • technical grade compounds I organic solvents can comprise up to 0.2% by weight of water.
  • water-free coating composition in the present invention is meant a coating composition containing at most 0.2% by weight of water, based on the total of coating composition and water, if present, being 100% by weight.
  • suitable volatile organic compounds are hydrocarbons, such as toluene, xylene, SOLVESSOTM 100, ketones, terpenes, such as dipentene or pine oil, halogenated hydrocarbons, such as dichloromethane, ethers, such as ethylene glycol dimethyl ether, esters, such as ethyl acetate, ethyl propionate, n-butyl acetate or ether esters, such as methoxypropyl acetate or ethoxyethyl propionate. Also mixtures of these compounds can be used.
  • hydrocarbons such as toluene, xylene, SOLVESSOTM 100
  • ketones such as dipentene or pine oil
  • halogenated hydrocarbons such as dichloromethane
  • ethers such as ethylene glycol dimethyl ether
  • esters such as ethyl acetate, ethyl propionate, n-butyl acetate or
  • exempt solvents may be part of the coating composition.
  • exempt solvents that are approved for use in paints and coatings include acetone, methyl acetate, parachlorobenzotrifluoride (commercially available under the name OXSOL®100), and volatile methyl siloxanes. Also tertiary butyl acetate is being considered as an exempt solvent.
  • the non-volatile compounds of the coating composition according to the present invention preferably comprise from 20 to 98% by weight, more preferably from 30 to 95% by weight, most preferably from 40 to 90% by weight, of the crosslinkable composition of the present invention comprising a), b), c) and d), and preferably from 2 to 80% by weight, more preferably from 5 to 70% by weight, most preferably from 10 to 60% by weight, of one or more additives and auxiliaries, the sum of the weight percentages of the crosslinkable composition and the one or more additives and auxiliaries not exceeding 100% by weight of non-volatile compounds.
  • one or more additives or auxiliaries may be part of one or more components of the crosslinkable composition, which means that one or more additives or auxiliaries are incorporated into one or more components of the crosslinkable composition such as for example into the isocyanate-reactive compound a); nevertheless, the one or more additives or auxiliaries, and the one or more components of the crosslinkable composition, are considered separately when it comes to their weight percentages in the non-volatile compounds.
  • Antioxidants optionally used in coating compositions are well known and are generally chosen from phenolic type anti-oxidants, phosphite based antioxidants, phosphonite type anti-oxidant, thioethers and blends thereof.
  • the coating composition according to the invention preferably comprises at least one anti-oxidant of the phosphite or phosphonite type.
  • Complexing agents are organic compounds preferably containing one or more -SH groups.
  • Preferred complexing agents are those of the general formula R-SH, wherein R can be an alkyl, alkenyl, aryl or aralkyl group.
  • the -SH group can be a primary, secondary or tertiary -SH group.
  • R can be a linear, cyclic or branched group and can comprise one or more other functional groups such as for example hydroxyl groups, primary, secondary or tertiary amine groups, silane or siloxane groups, ether groups, ester groups, carboxylic acid groups.
  • R is a linear or branched alkyl group of the general formula -CnH 2n+i wherein n is from 4 to 40, more preferably from 8 to 30.
  • n is from 4 to 40, more preferably from 8 to 30.
  • Examples are n-Ci 2 H 2 5SH, n-Ci 6 H 3 3SH , linear or branched molecules of formula CnH 23 SH , CI 2 H 25 SH and CI 3 H 27 SH, as well as mixtures thereof, and (CH 3 ) 2 (iPr)C- C(CH 3 ) 2 -C(CH 3 ) 2 SH.
  • R contains more than one other functional groups, these can be different or the same. Particularly hydroxyl or ester groups are preferred as other functional group.
  • n can be chosen in the range of 1 - 20, preferably in the range of 1 - 10 and particularly preferred n is 1 or 2.
  • R' can be any alkyl, alkenyl, aryl or aralkyi group, preferably containing from 1 to 24 carbon atoms, such as for example butyl, 2-ethylhexyl, iso-octyl, tridecyl, octadecyl.
