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EP1294790A1 - Melanges reactifs de substances a base de polyisocyanates inhibes par alcool propargylique, procede permettant de les produire et leur utilisation - Google Patents

Melanges reactifs de substances a base de polyisocyanates inhibes par alcool propargylique, procede permettant de les produire et leur utilisation

Info

Publication number
EP1294790A1
EP1294790A1 EP01951646A EP01951646A EP1294790A1 EP 1294790 A1 EP1294790 A1 EP 1294790A1 EP 01951646 A EP01951646 A EP 01951646A EP 01951646 A EP01951646 A EP 01951646A EP 1294790 A1 EP1294790 A1 EP 1294790A1
Authority
EP
European Patent Office
Prior art keywords
groups
reactive
group
salts
isocyanate
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP01951646A
Other languages
German (de)
English (en)
Inventor
Günther OTT
Georg SCHÖN
Hardy Reuter
Joachim Woltering
Ulrike RÖCKRATH
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
BASF Coatings GmbH
Original Assignee
BASF Coatings GmbH
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by BASF Coatings GmbH filed Critical BASF Coatings GmbH
Publication of EP1294790A1 publication Critical patent/EP1294790A1/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • 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
    • C08G18/18—Catalysts containing secondary or tertiary amines or salts thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
    • C08G18/3203—Polyhydroxy compounds
    • C08G18/3212—Polyhydroxy compounds containing cycloaliphatic groups
    • 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
    • C08G18/64—Macromolecular compounds not provided for by groups C08G18/42 - C08G18/63
    • C08G18/6415—Macromolecular compounds not provided for by groups C08G18/42 - C08G18/63 having nitrogen
    • C08G18/643—Reaction products of epoxy resins with at least equivalent amounts of amines
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
    • C08G18/78—Nitrogen
    • C08G18/79—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates
    • C08G18/791—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups
    • C08G18/792—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups formed by oligomerisation of aliphatic and/or cycloaliphatic isocyanates or isothiocyanates
    • C—CHEMISTRY; METALLURGY
    • 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
    • C08G18/81—Unsaturated isocyanates or isothiocyanates
    • C08G18/8141—Unsaturated isocyanates or isothiocyanates masked
    • C08G18/815—Polyisocyanates or polyisothiocyanates masked with unsaturated compounds having active hydrogen
    • C08G18/8191—Polyisocyanates or polyisothiocyanates masked with unsaturated compounds having active hydrogen with acetylenic compounds having active hydrogen

