Classifications

• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
  • C09D175/04—Polyurethanes
• • C—CHEMISTRY; METALLURGY
  • 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
  • C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
  • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
  • B01J31/22—Organic complexes
  • B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
  • B01J31/2208—Oxygen, e.g. acetylacetonates
  • B01J31/2217—At least one oxygen and one nitrogen atom present as complexing atoms in an at least bidentate or bridging ligand
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
  • B01J2231/005—General concepts, e.g. reviews, relating to methods of using catalyst systems, the concept being defined by a common method or theory, e.g. microwave heating or multiple stereoselectivity
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
  • B01J2531/001—General concepts, e.g. reviews, relating to catalyst systems and methods of making them, the concept being defined by a common material or method/theory
  • B01J2531/002—Materials
  • B01J2531/004—Ligands

Definitions

• the present invention relates to a condensation and / or addition reaction curable coating composition
• a condensation and / or addition reaction curable coating composition comprising at least one polymer as a binder, at least one crosslinking agent which can be reacted by condensation and / or addition reaction with the component (A), and (C) at least one specific Catalyst.
• the present invention also relates to the use of the particular catalyst for catalysing the cure of condensation and / or addition reaction curable coating compositions.
• condensation and / or addition reaction curable coating compositions comprising polymers as binders and crosslinking agents are known.
• different catalysts are used for curing these compositions.
• carboxylic acid salts of metal ions or organometallic compounds, such as dibutyltin dilaurate, are used for this purpose.
• a coating composition curable by condensation and / or addition reactions was found, containing (A) at least one polymer as binder,
• (B) at least one crosslinking agent which can be reacted by condensation and / or addition reaction with the component (A), as well as
• M is a divalent, trivalent or tetravalent metal cation
• R 1 a divalent aliphatic, aromatic or araliphatic hydrocarbon radical having 1 to 10 carbon atoms
• R 2 and R 5 independently of one another, are hydrogen or a monovalent aliphatic, aromatic or araliphatic organic radical having 1 to 10 carbon atoms, and
• R 3 , R 4 , R 6 and R 7 independently of one another, is hydrogen or a monovalent aliphatic, aromatic or araliphatic organic radical having 1 to 20 carbon atoms
• R 3 and R 6 independently of one another, are a divalent aliphatic, aromatic or araliphatic organic radical having 1 to 20 carbon atoms, R 4 and R 7 represent a covalent bond, and R 3 and R 6 have these covalent bonds with the carbon atoms are linked in the alpha position to the oxygen atom of the formula (I),
• the new coating compositions are also called coating compositions according to the invention and are the subject of the present invention. Preferred embodiments will become apparent from the following description and the appended claims.
• the present invention also relates to the use of the catalyst (C) for catalysing the curing of coating compositions which are curable by condensation and / or addition reaction, and coatings produced by application of the compositions to substrates and subsequent curing.
• the coating compositions according to the invention can be cured in an alternative, nevertheless fulfilling manner, compared to the prior art.
• the coating composition of the invention contains at least one polymer (A) as a binder and a crosslinking agent (B) which can be reacted by condensation and / or addition reaction with the component (A).
• Polymers (A) as binders are, for example, random, alternating and / or block-structured linear and / or branched and / or comb-like (co) polymers of ethylenically unsaturated monomers, or polyaddition resins and / or polycondensation resins. These terms are supplemented by Römpp Lexikon Lacke and Druckmaschine, Georg Thieme Verlag, Stuttgart, New York, 1998, page 457, "polyaddition” and “polyaddition resins (polyadducts)", and pages 463 and 464, "polycondensates”, “polycondensation” and “Polykondensationsharze", and pages 73 and 74, "binder", referenced.
• suitable (co) polymers are (meth) acrylate (co) polymers or partially saponified polyvinyl esters, in particular (meth) acrylate copolymers.
