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
  • C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
  • C09D133/04—Homopolymers or copolymers of esters
  • C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
• • 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
  • C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
  • C09D4/06—Organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond in combination with a macromolecular compound other than an unsaturated polymer of groups C09D159/00 - C09D187/00
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
  • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
  • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
  • B05D7/14—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to metal, e.g. car bodies
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
  • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
  • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
  • B05D7/24—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials for applying particular liquids or other fluent materials
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
  • C08F265/04—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00 on to polymers of esters
• • 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
  • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
  • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
  • C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
  • C08G63/52—Polycarboxylic acids or polyhydroxy compounds in which at least one of the two components contains aliphatic unsaturation
• • 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
  • C09D167/00—Coating compositions based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Coating compositions based on derivatives of such polymers
  • C09D167/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
• • 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
  • C09D167/00—Coating compositions based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Coating compositions based on derivatives of such polymers
  • C09D167/06—Unsaturated polyesters having carbon-to-carbon unsaturation
• • 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
  • C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
• • 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
  • C09D7/61—Additives non-macromolecular inorganic
• • 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
  • 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
  • C09D7/65—Additives macromolecular
• • 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
  • C08K3/00—Use of inorganic substances as compounding ingredients
  • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
  • C08K3/20—Oxides; Hydroxides
  • C08K3/22—Oxides; Hydroxides of metals
  • C08K2003/2237—Oxides; Hydroxides of metals of titanium
  • C08K2003/2241—Titanium dioxide
• • 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
  • C08K3/00—Use of inorganic substances as compounding ingredients
  • C08K3/30—Sulfur-, selenium- or tellurium-containing compounds
  • C08K2003/3045—Sulfates
• • 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
  • C08K5/16—Nitrogen-containing compounds

Definitions

• the present disclosure relates to the field of coatings, specifically to a Real Michael addition crosslinkable coating system comprising an adhesion promoter.
• Sherwin-Williams adopts a resin containing an epoxy skeleton to improve the adhesion of the coating; however, the epoxy resin is not suitable to be used as a single-layer coating due to its relatively poor light stability (Prior art document 1) .
• Allnex has also performed experiments with adhesion promoters, adopting adhesion promoters with or without silane to improve the adhesion of the coatings.
• Said method utilizes chemical bonds formed by silane and metal surfaces or a polar interaction between aromatic heterocyclic rings and metal surfaces to improve the adhesion of the coating on metal surfaces.
• the improvement of adhesion obtained by this method is not stable, and the adhesion may greatly vary on different substrates, so it is not well applied in the industry so far (Prior art documents 4 to 5) .
• the present disclosure provides a Real Michael addition crosslinkable coating system comprising an adhesion promoter, wherein the adhesion promoter is able to form a coordinate structure with a metal ion on a metal surface and simultaneously is able to react with resins in the Real Michael addition crosslinkable coating system, and thereby bonding to a crosslinked network of the coating, so that the adhesion of the Real Michael addition crosslinkable coating system to the metal surface is improved.
• the present disclosure solves the described technical problem by the following solution.
• a Real Michael addition crosslinkable coating system comprising: a component A containing two or more activated methylene or methine groups (CH) ; a component B containing two or more activated unsaturated carbon-carbon double bonds; a component C containing a catalyst or latent catalyst capable of initiating a Michael addition reaction; an adhesion promoter P; optionally a solvent; and optionally other components; characterized in that the adhesion promoter P comprises a compound, an oligomer, a polymer or their combinations, having at least one multidentate ligand structure Y and at least one group X or precursor moiety thereof capable of reacting with component A or B; and the group X or precursor moiety thereof is optionally identical to or part of the multidentate ligand structure Y.
• the multidentate ligand structure Y has a structure derived from ethylenediamine, hydroxyethyl ethylenediamine, diethylenetriamine, hydroxyethyl diethylenetriamine, triethylenetetramine, polyethyleneimine, propane diamine, ethanolamine, dimethylglyoxime, aminocarboxylic acid, hydroxyaminocarboxylic acid, phenanthroline, bipyridine, or porphyrin.
