EP3927758A1 - Nouveaux systèmes de revêtement transparent à deux composants contenant des esters de poly(acide aspartique) - Google Patents

Nouveaux systèmes de revêtement transparent à deux composants contenant des esters de poly(acide aspartique)

Info

Publication number
EP3927758A1
EP3927758A1 EP20705079.0A EP20705079A EP3927758A1 EP 3927758 A1 EP3927758 A1 EP 3927758A1 EP 20705079 A EP20705079 A EP 20705079A EP 3927758 A1 EP3927758 A1 EP 3927758A1
Authority
EP
European Patent Office
Prior art keywords
component
coating
polyaspartic acid
general formula
compounds
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
EP20705079.0A
Other languages
German (de)
English (en)
Inventor
Dorota Greszta-Franz
Jan Weikard
Holger Mundstock
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Covestro Deutschland AG
Original Assignee
Covestro Deutschland AG
Covestro Intellectual Property GmbH and Co KG
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 EP19158880.5A external-priority patent/EP3699219A1/fr
Priority claimed from EP20157828.3A external-priority patent/EP3868805A1/fr
Application filed by Covestro Deutschland AG, Covestro Intellectual Property GmbH and Co KG filed Critical Covestro Deutschland AG
Publication of EP3927758A1 publication Critical patent/EP3927758A1/fr
Pending legal-status Critical Current

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
    • C09D175/12—Polyurethanes from compounds containing nitrogen and active hydrogen, the nitrogen atom not being part of an isocyanate group
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/38—Low-molecular-weight compounds having heteroatoms other than oxygen
    • C08G18/3819—Low-molecular-weight compounds having heteroatoms other than oxygen having nitrogen
    • C08G18/3821—Carboxylic acids; Esters thereof with monohydroxyl 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
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/73—Polyisocyanates or polyisothiocyanates acyclic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
    • C08G18/78—Nitrogen
    • C08G18/79—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates
    • C08G18/791—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups
    • C08G18/792—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups formed by oligomerisation of aliphatic and/or cycloaliphatic isocyanates or isothiocyanates
    • C—CHEMISTRY; METALLURGY
    • 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
    • C09D175/02—Polyureas
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • 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
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/63—Additives non-macromolecular organic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59

Definitions

  • the present invention relates to two-component clearcoat systems containing
  • Polyaspartic acid esters with primary amino groups and small amounts of fumaric acid dialkyl ester a process for their production and their use for the production of coatings for vehicle repair applications and substrates coated therewith.
  • Two-component (2K) coating compositions which contain a polyisocyanate component as a binder in combination with a reactive component which is reactive toward isocyanate groups, in particular a polyhydroxyl component, have been known for a long time. They are suitable for the production of high-quality coatings that can be made hard, elastic, abrasion and solvent-resistant and, above all, weather-resistant.
  • EP0470461 describes a coating for vehicle repair applications which contains a polyisocyanate component and an isocyanate-reactive secondary diamine prepared from 3,3'-dimethyl-4,4'-diaminodicyclohexylmethane and maleic acid diethyl ester.
  • the isocyanate-reactive component also contains a hydroxyl-functional component of polyhydroxypolyacrylates or mixtures of polyhydroxypolyacrylates and polyester polyols.
  • WO2015130501 and WO2015130502 disclose polyaspartic acid ester compositions which have between 15 and 30% aspartic acid ester with primary amino groups (measured as area% in the gas chromatogram). In both documents, however, no advantage is recognized due to an increased content of aspartic acid ester with primary amino groups and polyaspartic acid ester compositions with an acceptable pot life could only be achieved by a further reaction with preferably cycloaliphatic polyisocyanates. It should be borne in mind that the coating agents produced in this way, due to the conventional
  • maleic acid ester is used as the vinylogous carbonyl compound.
  • a retro-Michael addition can take place as a further undesired side reaction in which dialkyl fumarate is formed by elimination of the polyamine as a secondary component.
  • a typical production process for a polyaspartic acid ester therefore requires a storage time of 4-6 weeks after most of the starting materials have reacted with one another. During this time, the so-called ripening of the product takes place, which manifests itself through stabilization of the viscosity.