• suitable polyaddition resins and / or polycondensation resins are polyesters, alkyds, polyurethanes, polylactones, polycarbonates, polyethers, epoxy resins, epoxy resin-amine adducts, polyureas, polyamides, polyimides, polyester-polyurethanes, polyether polyurethanes or polyester-polyether polyurethanes.
• the polymers (A) as binders contain, for example, thio, hydroxyl, amino, N-methylolamino-N-alkoxymethylamino, imino, carbamate, allophanate and / or carboxyl groups, preferably hydroxyl, primary and secondary amino and / or or carboxyl groups, especially hydroxyl groups.
• the coating composition contains a polymer (A) as a binder which contains hydroxyl groups and / or primary and / or secondary amino groups. It is therefore true that the coating composition in any case, but not necessarily exclusively, contains such a polymer as a binder.
• the coating composition of the invention contains at least one crosslinking agent (B).
• Crosslinking agents and their use in coating compositions are known to the person skilled in the art. In principle, these are components which have reactive functional groups which are complementary to the reactive functional groups of polymers used, for example, as binders, in particular the polymers (A) and can therefore be chemically crosslinked.
• binding agent and “crosslinking agent” are used in the context of the present invention for better clarity or for better differentiability. Both terms are known to the person skilled in the art and have a clarifying character to that extent.
• crosslinking takes place between the functional groups of a polymer as binder and the thus-complementary functional groups of the crosslinking agent.
• Typical combinations of polymers as binders and crosslinking agents are, for example, hydroxy- and / or carboxy-functional polymers as binders and free or blocked polyisocyanates and / or aminoplast resins, in particular melamine resins and benzoguanamine resins, ie, adducts containing methylol and / or methylol ether groups, or polycarbodiimides as crosslinking agents ,
• Crosslinking agents selected from the group consisting of free or blocked polyisocyanates, aminoplast resins, in particular melamine resins and benzoguanamine resins, and also polycarbodiimides are preferably used in the context of the present invention. Very particular preference is given to free or blocked, in particular blocked, polyisocyanates.
• the above therefore means that the coating composition according to the invention is thermally curable, that is, by chemical reaction of reactive functional groups as described above can take place a crosslinking (formation of a coating film), wherein the energetic activation of this chemical reaction by thermal energy and under catalytic action of catalysts , as the catalyst (C) described below, is possible.
• the content of polymers (A) as a binder is, for example, 5 to 50% by weight, based on the total amount of the coating composition according to the invention.
• the determination of the proportion of polymers (A) or of a particular polymer (A) is as follows: The solids of a binder dispersion of a polymer (A) to be added to the coating composition are determined. By taking into account the solids of the binder dispersion and the amount of dispersion used in the coating composition, the proportion of the polymer (A) in the overall composition can then be determined or determined. This method is basically used in this context for a variety of components to be used.
• the solids content in the context of the present invention unless stated otherwise, according to DIN EN ISO 3251 with a weighing of 1, 0 g sample, for example, 1, 0 g of the coating composition according to the invention, with a test period of 60 min and at a temperature of 125 ° C determined.
• the content of crosslinking agents (B) is, for example, 0.5 to 30% by weight, in each case based on the total amount of the coating composition according to the invention.
• the coating composition used according to the invention contains at least one specific complex as catalyst (C).
• the catalyst has a structure of the following formula (I).
• M is a divalent, trivalent or tetravalent metal cation
• R 1 a divalent aliphatic, aromatic or araliphatic hydrocarbon radical having 1 to 10 carbon atoms
• R 2 and R 5 independently of one another, are hydrogen or a monovalent aliphatic, aromatic or araliphatic organic radical having 1 to 10 carbon atoms, and