• reaction product formed by reacting a hydroxyalkyl polyamine compound with at least one compound selected from dialkyl malonate, acetoacetate, acrylic acid, acrylate, and acryloyl halide, and optionally other compounds;
• reaction product formed by reacting a polyamine compound with a multifunctional acrylate or acetylacetone and optionally other compounds;
• a polyamine compound containing a primary amino group or a secondary amine group wherein the hydroxyalkyl polyamine compound is preferably tetrahydroxyethyl ethylenediamine or tetrahydroxypropyl ethylenediamine; the polyamine compound in ii) is preferably an aliphatic polyamine, more preferably an aliphatic diamine; the multifunctional acrylate is preferably a difunctional acrylate monomer; the polyamine compound in iii) is preferably ethylenediamine, diethylenetriamine, triethylenetetramine, polyethyleneimine; and the alkyl has 1 to 10 carbon atoms, and is preferably methyl, ethyl, propyl, butyl, pentyl, or hexyl.
• the Real Michael addition crosslinkable coating system according to [1] or [2] which is provided in the form of two or more parts, preferably comprising a first part free of component C and containing components A and B, and a second part containing component C and free of components A and B; or preferably comprising a first part containing component A and free of components B and C, a second part containing component B and free of components A and C, and a third part containing component C and free of components A and B.
• a coating method of the Real Michael addition crosslinkable coating system comprising the following steps: applying the Real Michael addition crosslinkable coating system according to any one of [1] to [13] to a substrate surface and curing the coating; optionally mixing the respective components of the coating system prior to applying; and optionally performing a physical and/or chemical pre-treatment and/or pre-modification of the substrate surface prior to applying the coating system.
• An adhesion promoter P for a Real Michael addition crosslinkable coating system comprising one or more of the following i) and ii) :
• reaction product formed by reacting a hydroxyalkyl polyamine compound with at least one compound selected from dialkyl malonate, acetoacetate, acrylic acid, acrylate, and acryloyl halide, and optionally other compounds;
• the hydroxyalkyl polyamine compound is preferably tetrahydroxyethyl ethylenediamine or tetrahydroxypropyl ethylenediamine;
• the polyamine compound in ii) is preferably an aliphatic polyamine, more preferably an aliphatic diamine;
• the multifunctional acrylate is preferably a difunctional acrylate monomer; and
• the alkyl has 1 to 10 carbon atoms, and is preferably methyl, ethyl, propyl, butyl, pentyl, or hexyl.
• adhesion promoter P presents in an amount of 0.001 wt%to 80 wt%, preferably 0.01 wt%to 50 wt%, based on a total weight of the Real Michael addition crosslinkable coating system.
• the Real Michael addition crosslinkable coating system comprising an adhesion promoter of the present disclosure has a significantly improved adhesion to polar surfaces, in particular metal surfaces, and the said coating system has the characteristics of high solid content and low VOC at the same time, which may greatly promote the development of environment-friendly coatings, and may be widely applied to the field of coating engineering.
• multidentate ligand refers to a ligand having two or more coordination atoms
• the coordination atom refer to an atom that may form a coordination bond with a central atom, i.e., a metal or metalloid atom.
• Real Michael addition crosslinkable coating system refers to a coating system utilizing the Michael addition reaction to perform a crosslinking and curing process; unless otherwise indicated, the “coating system” and “coating” as used herein refers to a Real Michael addition crosslinkable coating system, optionally containing an adhesion promoter according to the present disclosure; “Real Michael addition crosslinkable coating system according to the present disclosure” or “coating system according to the present disclosure” then particularly refers to a Real Michael addition crosslinkable coating system comprising the adhesion promoter of the present disclosure.
• the adhesion of the Real Michael addition crosslinkable coating system referred to herein refers to the adhesion of the Real Michael addition crosslinkable coating system when coated according to the disclosure on the corresponding surface, which may be characterized by the adhesion test results described in the Examples section below.
• metal surface and “metal substrate surface” refer to a surface formed of metal atoms or ions on any substrate, for example, a surface of a metal substrate and a surface of a metal plating layer formed on other substrates by plating, spraying, chemical deposition and the like.
• C n-m alkyl refers to an alkyl group having n or more and m or less carbon atoms, including linear, branched, or cyclic alkyl groups.
• polyamine and “polyamine compound” refers to a compound, oligomer or polymer having two or more amino groups in a molecule, and the amino groups therein may be primary, secondary, or tertiary amine groups, for example aliphatic amines and aromatic amines, and the like.
• numerical range indicated by using “numerical value A to numerical value B” refers to a range including the endpoints of the numerical values A and B.
• the “preferred embodiment” and “embodiment” and the like mentioned mean that a particular element (e.g., feature, structure, property, and/or characteristic) described in connection with the embodiment is included in at least one embodiment described herein and may or may not be present in other embodiments.
• the element may be in combination in any suitable manner in the various embodiments.