  • Other complexing agents e) which are particularly preferred are esters from SH- functional acids, especially SH-functional carboxylic acids, and a polyol.
  • Preferred are those which are the reaction products of carboxylic acids of formula HS(CH 2 ) n COOH wherein n is from 1 to 20 and a polyol having an OH-functionality of 2 or more.
  • the polyol has usually an OH-functionality of 2 or more and can be monomeric, oligomeric or polymeric.
  • the amount of complexing agent in the coating composition according to the invention is generally such that the molar equivalents of -SH groups per molar equivalent of metal in the metal-based catalyst c) is in the range of 1 to 20 molar equivalents of SH per equivalent of metal from the metal-based catalyst c), preferably in the range of 2 to 10 molar equivalents of SH per equivalent of metal from the metal-based catalyst.
  • the coating composition of the present invention comprises one or more sag control agents.
  • Sag control agents are Theologically active compounds providing thixotropic properties to the coating composition.
  • Sag control agents are well known and are generally chosen from clay sag control agents, silica-based sag control agents, microgel sag control agents, amide-based sag control agents or sag control agents based on polyurea products.
  • the coating composition of the present invention preferably comprises a sag control agent based on a polyurea product, more preferably a polyurea product typically prepared from the reaction of a polyisocyanate with a monoamine, most preferably a polyurea product prepared from the reaction of benzylamine, S-alpha methyl benzyl amine or 3-methoxypropyl amine and the adducts (or derivatives) of hexamethylene diisocyanate.
  • a sag control agent based on a polyurea product, more preferably a polyurea product typically prepared from the reaction of a polyisocyanate with a monoamine, most preferably a polyurea product prepared from the reaction of benzylamine, S-alpha methyl benzyl amine or 3-methoxypropyl amine and the adducts (or derivatives) of hexamethylene diisocyanate.
  • a polyurea product based sag control agent is typically prepared by the reaction of a polyisocyanate or its isocyanurate, biuret or uretdione derivative with at least one mono-amine or, alternatively, by the reaction of effectively mono-isocyanates (including diisocyanates that have been selectively reacted at one side) with polyamines. It is noted that when a polyurea product is prepared by the reaction product of amines with a polyisocyanate, it is preferred to prepare a di-urea product or a tri-urea product. In the present application, polyurea product based sag control agent is also referred to as polyurea-based sag control agent.
  • Polyisocyanates used for the preparation of the polyurea product based sag control agent are preferably selected from the group consisting of aliphatic, cycloaliphatic, aralkylene, and arylene polyisocyanates, more preferably from the group consisting of substituted or unsubstituted linear aliphatic polyisocyanates (and their isocyanurates, biurets, uretdiones), and substituted or unsubstituted aralkylene and cyclohexylene polyisocyanates.
  • the polyisocyanate may contain other functional groups such as for example ether functionalities, ester functionalities or urethane functionalities.
  • the polyisocyanate usually contains 2 to 40 and preferably 4 to 12 carbon atoms between the NCO groups.
  • the polyisocyanate preferably contains at most on average four isocyanate groups, more preferably at most on average three isocyanate groups, and most preferably on average two isocyanate groups. It is even more preferred to use a symmetrical aliphatic or cyclohexylene diisocyanate.
  • Suitable diisocyanates are preferably selected from the group consisting of tetramethylene-1 ,4-diisocyanate, pentamethylene-1 ,5-diisocyanate, hexamethylene-1 ,6- diisocyanate (HMDI), trans-cyclohexylene-1 ,4-diisocyanate, dicyclohexylmethane-4,4'- diisocyanate, 1 ,5-dimethyl-(2,4-[omega]-diisocyanato methyl) benzene, 1 ,5-dimethyl(2,4- [omega]-diisocyanatoethyl) benzene, 1 ,3,5-trimethyl(2,4-[omega]diisocyanato-methyl) benzene, 1 ,3,5-triethyl(2,4-[omega]-diisocyanatomethyl) benzene, meta-xylylene
  • Preferred polyisocyanates are selected from the group consisting of hexamethylene-1 , 6- diisocyanate (HMDI), condensed derivatives of hexamethylene-1 , 6-diisocyanate (HMDI), such as uretdiones, biurets, isocyanurates (trimers), and asymmetrical trimers, many of which are marketed as DESMODUR® N and TOLONATETM HDB and TOLONATETM HDT.