Definitions

  • the present invention new reactive mixtures. Furthermore, the present invention relates to the use of the new reactive substance mixtures as coating materials, adhesives and sealing compounds or for their production. Furthermore, the present invention relates to a new method for producing coatings, adhesive layers and seals, which can be carried out emission-free
  • blocked polyisocyanates and processes for their preparation have long been known. Reference is made to US 4,444,954 A by way of example.
  • the blocked polyisocyanates are preferably used as crosslinking agents in externally crosslinking reactive substance mixtures, in particular coating materials, adhesives and sealants.
  • propargyl alcohol as a blocking agent for polyisocyanates is known from German patent applications DE 38 09 695 A1, DE 39 32 816 A1 or DE 41 42 734 A1.
  • the polyisocyanates partially blocked with propargyl alcohol are incorporated into binders by the reaction of the free isocyanate groups, which makes them self-crosslinking.
  • the polyisocyanates completely blocked with propargyl alcohol 5 serve as crosslinking agents in externally crosslinking reactive mixtures.
  • Sealants in which the one type of complementary reactive functional groups, which bring about the crosslinking, in a binder, and the other type in a hardener or Crosslinking agents are present.
  • adhesives and designated 'sealants wherein the complementary reactive functional groups present in a component.
  • the crosslinking of the blocked polyisocyanates known from German patent application DE 38 09 695 A1 is catalyzed by catalysts, such as salts or complexes of metals, such as, for example, lead, zinc, iron, tin, manganese and bismuth.
  • Preferred metal catalysts are lead compounds, such as lead carboxylates with 1 to 10 carbon atoms or tin compounds, such as dibutyltin diacetate, dibutyltin dilaurate or dibutyltin oxide.
  • these catalysts accelerate the elimination of the blocking agents from the blocked polyisocyanates and the conversion of isocyanate-reactive functional groups in the binders and / or reactive diluents to form urethane, thiourethane and / or urea groups.
  • the coatings, adhesive layers and seals that contain urethane, thiourethane and / or urea groups in their three-dimensional network offer in terms of pigmentability, flow, hardness, flexibility, scratch resistance, chemical resistance, weather resistance, adhesion and of Glanzes clear advantages over coatings, adhesive layers and seals that are based on a different crosslinking chemistry.
  • Emission-hardenable reactive substance mixtures that deliver three-dimensional networks with urethane and / or urea groups have long been known.
  • these are pure two- or multi-component systems, in which unblocked polyisocyanates are used as crosslinking agents.
  • These harden already at room temperature.
  • the crosslinking agents must be stored separately from the other constituents of the substance mixture until shortly before application, which requires more complex technology and logistics. It also makes the production of powder coatings and powder coating dispersions (powder slurries) very difficult, if not prevented.
  • Epoxy resins containing propargyl groups and amino groups are known from European patent application EP 0 852 252 A1.
  • the epoxy resins containing propargyl groups are used to produce cathodically depositable electrocoat materials which are self-crosslinking via amino groups and propargyl groups or via the acetylenically unsaturated bonds.
  • the cathodically separable Electrocoat also contains a component such as tetrabutylammonium bromide, which, after its activation by the electrolysis, catalyzes the thermal hardening of the deposited electrocoat layer. As a result, the electrocoat layer can be cured at comparatively low temperatures. If, on the other hand, the electrocoat material is not applied electrophoretically, but rather, for example, by doctoring onto a substrate, the resulting lacquer layer crosslinks only at 200 ° C.
  • the object of the present invention is to provide novel reactive compositions, especially coating materials, adhesives and sealing compounds, especially one-component coating materials, adhesives and sealants, that exhibit the technological property profile of the known reactive mixtures, if not ⁇ even surpass, and moreover emission- can be hardened.
  • the new reactive substance mixtures should be able to be provided in the form of finely divided powders, powder slurries, aqueous solutions or dispersions, organic solutions or dispersions or essentially water and solvent-free liquid systems (100% systems).
  • the new process and the new reactive substance mixtures should allow the resulting new coatings, adhesive layers and seals to be crosslinked with actinic radiation.
  • (C) at least one catalyst which catalyzes the addition of the isocyanate-reactive functional groups from (B) to the acetylenically unsaturated triple bond of the propargyl groups,
  • the new process for the production of coatings, adhesive layers and seals is referred to below as the “curing process according to the invention”.