  • dialkyl fumarate Because the conversion continues to rise within this time, the content of dialkyl fumarate also falls. This storage over several weeks leads to considerable logistics costs within production. Although the product is only delivered to the customer after storage, it still contains substantial amounts of dialkyl fumarate, which can cause severe sensitization. Diethyl fumarate, for example, is classified as VOC (volatile organic compounds) and thus prevents the provision of VOC-free coatings. Another disadvantage caused by the presence of dialkyl fumarate is the lowering of the glass transition temperature of a paint film due to its plasticizing effect.
  • reaction time can be extended or the reaction temperature can be increased.
  • the former is ruled out for economic reasons.
  • EP0816326 discloses a process for accelerating the addition of the polyamine to dialkyl maleate or for reducing the dialkyl fumarate by adding a special catalyst. Since, despite the use of a catalyst, the necessity of storage cannot be avoided, this approach does not lead to a finally satisfactory result.
  • EP1197507 describes the addition of thiol compounds as scavengers for dialkyl fumarate. Since the thiol compounds are known to cause considerable odor nuisance, this solution cannot be implemented in practice either. A theoretical possibility of working up by distillation is mentioned, for example, in EP0403921. It is a distillative removal of dialkyl fumarate within a process in which an excess of dialkyl maleate is used.
  • DE 102006002153 likewise describes a product which is produced using an excess of dialkyl maleate and subsequent removal of dialkyl fumarate by distillation. It is a diaspartic acid ester that is free from primary amino groups.
  • WO2018 / 074884 which had not yet been published at the time of the application for a patent, also describes the distillation of polyaspartic acid esters and, more generally, their use in coating compositions. Clear lacquers that necessarily contain water scavengers and / or hydrolysis inhibitors are not described.
  • the coating compositions based on polyaspartic acid esters disclosed in the prior art have fast curing times with a sufficient pot life and are distinguished by good mechanical and optical properties.
  • coating compositions tend to have deficiencies in the adhesion and interlayer adhesion in a multilayer structure. In vehicle repair practice, this sensitivity to moisture requires longer storage times for the painted parts before they can be installed on a vehicle.
  • the object of the present invention is thus to provide a coating composition based on polyaspartic acid ester with a balanced drying performance, i. with fast curing times with a sufficient pot life, which also leads to coatings with improved water resistance.
  • the object of the present invention could be achieved by providing two-component coating compositions (2K coating agents) containing polypartic acid esters with primary amino groups and small amounts of dialkyl fumarate.
  • the present invention relates to two-component
  • components A containing polyaspartic acid esters are compositions containing one or more polyaspartic acid esters of the general formula (I)
  • X represents an m-valent organic radical, optionally containing one or more heteroatoms, as obtained by removing the primary amino groups from a corresponding polyamine having (cyclo) aliphatically or araliphatically bound primary amino groups and having a molecular weight range of 60 to 6000 g / mol can, and the further, isocyanate-reactive and / or at temperatures up to 100 ° C inert functional groups can contain,
  • n stands for m-1
  • X, radicals RI and R2 have the abovementioned meanings, characterized in that the proportion of the compounds of the general formula (II) corresponds to> 4% to ⁇ 20% of the GC surface (measured as% area in the gas chromatogram), the Sum of the GC surface areas of the compounds of the two general formulas (I) and (II) is 100% and in component A dialkyl fumarate is present in amounts of> 0.01 to ⁇ 1.2% by weight, based on the total weight of component A.
  • compositions containing one or more polyaspartic acid esters are preferred, compositions containing one or more polyaspartic acid esters of the general formulas (I) and (II) in which RI and R2 represent identical or different alkyl radicals each having 1 to 18 carbon atoms, preferably identical or different alkyl radicals each having 1 to 8 Carbon atoms and very particularly preferably each alkyl radicals such as methyl, ethyl, propyl, iso-propyl, butyl or iso-butyl radicals. Most preferred is ethyl.
  • Polyaspartic acid ester-containing components A are compositions containing one or more polyaspartic acid esters of the general formulas (I) and (II), in which X stands for organic radicals obtained by removing the primary amino groups from a corresponding, (cyclo) aliphatically or araliphatically bound primary Polyamine containing amino groups are obtained, selected from the following group: all known polyamines with primary amino groups which correspond to the general formula (III).