• It is an object of the present disclosure to provide a Real Michael addition crosslinkable coating system comprising: a component A containing two or more activated methylene or methine groups (CH) ; a component B containing two or more activated unsaturated carbon-carbon double bonds; a component C containing a catalyst or latent catalyst capable of initiating a Michael addition reaction; an adhesion promoter P; optionally a solvent; and optionally other components; characterized in that the adhesion promoter P comprises a compound, oligomer, polymer or their combinations having at least one multidentate ligand structure Y and at least one group X or precursor moiety thereof capable of reacting with component A or B, wherein the group X or precursor moiety thereof is optionally identical to or part of the multidentate ligand structure Y.
• the molar ratio of the activated unsaturated carbon-carbon double bond to the active C-H bond contained in the activated methylene or methine group is between 0.3 and 3, preferably between 0.5 and 2, and particularly preferably between 0.75 and 1.5.
• the activated unsaturated carbon-carbon double bond herein refers to the sum of the activated unsaturated carbon-carbon double bond contained in all components of the Real Michael addition crosslinkable coating system; likewise, the active C-H bond contained in the activated methylene or methine group herein refers to the sum of the active C-H bond contained in the activated methylene or methine group contained in all components of the Real Michael addition crosslinkable coating system.
• the coating system of the present disclosure may include one or more adhesion promoters P to improve adhesion of the Real Michael addition crosslinkable coating system to polar surfaces, in particular metal surfaces.
• the adhesion promoter P comprises a compound, oligomer, polymer or their combinations having at least one multidentate ligand structure Y and at least one group X or precursor moiety thereof capable of reacting with component A or B.
• the multidentate ligand structure Y therein is capable of complexing metal ions, and the group X is bonded to the crosslinked network of the coating by reacting with resins in the Real Michael addition crosslinkable coating system. Therefore, the adhesion promoter P significantly improves the adhesion of the Real Michael addition crosslinkable coating system to metal surfaces by interacting with the metal surface and the resin component in the coating simultaneously.
• the adhesion promoter P comprises a compound.
• the compound is a low-molecular-weight compound having at least one multidentate ligand structure Y and at least one group X or precursor moiety thereof capable of reacting with component A or B.
• the positions of the multidentate ligand structure Y and group X or precursor moiety thereof in the compound are not particularly limited, and the two may be directly bonded together or may be separately bonded to other structural moieties in the said compound, for example to an alkylene or arylene group in the said compound.
• the adhesion promoter P comprises an oligomer and/or polymer, and the multidentate ligand structure Y and the group X or precursor moiety thereof exist independently of one another in at least one of the following positions: main chain, side chain, and chain end of the oligomer or polymer.
• the multidentate ligand structure Y is located at the main chain, and the group X or precursor moiety thereof is located at the main chain, side chain, or chain end; or the multidentate ligand structure Y is located at the side chain, and the group X or precursor moiety thereof is located at the main chain, side chain, or chain end; or the multidentate ligand structure Y is located at the chain end, and the group X or precursor moiety thereof is located at the main chain, side chain, or chain end.
• the polymer is selected from polyester, polyether, polyamide, polyurethane, polycarbonate, polyolefin, and epoxy-type polymer.
• a suitable multidentate ligand structure Y preferably contains nitrogen atom as electron-pair donor, more preferably selected from multidentate ligand structures based on polyamines, amino alcohols, ketoximes, and nitrogen-containing heterocycles.
• the multidentate ligand structure of polyamine may include 2 to 30, preferably 2 to 10 amine groups, wherein the amine groups are preferably bonded to each other by linear, branched, or cyclic alkyl groups, and the amine groups may be primary, secondary, or tertiary amine groups.
• the multidentate ligand structure based on amino alcohol is a multidentate ligand structure containing amine groups and alcoholic hydroxyl groups, and the number of the amine groups and the alcoholic hydroxyl groups is independently preferably 1 to 5; and between the amine group and the alcoholic hydroxyl group, or in the case of including a plurality of amine groups or a plurality of alcoholic hydroxyl groups, the plurality of the amine groups and the plurality of alcoholic hydroxyl groups are preferably bonded to each other by linear, branched, or cyclic alkyl groups, wherein an O atom in the alcoholic hydroxyl group may also serve as a coordination atom.
