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
• • 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
  • B05D7/02—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 macromolecular substances, e.g. rubber
• • 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
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/08—Processes
  • C08G18/16—Catalysts
  • C08G18/22—Catalysts containing metal compounds
  • C08G18/24—Catalysts containing metal compounds of tin
  • C08G18/244—Catalysts containing metal compounds of tin tin salts of carboxylic acids
  • C08G18/246—Catalysts containing metal compounds of tin tin salts of carboxylic acids containing also tin-carbon bonds
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
  • C08G18/40—High-molecular-weight compounds
  • C08G18/62—Polymers of compounds having carbon-to-carbon double bonds
  • C08G18/6216—Polymers of alpha-beta ethylenically unsaturated carboxylic acids or of derivatives thereof
  • C08G18/622—Polymers of esters of alpha-beta ethylenically unsaturated carboxylic acids
  • C08G18/6225—Polymers of esters of acrylic or methacrylic acid
• • 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

Definitions

• the present invention relates to a two-component system, a process for producing a coating on a substrate, in particular on automobile bodies or automobile parts, and coatings obtainable by the process. Moreover, the invention relates to the use of component A) or B) in the two-component system and coated with the coating substrates, in particular coated automobile bodies or automotive parts.
• Polyurethane coatings have been known for a long time and are used in many fields. They are usually prepared from a hydroxyl component (component A)) and a polyisocyanate components (component B)) by mixing immediately before application (two-component technology).
• the hydroxyl component in two-component systems is subject to general water content specifications, so solvents with a maximum water content of 500 ppm are specified as suitable for polyurethane chemistry. However, water levels well below 500 ppm are usually desired because the water content of the hydroxyl component has an effect on changing the stoichiometry of the curing reaction of the paint. This is evident, for example, in a two-component polyurethane clearcoat for the plastic coating as follows: Crosslinking ratio 100 parts of polyol component to 35 parts of hardener. Equivalent weight hardener Delivery form (NCO): 306 g. Per equivalent of hardener, 875 g of polyol component must be used.
• NCO Equivalent weight hardener Delivery form
• the stoichiometry of the crosslinking would already be unacceptably strongly influenced, so that in practice the water content in the polyol component is kept below 500 ppm or at most below 1000 ppm.
• WO 2013/076208 A1 discloses a solvent-containing clearcoat coating composition comprising a polyacrylate component and a crosslinker component having a water content as low as possible of not more than 1% by weight, based on the total amount of the composition.
• WO 2013/076208 A1 gives the water content only as a deficiency nition of the term "solvent-containing" used there and does not address the crosslinking reaction.
• polyisocyanate components based on aliphatic polyisocyanates are generally used which, compared to products with aromatically bound isocyanate groups, react significantly more slowly with the hydroxyl component. In most cases, therefore, the reaction must be catalyzed. In addition, where possible, it is heated to further accelerate the reaction.
• organic tin compounds in particular dibutyltin dilaurate (DBTL), have proved successful as catalysts.
• DBTL dibutyltin dilaurate
• WO 2011/051247 A1 describes polyisocyanate polyaddition products for use inter alia in the coating sector, in which polyisocyanates are reacted with NCO-reactive compounds in the presence of a thermolatenten inorganic tin-containing catalyst.
• polyisocyanates are reacted with NCO-reactive compounds in the presence of a thermolatenten inorganic tin-containing catalyst.
• not all two-component systems require a reproducibly extended pot life, which is required for coating agents, compared to standard catalysts, in particular DBTL.
• the physical properties, in particular the hardness development, of the coatings obtainable from the two-component system are at least equivalent to the coatings known from the prior art and produced with non-thermolatent catalysts.
• a two-component system comprising a component A), comprising at least one NCO-reactive compound, and a component B) comprising at least one polyisocyanate, characterized in that the component A)> 400 to ⁇ 9500 ppm by weight of water, based on the total weight of component A), and component A) and / or component B) contains at least one thermolatent inorganic tin-containing catalyst.
• component A) contains> 501 to ⁇ 6500 ppm by weight, preferably> 700 to ⁇ 5000 ppm by weight, more preferably> 1001 to ⁇ 4000 ppm by weight and very particularly preferably> 1400 to ⁇ 2400 ppm by weight of water, based on the total weight of component A).
• the water content is determined by titration according to Karl Fischer as a volumetric method according to DIN 53715 (DIN 53715 was prepared on the basis of DIN 51777 Part 1 (1973 edition)).