  • ethylenediamine 1,2-diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane, 2,5-diamino-2,5-dimethylhexane, 1,5-diamino-2-methylpentane (Dytek ®A, DuPont), 1,6-diaminohexane, 2,2,4- and / or 2,4,4-trimethyl-l, 6-diaminohexane, 1,11-diaminoundecane, 1,2-diaminododecane or triaminononane, Etheramines, such as, for example, 4,9-dioxadodecane-1, 12-diamines, 4,7,10-trioxatridecane-1,13 -diamines, or higher molecular weight polyether polyamines with aliphatically bonded primary amino groups, such as those used, for example
  • Aliphatic polycyclic polyamines such as tricydodecane dismethylamine (TCD diamine) or bis (aminomethyl) norbornane, amino-functional siloxanes, for example diaminopropylsiloxane G10 DAS, can also be used (From Momentive), fatty alkyl-based amines, such as, for example, Fentamine from Solvay, dimer fatty acid diamines such as, for example, Priamine from Croda.
  • TCD diamine tricydodecane dismethylamine
  • amino-functional siloxanes for example diaminopropylsiloxane G10 DAS
  • fatty alkyl-based amines such as, for example, Fentamine from Solvay
  • dimer fatty acid diamines such as, for example, Priamine from Croda.
  • compositions containing one or more polyaspartic acid esters of the general formulas (I) and (II) in which X stands for organic radicals obtained by removing the primary amino groups from one of the polyamines of the general formula (III), where m 2 and X is a cyclic hydrocarbon radical having at least one cyclic carbon ring.
  • polyaspartic acid ester-containing components A compositions containing one or more polyaspartic acid esters of the general formulas (I) and (II) in which X stands for organic radicals obtained by removing the primary amino groups from one of the polyamines of the general formula (III) , selected from the group: polyether polyamines with aliphatically bonded primary amino groups, 1,2 diaminopropane, 1,4-diaminobutane, 1,6-diaminohexane, 1,5-diamino-2-methylpentane, 2,5-diamino-2,5-dimethylhexane , 2,2,4- and / or 2,4,4-trimethyl-1,6-diaminohexane, 1,11-diaminounodecane, 1,12-diaminododecane, l-amino-3,3,5-trimethyl-5- aminomethylcyclohexane, 2,4- and / /
  • Components A containing polyaspartic acid esters are particularly preferred.
  • Components A containing polyaspartic acid esters are very particularly preferred.
  • Index m stands for an integer> 1 and preferably for 2.
  • X stands for an m-valent organic radical, optionally containing one or more heteroatoms, as obtained by removing primary amino groups from polyether polyamines with aliphatically bound primary amino groups, 1,2 diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane, 1 , 6-diaminohexane, 1,5-diamino-2-methylpentane, 2,5 diamino-2,5-dimethylhexane, 2,2,4- and / or 2,4,4-trimethyl-1,6-diaminohexane, 1 , 11-diaminounodecane, 1,12-diaminododecane, 1-amino-3,3,5-trimethyl-5-aminomethylcyclohexane, 2,4- and / or 2,6-hexahydrotoluylenediamine, 2,4'- and / or 4, 4'-diamino dicyclo
  • RI and R2 stand for identical or different alkyl radicals each with 1 to 8 carbon atoms
  • n stands for m-1
  • X, radicals RI and R2 have the meanings given above, characterized in that the proportion of the compounds of the general formula (II) corresponds to> 4 to ⁇ 20% of the GC surface (measured as area% in the gas chromatogram), the sum being the GC surface area of the compounds of the two general formulas (I) and (II) is 100% and in component A dialkyl fumarate is present in amounts of> 0.01 to ⁇ 1.2% by weight, based on the total weight of component A .
  • compositions containing one or more polyaspartic acid esters are very particularly preferred.
  • X stands for an m-valent organic radical, as it is obtained by removing primary amino groups from 3,3‘-dimethyl
  • Diaminodicyclohexylmethane, l, 5-diamino-2-methylpentane can be obtained,
  • RI and R2 for identical or different alkyl radicals selected from the group
  • n stands for m-1
  • X, radicals RI and R2 have the meanings given above, characterized in that the proportion of the compounds of the general formula (II) corresponds to> 4% to ⁇ 20% of the GC surface (measured as area% in the gas chromatogram), the sum of the GC surfaces of the compounds of the two general formulas (I ) and (II) is 100% and in component A dialkyl fumarate is present in amounts of> 0.01 to ⁇ 1% by weight, based on the total weight of component A.