• R 3 , R 4 , R 6 and R 7 independently of one another, is hydrogen or a monovalent aliphatic, aromatic or araliphatic organic radical having 1 to 20 carbon atoms
• R 3 and R 6 independently of one another, are a divalent aliphatic, aromatic or araliphatic organic radical having 1 to 20 carbon atoms, R 4 and R 7 represent a covalent bond, and R 3 and R 6 have these covalent bonds with the carbon atoms are linked in the alpha position to the oxygen atom of the formula (I),
• radicals R 3 and R 4 satisfy the definition under (i) and the radicals R 6 and R 7 satisfy the definition under (ii).
• the catalyst is a complex. Accordingly, the bonds between metal cation and electron donor (oxygen, nitrogen) shown in formula (I) are not classical covalent bonds, but rather complex bonds between metal cation and ligand.
• metal cation M so divalent, trivalent or tetravalent metal cations come into question.
• all main group and subgroup metal cations available in this regard preferably 3d metal cations, are conceivable. Examples are V (III), V (IV), Cr (III), Mn (III), Fe (II), Fe (II), Co (II), Co (III), Ni (II), Cu ( II), Bi (III) and Zn (II).
• the structure of formula (I) carries one or two positive charges. This at least one charge is then easily compensated by, for example, inorganic anions such as, for example, chloride, nitrate, tetraphenylborate or hydroxide.
• An aliphatic compound is a saturated or unsaturated, organic (ie containing carbon and hydrogen) compound that is not aromatic or non-araliphatic.
• An aliphatic compound may, for example, consist exclusively of carbon and hydrogen (aliphatic hydrocarbon) or, in addition to carbon and hydrogen, also contain heteroatoms in the form of bridging or terminal functional groups or molecular units, which are mentioned below.
• the term aliphatic compound thus includes both cyclic and acyclic aliphatic compounds and also applies in the context of the present invention as a corresponding generic term.
• Acyclic aliphatic compounds may be straight chain (linear) or branched.
• Linear in this context means that the respective connection no Branched with respect to the carbon chain, but the carbon atoms are arranged exclusively in a linear sequence in a chain.
• Branched or non-linear means in the context of the present invention that the respective considered compound has a branch in the carbon chain, that is, unlike the linear compounds at least one carbon atom of the respective compound is a tertiary or quaternary carbon atom.
• Cyclic aliphatic compounds or cyclic-aliphatic compounds are those compounds in which at least part of the carbon atoms present in the molecule are linked so that one or more rings are formed.
• acyclic straight-chain or branched aliphatic groups or molecular moieties may be present in a cyclic-aliphatic compound.
• functional groups or molecular fractions are those groups which contain or consist of heteroatoms, such as, for example, oxygen and / or sulfur.
• the functional groups may be bridging, that is, for example, represent an ether, ester, keto or sulfonyl group, or be terminal, such as hydroxyl groups, sulfone groups or carboxyl groups. It is also possible for bridging and terminal functional groups to be present at the same time in an aliphatic compound.
• An aliphatic radical is accordingly a radical which fulfills the conditions mentioned above for the aliphatic compounds but is only a part of a molecule.
• An aromatic compound is known to be a cyclic, planar organic compound having at least one aromatic system, that is, at least one conjugated ⁇ -system ring system according to the Hückel aromaticity criteria.
• it may be a pure hydrocarbon compound (for example, benzene).
• certain heteroatoms are incorporated into the ring structure (for example, pyridine).
• the one or more aromatic ring systems can in one aromatic compound further straight-chain and / or branched hydrocarbon groups and bridging and / or terminal functional groups may be part of the aromatic compound, as long as they form part of the conjugated ⁇ -system.
• two phenyl rings linked by a keto group or an ether group are also aromatic compounds.
• aromatic radical is therefore in the context of the invention a radical which fulfills the conditions mentioned above for the aromatic compounds, but is only a part of a molecule.
• An araliphatic compound is an organic compound containing aromatic and aliphatic moieties. Such a mixed aromatic-aliphatic compound must therefore also contain an aliphatic group in addition to an aromatic group.