• the measuring range of the water content is 0.01 - ⁇ 99 wt.%.
• the pot life is defined as the time in which the paint has doubled its viscosity (indirectly determined by doubling the flow time in the DIN cup, 4 mm).
• the component A) of the two-component system contains water in the abovementioned quantitative ranges.
• This water can be introduced in any way in the component A), wherein the paths can also complement each other to get to the required total amount of water in the component A).
• corresponding amounts of water can be introduced by way of production via the compounds contained in component A), in particular the NCO-reactive compound. It is likewise possible to add water to component A) itself.
• the water in component A) has been added separately and / or contained in the NCO-reactive compound as a result of the preparation.
• the terms “comprising” or “containing”, “consisting essentially of” and particularly preferably “consisting of” preferably mean.
• Component A) according to the invention comprises at least one NCO-reactive (isocyanate-reactive) compound.
• NCO-reactive compound is understood as meaning a compound which can react with polyisocyanates to give polyaddition compounds, in particular polyurethanes.
• polyisocyanates are compounds having at least two isocyanate groups per molecule.
• NCO-reactive compounds it is possible to use all compounds known to the person skilled in the art which have an average OH or NH functionality of at least 1.5.
• These may be, for example, low molecular weight diols (for example 1,2-ethanediol, 1,3- or 1,2-propanediol, 1,4-butanediol), triols (for example glycerol, trimethylolpropane) and tetraols (for example pentaerythritol), but short-chain polyamines also polyhydroxy compounds, such as polyether polyols, polyester polyols, polyurethane polyols, polysiloxane polyols, polycarbonate polyols, polyether polyamines, polybutadiene polyols, polyacrylate polyols and / or polymethacrylate polyols and their copolymers, referred to below as polyacrylate polyols.
• diols for example 1,2-
• the NCO-reactive compound is a polyhydroxy compound.
• the polyhydroxy compounds preferably have mass-average molecular weights Mw> 500 daltons, measured by gel permeation chromatography (GPC) against a polystyrene standard, more preferably between 800 and 100,000 daltons, in particular between 1,000 and 50,000 daltons.
• the polyhydroxy compounds preferably have an OH number of 30 to 400 mg KOH / g, in particular between 100 and 300 KOH / g.
• the hydroxyl number (OH number) indicates how many mg of potassium hydroxide are equivalent to the amount of acetic acid bound by 1 g of substance in the acetylation.
• the sample is boiled in the determination with acetic anhydride-pyridine and the resulting acid is titrated with potassium hydroxide solution (DIN 53240-).
• the glass transition temperatures, measured by means of DSC measurements according to DIN-EN-ISO 1 1357-2, of the polyhydroxy compounds are preferably between -150 and 100 ° C., more preferably between -120 ° C. and 80 ° C.
• Polyether polyols are accessible in a conventional manner by alkoxylation of suitable starter molecules under base catalysis or use of double metal cyanide compounds (DMC compounds).
• Suitable starter molecules for the preparation of polyether polyols are, for example, simple, low molecular weight polyols, water, organic polyamines having at least two N-H bonds or any mixtures of such starter molecules.
• Preferred starter molecules for the preparation of polyether polyols by alkoxylation, in particular by the DMC process are in particular simple polyols such as ethylene glycol, 1,3-propylene glycol and 1,4-butanediol, 1,6-hexanediol, neopentyl glycol, 2-ethylhexanediol-1 , 3, glycerol, trimethylolpropane, pentaerythritol and low molecular weight, hydroxyl-containing esters of such polyols with dicarboxylic acids of the type exemplified below or low molecular weight ethoxylation or propoxylation of such simple polyols or any mixtures of such modified or unmodified alcohols.
• Alkylene oxides which are suitable for the alkoxylation are, in particular, ethylene oxide and / or propylene oxide, which can be used in any order or also in a mixture in the alkoxylation.
• polyester polyols are described, for example, in EP-A-0 994 1 17 and EP-A-1 273 640.