• the multidentate ligand structure Y based on polyamine and amino alcohol is selected from the structures represented by the general formula (1) :
• R 1 , R 2 , R 3 , and R 4 are selected independently of one another from a hydrogen atom and an alkyl having 1 to 20 C atoms, wherein the alkyl is a linear, branched, or cyclic alkyl, and one or more hydrogen atoms therein are optionally substituted by halogen, -OH, -SH, -CN, or -NO 2 ; s is an integer from 2 to 5 and is identical to or different from each other when s occurs multiple times; and n is an integer from 2 to 50.
• R 1 , R 2 , R 3 , and R 4 are selected independently of one another from a hydrogen atom and an alkyl having 1 to 10 C atoms, wherein the alkyl is a linear, branched, or cyclic alkyl, and one or more hydrogen atoms therein are optionally substituted by halogen, -OH, or -SH; s is 2, 3, or 4, and is identical to or different from each other when s occurs multiple times; and n is an integer from 2 to 10.
• R 1 and R 2 are selected from a linear alkyl having 1 to 6 C atoms, wherein one or more hydrogen atoms in the alkyl may be substituted by halogen, -OH, or -SH;
• R 3 and R 4 are hydrogen atoms, s is 2, 3, or 4, and is identical to or different from each other when s occurs multiple times; and
• n is an integer from 2 to 10.
• R 1 and R 2 are alkyl groups having 1 to 6 C atoms which are substituted by -OH group at the end;
• R 3 and R 4 are hydrogen atoms;
• s is 2 or 3, and is identical to or different from each other when s occurs multiple times; and
• n is 2, 3, 4 or 5.
• R 2 , R 3 , and R 4 in each structural unit may be the same or different from R 2 , R 3 , and R 4 in other structural units, respectively.
• the multidentate ligand structure Y may have a skeleton structure of N ⁇ C ⁇ C ⁇ N, N ⁇ C ⁇ C ⁇ C ⁇ N, N ⁇ C ⁇ C ⁇ O, or N ⁇ C ⁇ C ⁇ C ⁇ O, wherein N atom and C atom, and C atom and C atom are connected independently of one another by a single bond, a double bond or a triple bond; C atom and O atom are connected by a single bond or a double bond; wherein N and O are coordination atoms.
• These skeleton structures may exist at any position in the structure of the compound, oligomer or polymer, for example, as part of the compound structure or as at least a part of the main chain, side chain and chain end structures of the oligomer or polymer.
• Particularly preferred multidentate ligand structure Y has a structure derived from ethylenediamine, hydroxyethyl ethylenediamine, diethylenetriamine, hydroxyethyl diethylenetriamine, triethylenetetramine, polyethyleneimine, propane diamine, ethanolamine, dimethylglyoxime, aminocarboxylic acid, and hydroxyaminocarboxylic acid.
• the multidentate ligand structure Y of nitrogen-containing heterocycle is a heterocyclic structure that may form two or more coordination bonds with one central atom, wherein at least one of the coordination atoms is a nitrogen atom.
• such multidentate ligand structures may be selected from structures of phenanthroline, bipyridine, and porphyrin.
• the compound, oligomer and/or polymer included in the adhesion promoter P of the present disclosure may contain 1 to 50, preferably 1 to 20, more preferably 1 to 10, and most preferably 1 to 5 groups X or precursor moieties thereof capable of reacting with the resin in the Real Michael addition crosslinkable coating system.
• the specific group X is not particularly limited and may be any group capable of reacting with the resin in the coating, and those skilled in the art may select a suitable group X according to the resin in the coating system.
• the group X itself is a group capable of reacting with the resin in the coating and is preferably one or more of a primary amine group, a secondary amine group, an epoxy group, and a mercapto group.
• the group X is a group capable of undergoing a Michael addition reaction, i.e., a group containing an activated methylene or methine group or an activated unsaturated carbon-carbon double bond.
• the group X is the group capable of undergoing a Michael addition reaction
• the compound, oligomer or polymer included in the adhesion promoter P described in the present disclosure reacts with the resin in the coating during the curing process of the coating, thus bonding to the polymer crosslinking network formed by the curing of the coating.
• the adhesion promoter P may be used to partially or completely replace the corresponding resin component in the Real Michael addition crosslinkable coating system.
• the group X may also be present in the form of its precursor moiety.
• the precursor moiety of the group X refers to a structural moiety that becomes the group X after conversion, and the said precursor moiety itself does not react with the resin in the coating but forms the group X capable of reacting with the resin in the coating after conversion.
• the conversion includes any means of converting the said precursor moiety to a reactive group X, such as hydrolysis, alcoholysis, ammonolysis, acidolysis, oxidation and reduction, and the like, preferably hydrolysis.