  • the substance mixtures according to the invention made it possible to carry out the curing process according to the invention without emissions.
  • the curing process according to the invention provided coatings, adhesive layers and seals which, in the cured state, could still be crosslinked with actinic radiation.
  • the mixtures according to the invention contain polyisocyanates (A), which are partially or completely blocked with propargyl alcohol, as crosslinking agents.
  • the blocked polyisocyanates (A) can be partially blocked. This means that they still contain at least one free isocyanate group.
  • Blocked polyisocyanates of this type are used in particular as intermediates for the targeted introduction of isocyanate groups blocked with propargyl alcohol into compounds which contain isocyanate-reactive functional groups, such as primary amino groups, Hydroxyl groups and / or thiol groups, especially hydroxyl groups.
  • the incorporation results in more highly functional blocked polyisocyanates (A) which - provided there are still excess isocyanate-reactive functional groups - have self-crosslinking properties.
  • suitable compounds of this type are the binders and reactive diluents (B) described below.
  • the free isocyanate groups can furthermore be blocked with customary and known blocking agents, so that mixed-blocked polyisocyanates (A) result which are used as crosslinking agents in the mixtures according to the invention, which are one-component systems. This is mainly used to realize special technical effects in deblocking and networking.
  • partially blocked polyisocyanates (A) can be used as crosslinking agents in the mixtures according to the invention, which are two- or multi-component systems.
  • the blocked polyisocyanates (A) are preferably completely blocked.
  • blocked polyisocyanates (A) it is essential that at least one isocyanate group is blocked with propargyl alcohol. According to the invention, it is particularly advantageous if all isocyanate groups are blocked with propargyl alcohol.
  • polyisocyanates to be blocked Practically all customary and known aromatic, aliphatic and cycloaliphatic di- and polyisocyanates can be considered as the polyisocyanates to be blocked.
  • the diisocyanates and polyisocyanates come into consideration, which are referred to in the art as paint polyisocyanates.
  • suitable aromatic diisocyanates to be blocked are tolylene diisocyanate, xylylene diisocyanate, bisphenylene diisocyanate, naphthylene diisocyanate or diphenylmethane diisocyanate.
  • Suitable acyclic aliphatic diisocyanates to be blocked are trimethylene diisocyanate, tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate,
  • Heptane methylene diisocyanate or diisocyanates derived from dimer fatty acids such as those sold by Henkel under the trade name DDI 1410 and described in the patents WO 97/49745 and WO 97/49747, in particular 2-heptyl-3,4-bis (9-isocyanatononyl ) -1-pentyl-cyclohexane, or 1, 2-, 1, 4- or 1, 3- bis (isocyanatomethyl) cyclohexane, 1, 2-, 1, 4- or 1, 3-bis (2-isocyanatoeth-1 -yl) cyclohexane, 1, 3-bis (3-isocyanatoprop-1-yl) cyclohexane or 1, 2-, 1, 4- or 1, 3-bis (4-isocyanatobut-1-yl) cyclohexane, in particular
  • polyurethane prepolymers containing isocyanate groups which can be prepared by reaction of polyols with an excess of the aromatic, aliphatic and cycloaliphatic, preferably aliphatic and cycloaliphatic, diisocyanates described above and are preferably low-viscosity.
  • cycloaliphatic diisocyanate denotes a diisocyanate in which at least one isocyanate group is bonded to a cycloaliphatic radical.
  • Polyisocyanates containing isocyanurate, biuret, allophanate, iminooxadiazinedione, urethane, urea, carbodiimide and / or uretdione groups can also be used, which are prepared in a conventional and known manner from the diisocyanates described above.
  • Examples of suitable production processes and polyisocyanates are, for example, from the patents and patent applications CA 2,163,591 A1, US 4,419,513 A1, US 4,454,317 A1, EP 0 646,608 A1, US 4,801,675 A1, EP 0 183 976 A1, DE 40 15 155 A 1, EP 0 303 150 A 1, EP 0 496 208 A 1, EP 0 524 500 A 1, EP 0 566 037 A 1, US 5,258,482 A 1, US 5,290,902 A 1, EP 0 649 806 A 1, DE 42 29 183 A 1 or EP 0 531 820 A 1 are known.
  • Electron radiation can be activated.
  • suitable connections of this type are the urethane (meth) acrylates described in the European patent application EP 0 928 800 A1, which have (meth) acrylate groups and free isocyanate groups.
  • oligomers are understood to mean resins which contain at least 2 to 15 monomer units in their molecule.
  • polymers are understood to be resins which contain at least 10 monomer units in their molecule.
  • Oligomeric, preferably trimers, in particular isocyanurate, of hexamethylene diisocyanate are particularly preferably used.
  • phenols such as phenol, cresol, xylenol, nitrophenol, chlorophenol, ethylphenol, t-butylphenol, hydroxybenzoic acid, esters of this acid or 2,5-di-tert-butyl-4-hydroxytoluene;
  • lactams such as ⁇ -caprolactam, ⁇ -valerolactam, ⁇ -butyrolactam or ß-propiolactam
  • active methylenic compounds such as diethyl malonate, dimethyl malonate, ethyl or methyl acetoacetate or acetylacetone;