• Polyester polyols can be prepared in a known manner by polycondensation of low molecular weight polycarboxylic acid derivatives, for example succinic acid, adipic acid, suberic acid, azelaic acid, sebacic acid, dodecanedioic acid, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, tetrachlorophthalic anhydride, endomethylenetetrahydrophthalic anhydride, glutaric anhydride, maleic acid, maleic anhydride, fumaric acid, dimer fatty acid, trimer fatty acid, phthalic acid , Phthalic anhydride, isophthalic acid, terephthalic acid, citric acid or trimellitic acid, with low molecular weight polyols, such as, for example, ethylene glycol, Diethylene glycol
• polyester polyols such as, for example, lactic acid, cinnamic acid or ⁇ -hydroxycaproic acid can also be polycondensed to form polyester polyols.
• polyester polyols of oleochemical origin can be prepared, for example, by complete ring opening of epoxidized triglycerides of an at least partially olefinically unsaturated fatty acid-containing fat mixture with one or more alcohols having 1 to 12 carbon atoms and subsequent partial transesterification of the triglyceride derivatives to alkyl ester polyols having 1 to 12 carbon atoms in the Alkyl residue can be produced.
• Polyurethane polyols are preferably prepared by reacting polyesterpolyol prepolymers with suitable di- or polyisocyanates and are described, for example, in EP-A-1 273 640.
• Suitable polysiloxane polyols are described, for example, in WO-A-01/09260, where the polysiloxane polyols cited therein can preferably be used in combination with other polyhydroxy compounds, in particular those having higher glass transition temperatures.
• the polyacrylate polyols very particularly preferred according to the invention are generally copolymers and preferably have mass-average molecular weights Mw between 1000 and 20,000 daltons, in particular between 1,500 and 10,000 daltons, in each case measured by gel permeation chromatography (GPC) against a polystyrene standard.
• the glass transition temperature of the copolymers is generally between -100 and 100 ° C, in particular between -50 and 80 ° C (measured by DSC measurements according to DIN-EN-ISO 1 1357-2).
• the polyacrylate polyols preferably have an OH number of 60 to 250 mg KOH / g, in particular between 70 and 200 mg KOH / g, and an acid number between 0 and 30 mg KOH / g.
• the acid number indicates the number of mg of potassium hydroxide consumed for the neutralization of 1 g of the respective compound (DIN EN ISO 21 14).
• suitable polyacrylate polyols are known per se to the person skilled in the art. They are obtained by free-radical polymerization of hydroxyl-containing, olefinically unsaturated monomers or by free-radical copolymerization of hydroxyl-containing, olefinically unsaturated monomers with optionally other olefinically unsaturated monomers.
• saturated monomers such as ethyl acrylate, ethyl methacrylate, propyl acrylate, propyl methacrylate, isopropyl acrylate, isopropyl methacrylate, butyl acrylate, butyl methacrylate, isobutyl acrylate, isobutyl methacrylate, tert-butyl acrylate, tert-butyl methacrylate, amyl acrylate, amyl methacrylate, hexyl acrylate, hexyl methacrylate, ethylhexyl acrylate, ethylhexyl methacrylate , 3,3,5-trimethylhexyl acrylate, 3,3,5-trimethylhexyl methacrylate, stearyl acrylate, stearyl methacrylate,
• Lauryl acrylate or lauryl methacrylate, cycloalkyl acrylates and / or cycloalkyl methacrylates such as cyclopentyl acrylate, cyclopentyl methacrylate, isobornyl acrylate, isobornyl methacrylate or in particular cyclohexyl acrylate and / or cyclohexyl methacrylate.
• Suitable hydroxyl-containing, olefinically unsaturated monomers are in particular 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2
• vinylaromatic hydrocarbons such as vinyltoluene, alpha-methylstyrene or, in particular, styrene, amides or
• Component B) according to the invention comprises at least one polyisocyanate.
• polyisocyanate all polyisocyanates known to the person skilled in the art for the preparation of polyisocyanate polyaddition products, in particular polyurethanes, in particular the group of organic aliphatic, cycloaliphatic, araliphatic and / or aromatic polyisocyanates having at least two isocyanate groups per molecule and mixtures can be used from that.
• polyisocyanates are di- or tri-isocyanates, e.g. 1, 4-butane diisocyanate, 1,5-pentane diisocyanate (pentamethylene diisocyanate, PDI), 1,6-hexane diisocyanate
• Triisocyanatononane, TIN 4,4'-methylenebis (cyclohexylisocyanate) (H 12 MDI), 3,5,5-trimethyl-1-isocyanato-3-isocyanatomethylcyclohexane (isophorone diisocyanate, IPDI), 1,3- and 1 , 4-bis (isocyanatomethyl) cyclohexane (HfrXDI), 1,5-naphthalene diisocyanate, diisocyanatodiphenylmethane (2,2'-, 2,4'- and 4,4'-MDI or mixtures thereof),
• component B) contains as polyisocyanate an aliphatic and / or cycloaliphatic polyisocyanate.