• Such precursor moieties may be selected from one or more of a ketimine group, an aldimine group, and an oxazolidinyl group.
• the adhesion promoter P does not react with other components in the coating system upon storage, thereby improving the storage stability of the coating system.
• the adhesion promoter P described in the present disclosure comprises one or more of the following i) , ii) and iii) :
• reaction product formed by reacting a hydroxyalkyl polyamine compound with at least one compound selected from dialkyl malonate, acetoacetate, acrylic acid, acrylate, or acryloyl halide, and optionally other compounds;
• reaction product formed by reacting a polyamine compound with a multifunctional acrylate or acetylacetone and optionally other compounds;
• a polyamine compound containing at least one primary or secondary amine group wherein the hydroxyalkyl polyamine compound is preferably tetrahydroxyethyl ethylenediamine or tetrahydroxypropyl ethylenediamine; the polyamine compound in ii) is preferably an aliphatic polyamine, more preferably an aliphatic diamine; the multifunctional acrylate is preferably a difunctional acrylate monomer; the polyamine compound in iii) is preferably ethylenediamine, diethylenetriamine, triethylenetetramine, polyethyleneimine; and the alkyl has 1 to 10 carbon atoms, and is preferably methyl, ethyl, propyl, butyl, pentyl, or hexyl.
• the adhesion promoter P described in the present disclosure more preferably contains the reaction product formed by reacting the hydroxyalkyl polyamine compound and the dialkyl malonate and optionally other compounds and/or the reaction product formed by reacting the aliphatic polyamine and the difunctional acrylate monomer or acetylacetone and optionally other compounds;
• the alkyl has 1 to 10 carbon atoms, and is preferably methyl, ethyl, propyl, butyl, pentyl, or hexyl.
• the adhesion promoter P comprises the reaction product of tetrahydroxyethyl ethylenediamine or tetrahydroxypropyl ethylenediamine with diethyl malonate and optionally other compounds, the reaction product of ethylenediamine with the difunctional acrylate monomer and optionally other compounds, and/or the reaction product of ethylenediamine with acetylacetone and optionally other compounds.
• the adhesion promoter P of the present disclosure comprises a polyamine compound containing a primary or secondary amine group, preferably an aliphatic polyamine compound, and particularly preferably one or more selected from ethylenediamine, diethylenetriamine, triethylenetetramine, and polyethyleneimine.
• the adhesion promoter P may be used as a separate component or mixed with the catalyst C in advance but cannot be mixed with component A or component B in advance.
• the compound, oligomer or polymer included in the adhesion promoter P described in the present disclosure may be prepared by a conventional method in the art, for example, by reacting a compound containing the multidentate ligand structure Y with a compound containing the group X or precursor moiety thereof, and by polymerizing a monomer containing the multidentate ligand structure Y with a monomer containing the group X or precursor moiety thereof and optionally other monomers.
• the number average molecular weight of the oligomer or polymer contained in the adhesion promoter P described in the present disclosure is no more than 10000, preferably no more than 5000, and particularly preferably no more than 2000.
• the adhesion promoter P described in the present disclosure may be added to the coating system during the production of the coating and may also be added to the coating system before applying the coating system to the substrate. It is preferred to apply a shear force to the coating system after the addition so as to thoroughly mix the components.
• the amount of the adhesion promoter P is 0.001wt%to 80wt%, preferably 0.01wt%to 50wt%, based on the total weight of the Real Michael addition crosslinkable coating system.
• the present disclosure accordingly provides an adhesion promoter P for a Real Michael addition crosslinkable coating system as described in the context.
• the adhesion promoter P comprises one or more of the following i) , ii) and iii) :
• reaction product formed by reacting a hydroxyalkyl polyamine compound with at least one compound selected from dialkyl malonate, acetoacetate, acrylic acid, acrylate, or acryloyl halide, and optionally other compounds;
• reaction product formed by reacting a polyamine compound with a multifunctional acrylate or acetylacetone and optionally other compounds;
• a polyamine compound containing at least one primary or secondary amine group wherein the hydroxyalkyl polyamine compound is preferably tetrahydroxyethyl ethylenediamine or tetrahydroxypropyl ethylenediamine; the polyamine compound in ii) is preferably an aliphatic polyamine, more preferably an aliphatic diamine; the multifunctional acrylate is preferably a difunctional acrylate monomer; the polyamine compound in iii) is preferably ethylenediamine, diethylenetriamine, triethylenetetramine, polyethyleneimine; the alkyl has 1 to 10 carbon atoms, and is preferably methyl, ethyl, propyl, butyl, pentyl, or hexyl.