  • X stands for an m-valent organic radical such as can be obtained by removing primary amino groups from 3,3'-dimethyl-4,4'diamino-dicyclohexylmethane, 2,4'- and / or 4,4'-diaminodicyclohexylmethane ,
  • RI and R2 stand for ethyl residues
  • n stands for m-1
  • X, radicals RI and R2 have the meanings given above, characterized in that the proportion of the compounds of the general formula (II) corresponds to> 5 to ⁇ 20% of the GC surface area (measured as area% in the gas chromatogram), the sum being the GC surface area of the compounds of the two general formulas (I) and (II) is 100% and in component A dialkyl fumarate is present in amounts of> 0.01 to ⁇ 0.1% by weight, based on the total weight of component A. .
  • Components A containing polyaspartic acid esters are preferred.
  • the platinum-cobalt color number is measured in accordance with DIN EN ISO 6271: 2016-05.
  • Components A containing polyaspartic acid ester, as described above, can be produced by the following process: Implementation of polyamines of the general formula (III),
  • m represents an m-valent organic radical, optionally containing one or more heteroatoms, as can be obtained by removing the primary amino groups from a polyamine having (cyclo) aliphatically or araliphatically bonded primary amino groups and having a molecular weight range of 60 to 6000 g / mol, and which can contain further functional groups which are reactive towards isocyanate groups and / or which are inert at temperatures up to 100 ° C., m is an integer> 1, preferably 2, with compounds of the general formula (IV)
  • each alkyl radical preferably for identical or different organic radicals, preferably for identical or different alkyl radicals with 1 to 18 carbon atoms each, particularly preferably for identical or different alkyl radicals with 1 to 8 carbon atoms each, very particularly preferably for each alkyl radicals such as methyl, ethyl, propyl, iso-propyl, butyl or iso-butyl radicals, and most preferably ethyl, and removal of the unreacted portion of the compound of the general formula (IV) by distillation.
  • the process described above for preparing the components A containing polyaspartate is preferably carried out in two steps.
  • the unreacted portion of the compounds of the general formula (IV) is removed by distillation.
  • Suitable conditions during the distillation are a pressure range between 0.01 and 2 mbar and a temperature of the bottom outlet at the outlet from the distillation apparatus is ⁇ 170 ° C and> the temperature that results from the following formula (V):
  • T (sump discharge) 27 x In (p) + 150 (V) where T (sump discharge) is the temperature of the sump discharge in ° C and
  • Maintaining this pressure range ensures that, on the one hand, moderate temperatures in the bottom outlet are sufficient to deplete the dialkyl fumarate to the desired extent and, on the other hand, the process can still be used on an industrial scale. If the pressure is lower, the gas density becomes too low and the equipment required is therefore so large that the process is disadvantageous from an economic point of view.
  • the temperature of the bottom outflow is preferably ⁇ 170 ° C., but at least 20 K above the temperature resulting from the formula (V), particularly preferably it is between 20 K and 40 K above the temperature resulting from the formula ( V) does not give above 170 ° C.
  • aliphatic polycyclic polyamines such as tricyclodecane dismethylamine (TCD diamine) or bis (aminomethyl) norbornane, amino-functional siloxanes, for example diaminopropylsiloxane G10 DAS (from Momentive), fatty alkyl-based amines such as, for example, fentamines from Solvay, dimer fatty acid diamines such as, for example, Priamine from Croda.
  • TCD diamine tricyclodecane dismethylamine
  • amino-functional siloxanes for example diaminopropylsiloxane G10 DAS (from Momentive
  • fatty alkyl-based amines such as, for example, fentamines from Solvay
  • dimer fatty acid diamines such as, for example, Priamine from Croda.
  • polyamines of the general formula (III) in which m 2 and X is a cyclic hydrocarbon radical having at least one cyclic carbon
  • AMCA Aminomethyl-1-methylcyclohexylamine
  • araliphatic diamines e.g. 1,3-bis (aminomethyl) benzene or m-xylylenediamine.