• component B) contains as polyisocyanate a derivative of hexamethylene diisocyanate and / or pentamethylene-end-diisocyanate, in particular a hexamethylene diisocyanate trimer and / or a pentamethylene diisocyanate trimer.
• the ratio of polyisocyanates to NCO-reactive compounds in the two-component system based on the amounts of isocyanate groups to NCO-reactive groups is from 0.8 to 1.0 to 2.0 to 1.0. Particularly preferred is a ratio of 1.0 to 1.0 to 1.5 to 1.0. Most preferred is a ratio of 1.05 to 1.0 to 1.25 to 1.0.
• Component A) and / or B) of the two-component system according to the invention contains at least one thermolatent inorganic tin-containing catalyst.
• the term "inorganic” is to be understood as meaning that the compounds to be used as a thermolatent inorganic tin-containing catalyst do not have a direct tin-carbon bond.
• thermolatent inorganic tin-containing catalyst means in particular any catalyst which has no direct tin-carbon bond and which does not accelerate or substantially accelerate the crosslinking reaction of the at least one polyisocyanate with the at least one NCO-reactive compound to form a urethane bond below 25 ° C, in particular below 30 ° C, preferably below 40 ° C
• the presence of the thermolatent catalyst in the coating below 25 ° C., in particular below 30 ° C., preferably below 40 ° C. does not have any significant effect Influence on the reaction rate of the already running reaction.
• thermolatent inorganic tin-containing catalyst used in the two-component system comprises cyclic tin compounds of the formula I, II or III or mixtures thereof:
• D is -O-, -S- or -N (R1) - wherein Rl is a saturated or unsaturated, linear or branched, aliphatic or cycloaliphatic or an optionally substituted, aromatic or araliphatic radical having up to 20 carbon atoms, optionally Heteroatoms from the series oxygen, sulfur, nitrogen may contain, or for hydrogen or the rest
• D * is -O- or -S-;
• X, Y and Z are identical or different radicals selected from alkylene radicals of the formulas -C (R2) (R3) -, -C (R2) (R3) -C (R4) (R5) - or -C (R2) ( R3) - C (R4) (R5) -C (R6) (R7) - or ortho-arylene radicals of the formulas
• R 2 to R 1 independently of one another are saturated or unsaturated, linear or branched, aliphatic or cycloaliphatic or optionally substituted, aromatic or araliphatic radicals having up to 20 carbon atoms, which may optionally contain heteroatoms from the series oxygen, sulfur, nitrogen, or represent hydrogen;
• D is -N (R1) - R 1 is preferably hydrogen or an alkyl, aralkyl, alkaryl or aryl radical having up to 20 C atoms or the radical particularly preferably hydrogen or an alkyl, aralkyl, alkaryl or aryl radical having up to 12 C atoms or the radical very particularly preferably hydrogen or a methyl, ethyl, propyl, butyl, hexyl or octyl radical, where propyl, butyl, hexyl and octyl for all isomeric propyl,
• Butyl, hexyl and octyl radicals are to Ph-, CH3PI1- or the rest
• D * is -O-.
• X, Y and Z are the te -C (R2) (R3), -C (R2) (R3) -C (R4) (R5) - or the ortho-arylene radical
• R 2 to R 7 are preferably hydrogen or alkyl, aralkyl, alkaryl or
• Aryl radicals having up to 20 carbon atoms more preferably hydrogen or alkyl, aralkyl, alkaryl or aryl radicals having up to 8 carbon atoms, most preferably hydrogen or alkyl radicals having up to 8 carbon atoms, even more preferred to hydrogen or methyl.
• R 8 to R 11 are preferably hydrogen or alkyl radicals having up to 8 carbon atoms, more preferably hydrogen or methyl.
• R 12 is preferably hydrogen or an alkyl, aralkyl, alkaryl or
• Aryl radical having up to 20 carbon atoms particularly preferably hydrogen or an alkyl, aralkyl, alkaryl or aryl radical having up to 12 C atoms, most preferably hydrogen or a methyl, ethyl, propyl, butyl -, hexyl or octyl radical, wherein propyl, butyl, hexyl, and octyl are all propylene, butyl, hexyl and octyl radicals.