• the adhesion promoter P comprises the reaction product of the hydroxyalkyl polyamine compound, the dialkyl malonate and optionally other compounds and/or the reaction product of the aliphatic polyamine, the difunctional acrylate monomer or acetylacetone and optionally other compounds; and the alkyl has 1 to 10 carbon atoms, and is preferably ethyl, propyl, butyl, pentyl, or hexyl.
• the present disclosure accordingly provides the use of the adhesion promoter P as described in the context for improving the adhesion of the Real Michael addition crosslinkable coating system to polar surfaces, in particular metal surfaces.
• Component A Component Containing Activated Methylene or Methine groups (CH)
• Component A containing activated methylene or methine groups is known in the art and is preferably an oligomer or polymer such as polyesters, polyurethanes, polycarbonates, polyacrylates, epoxy resins, polyamides and polyethylene resins containing activated methylene or methine groups in the main chain, side chain or both; preferably polyesters, polyurethanes or polycarbonates.
• a suitable component A is preferably a polymer having the structure represented by the general formula (2) :
• the component A is selected from one or more of the polymers formed by polymerizing malonates, acetoacetates, and/or acetylacetone with other monomers, wherein the other monomers are selected from polyols, polyol esters, isocyanates, polyamines, and epoxy compounds.
• Such component A may be selected, for example, from polyesters, polyurethanes and epoxy esters containing malonate groups, and oligomers or polymers containing acetoacetate groups.
• the polyesters containing malonate groups are preferably obtainable by a transesterification of dimethyl malonate or diethyl malonate with polyfunctional alcohols.
• the polyurethanes containing malonate groups are obtainable by reaction of polyisocyanates with polyols and hydroxyl-containing esters of malonic acid or by the transesterification of dialkyl malonates with hydroxyl-containing polyurethanes.
• the epoxy esters containing malonate groups are obtainable by esterification of malonic acids or a malonic acid monoesters or acid functionalized malonate polyesters with epoxy resins.
• the oligomers or polymers containing acetoacetate groups are obtainable by the transesterification of polyols and/or hydroxyl-functionalized polyethers, polyesters, polyacrylates, vinyl groups and epoxy oligomers or polymers with diketenes or alkyl acetoacetates, such components may also be obtained by copolymerizing acetoacetate group-containing (meth) acrylic monomers with other vinyl groups and/or (meth) acrylic functionalized monomers.
• component A is a polymer formed by copolymerizing C 1-10 alkyl malonates with C 1-10 diols and optionally aliphatic diacids; particularly preferably, component A is a polymer formed by copolymerizing C 2-4 alkyl malonates with C 3-8 diols and optionally aliphatic diacids; and most preferably, component A is a polymer obtained by polymerizing diethyl malonate with neopentyl glycol and optionally aliphatic diacids.
• the aliphatic diacid monomers are used for adjusting the glass transition temperature of component A, and can be selected by those skilled in the art according to actual requirements, and linear or branched aliphatic diacids with 1 to 20 carbon atoms are preferred, including but not limited to oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, azelaic acid, and sebacic acid.
• Component A in the present disclosure contains at least one malonate and/or acetoacetate group, preferably component A contains 1 to 50, particularly preferably 2 to 10 malonate and/or acetoacetate groups.
• Component A preferably has a number average molecular weight of 100 to 10000, preferably 100 to 5000, and particularly preferably 200 to 2500. Furthermore, it is also possible to use a malonate and/or acetoacetate having two active C-H groups as reactive solvent.
• the amount of component A is 3%to 70%, preferably 5%to 60%, and particularly preferably 10%to 50%of the total mass of the coating.
• Component B Component Containing Activated Unsaturated Carbon-Carbon Double Bonds
• the coating system of the present disclosure may contain one or more components B, and when the plurality of components B are contained, each component B is independently a monomer, dimer, oligomer or polymer containing two or more activated unsaturated carbon-carbon double bonds.
• Component B may generally be an olefinic unsaturated component in which the carbon-carbon double bonds are activated via an electron-withdrawing group, such as a carbonyl activation at ⁇ -position.
• an electron-withdrawing group such as a carbonyl activation at ⁇ -position.
• the groups containing an activated unsaturated carbon-carbon double bond include acryloyl groups, maleate groups, fumarate groups, itaconate groups, and the like.