  • HMDI hexamethylene-1 , 6- diisocyanate
  • HMDI condensed derivatives of hexamethylene-1 , 6-diisocyanate
  • trimers uretdiones
  • trimers isocyanurates
  • asymmetrical trimers many of which are marketed as DESMODUR® N and TOLONATETM HDB and TOLONATETM HDT.
  • polyisocyanates are selected from the group consisting of HMDI, its isocyanurate trimer and its biuret, trans-cyclohexylene-1 , 4-diisocyanate, para- and meta- xylylene diisocyanate, and toluene diisocyanate. Most preferred polyisocyanate is HMDI or its isocyanurate.
  • polyisocyanate thus stands for polyisocyanates and polyisocyanate-generating compounds.
  • the amines used to prepare polyurea product based sag control agent comprise mono-amines. Many monoamines can be used in combination with the polyisocyanates to create polyurea reaction products. Primary and secondary aliphatic as well as aromatic amines can be used. Preferably, primary amines are used; of these n-alkylamines and ether-substituted n-alkylamines are particularly useful in accordance with this invention.
  • the amines may comprise other functional groups, such as hydroxy groups, ester groups, urethane groups.
  • Preferred monoamines include n- aliphatic amines, especially n-alkylamines such as hexylamine; cyclohexylamine; benzylamine; 3-methoxypropylamine; S-alpha-methylbenzylamine and 2-phenethylamine, as well as mixtures thereof.
  • n-alkylamines such as hexylamine; cyclohexylamine; benzylamine; 3-methoxypropylamine; S-alpha-methylbenzylamine and 2-phenethylamine, as well as mixtures thereof.
  • Specifically preferred polyurea product based sag control agent are the adducts of (derivatives of) HMDI and benzylamine, the adducts of (derivates of ) HMDI and S-alpha-methylbenzylamine, the adducts of (derivatives of) HMDI and 3- methoxypropylamine, or mixture
  • diamines e.g. ethylenediamine
  • the use of diamines (e.g. ethylenediamine) as component next to mono-amines may also be an option to create high melting point polyureas.
  • the monoamine or part of the monoamine used to prepare the polyurea product based sag control agent can be a chiral monoamine.
  • Thixotropic agents comprising polyurea products as claimed in U.S. Pat. No. 8,207,268 are considered to be part of this invention.
  • the polyurea formation reaction may be carried out in the presence of an inert solvent, for example acetone, methyl isobutyl ketone, N-methyl pyrrolidone, benzene, toluene, xylene, butyl acetate or an aliphatic hydrocarbon such as petroleum ether, alcohols, and water, or mixtures thereof.
  • an inert solvent for example acetone, methyl isobutyl ketone, N-methyl pyrrolidone, benzene, toluene, xylene, butyl acetate or an aliphatic hydrocarbon such as petroleum ether, alcohols, and water, or mixtures thereof.
  • inert solvent for example acetone, methyl isobutyl ketone, N-methyl pyrrolidone, benzene, toluene, xylene, butyl acetate or an aliphatic hydrocarbon such as petroleum ether, alcohols, and water, or mixtures thereof
  • the polyurea formation reaction may be carried out in the presence of any component of the coating composition in particular in the presence of isocyanate-reactive compound a) or in the presence of polyisocyanate crosslinker b).
  • the polyurea formation reaction is carried out in the presence of isocyanate-reactive compound a).
  • the isocyanate-reactive compound a) is highly reactive with either the isocyanate or the amine, the isocyanate-reactive compound a) and that particular highly reactive isocyanate or amine cannot be premixed.
  • the polyisocyanate crosslinker b) is highly reactive with the amine, the polyisocyanate crosslinker b) and that amine cannot be premixed.
  • highly reactive is meant that more than 30% of the isocyanate or amine reacts with the isocyanate-reactive compound a) or the polyisocyanate crosslinker b), respectively, before the complementary amine or isocyanate, required for the polyurea synthesis, are mixed.