• L3 and L4 are Cl, MeO, EtO, PrO, BuO, HexO, OctO, PhO, formate, acetate, propanoate, butanoate, pentanoate, hexanoate, octanoate,
• Pr, Bu, Hex and Oct represent all isomeric propyl, butyl, hexyl and octyl radicals, even more preferably Cl, MeO, EtO, PrO, BuO, HexO- , OctO-, PhO-, hexanoate, laurate, or benzoate, wherein Pr, Bu, Hex and Oct stand for all isomeric propyl, butyl, hexyl and octyl radicals.
• R15 to R20 are preferably hydrogen or alkyl, aralkyl, alkaryl or
• Aryl radicals having up to 20 carbon atoms more preferably hydrogen or alkyl, aralkyl, alkaryl or aryl radicals having up to 12 carbon atoms, very particularly preferably hydrogen, methyl, ethyl, propyl, butyl, Hexyl, or octyl radicals, wherein propyl, butyl, hexyl, and octyl for all isomeric propyl, butyl, hexyl and octyl radicals.
• L1-XDY-L2 preferably represents: HN [CH 2 CH 2 O-] 2 , HN [CH 2 CH (Me) O-] 2 , HN [CH 2 CH (Me) O -] [CH (Me ) CH 2 0-], HN [CH 2 C (Me) 2 O-] 2 , HN [CH 2 C (Me) 2 O-]
• BuN [CH 2 CH (Me) O-] 2 BuN [CH 2 CH (Me) O-] [CH (Me) CH 2 O-]
• BuN [CH 2 C (Me) 2 O-] 2 BuN [CH 2 C (Me) 2 O-] [C (Me) 2 CH 2 O-]
• thermolatent catalysts suitable according to the invention are described, for example, in: EP 2 900 716 A1, EP 2 900 717 A1, EP 2 772 496 A1, EP 14182806, J. Organomet. Chem. 2009 694 3184-3199, Chem. Heterocycl. Comp. 2007 43 813-834, Indian J. Chem. 1967, 5 643-645 and in literature cited therein, the entire disclosure of which is hereby incorporated by reference.
• tin compounds tend to oligomerize, so that polynuclear tin compounds or mixtures of mononuclear and polynuclear tin compounds are frequently present.
• the tin atoms are preferably linked to one another via oxygen atoms ('oxygen bridges').
• oxygen atoms 'oxygen bridges'.
• Typical oligomeric complexes arise, e.g. by condensation of the tin atoms over oxygen or sulfur, e.g. x- O
• thermolatent catalyst is selected from the group of mono- or polycyclic tin compounds of the type:
• thermolatent catalyst is selected from:
• thermolatent inorganic tin-containing catalysts may be combined with other catalysts / activators known in the art; For example, titanium, zirconium, bismuth, tin (II) - and / or iron-containing catalysts, as described for example in WO 2005/058996. It is also possible to add amines or amidines. In addition, in the polyisocyanate Polyaddition reaction also acidic compounds, such as 2-ethylhexanoic acid or alcohols may be added to the reaction control.
• thermolatent inorganic tin-containing catalyst to be used according to the invention can be varied within a wide range and preferably amounts to> 50 to ⁇ 5000 ppm by weight, preferably to> 100 to ⁇ 3000 ppm by weight, more preferably to> 300 to ⁇ 2500 ppm by weight and very particularly preferably to> 500 to ⁇ 1500 ppm by weight of tin, based on the total amount of polyisocyanate in component B).
• both component A) and component B) may contain conventional auxiliaries and additives in effective amounts.
• Effective amounts of solvent are preferably up to 150 wt .-%, more preferably up to 100 wt .-% and in particular up to 70 wt .-%, each based on the nonvolatile constituents of the two-component system according to the invention.
• Effective amounts of other additives are preferably up to 25 wt .-%, more preferably up to 10 wt .-% and in particular up to 5% by weight, each based on the non-volatile constituents of the two-component system according to the invention.
• auxiliaries and additives are, in particular, light stabilizers, such as UV absorbers and sterically hindered amines (HALS), furthermore stabilizers, fillers and antisettling agents, defoaming agents, anticrater agents and / or wetting agents, leveling agents, film-forming auxiliaries, reactive diluents, solvents, substances for Rheology control, panty additives and / or components that prevent soiling and / or improve the cleanability of the cured coatings, and matting agents.