  • alcohols such as methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, t-butanol, n-amyl alcohol, t-amyl alcohol, lauryl alcohol, ethylene glycol monomethyl ether,
  • Diacetone alcohol ethylene chlorohydrin, ethylene bromohydrin, 1, 3-dichloro-2-propanol, 1, 4-cyclohexyldimethanol or
  • mercaptans such as butyl mercaptan, hexyl mercaptan, t-butyl mercaptan, t-dodecyl mercaptan, 2-mercaptobenzothiazole, thiophenol, methylthiophenol or ethylthiophenol;
  • acid amides such as acetoanilide, acetoanisidinamide, acrylic amide, methacrylamide, acetic acid amide, stearic acid amide or benzamide;
  • imides such as succinimide, phthalimide or maleimide
  • amines such as diphenylamine, phenylnaphthylamine, xylidine, N-phenylxylidine, carbazole, aniline, naphthylamine, butylamine, dibutylamine or butylphenylamine;
  • imidazoles such as imidazole or 2-ethylimidazole
  • ureas such as urea, thiourea, ethylene urea, ethylene thiourea or 1,3-diphenylurea
  • carbamates such as phenyl N-phenylcarbamate or 2-oxazolidone
  • imines such as ethyleneimine
  • oximes such as acetone oxime, formal doxime, acetaldoxime, acetoxime, methyl ethyl ketoxime, diisobutyl ketoxime, diacetyl monoxime,
  • xiv) salts of sulfurous acid such as sodium bisulfite or potassium bisulfite
  • xv) hydroxamic acid esters such as benzyl methacrylohydroxamate (BMH) or allyl methacrylohydroxamate; or
  • substituted pyrazoles such as 3,5- or 3,4-dimethylpyrazole, imidazoles or triazoles.
  • the essential performance properties of the blocked polyisocyanates (A) such as e.g. the stoving temperature is mainly determined by the isocyanate groups blocked with propargyl alcohol.
  • the blocking has no peculiarities, but takes place by stoichiometric reaction of the di- and polyisocyanates to be blocked with the propargyl alcohol to be used according to the invention in the melt or in at least one organic solvent which is essentially inert to isocyanates, preferably under a protective gas atmosphere and in the presence of a suitable one Catalyst such as an organotin compound, such as it is described in European patent EP 0 159 117 B1 or the German patent application DE 44 41 418 A1 for 3,5-dimethylpyrazole.
  • the blocked polyisocyanates (A) can be used for all purposes in which blocked di- and polyisocyanates are usually used.
  • the mixtures according to the invention are reactive. This means that they are stable in storage at room temperature for a more or less long period of time, preferably for at least 6 hours in the case of two- or multi-component systems or for at least several weeks, in particular for at least one year in the case of one-component systems, and only after addition of energy, especially thermal energy, react to the desired end products.
  • the substance mixtures according to the invention can be used by everyone
  • the substance mixtures according to the invention are preferably used as coating materials, adhesives and sealants. They are particularly preferably used as coating materials according to the invention.
  • the content of blocked polyisocyanates (A) in the coating materials of the invention can vary extremely widely. Since the blocked polyisocyanates (A) can completely replace the conventional blocked di- and polyisocyanates in the function of crosslinking agents for thermally curable coating materials, they can be used in the customary amounts known from the prior art. However, due to their advantageous performance properties, they can often be used in smaller quantities. On the other hand, because of their ability to subsequently crosslink when irradiated with actinic radiation, they can be used in excess quantities over the binders and reactive diluents (B). They are preferably in an amount of 5 to 70, preferably 6 to 67, particularly preferably 7 to 63, very particularly preferably 8 to 60 and in particular 9 to 57% by weight, in each case based on the solids of the coating material of the invention.
  • the coating materials of the invention contain at least one constituent (B), which on average is at least two contains isocyanate-reactive functional groups in the molecule. It is preferably at least one binder and / or at least one reactive diluent (B).
  • the coating materials of the invention contain customary and known binders (B), as described, for example, in Römpp Lexikon Lacke und Druckmaschine, Georg Thieme Verlag, Stuttgart, New York, 1998, under the keyword “Binders”, pages 73 and 74.
  • binders are statistical, alternating and / or block-like linear and / or branched and / or comb-like oligomeric or polymeric (co) polymers of ethylenically unsaturated monomers, or polyaddition resins and / or polycondensation resins as used in Römpp Lexikon Lacke und Druckmaschine, Georg Thieme Verlag, Stuttgart, New York, 1998, page 457: “Polyaddition” and “Polyadditionharze (polyadducts)", pages 463 and 464: "Polycondensates", “Polycondensation” and “Polycondensation Resins”.
  • the binders contain the isocyanate-reactive functional groups described above.
  • they can contain further reactive functional groups which can undergo thermally initiated crosslinking reactions with the complementary reactive functional groups of the customary and known crosslinking agents which may be present and described below. They can also contain groups that can be activated with actinic radiation, such as acrylate groups.