  • the polyurea product based sag control agent is prepared in the presence of isocyanate-reactive compound a). This can be done by mixing a mixture of the isocyanate-reactive compound a) and isocyanate with the amine, or by mixing the isocyanate with a mixture of the isocyanate-reactive compound a) and amine, or by mixing a mixture of isocyanate-reactive compound a) and amine with a mixture of isocyanate-reactive compound a) and isocyanate, or by mixing the isocyanate and the amine with the isocyanate-reactive compound a) simultaneously.
  • the preparation of the polyurea product based sag control agent may be carried out in any convenient manner, generally with the reactants being vigorously stirred, in a batch or in a continuous process. Amine components may be added to isocyanate or isocyanate may be added to amine components, whichever is most convenient. Alternatively the polyurea product based sag control agent can be formed in a separate reaction and mixed with the isocyanate-reactive compound a), usually under proper stirring.
  • the particle size of polyurea product is preferably less than 15 pm as determined by ISO 1524.
  • the at least one sag control agent is part of one or more components of the crosslinkable composition, which means that the at least one sag control agent is incorporated into one or more components of the crosslinkable composition such as for example the isocyanate-reactive compound a); nonetheless, the at least one sag control agent and the one or more components of the crosslinkable composition are considered separately when it comes to their weight percentages in the non-volatile compounds.
  • thermolatent metal-based catalyst is present in at least binder module i) and/or crosslinker module ii); and o in a preferred embodiment the carboxylic acid d) of binder module i) is a tertiary carboxylic acid d), o in another preferred embodiment binder module i) comprises sag control agents.
  • a kit of parts for preparing a coating composition comprises: i. a binder module comprising at least one isocyanate-reactive compound a), at least one carboxylic acid d), and optionally at least one sag control agent, ii.
  • binder module i) comprises sag control agents.
  • carboxylic acid d) is a tertiary carboxylic acid d
  • thermolatent metal-based catalyst c), and optionally one or more sag control agent may be distributed over modules i), ii), and/or iii);
  • the binder module comprises:
  • 0.05 to 12 % by weight preferably from 0.1 to 6 % by weight, more preferably from 0.2 to 3.0 % by weight, of aromatic carboxylic acid and/or tertiary carboxylic acid d); and optionally from 0.1 to 4 % by weight, preferably from 0.15 to 3.5 % by weight, more preferably from 0.2 to 3 % by weight, of at least one sag control agent, preferably a polyurea-based sag control agent; optionally from 0.001 to 10 % by weight, preferably from 0.002 to 5 % by weight, more preferably from 0.005 to 1 % by weight, of thermolatent metal-based catalyst c); wherein the total of a), d), water-free volatile organic solvent, optional c),and optional polyurea sag control agent is 100% by weight.
  • the isocyanate-reactive compound a) is provided to binder module i) either as a solution in water-free volatile organic solvent comprising carboxylic acid d), or as a solution in water-free volatile organic solvent comprising sag control agent, or as a solution in water-free volatile organic solvent comprising carboxylic acid d) and sag control agent.
  • the other components of the coating composition may be distributed in different ways over the modules as described above, as long as the modules exhibit the required storage stability.
  • Components of the coating composition which react with each other upon storage are preferably not combined in one module. If desired, the components of the coating composition may be distributed over even more modules, for example 4 or 5 modules.
  • the coating composition of the invention characterized by an extended potlife and accelerated film hardness build-up at low baking conditions, provides coatings with improved chemical resistance, film hardness and appearance.
  • the coating compositions of the invention can be applied to any substrate such as for example, metal, e.g., iron, steel, tinplate and aluminum, plastic, wood, glass, synthetic material, paper, leather, concrete or another coating layer, said another coating layer can be comprised of the coating composition of the present invention or it can be a different coating composition.
  • the coating compositions of the present invention show particular utility as clear coats, base coats, pigmented top coats, primers, and fillers.
  • the coating composition according to the invention is very suitable for use as a clear coat.
  • a clear coat is essentially free of pigments and is transparent for visible light.