• light stabilizers such as UV absorbers and sterically hindered amines (HALS)
• HALS sterically hindered amines
• fillers and antisettling agents fillers and antisettling agents
• defoaming agents anticrater agents and / or wetting agents
• leveling agents film-forming auxiliaries
• reactive diluents solvents
• panty additives and / or components that prevent soiling and / or improve the cleanability of the cured coatings,
• sunscreens in particular UV absorbers such as substituted benzotriazoles, S-phenyltriazines or oxalanilides and sterically hindered amines in particular with 2,2,6,6-tetramethyl-piperidyl structures - referred to as HALS
• Stabilizers such as radical scavengers and other polymerization inhibitors such as hindered phenols stabilize paint components during storage and are intended to prevent discoloration during curing.
• acidic stabilizers such as alkyl-substituted phosphoric acid esters.
• the two-component system according to the invention can furthermore comprise pigments, dyes and / or fillers.
• the pigments used for this purpose are also metallic or other effect pigments, dyes and / or fillers are known to the person skilled in the art.
• Preferred fillers are compounds which do not adversely affect the appearance of the coating. Examples are nanoparticles based on silicon dioxide,
• anti-settling agents may be expedient in order to prevent separation of the constituents during storage.
• Wetting and leveling agents improve the surface wetting and / or the course of paints.
• fluorosurfactants silicone surfactants and special polyacrylates.
• Rheology-controlling additives are important for controlling the properties of the two-component system during application and during the development phase on the substrate and are described, for example, in the patent specifications WO 94/22968, EP-A-0 276 501, EP-A-0 249 201 or WO 97/12945 known; crosslinked polymeric microparticles such as disclosed in EP-A-0081227; inorganic phyllosilicates such as aluminum-magnesium silicates, sodium-magnesium and sodium-magnesium-fluorine-lithium phyllosilicates of the montmorillonite type; Silicas such as Aerosil®; or synthetic polymers having ionic and / or associative groups such as polyvinyl alcohol, poly (meth) acrylamide, poly (meth) acrylic acid, polyvinylpyrroli
• the two-component system according to the invention can be used solvent-free, but preferably contains at least one solvent in component A) and / or component B).
• solvent used in component A) should contain residues of water as a result of the preparation, the water content can be determined with the Karl Fischer titration given above, so that the water content of component A) can be adjusted accordingly.
• Suitable solvents are used in a manner known to those skilled in the art, tailored to the two-component system used and the application method. Solvents should dissolve the components used and promote their mixing and avoid incompatibilities.
• solvents come into consideration, which come in the two-component technology used. Examples are ketones such as acetone, methyl ethyl ketone or hexanone, esters such as ethyl acetate, butyl acetate,
• Methoxypropyl acetate substituted glycols and other ethers, aromatics such as xylene or solvent naphtha such as e.g. Fa. Exxon-Chemie and mixtures of these solvents.
• the two-component system according to the invention can be used very well for coating a substrate.
• a further subject of the present invention is therefore a process for producing a coating on a substrate, comprising the following steps: a) providing a substrate; bl) application of at least one two-component system according to the invention; cl) curing the coating with heat. Furthermore, the two-component system, the water even when applying the
• the relative humidity of the application atmosphere is> 30 to ⁇ 80%, preferably> 35 to ⁇ 75% and more preferably> 45 to ⁇ 65%.
• Another object of the present invention is therefore a method for producing a coating on a substrate, comprising the following steps: a2) providing a substrate; b2) applying at least one two-component system comprising a component A) comprising at least one NCO-reactive compound, and a component B) comprising at least one polyisocyanate, wherein component A) and / or component B) at least one thermolatenten inorganic tin containing catalyst; c2) hardening of the coating with heat supply, wherein the two-component system when applied in step b2) from the application atmosphere from> 400 to ⁇ 9500 ppm by weight of water, based on the total weight of component A) receives.
• the two-component system when applied in step b2) > 501 to ⁇ 6500 ppm by weight, preferably> 700 to ⁇ 5000 ppm by weight, more preferably> 1001 to ⁇ 4000 ppm by weight and very particularly preferably> 1400 to ⁇ 2400 ppm by weight of water, based on the total weight of component A).