• component B is known in the art, such as acrylates, acrylamides, polyesters based on maleic acid, fumaric acid, and/or itaconic acid, and polyesters based on maleic anhydride and/or itaconic anhydride.
• component B may also be a polymer with pendants of the aforementioned groups containing activated unsaturated carbon-carbon double bonds, and the polymer is preferably polyester, polyurethane, polyether or alkyd resin.
• a preferred component B is a component containing acryloyl groups, and more preferably one or more selected from the group consisting of hexanediol diacrylate, trimethylolpropane triacrylate (TMPTA) , pentaerythritol triacrylate and di (trimethylolpropane) tetraacrylate (Di-TMPTA) .
• the amount of the component B is 2%to 60%, preferably 3%to 50%, and particularly preferably 5%to 40%of the total mass of the coating.
• Component C catalyst component
• component C which may be any catalyst and/or latent catalyst known in the art that is capable of initiating the Michael addition reaction and is preferably a latent catalyst.
• Suitable catalysts include strong organic bases, preferably amidine type catalysts or tertiary amine type catalysts.
• Suitable latent catalysts are latent catalysts for Michael addition systems described in patents WO2011/124663A1 and WO/2018/005077A1.
• the latent catalyst is preferably a latent catalyst based on a substituted carbonate or carbamate.
• a suitable latent catalyst C is preferably a latent catalyst having a structure represented by the general formula (3) or general formula (4) :
• R, R 1 , and R 2 are selected independently of one another from hydrogen and an alkyl having 1 to 22 carbon atoms, wherein the alkyl may be linear or branched, preferably methyl, ethyl, propyl, butyl and combinations thereof.
• the alkyl is optionally substituted.
• a n+ is a cationic group of non-acidic hydrogen, and n is a positive integer greater than or equal to 1.
• a n+ is an alkali metal, an alkaline earth metal or a quaternary ammonium, sulfonium or phosphonium compound.
• a n+ is a polyvalent metal cation, or a compound or cationic polymer bearing more than one quaternary ammonium, sulfonium, or phosphonium group.
• the amount of the catalyst C is 0.01%to 15%, preferably 0.1%to 10%, and particularly preferably 0.5%to 8%of the total mass of the coating system.
• the Real Michael addition crosslinkable coating system of the present disclosure optionally includes a solvent for dissolving certain components or for adjusting the viscosity to adapt a coating method such as spraying, and the present disclosure has no particular limitation on the solvent, which may be any solvent known in the art that may be used in a Real Michael addition crosslinkable coating system, those skilled in the art can select a suitable solvent for a particular coating system.
• the solvent is an organic solvent; more specifically, a single organic solvent or a mixed solvent containing multiple organic solvents.
• the organic solvent may be a conventional coating solvent free of acidic impurities, such as the solvents of esters, alcohols, ethers, and ketones.
• the ester solvents may be selected from C 2-6 alkyl esters of C 2-6 fatty acids, examples thereof include but are not limited to ethyl acetate, propyl acetate, butyl acetate, pentyl acetate, hexyl acetate and the like;
• the alcoholic solvents may be selected from C 2-6 monohydric or polyhydric alcohols, example thereof include but are not limited to ethanol, propanol, isopropanol, butanol and the like;
• the ether solvents may be selected from diethyl ether, tetrahydrofuran, dioxane, and the like.
• Preferred solvents are reactive solvents capable of reacting with component A or B, and the solvents may be selected from monomers or dimers having activated methylene or methine groups, monomers or dimers having activated unsaturated carbon-carbon double bonds, and preferably selected from alkyl acetoacetates, dialkyl malonates, and diacrylates.
• the amount of a non-reactive organic solvent is 0 wt%to 35 wt%, preferably 1 wt%to 20 wt%, more preferably 2 wt%to 15 wt%, with respect to the total weight of the Real Michael addition crosslinkable coating system.
• the solvent is water, or water and organic solvents.
• the Real Michael addition crosslinkable coating system of the present disclosure may also optionally include other components, including but not limited to, fillers, pigments, reaction regulators, dispersants, leveling agents, defoamers, thickeners, anti-aging agents, antifoulants, flatting agents, and other adhesion promoters.
• reaction regulators and other adhesion promoters which may be any of the reaction regulators including pot life extenders and open time extenders, and adhesion promoters known in the art for use in Real Michael addition crosslinkable coating systems, those skilled in the art may specifically select as desired.
• the present disclosure has no particular limitation on fillers, pigments, dispersants, leveling agents, defoamers, thickeners, anti-aging agents, antifoulants and flatting agents, which may be any corresponding substances known to be used in coatings, those skilled in the art may specifically select as desired.