• an araliphatic group within the meaning of the invention is a group which fulfills the conditions stated above for the araliphatic compounds but is only a part of a molecule.
• a monovalent residue is a residue that is apparently linked via a covalent bond to the rest of the molecule.
• a divalent radical is therefore a radical linked to the rest of the molecule via two covalent bonds.
• the radicals R 4 and R 7 replaced the covalent bonds between R 4 and R 7 shown in formula (I) and the carbon atoms in the alpha position relative to the oxygen atoms, so that finally a ring structure results.
• the radical R 6 can be designed such that a phenyl ring, which of course can also be further substituted, results.
• the CC double bond given in formula (I) is of course part of the conjugated ⁇ -system.
• the characterization of the CC double bond in formula (I) in any case only represents a possible limiting structure.
• mesomeric boundary structures can basically be realized in the structure according to formula (I).
• the radical R 1 is in a first preferred embodiment, an acyclic aliphatic hydrocarbon radical having 1 to 10, preferably 2 to 10, more preferably 2 to 6, most preferably 2 to 4 carbon atoms.
• the radical R 1 is an aromatic hydrocarbon radical having 6 to 10, more preferably 6 carbon atoms.
• the radicals R 2 and R 5 are preferably hydrogen or a monovalent aliphatic, hydrocarbon radical having 1 to 10 carbon atoms, more preferably hydrogen or a monovalent aliphatic hydrocarbon radical having 1 to 2 carbon atoms, very particularly preferably hydrogen.
• the radicals R 3 , R 4 , R 6 and R 7 according to variant (i) are preferably hydrogen or a monovalent aliphatic hydrocarbon radical having 1 to 10 carbon atoms, more preferably hydrogen or a monovalent aliphatic hydrocarbon radical having 1 to 2 carbon atoms. Most preferably, R 3 and R 6 are hydrogen and R 4 and R 7 are methyl radicals.
• radicals R 3 , R 4 , R 6 and R 7 is preferably the variant (ii) according to the above definition. It is preferred that the radicals R 3 and R 6 are designed so that a benzene ring, which of course may also be further substituted, results, in which case the in the formula (I) drawn CC double bonds part of the conjugated ⁇ system are.
• the ligand is based on bis (salicylidene) ethylenediamine.
• the catalyst is a complex of doubly deprotonated bis (salicylidene) ethylenediamine with a metal cation.
• the content of catalysts (C) is preferably from 0.01 to 3.00 wt .-%, each based on the total amount of the coating composition of the invention.
• the coating composition used according to the invention may contain one or more commonly used pigments, fillers and solvents, such as water or organic solvents. It is also possible to contain various additives as component (D) from components (A) to (C) already described.
• these additives (D) are selected from the group consisting of waxes, antioxidants, antistatic agents, wetting and dispersing agents, emulsifiers, flow control agents, solubilizers, defoaming agents, wetting agents, stabilizers, preferably heat and / or heat stabilizers, process stabilizers and UV and / or light stabilizers, light stabilizers, deaerators, inhibitors, catalysts, flexibilizers, flame retardants, organic solvents such as butyl glycol and / or butyl glycol acetate, reactive diluents, water repellents, hydrophilicizing agents, thickeners, thixotropic agents, impact modifiers, blowing agents, process auxiliaries, plasticizers, fibrous Solids and mixtures of the aforementioned additives.
• the additive content of additive (G) in the coating composition according to the invention can vary very widely depending on the intended use.
• the coating composition of the invention preferably has a solids content of 10 to 85 wt .-%.
• Solid content non-volatile content
• Solid content is to be understood as the proportion by weight which, under defined conditions, remains as residue on evaporation.
• the solid state body according to DIN EN ISO 3251 is determined (60 minutes, 130 ° C).
• the coating composition of the invention can be prepared by mixing and dispersing and / or dissolving the respective components of the coating composition described above by means of a high speed stirrer, stirred tank, stirred mills, dissolver, kneader, or in-line dissolver.
• the present invention also relates to the use of the particular catalyst for catalysing the cure of condensation and / or addition reaction curable coating compositions.
• the present invention relates to a coating which has been produced by application and curing of the coating composition according to the invention to a substrate.