• a two-component system which, for example, due to its production does not contain enough water and / or is used without addition of water in component A) in the process according to the invention, can have water contents of> 400 to ⁇ 9500 ppm by weight, preferably> 501 to ⁇ 6,500 ppm by weight, more preferably> 700 to ⁇ 5,000 ppm by weight, very particularly preferably> 1001 to ⁇ 4,000 ppm by weight, and very particularly preferably> 1400 to ⁇ 2,400 ppm by weight of water , based on the total weight of component A), absorb when applied to the substrate.
• step a) stands for step a) and / or step a2)
• step b) stands for step b1) and / or step b2)
• step c) stands for step c1) and / or step c2).
• the substrates can be uncoated or coated.
• primers, fillers and / or basecoats may already have been applied to the substrate as a coating, before it is used in the process according to the invention.
• primers are, in particular, cathodic dipcoats used in automotive finishing, solvent-based or aqueous primers for plastics, in particular for plastics with low surface tension, such as PP or PP-EPDM.
• Suitable basecoat films are known to the person skilled in the art, for example, from A. Goldschmidt, H. Streitberger, "BASF Handbuch Lackiertechnik", Vincentz-Verlag, Hannover, D, 2002.
• Suitable substrates are, for example, one or more materials comprising substrates, in particular so-called composite materials.
• a substrate which is composed of at least two materials is referred to as a composite material according to the invention.
• Suitable materials include wood, metal, plastic, paper, leather, textiles, felt, glass, wood materials, cork, inorganic bonded substrates such as wood and fiber cement boards, electronic assemblies or mineral substrates.
• Suitable composite types are, for example, particle composites, also as Disperse materials referred fiber composites, composite materials, also referred to as laminates, interpenetration composite materials and structural composites.
• Suitable metals are, for example, steel, aluminum, magnesium and alloys of metals, as used in the applications of the so-called wire, coil, Can or
• Container painting is used, and the like.
• plastic also fiber-reinforced plastics, such as glass or carbon fiber reinforced plastics, and plastic blends of at least two or more plastics understood.
• plastics which are suitable according to the invention are ABS, AMMA, ASA, CA, CAB, EP, UF, CF, MF, MPF, PF, PAN, PA, PE, HDPE, LDPE, LLDPE, UHMWPE, PET, PMMA, PP, PS, SB, PUR, PVC, RF, SAN, PBT, PPE, POM, PUR-RIM, SMC, BMC, PP-EPDM and UP (abbreviated to DIN 7728T1).
• the substrate has a surface which is completely or partially made of plastic and / or metal.
• the substrate consists at least partially of a composite material, in particular of a composite material comprising plastic and / or metal.
• the substrate comprises metal
• the substrate may be 80 wt .-%, 70 wt .-%, 60 wt .-%, 50 wt .-%, 25 wt .-%, 10 wt. -%, 5 wt .-%, 1 wt .-% consist of metal.
• the substrate to be provided in step a) is a body or parts thereof comprising one or more of the aforementioned materials.
• the body or its parts comprises one or more materials selected from metal, plastic or mixtures thereof.
• the substrate to be provided in step a) is a plastic part from the "Consumer Electronics" area.
• the application of the two-component system in step b) of the process according to the invention can be carried out from solution.
• Suitable application methods include, for example, printing, brushing, rolling, casting, dipping, fluidized bed processes and / or spraying such as compressed air spraying, airless spraying, high rotation, electrostatic spray application (ESTA), optionally combined with hot spray application such as hot spraying.
• Air-hot spraying Particularly preferred here is the application by means of spraying such as compressed air spraying, airless spraying, high rotation, electrostatic spray application (ESTA), optionally associated with hot spray application such as hot air hot spraying.
• the two-component system to be applied in step b) can be applied both after the mixing of components A) and B) and can only be mixed immediately upon application.
• the mixed two-component system has a limited shelf life, the so-called pot life, since the crosslinking reaction is already progressing slowly after mixing.
• the advantageous effect of the extended pot life for example in an improved paint optics, since the two-component system of the invention can form a uniform film on the substrate and at the same time the hardness development surprisingly remains at a high level, since the catalytic activity of the thermolatenten inorganic Tin-containing catalyst is not affected. It has proven to be particularly practical for the process according to the invention if the curing in step c) takes place at a substrate temperature of below 120 ° C., preferably below 110 ° C., more preferably below 100 ° C., in particular below 90 ° C.
• the curing in step c) of the method according to the invention is advantageously substantially completed in less than 45 minutes.
• the curing in step c) is substantially complete in less than 40 minutes, more preferably less than 35 minutes, most preferably less than 30 minutes.