  • the coating composition according to the invention contains at least one low molecular weight compound and / or a comparatively low molecular weight oligomer. These compounds and oligomers are also referred to as reactive diluents (B).
  • Suitable reactive diluents (B) are the polyhydroxy- and / or polythiol-functionalized cyclic and / or acyclic alkanes with 9 to 16 carbon atoms in the molecule, such as the positionally isomeric diethyloctanediols, as described in German patent application DE 198 09 643 A1, which hyperbranched Compounds with a tetrafunctional central group, as described in German patent application DE 198 40 605 A1, or the hydroformylated and hydrogenated oligomers, obtainable by metathesis of acyclic monoolefins and cyclic monoolefins, hydroformylation of the resulting oligomers and subsequent hydrogenation, as described in German patent application DE 198 05 421 A1 can be described.
  • This variant of the coating material of the invention is used in particular when its solids content is to be particularly high, for example up to 100% by weight in the case of the liquid 100% systems.
  • the content of these binders and / or reactive diluents (B) in the coating compositions according to the invention can likewise vary extremely widely and depends in particular on the functionality of the binders and / or reactive diluents on the one hand and the blocked polyisocyanates (A) on the other.
  • the content is preferably 30 to 95, preferably 33 to 94, particularly preferably 37 to 93, very particularly preferably 40 to 92 and in particular 43 to 91% by weight, in each case based on the solids of the coating material of the invention.
  • the coating material of the invention contains at least one catalyst (C) for thermal crosslinking.
  • the catalyst (C) to be used according to the invention controls the crosslinking reaction in such a way that it does not undergo thermal curing in the "classic sense” by splitting off the propargyl alcohol from the blocked polyisocyanates according to the invention and reacting the deblocked isocyanate groups with the isocyanate-reactive groups in the binders and / or reactive diluents (B) with the formation of urethane, thiourethane and / or urea groups, especially urethane groups.
  • the catalysts (C) control the crosslinking reaction in the curing process according to the invention in such a way that during thermal curing they predominantly or entirely in the sense of adding the isocyanate-reactive groups of the binders and / or reactive diluents (B) to the propargyl groups of the blocked polyisocyanates (A) Formation of vinyl ether, vinyl thioether and / or enamines, especially vinyl ether groups, takes place.
  • the resulting coatings of the invention are furthermore distinguished by the fact that they can be post-crosslinked with actinic light because of the vinyl groups contained therein.
  • Actinic light is understood to mean electromagnetic radiation such as near infrared, visible light or UV light, in particular UV light, and corpuscular radiation such as electron radiation.
  • catalytically active organometallic chelates such as zinc acatylacetonate
  • Alkali metal hydroxides such as NaOH or KOH
  • Alkali metal alcoholates such as sodium or potassium ethanolate, isopropoxide or tert-butoxide
  • Onium salts such as ammonium, phosphonium or sulfonium salts, preferably the fully alkylated and / or arylated ammonium, phosphonium or sulfonium salts, in particular the N, N, N, N-tetramethyl, tetraethyl, tetrapropyl or tetrabutylammonium salts or N. , N, N-Trimethyi-N-cetylammonium salts, triethylphenylphosphonium salts or
  • quaternary ammonium salts which are produced from epoxides or epoxy resins and tertiary amines, or
  • ternary sulfonium salts made from epoxies or epoxy resins and secondary sulfides.
  • N, N, N-trimethyl-N-cetylammonium bromide is very particularly preferably used.
  • the catalysts (C) in the coating materials according to the invention are preferably in an amount of 0.01 to 5, preferably 0.05 to 4.5, particularly preferably 0.1 to 4, very particularly preferably 0.5 to 4 and in particular 0, 7 to 3.5 wt .-%, each based on the solid of the coating material of the invention.
  • the coating materials of the invention can also contain conventional and known crosslinking agents in minor amounts, which means that the blocked polyisocyanates (A) still before determining the curing properties of the coating materials in the main.
  • Suitable additional crosslinking agents are aminoplast resins, as described, for example, in Römpp Lexikon Lacke und Druckmaschine, Georg Thieme Verlag, 1998, page 29, “Aminoharze”, the textbook “Lackadditive” by Johan Bieleman, Wiley-VCH, Weinheim, New York, 1998, Pages 242 ff., The book “Paints, Coatings and Solvents", second completely revised edition, Edit. D. Stoye and W. Freitag, Wiley-VCH, Weinheim, New York, 1998, pages 80 ff., The patents US 4,710,542 A1 or EP-B-0 245 700 A1 as well as in the article by B.
  • the coating compositions according to the invention can contain at least one additive.