• the amount of the reaction regulators is no more than 20%of the total weight
• the amount of the anti-aging agents is no more than 10%of the total weight
• the sum of the amounts of the fillers and the pigments are no more than 75%of total weight
• the amount of the flatting agents is no more than 25%of total weight.
• the Real Michael addition crosslinkable coating system according to the present disclosure is preferably provided in the form of multiple parts, more preferably in the form of two or three parts, wherein component A, component B and component C are not present in one part at the same time.
• the Real Michael addition crosslinkable coating system is provided in the form of two parts, including a first part free of component C and containing components A and B, and a second part containing component C and free of components A and B.
• the Real Michael addition crosslinkable coating system is provided in the form of three parts, including a first part containing component A and free of components B and C, a second part containing component B and free of components A and C, and a third part containing component C and free of components A and B.
• One or more of the above parts contain the adhesion promoter P without impairing the effect of the present disclosure.
• the coating method of the present disclosure also includes a step of performing a physical and/or chemical treatment and/or modification of the substrate surface.
• the thickness of the coat is 5 to 500 ⁇ m, preferably 10 to 300 ⁇ m, and particularly preferably 30 to 300 ⁇ m.
• the curing temperature of the coat is -20 to 150 °C, preferably 0 to 100 °C, and particularly preferably room temperature.
• the present disclosure accordingly also relates to a coat obtained after applying and curing of the Real Michael addition crosslinkable coating system according to the present disclosure and to an article comprising the coating according to the present disclosure or obtained by the coating method according to the present disclosure.
• the coating has flaked along the edges and/or at the intersection of the cuts.
• a crosscut area significantly greater than 5%, but not significantly greater than 15%is affected.
• the coating has flaked along the edges partly or wholly in large ribbons, and/or it has flaked partly or wholly on different parts of the squares.
• the coating has flaked along the edges of the cuts in large ribbons and/or same squares have detached partly or wholly.
• the coatings were applied to phosphated steel plates.
• Preparation Example 1 Preparation of Malonate-Containing Adhesion Promoter P1: 118 g of tetrahydroxyethyl ethylenediamine, 400 g of diethyl malonate, and 15 g of an ethanol solution of 10 wt%sodium hydroxide were added into a four-neck flask with a stirrer and a thermometer. The reaction mixture was heated to 130 °C, and the distilled solvent and ethanol generated by the reaction were collected, and then the reaction mixture was gradually heated to 180 °C, and the temperature was kept constant for 1 hour. The product was obtained. The theoretical malonate equivalent of the product was 202 g/equivalent and the active C-H bond equivalent was 101 g/equivalent.
• HDDA hexanediol diacrylate
• Preparation Example 4 Preparation of Malonate-Containing Polyester Resin A: 416 g of neopentyl glycol, 560 g of diethyl malonate, and 5 g of an ethanol solution of sodium hydroxide (10wt%) were added to a four-neck flask with a stirrer and a thermometer. The reaction mixture was heated to 130 °C, and the distilled solvent and the reaction product were collected. Then, the temperature was gradually increased to 200 °C, and the ethanol was removed under the condition of reduced pressure. The theoretical hydroxyl value of the obtained product was 85 mg KOH/g, the malonate equivalent was 186 g/equivalent, and the active C-H bond equivalent was 93 g/equivalent.
• the coatings were formulated as shown in Table 1, and then the two parts were thoroughly mixed and sprayed on a phosphated steel plate. After 24 hours, the adhesion was tested by the method described in ISO/DIN 2409. It was found that the adhesion of Example 1 and Example 2 was very good, and the classification of the test was 0, and the adhesion of Comparative Example 1 was very poor, and the classification of the test was 5.
• the coatings were prepared as shown in Table 2, and then the two parts were thoroughly mixed and sprayed on a phosphated steel plate. After 24 hours, the adhesion was measured by the method described in ISO/DIN 2409. It was found that the adhesion of Example 3, Example 4, and Example 5 was very good, and the classification of the test was 0.
• the tetramethylethylenediamine used in Comparative Example 2 was a compound containing the multidentate ligand structure Y but not the functional group X because it did not have N-H functional group. The adhesion of Comparative Example 2 was very poor, and the classification of the test was 5.
• the Real Michael addition crosslinkable coating system containing an adhesion promoter according to the present disclosure may be used for coating various polar surfaces, in particular metal surfaces.

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