  • Polyamines of the general formula (III) are also preferably used in the process according to the invention, selected from the group: polyether polyamines with aliphatically bound primary amino groups, 1,2 diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane, 1,6-diaminohexane, 1,5-diamino-2-methylpentane, 2,5 diamino-2,5-dimethylhexane, 2,2,4- and / or
  • 3,3'-dimethyl-4,4'-diamino-dicyclohexylmethane, 2,4'- and / or 4,4'-diaminodicyclohexylmethane, 1,5-diamino-2-methylpentane are particularly preferred and their use is very particularly preferred of 2,4- and / or 4,4'-diaminodicyclohexyl methane.
  • Polyamines of the general formula (III) are particularly preferably used in the process according to the invention, selected from the group: Polyether polyamines with aliphatically bound primary amino groups, 1,2 diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane, 1,6-diaminohexane, 1,5-diamino-2-methylpentane, 2,5 diamino-2,5-dimethylhexane, 2,2,4- and / or
  • Polyamines of the general formula (III) are very particularly preferably used in the process according to the invention, selected from the group 3,3'-dimethyl-4,4'diaminodicyclohexylmethane, 2,4'- and / or 4,4'-diaminodicyclohexylmethane, l, 5-diamino-2-methylpentane.
  • Preferred compounds of the general formula (IV) which are used in the process described above are maleic or fumaric acid esters of the general formula (IV) in which RI and R2 are identical or different organic radicals each having 1 to 18 carbon atoms.
  • RI and R2 are preferably, independently of one another, linear or branched alkyl radicals having 1 to 8 carbon atoms, particularly preferably in each case alkyl radicals such as methyl, ethyl, propyl, isopropyl, butyl or isobutyl radicals and very particularly preferred for ethyl.
  • maleic acid dimethyl ester diethyl ester, di-n or isopropyl ester, di-n-butyl ester, di-2-ethyl-hexyl ester or the corresponding fumaric acid ester.
  • Maleic acid diethyl ester is very particularly preferred.
  • the two-component coating compositions according to the invention contain at least one polyisocyanate component B.
  • Suitable polyisocyanate components B are organic polyisocyanates with an average NCO functionality of at least 2 and a molecular weight of at least 140 g / mol.
  • Unmodified organic polyisocyanates with a molecular weight of 140 to 300 g / mol, paint polyisocyanates with a molecular weight in the range of 300 to 1000 g / mol, and NCO prepolymers containing more than 400 g / mol of urethane, urea and / or allophanate groups are particularly suitable. mol lying molecular weight or mixtures thereof.
  • the term “paint polyisocyanates” is to be understood as meaning compounds or mixtures of compounds which can be obtained from simple polyisocyanates by known oligomerization reactions. Suitable oligomerization reactions are e.g. carbodiimidization, dimerization, trimerization, biuretization, urea formation, urethanization, allophanatization and / or cyclization with the formation of oxadiazine structures. In the case of oligomerization, several of the reactions mentioned can take place simultaneously or in succession.
  • the "paint polyisocyanates” are preferably biuret polyisocyanates, isocyanurate group-containing polyisocyanates, isocyanurate and uretdione group-containing polyisocyanate mixtures, urethane and / or allophanate group-containing polyisocyanates or isocyanurate and allophanate group-containing polyisocyanates based on simple organic isocyanate groups.
  • polyisocyanate component B is also suitable as polyisocyanate component B are the isocyanate group-containing prepolymers based on simple organic polyisocyanates and / or based on paint polyisocyanates on the one hand and organic polyhydroxy compounds with a molecular weight of over 300 g / mol on the other.
  • paint polyisocyanates containing urethane groups are derivatives of low molecular weight polyols in the molecular weight range from 62 to 300 g / mol
  • suitable polyols are, for example, ethylene glycol, propylene glycol, trimethylolpropane, glycerol or mixtures of these alcohols
  • polyhydroxy compounds of one over 300 g / mol, preferably over 400 g / mol, particularly preferably one are used to prepare the prepolymers containing isocyanate groups between 400 and 8000 g / mol molecular weight is used.
  • Such polyhydroxyl compounds are in particular those which have 2 to 6, preferably 2 to 3, hydroxyl groups per molecule and are selected from the group consisting of ether, ester, thioether, carbonate and polyacrylate polyols and mixtures of such polyols.