  • the clear coat composition may comprise matting agents, for example silica based matting agents, to control the gloss level of the coating.
  • the coating composition according to the present invention was found to be particularly suitable for use in crosslinkable clear coat compositions used in coating processes using different coating layers wherein the number of bake curing steps is reduced compared to a standard multilayer coating process.
  • the coating processes with reduced number of bake curing steps are more economic with regard to paint and energy consumption compared to standard ways of application, in which usually a primer layer is applied on an electrodeposition coating, followed by a first bake curing step, and subsequent application of an aqueous basecoat layer, flash-off, application of a clear coat layer and second bake curing.
  • a process with reduced number of bake curing steps is often characterized in elimination of the primer layer as well as the first bake curing step.
  • a first aqueous colored layer is applied on a substrate such as a metal, optionally comprising an electrodeposition layer, followed by flash-off, application of an aqueous basecoat layer , another flash-off and application of a clear coat layer followed by one bake curing step for all layers simultaneously.
  • crosslinkable compositions according to the invention yielded coating compositions, more particularly clear coat compositions, with very good chemical resistance and hardness and good appearance in a coating process with reduced number of bake curing steps.
  • the coating composition of the current invention is also suitable as pigmented topcoat for coating objects such as bridges, pipelines, industrial plants or buildings, oil and gas installations, or ships.
  • the compositions are also suitable for finishing and refinishing automobiles and large transportation vehicles, such as trains, trucks, buses, and airplanes.
  • the coating composition of the current invention can be applied by spraying, brushing, draw-down or any other method to transfer a composition to a substrate.
  • the invention also relates to a method of providing a coating, preferably a coating for at least a part of a transportation vehicle, more preferably a coating for at least one part of the exterior surface of a transportation vehicle, wherein the method comprises the steps of applying a coating composition according to the invention to at least a part of a transportation vehicle, and curing the applied coating composition, preferably in a temperature range of 5 to 180° C, more preferably of 40 to 140° C, or most preferably of 60 to 120° C.
  • Paint formulations were prepared according to the compositions as listed in Table 1 and Table 2 wherein example 1 to 6 are according to the invention, comprising thermolatent tin-based catalyst and aromatic carboxylic acid (Ex. 1) or comprising thermolatent tin-based catalyst and tertiary carboxylic acid (Ex.2 to Ex.6).
  • Comparative examples 1 to 4 comprise a thermolatent tin-based catalyst in combination with a secondary carboxylic acid (Comp. Ex. 1) or with primary carboxylic acid (Comp. Ex. 2 and 3) or without carboxylic acid (Comp. Ex.4); while comparative example 5 comprises tertiary carboxylic acid and dibutyl tin dilaurate (being a non-thermolatent catalyst).
  • SETALUX® 61230 BA-60 is an acrylic polyol with 3.5 % OH, modified with a polyurea- based sag control agent.
  • SETALUX® 1232 is an acrylic polyol with 3.6% OH providing fast drying and good hardness.
  • SETAL® 1624 is a polyester polyol with 6.5 % OH providing good hardness.
  • SOLVESSOTM 100 is a mixture of aromatic solvents.
  • TINUVIN® 292 is a mixture of two active tertiary amine ingredients: bis(1 ,2, 3, 6, 6- pentramethyl-4- piperidyl)sebacate and methyl(1 ,2,2,6,6-pentamethyl-4- piperidyl)sebacate.
  • TINUVIN® 1130 is a benzotriazole-based UV absorber.
  • MODAFLOW® 9200 is a low-viscosity flow modifier available from allnex.
  • TOLONATETM HDT- LV is a solvent free low viscosity aliphatic polyisocyanate based on hexamethylene diisocyanate.
  • compositions according to the invention displayed much better coating properties compared to compositions not according to the invention.
  • Coating composition of Comparative Example 4 (comprising thermolatent tin-based catalyst but without tertiary carboxylic acid) had a potlife of more than 2.5 h, comparable to coating compositions of Example 4, 5 and 6, according to the invention, comprising thermolatent tin- based catalyst and tertiary carboxylic acid.