  • suitable additives are organic and inorganic color and / or effect pigments, organic and inorganic fillers, reactive thinners curable with actinic radiation (cf. Römpp Lexikon Lacke und Druckmaschine, Stuttgart, New York, 1998, pages
  • low-boiling organic solvents and / or high-boiling organic solvents (“long solvents”), binders curable with actinic radiation, UV absorbers, light stabilizers, free radical scavengers, thermolabile free radical initiators, photoinitiators, catalysts for crosslinking, venting agents, slip additives, Polymerization inhibitors, defoamers, emulsifiers, wetting agents, adhesion promoters, leveling agents, film-forming aids, rheology-controlling additives or flame retardants
  • suitable paint additives are described in the textbook "Paint Additives” by Johan Bieleman, Wiley-VCH, Weinheim, New York, 1998. 5
  • the coating materials according to the invention can be single-component systems or two- or multi-component systems. Preferably it is
  • the coating materials of the invention can be essentially free of water and / or organic solvents and can be in powder or liquid form (100% systems).
  • “essentially free” means that the content of 5 water and / or organic solvents is below 5.0, preferably below 3.0, preferably below 2.0, particularly preferably below 1.0, very particularly preferably is below 0.5% by weight and in particular below the gas chromatographic detection limit.
  • they can be used, for example, as powder fillers, powder base coats, powder clear coats or liquid clear coats.
  • it can also be a water-based coating material, in particular an electrocoat, a water filler, a water-based paint, a water-clear paint or an aqueous powder coating dispersion (unpigmented powder slurry clear coat or pigmented powder slurry base coat).
  • a water-based coating material in particular an electrocoat, a water filler, a water-based paint, a water-clear paint or an aqueous powder coating dispersion (unpigmented powder slurry clear coat or pigmented powder slurry base coat).
  • the coating materials of the invention has no special features but instead takes place in conventional manner by mixing the ingredients described above in suitable 'mixing equipment such as stirred tanks, dissolvers, stirred mills, static mixers, toothed-wheel dispersers or extruder, according to the preparation of appropriate coating materials.
  • suitable 'mixing equipment such as stirred tanks, dissolvers, stirred mills, static mixers, toothed-wheel dispersers or extruder, according to the preparation of appropriate coating materials.
  • the application of the coating materials according to the invention can be carried out by all customary application methods, e.g. Electrocoating, spraying, knife coating, brushing, pouring, dipping, soaking, trickling or rolling.
  • the substrate to be coated can rest as such, with the application device or system being moved.
  • the substrate to be coated in particular a coil, can also be moved, the application system being stationary relative to the substrate or being moved in a suitable manner.
  • the thermal curing of the applied coating materials according to the invention likewise has no special features in terms of method, but is carried out in a customary and known manner by heating with Infrared or near infrared radiation or with hot air blowers, optionally supported by radiation with actinic radiation, if the coating materials according to the invention contain appropriate components.
  • the particular advantage of the coating materials according to the invention is particularly apparent here, namely that the thermal crosslinking takes place completely at temperatures below 160, preferably 150 and in particular 140 ° C., which allows the coating of comparatively heat-sensitive substrates.
  • the basecoats and / or clearcoats of the invention are outstandingly suitable for the production of color and / or effect multicoat paint systems according to the invention by the wet-on-wet process, in which a basecoat film is applied, dried and covered with a clearcoat film, followed by a basecoat film Clear coat layer to be cured together.
  • this method is used with advantage in motor vehicle painting and refinishing.
  • the pigmented powder slurries according to the invention are outstandingly suitable for the production of combination effect layers.
  • This is to be understood as painting that fulfills at least two functions in a coloring and / or effect painting. Functions of this kind are in particular protection against corrosion, the imparting of adhesion, the absorption of mechanical energy and the coloring and / or effect. According to the invention
  • Combination effect layer especially the absorption of mechanical energy and the coloring and / or effect at the same time; it therefore fulfills the functions of a filler paint or stone chip protection primer and a base coat.
  • the combination effect layer furthermore corrosion protection effect and / or adhesion promoting effect.
  • the coating materials according to the invention also come for the coating of buildings indoors and outdoors, for the painting of furniture, windows or doors and for industrial painting, including coil coating, container coating and the impregnation or coating of electrical engineering Components.