  • the higher molecular weight polyols mentioned can also be used in mixtures with the lower molecular weight polyols mentioned, so that mixtures of low molecular weight, urethane group containing paint polyisocyanates and higher molecular weight NCO prepolymers, which are also suitable as inventive polyisocyanate component b) result directly .
  • Suitable simple organic polyisocyanates are 1,4-diisocyanatobutane, 1,5-diisocyanatopentane, 1,6-diisocyanatohexane (HDI), 1,5-diisocyanato-2,2-dimethylpentane, 2,2,4- and 2, 4,4-trimethyl-1,6-diisocyanatohexane, tetramethylxylylene diisocyanate (TMXDI) 1- isocyanato-3,3,5-trimethyl-5-isocyanatomethylcyclohexane (isophorone diisocyanate, IPDI), 1- isocyanato-l-methyl-4- (3) -isocyanatomethylcyclohexane, dicyclohexylmethane-2,4'- and / or 4,4'-diisocyanate, 1,10-diisocyanatodecane, 1,12-diisocyanatododecane, cycl
  • the two-component composition according to the invention can contain further components which are reactive toward isocyanate groups (components C).
  • This can be, for example, low molecular weight polyols in the molecular weight range from 62 to 300 g / mol, for example ethylene glycol, propylene glycol, trimethylolpropane, glycerol or mixtures of these alcohols, or polyhydroxy compounds one over 300 g / mol, preferably over 400 g / mol, particularly preferably one between 400 and 20000 g / mol loved
  • Such polyhydroxyl compounds are in particular those which have 2 to 6, preferably 2 to 3, hydroxyl groups per molecule and are selected from the group consisting of ether, ester, thioether, polyurethane, carbonate and polyacrylate polyols and mixtures of such polyols.
  • the two-component composition according to the invention contains at least one water scavenger and / or a hydrolysis protection agent (component Dl).
  • hydrolysis protective agents e.g. Carbodiimides into consideration.
  • composition according to the invention can contain further auxiliaries and additives typical for coating technology with polyisocyanate polyaddition compounds, in particular for polyurethane compounds (component D2).
  • auxiliaries and additives typical for coating technology with polyisocyanate polyaddition compounds, in particular for polyurethane compounds (component D2).
  • catalysts / activators such as, for example, titanium, zirconium, bismuth, tin and / or iron-containing catalysts, as described, for example, in WO 05058996. It is also possible to add amines or amidines.
  • auxiliaries and additives D2 are in particular light stabilizers such as UV absorbers and sterically hindered amines (HALS), furthermore stabilizers, defoaming agents, anti-cratering agents and / or wetting agents, leveling agents, film-forming auxiliaries, reactive thinners, biocides, solvents or substances Rheology control,
  • light stabilizers such as UV absorbers and sterically hindered amines (HALS)
  • HALS sterically hindered amines
  • light stabilizers in particular UV absorbers, such as substituted benzotriazoles, S-phenyltriazines or oxalanilides and sterically hindered amines, in particular with 2,2,6,6-tetramethylpiperidyl structures - referred to as HALS - is described by way of example in A. Valet , Light stabilizers for paints, Vincentz Verlag, Hanover, 1996.
  • Stabilizers such as radical scavengers and other polymerization inhibitors such as sterically hindered phenols stabilize paint components during storage and are intended to prevent discoloration during curing.
  • Wetting and leveling agents improve surface wetting and / or the flow of paints. Examples are fluorosurfactants, silicone surfactants and special polyacrylates.
  • Rheology-controlling additives are important for controlling the properties of the two-component system during application and in the flow phase on the substrate and are known, for example, from the patent specifications WO 9422968, EP0276501, EP0249201 or WO 9712945.
  • the composition can contain solvents.
  • the solvent can be an organic solvent or a mixture of organic solvents or water or a mixture of organic solvent (s) and water.
  • Suitable solvents are to be used in a manner known to Lachmann, tailored to the composition and the application method. Solvents should dissolve the components used and promote their mixing and avoid incompatibilities. Furthermore, during application and curing, they should leave the coating in accordance with the crosslinking reaction taking place, so that a solvent-free coating with the best possible appearance and without voids such as pits or pinholes is created. Solvents that are used in two-component technology are particularly suitable.