  • Coating compositions prepared according to the compositions listed in Table 2, were sprayed on a black waterborne basecoat and after a flash-off for 10 minutes at room temperature, dried for 30 minutes at 80 °C.
  • Coatings compositions were analyzed for potlife; the coatings were evaluated for Kbnig hardness, DOI and long wave. Coating composition potlife and coating properties of the coatings obtained from the coating compositions of table 2 are reported in table 4.
  • Persoz hardness and Konig hardness were measured in a climatized room at 23° C, and 55+/-5% relative humidity. Hardness was measured with a pendulum according to Persoz or Konig as described in ASTM D 4366 and ISO 1522-1973.
  • Pancreatin resistance was determined using a gradient oven test according to ISO 2812- 5:2018.
  • the coating compositions according to the present invention display longer potlife; the coatings obtained from the coating compositions of the present invention show an improved combination of properties more particularly an improved chemical resistance, higher hardness, and improved appearance compared to the prior art coating compositions.

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Abstract

La présente invention concerne une composition réticulable comprenant a) au moins un composé réactif à l'isocyanate, b) au moins un agent de réticulation polyisocyanate ayant des groupes isocyanate libres, c) au moins un catalyseur à base de métal thermolatent pour catalyser la réaction entre les groupes réactifs à l'isocyanate du composé réactif à l'isocyanate a) et les groupes isocyanate dudit agent de réticulation polyisocyanate b), d) au moins un acide carboxylique aromatique, et/ou au moins un acide carboxylique tertiaire. La présente invention concerne également une composition de revêtement comprenant ladite composition réticulable et un procédé d'application de ladite composition de revêtement.
PCT/EP2025/052835 2024-02-08 2025-02-04 Composition réticulable non aqueuse Pending WO2025168572A1 (fr)

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Citations (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3808162A (en) 1972-10-10 1974-04-30 Minnesota Mining & Mfg Preparation of urethanes and catalysts therefor
EP0435306A2 (fr) 1989-12-28 1991-07-03 Hoya Corporation Composé de polythiole et matière optique et produit fabriqué à partir de celui-ci
US5214086A (en) 1991-09-04 1993-05-25 Basf Corporation Coating compositions which may be ambient cured
EP0665219A1 (fr) 1994-01-26 1995-08-02 Mitsui Toatsu Chemicals, Incorporated Polythiol, procédé pour sa préparation, résine contenant du soufre à base d'uréthane préparée à partir du polythid, procédé de préparation de la résine, et lentille
US6486298B1 (en) 2000-12-22 2002-11-26 Essilor International Compagnie Generale D'optique Diepisulfide based prepolymers and their use in the optical field
WO2005019362A1 (fr) 2003-08-14 2005-03-03 Ppg Industries Ohio, Inc. Revetements urethane a delai maximal d'utilisation accru
WO2007020270A1 (fr) 2005-08-17 2007-02-22 Akzo Nobel Coatings International B.V. Composition de revetement comprenant un polyisocyanate et un polyol
WO2011051247A1 (fr) 2009-10-30 2011-05-05 Bayer Materialscience Ag Utilisation de catalyseurs à l'étain pour la production de revêtements en polyuréthane
US8207268B2 (en) 2005-06-28 2012-06-26 Nuplex Resins B.V. Polyurea product as thixotropic rheology modifying agent
WO2013131835A2 (fr) 2012-03-07 2013-09-12 Akzo Nobel Coatings International B.V. Composition de revêtement liquide non aqueux
EP2772496A1 (fr) 2013-02-28 2014-09-03 Bayer MaterialScience AG Synthèse directe d'alcoxydes d'étain (II) et (IV) à partir d'étain élémentaire et alcools en présence de réactifs d'activation