  • industrial painting they are suitable for painting practically all parts for private or industrial use such as radiators, household appliances, small parts made of metal such as screws and nuts, hubcaps, rims, packaging or electrical engineering components such as motor windings or transformer windings.
  • the adhesives and sealing compounds according to the invention are outstandingly suitable for the production of adhesive layers and seals which, even under climatically extreme and / or rapidly changing climatic conditions, have a particularly high adhesive strength and sealing capacity in the long term.
  • the primed or unprimed substrates made of metal, glass, plastic, textile, wood, paper, cardboard or mineral materials or composites of these materials, which are coated with at least one coating according to the invention, have at least one adhesive layer according to the invention and are usually used in the above-mentioned technological fields are glued and / or sealed with at least one seal according to the invention, with a particularly advantageous application-related property profile, a particularly long service life, which makes them economically particularly attractive.
  • the resulting binder solution was kept at 60 ° C for 2 hours. Then it was heated to 90 ° C for an hour until their viscosity remained constant. After a short cooling it was carried out. Your key figures were:
  • Solids content 72% by weight (1h / 130 ° C) base content: 1, 03 eq / g
  • Viscosity 3.4 dPas (40% by weight in propylene glycol methyl ether;
  • a clear lacquer consisting of 48.6 parts by weight of the binder solution of preparation example 1, 18.8 parts by weight of the blocked polyisocyanate (A) of preparation example 3 and 32.6 parts by weight of sec-butanol were knife-coated onto phosphated steel sheets using a box doctor blade with a wet film thickness of 100 ⁇ m.
  • the clearcoat layers were allowed to evaporate for 30 minutes and baked in at 160, 180 and 200 ° C. for 20 minutes.
  • the quality of the crosslinking was then tested on the basis of the solvent resistance by rubbing the clearcoats with a cloth soaked in methyl isobutyl ketone based on the MEK test , 100 double strokes were used here.
  • the degree of destruction of the clearcoats was assessed visually and rated as follows:
  • the burn-in loss i.e. The percentage difference between the solids determined at the baking temperature and the solids determined at 130 ° C was determined with a sample weight of 1 g each.
  • the heating time was 1 hour.
  • the clearcoat showed no burn-in loss even at a baking temperature of 200 ° C.
  • the comparative experiment V1 was repeated, except that the clear lacquer in comparison test V2, 1 part by weight of a commercially available bismuth salt (K-Kat from King Industries),
  • Table 1 gives an overview of the resistance to solvents and the burn-in loss.
  • the clearcoats as substantiated by the stoving loss, had not been crosslinked in accordance with the curing process according to the invention.
  • the crosslinking temperatures were comparatively high.
  • the clearcoats were clear and showed no surface defects.
  • Example 1 0.75 parts by weight of zinc acetylacetonate
  • Example 2 0.75 parts by weight of a 48% aqueous solution of KOH and
  • Example 3 0.75 parts by weight of N, N, N-trimethy) -N-cetylammonium bromide
  • Table 2 gives an overview of the solvent resistance and the burn-in loss.
  • Table 2 Solvent resistance and burn-in loss (Examples 6 to 8)
  • the clear coats had been crosslinked according to the curing process according to the invention, as substantiated by the stoving loss. Because the respective burn-in loss corresponded approximately to the amount of catalyst used. The clearcoats were clear and showed no surface defects. It should be emphasized that the maximum solvent stability was already reached at a temperature of 160 ° C.
  • the clearcoat already had a solvent stability of grade 1 at a baking temperature of 120 ° C .; the grade 0 was already reached at 130 ° C.
  • DMA dynamic mechanical analysis
  • the investigation showed a start of crosslinking at 122 ° C (onset temperature, tan. Delta) or 123 ° C (onset temperature, E ' module). A noticeable burn-in loss only occurred at 150 ° C (0.8%); at 200 ° C it was only 2.9%.
  • the clear coat was prepared by mixing 546 parts by weight of the binder solution according to Preparation Example 2, 589 parts by weight of the blocked polyisocyanate (A) of Preparation Example 3, 274 parts by weight of sec-butanol, 45 parts by weight of solvent naphtha, 30 parts by weight of butylglycol acetate, 13 parts by weight of N, N, N-Trimethy ! -N- cetylammonium bromide, 2 parts by weight of NaOH (50% in water) and one part by weight of a commercially available leveling agent (Byk® 333 from Byk Chemie GmbH). It was sprayed onto bare mirror sheets with a pneumatic cup gun, so that dry film thicknesses of 40 to 50 ⁇ m resulted. The clear lacquer layers were then flashed off for 10 minutes, predried at 80 ° C. for 10 minutes and baked at 150 ° C. for 30 minutes.