• the present invention relates to a process for the preparation of this coating by application of the coating composition to a substrate and subsequent thermal curing.
• substrates known to the person skilled in the art such as metallic substrates or plastic substrates, are suitable as substrates.
• the substrates can have any desired shape per se.
• the application of the coating composition according to the invention takes place in the manner known to the person skilled in the art and can be carried out, for example, by rolling, dipping, knife coating, spraying, for example by compressed air spraying, airless spraying, high rotation, electrostatic spray application (ESTA), optionally combined with hot spray application such as hot spraying. Air (hot-spraying) are performed. Preference is given to rolling processes.
• hardening more precisely complete curing, is familiar to the person skilled in the art To understand the meaning of the term. Accordingly, hardening, more precisely complete curing of a coating layer, means the transfer of such a layer into the ready-to-use state, that is to say into a state in which the substrate equipped with the respective coating layer can be transported, stored and used as intended.
• a cured coating layer is thus no longer particularly soft or tacky, but conditioned as a hard coating film. Its properties such as hardness, adhesion to the substrate or abrasion resistance are no longer improved even with further exposure to curing conditions as described below.
• the crosslinking structure of the paint layer can not be increased by further exposure to curing conditions as described below, optionally still existing reactive complementary functional groups of the components such as polymers as binders and crosslinking agents are no longer movable by the strength of the coating and therefore not more available for further curing reaction.
• Complete thermal curing may preferably be carried out at a temperature between 40 and 220 ° C for a time of 5 to 180 minutes.
• the indicated temperatures are in each case understood as oven temperatures, that is to say as the ambient temperature of the room in which the coated substrate is hardened.
• the coatings produced by using the coating composition according to the invention have a dry film thickness of, for example, 5 to 500 micrometers. Examples
• component (A) or component (B) of coating compositions a commercially available hydroxyl-functional polymer (bisphenol A-based polyetheramine) and a commercially available blocked polyisocyanate (alcohol-blocked, oligomeric methylene diphenyl isocyanate) were used.
• hydroxyl-functional polymer bisphenol A-based polyetheramine
• blocked polyisocyanate alcohol-blocked, oligomeric methylene diphenyl isocyanate
• the two components (A) and (B) were mixed together (25:15 by weight), with an amount of 6 mmol per 100 g non-volatile content of the components (A) and (B) of the respective catalyst in a suitable solvent dissolved as isopropanol or tetrahydrofuran and then exposed the mixture to a temperature of 180 ° C for a period of 20 minutes. Subsequently, the gel fraction (the crosslinked fraction) was determined. The above reaction mixture was placed in THF for 24 hours, then filtered and the filter residue dried at 75 ° C for 4 hours and weighed. The larger the amount of gel, the greater is obviously the proportion of components (A) and (B) crosslinked together. A high gel content is thus obviously equivalent to a high catalytic activity of the catalyst used. Table 1 shows the results.

Landscapes

• Chemical & Material Sciences (AREA)
• Engineering & Computer Science (AREA)
• Materials Engineering (AREA)
• Organic Chemistry (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Life Sciences & Earth Sciences (AREA)
• Wood Science & Technology (AREA)
• Inorganic Chemistry (AREA)
• Paints Or Removers (AREA)
• Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Applications Claiming Priority (2)

Publications (1)

Family

ID=57003376

Family Applications (1)

Country Status (5)

Families Citing this family (2)

Family Cites Families (24)

• 2017
  • 2017-09-13 JP JP2019515847A patent/JP7028864B2/ja active Active
  • 2017-09-13 CN CN201780057478.XA patent/CN109715750B/zh not_active Expired - Fee Related
  • 2017-09-13 WO PCT/EP2017/072949 patent/WO2018054725A1/de unknown
  • 2017-09-13 US US16/335,352 patent/US11015079B2/en active Active
  • 2017-09-13 EP EP17764414.3A patent/EP3516001A1/de not_active Withdrawn

Also Published As

Similar Documents

Legal Events