  • organic solvents examples include ketones such as acetone, methyl ethyl ketone or hexanone, esters such as ethyl acetate, butyl acetate, methoxyproyl acetate, substituted glycols and other ethers, aromatics such as xylene or solvent naphtha such as La. Exxon chemistry and mixtures of the solvents mentioned. If the NCO-reactive part of the composition is in the form of an aqueous dispersion, water is also suitable as a solvent or diluent.
  • the ratio of the polyisocyanate component B to the polyaspartic acid ester-containing component A in the composition, based on the amounts of moles of the polyisocyanate groups to the NCO-reactive groups, is preferably from 0.5 to 1.0 to 3.0 to 1.0.
  • a ratio of 0.9 to 1.0 to 1.5 to 1.0 is particularly preferred.
  • a ratio of 1.05 to 1.0 to 1.25 to 1.0 is very particularly preferred.
  • the two-component composition according to the invention is preferably not a foamable or foam-forming composition.
  • the composition is preferably not radically polymerizable, especially not photo-polymerizable, i. the composition does not harden through radical processes, in particular not through radical polymerization processes which are initiated by actinic radiation.
  • the two-component coating composition according to the invention is produced by methods known per se in lacquer technology.
  • An isocyanate-reactive (R) and an isocyanate-containing component (H) are first prepared separately by mixing the respective isocyanate-reactive components A and C, or by mixing the respective polyisocyanate components B.
  • the auxiliaries and additives D1 and D2 are preferably added to the isocyanate-reactive component R.
  • the components R and H produced in this way are only mixed immediately before or during application. If mixing takes place before application, it must be ensured that the reaction of the components starts after mixing. Depending on the choice of components and additives, the reaction will take place at different speeds.
  • the processing time within which the composition must be applied also known as the pot life and defined as the time from mixing the components to doubling the flow time, is then, depending on the selection of the components, in the range from 1 minute to 24 hours, usually in the range from 10 minutes to 8 hours.
  • the pot life is determined by methods known to those skilled in the art.
  • the invention also relates to a method for producing a coating on a substrate which comprises at least the following steps:
  • Coating composition on at least a portion of a substrate to be coated and
  • the substrates can already be completely or partially coated with one or more layers of lacquer. These lacquer layers can still be uncured or moist, partially cured or fully cured, and the further lacquer layers on the substrate are preferably partially or fully cured.
  • lacquer layers are primers, primers, fillers, fillers, base lacquers or substrates that have already been completely lacquered, which are coated again after any pretreatment such as sanding or plasma activation.
  • substrates such as those used in refinishing or painting in the context of renovations or maintenance, e.g. occur in vehicles, in particular in ships, aircraft, motor vehicles such as cars, trucks, buses, large vehicles, rail vehicles.
  • preferred objects of the present invention are therefore the use of the above-described two-component coating compositions for the production of clear lacquers on substrates, in particular those that occur in refinishing or painting in the context of renovations or maintenance, especially in the case of vehicles, the method described above for Coating these special substrates, as well as the coated substrates themselves obtainable in this way.
  • the coating composition can be applied by conventional application methods. Examples of application methods are brushing, roller application, knife coating, dipping and spraying, with spray application being preferred. After an optional flash-off time, the application is followed by curing or drying of the composition according to the invention on the substrate or object. This takes place according to the methods customary in coating technology either under ambient conditions with regard to temperature and humidity or under forced conditions, for example by increasing the temperature in ovens, using radiation such as infrared, near-infrared or microwave radiation, and using dehumidified and / or heated air or others Gases. It is preferable to forego the use of devices for forced curing.
  • the applied coating composition is cured, for example, at temperatures from -20 to 100 ° C, preferably from -10 to 80 ° C, more preferably from 0 to 60 ° C and most preferably from 10 to 40 ° C. Although not preferred, lower cure temperatures can also be used but will result in longer cure times. It is also possible, although not preferred, to cure the composition at higher temperatures, for example 80 to 160 ° C. or higher.
  • a further coating layer can be applied and likewise cured.
  • Another object of the invention is the use of the two-component coating composition according to the invention for producing water-resistant coatings.