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

Abstract

L'invention concerne des mélanges réactifs de substances qui contiennent ou consistent en (A) au moins un polyisocyanate dont les groupes isocyanate sont inhibés partiellement ou entièrement par de l'alcool propargylique ; (B) au moins un constituant contenant en moyenne statistique au moins deux groupes fonctionnels réactifs à l'isocyanate dans la molécule ; (C) au moins un catalyseur qui catalyse l'addition des groupes fonctionnels réactifs à l'isocyanate de (B) sur la liaison triple insaturée par acétylène des groupes propargyle. L'invention concerne également leur utilisation comme matériaux de revêtement, adhésifs et matériaux d'étanchéité.
EP01951646A 2000-06-30 2001-06-29 Melanges reactifs de substances a base de polyisocyanates inhibes par alcool propargylique, procede permettant de les produire et leur utilisation Withdrawn EP1294790A1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE10031987A DE10031987A1 (de) 2000-06-30 2000-06-30 Mit Propargylalkohol blockierte Polyisocyanate, Verfahren zu ihrer Herstellung und ihre Verwendung
DE10031987 2000-06-30
PCT/EP2001/007425 WO2002002665A1 (fr) 2000-06-30 2001-06-29 Melanges reactifs de substances a base de polyisocyanates inhibes par alcool propargylique, procede permettant de les produire et leur utilisation

Publications (1)

Publication Number Publication Date
EP1294790A1 true EP1294790A1 (fr) 2003-03-26

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Country Status (7)

Country Link
US (1) US6743484B2 (fr)
EP (1) EP1294790A1 (fr)
JP (1) JP2004502804A (fr)
AU (1) AU2001272519A1 (fr)
BR (1) BR0110974A (fr)
DE (1) DE10031987A1 (fr)
WO (1) WO2002002665A1 (fr)

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US20050129882A1 (en) * 2003-12-16 2005-06-16 Snow Larry G. Processes for preparing printable and printed articles
WO2007096290A1 (fr) * 2006-02-24 2007-08-30 Ciba Holding Inc. Nouveau dispersant de type polyuréthane
DE102009007624A1 (de) 2009-02-05 2010-08-12 Basf Coatings Ag Beschichtungsmittel für korrosionsstabile Lackierungen
DE102009007632A1 (de) 2009-02-05 2010-08-12 Basf Coatings Ag Beschichtungsmittel für korrosionsstabile Lackierungen
US8962771B2 (en) 2010-06-11 2015-02-24 Dow Global Technologies Llc Reactive isocyanate-terminated prepolymers for binder applications
EP2980113B1 (fr) * 2013-03-29 2017-09-20 Mitsui Chemicals, Inc. Composition polymérisable pour matière optique, matière optique et procédé de production de matière optique
JP6701727B2 (ja) * 2015-12-25 2020-05-27 三菱ケミカル株式会社 粘着剤組成物、これを架橋させてなる粘着剤、マスキングフィルム用粘着剤、耐熱粘着フィルム用粘着剤、マスキング用耐熱粘着フィルム
US11174334B2 (en) * 2019-11-25 2021-11-16 Covestro Llc Allophanate carbamate azido-alkyne click compositions

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US4444954A (en) 1982-09-30 1984-04-24 The Sherwin-Williams Company Water reducible quaternary ammonium salt containing polymers
JPS62232424A (ja) 1986-04-02 1987-10-12 Showa Highpolymer Co Ltd 硬化可能な組成物
DE3809695A1 (de) * 1988-03-23 1989-10-12 Hoechst Ag Haerter fuer kunstharze, diesen enthaltende haertbare mischungen sowie deren verwendung
DE3932816A1 (de) 1989-09-30 1991-04-11 Hoechst Ag Verwendung von vernetzten polymermikroteilchen in lacken als fuellstoffersatz und/oder als vernetzender fuellstoff
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DE19616496A1 (de) 1996-04-25 1997-10-30 Bayer Ag Abspaltfreier Polyurethan-Pulverlack mit niedriger Einbrenntemperatur
DE19617188A1 (de) 1996-04-29 1997-11-06 Synthopol Chemie Dr Koch Pulverlackbeschichtungsmittel auf Basis von hydroxylgruppenhaltigen Polyestern
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Also Published As

Publication number Publication date
US20030144383A1 (en) 2003-07-31
WO2002002665A1 (fr) 2002-01-10
JP2004502804A (ja) 2004-01-29
AU2001272519A1 (en) 2002-01-14
BR0110974A (pt) 2003-04-15
US6743484B2 (en) 2004-06-01
DE10031987A1 (de) 2002-01-24

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