EP2900717A1 (fr) 2012-09-25 2015-08-05 Bayer Materialscience AG Produits de polyaddition de polyisocyanate
EP2900716A1 (fr) 2012-09-25 2015-08-05 Bayer Materialscience AG Produits de polyaddition de polyisocyanate
US20190106527A1 (en) * 2017-10-10 2019-04-11 Allnex Netherlands Bv Non-aqueous crosslinkable composition
WO2019072433A1 (fr) 2017-10-10 2019-04-18 Allnex Netherlands Bv Composition réticulable non aqueuse
US10815330B2 (en) 2016-04-22 2020-10-27 Covestro Deutschland Ag Thermolatently catalysed two-component system
WO2023161345A1 (fr) * 2022-02-28 2023-08-31 Covestro Deutschland Ag Utilisation de catalyseurs spécifiques pour la préparation de revêtements de polyuréthane

Patent Citations (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3808162A (en) 1972-10-10 1974-04-30 Minnesota Mining & Mfg Preparation of urethanes and catalysts therefor
EP0435306A2 (fr) 1989-12-28 1991-07-03 Hoya Corporation Composé de polythiole et matière optique et produit fabriqué à partir de celui-ci
US5214086A (en) 1991-09-04 1993-05-25 Basf Corporation Coating compositions which may be ambient cured
EP0665219A1 (fr) 1994-01-26 1995-08-02 Mitsui Toatsu Chemicals, Incorporated Polythiol, procédé pour sa préparation, résine contenant du soufre à base d'uréthane préparée à partir du polythid, procédé de préparation de la résine, et lentille
US6486298B1 (en) 2000-12-22 2002-11-26 Essilor International Compagnie Generale D'optique Diepisulfide based prepolymers and their use in the optical field
WO2005019362A1 (fr) 2003-08-14 2005-03-03 Ppg Industries Ohio, Inc. Revetements urethane a delai maximal d'utilisation accru
US8207268B2 (en) 2005-06-28 2012-06-26 Nuplex Resins B.V. Polyurea product as thixotropic rheology modifying agent
WO2007020270A1 (fr) 2005-08-17 2007-02-22 Akzo Nobel Coatings International B.V. Composition de revetement comprenant un polyisocyanate et un polyol
WO2011051247A1 (fr) 2009-10-30 2011-05-05 Bayer Materialscience Ag Utilisation de catalyseurs à l'étain pour la production de revêtements en polyuréthane
WO2013131835A2 (fr) 2012-03-07 2013-09-12 Akzo Nobel Coatings International B.V. Composition de revêtement liquide non aqueux
EP2900717A1 (fr) 2012-09-25 2015-08-05 Bayer Materialscience AG Produits de polyaddition de polyisocyanate
EP2900716A1 (fr) 2012-09-25 2015-08-05 Bayer Materialscience AG Produits de polyaddition de polyisocyanate
US20150240024A1 (en) * 2012-09-25 2015-08-27 Bayer Materialscience Ag Polyisocyanate-polyaddition productions
EP2772496A1 (fr) 2013-02-28 2014-09-03 Bayer MaterialScience AG Synthèse directe d'alcoxydes d'étain (II) et (IV) à partir d'étain élémentaire et alcools en présence de réactifs d'activation
US10815330B2 (en) 2016-04-22 2020-10-27 Covestro Deutschland Ag Thermolatently catalysed two-component system
US20190106527A1 (en) * 2017-10-10 2019-04-11 Allnex Netherlands Bv Non-aqueous crosslinkable composition
WO2019072433A1 (fr) 2017-10-10 2019-04-18 Allnex Netherlands Bv Composition réticulable non aqueuse
WO2023161345A1 (fr) * 2022-02-28 2023-08-31 Covestro Deutschland Ag Utilisation de catalyseurs spécifiques pour la préparation de revêtements de polyuréthane

Non-Patent Citations (5)

* Cited by examiner, † Cited by third party
Title
CHEM. HETEROCYCL. COMP, vol. 43, 2007, pages 813 - 834
INDIAN J. CHEM, vol. 5, 1967, pages 643 - 645
J. ORGANOMET. CHEM., vol. 694, 2009, pages 3184 - 3189
no. 1622456-43-2
YOKOYAMA T ET AL: "The Effects of Heat Treatment on Dissipation Factors of Silicone Rubber", IEEE TRANSACTIONS ON ELECTRICAL INSULATION, IEEE, US, vol. EI-1, no. 5, October 1980 (1980-10-01), pages 373 - 381, XP011162458, ISSN: 0018-9367 *

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