  • PACM 20 a mixture of 2,4 and 4,4'-diaminodicyclohexyl methane, manufactured by Evonik
  • Desmodur N 3900 a low-viscosity HDI trimer with approx. 23.5% NCO, manufacturer Covestro Byk 331: polyether modified polydimethylsiloxane surface additive, manufacturer BYK
  • Tinuvin 384-2 benzene propanoic acid, 3- (2H-benztriazol-2-yl) -5- (l, l-dimethylethyl) -4-hydroxy-, C7-9-branched and linear alkyl ester, a spruce stabilizer from BASF
  • Substrate Coil coat coated test panels, gray, supplier: Heinz Zanders für-Blech-Fogiding in Solingen
  • the diethyl fumarate contents were determined quantitatively with the aid of a GC method with an internal standard.
  • a 6890 gas chromatograph from Agilent with a standard GC capillary (100% polysiloxane phase) and an FID detector was used.
  • the temperature of the injector (split outlet) was 180 ° C., and helium was used as the carrier gas.
  • the limit of quantification for this method was 300 ppm.
  • GC-MS measurements were made with a 6890 gas chromatograph and mass spectrum detector 5973 from Agilent with standard ionization (electron impact) with 70 eV, a standard GC capillary (100% polysiloxane phase) and split injection at 250.degree Injector temperature carried out. The% areas of the gas chromatogram were evaluated.
  • the Hazen color numbers were determined on a FICO 400 color measuring device from Hach Fange GmbH, Düsseldorf, in accordance with DIN EN ISO 6271: 2016-05.
  • Coating structure the substrate was coated with a basecoat Permahyd series 280, deep black, (supplier: Spies Hecker GmbH in Cologne) using an air pressure spraying process with a Sata Jet RP, nozzle 1.3 mm / 2.1 bar) and dried for 20 minutes at room temperature, (Dry film thickness 15 ⁇ m).
  • 2K clear coats were made by mixing Components A and B are applied to the precoated substrate immediately before application by stirring for 15 seconds with a wooden spatula and by air pressure spraying with a Sata Jet RP, 1.3 mm / 2.1 bar nozzle. Drying took place at room temperature (24 ° C./30% relative humidity) for 7 days. Brilliant, high-gloss coatings with a layer thickness of 50-60 ⁇ m were obtained.
  • the comparative coating from example 3 showed bubbles in the condensation water test after 96 hours, while the coating according to the invention from example 4 did not show the first bubble formation until after 240 hours.
  • Coatings are considered to be water-resistant or water-stable if the condensation test (according to DIN EN ISO 6270-2: 2017) does not result in any change in the coating even after 100 hours, preferably also after 150 hours, very particularly preferably also after 200 hours (evaluation according to DIN EN ISO 4628-2: 2016). Table 3. Technical properties of coatings

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

Abstract

La présente invention concerne des systèmes de revêtement transparent à deux composants contenant des esters de poly(acide aspartique) comportant des groupes amino primaires, ainsi que de faibles quantités de dialkylester d'acide fumarique. L'invention concerne en outre un procédé de préparation de ces systèmes de revêtement transparent et leur utilisation pour la production de revêtements destinés à des applications dans le domaine de la réparation automobile ainsi que des substrats ainsi revêtus.
EP20705079.0A 2019-02-22 2020-02-20 Nouveaux systèmes de revêtement transparent à deux composants contenant des esters de poly(acide aspartique) Pending EP3927758A1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
EP19158880.5A EP3699219A1 (fr) 2019-02-22 2019-02-22 Nouveaux systèmes de revêtement transparent à deux composants contenant un ester d'acide polyaspartique
EP20157828.3A EP3868805A1 (fr) 2020-02-18 2020-02-18 Nouveaux systèmes de laque transparent à deux composants contenant des esters d'acide polyaspartique
PCT/EP2020/054418 WO2020169700A1 (fr) 2019-02-22 2020-02-20 Nouveaux systèmes de revêtement transparent à deux composants contenant des esters de poly(acide aspartique)

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EP (1) EP3927758A1 (fr)
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EP4137524A1 (fr) 2021-08-17 2023-02-22 Covestro Deutschland AG Nouveaux systèmes de revêtement à deux composants contenant des esters d'acide polyasparagique

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US20220098437A1 (en) 2022-03-31
CN113412295B (zh) 2023-08-25

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