• Substantially complete as used herein means that the residual isocyanate content after curing in step c) is less than 20%, preferably less than 15%, more preferably less than 10%, most preferably less than 5%, most preferably less than 3%, based on the isocyanate content of the polyisocycanate in step b).
• the percentage of isocyanate groups still present can be determined by comparing the content of isocyanate groups in% by weight in step b) with the content of isocyanate groups in% by weight after curing in step c), for example by comparing the isocyanate band intensity at approx 2270 cm -1 by means of IR spectroscopy According to a particular embodiment of the method according to the invention
• Step c) a further step dl) and / or step d2) connect, in which the coating is peeled from the substrate again to produce a film.
• Another object of the present invention is the component A) for use in the two-component system according to the invention.
• Another object of the present invention is the component B) for use in the two-component system according to the invention.
• the invention further relates to a coating which was produced by the method according to the invention or can be produced.
• Another object of the invention are substrates which are coated with the coating according to the invention.
• the substrate coated with the coating according to the invention is a body, in particular a vehicle or parts thereof.
• the vehicle can be one or more
• Suitable materials are, for example, metal, plastic or mixtures thereof.
• the vehicle may be any vehicle known to those skilled in the art.
• the vehicle may be a motor vehicle, truck, motorcycle, scooter, bicycle or the like. It is preferably in the
• Vehicle to a motor vehicle and / or truck, particularly preferably it is a motor vehicle.
• the substrate coated with the coating according to the invention is a body or parts thereof which comprises one or more of the materials selected from metal, plastic or mixtures thereof.
• the substrate to be provided in step a) is a plastic part from the "Consumer Electronics" area.
• the flow time was determined in accordance with DIN 53211 (DIN 53211 was withdrawn in October 1996) by means of DIN cup 4 mm from BYK Gardner, whereby the determination was carried out without exact temperature control at room temperature, since this is not absolute but only comparative Values act.
• the pendulum damping was determined in an air-conditioned room at 23 ° C and 50% relative humidity by means of pendulum damping tester from BYK Gardner according to standard ISO 1522.
• the water content was determined by titration according to Karl Fischer as a volumetric method according to DIN 53715 (DIN 53715 was prepared in accordance with DIN 51777 Part 1 (1973 edition)). The water content was measured with a titration machine Titrando 841, Messrs. Methrom. The measuring range of the water content was 0.01 - ⁇ 99 wt.%.
• solvent-based clearcoats based on an OH-containing acrylate polyol were used produced.
• components A and B were weighed in succession and mixed.
• the pot life is defined as the time in which the paint has doubled its viscosity (indirectly determined by doubling the flow time in the DIN cup, 4 mm).
• Table 1 Prepared clearcoat formulations
• mixtures A and B were then mixed homogeneously with one another by stirring with the laboratory stirrer (60 sec. At 1000 rpm). Then, the mixed system was allowed to rest for 60 seconds to then determine the initial drainage time by means of DIN cup 4 mm at room temperature.
• latkat 4,12-di-n-butyl-2,6, 10,14-tetramethyl-1, 7,9,15-tetraoxa-4,12-diazastannaspiro [7.7] pentadec;
• DBTL dibutyltindilaurate
• thermolatent catalyst shows differences in pot life depending on the content of water in the mixed system. At 350 ppm water (Comparative Example 1) in the system, the pot life is significantly shorter (similar to Comparative Examples 9 and 10) than in Examples 2 to 8 according to the invention.
• the pendulum damping according to König was determined in accordance with ISO 1522. Of all three glass plates, König's pendulum damping was redetermined after 24 hours in the climatic chamber.
• thermolatent catalyst It could be proven that the hardness development and the associated physical properties do not change adversely with the addition of moisture into the two-component system. The catalytic effect of the thermolatent catalyst is retained.
• thermolatenten catalyst without negatively influencing the catalytic activity of the thermolatenten catalyst for curing the applied two-component system by increasing the temperature.

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• 2017
  • 2017-04-18 CN CN201780024966.0A patent/CN109071999B/zh not_active Expired - Fee Related
  • 2017-04-18 EP EP17717726.8A patent/EP3445827A1/de not_active Withdrawn
  • 2017-04-18 US US16/093,819 patent/US10815330B2/en not_active Expired - Fee Related
  • 2017-04-18 KR KR1020187029953A patent/KR102378119B1/ko active Active
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• 2022
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