WO2003033605A1 - Susbtance de revetement non aqueuse constituee d'un composant unique, durcissable thermiquement et par rayonnement actinique, son procede de production et son utilisation - Google Patents

Susbtance de revetement non aqueuse constituee d'un composant unique, durcissable thermiquement et par rayonnement actinique, son procede de production et son utilisation Download PDF

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Publication number
WO2003033605A1
WO2003033605A1 PCT/EP2002/011396 EP0211396W WO03033605A1 WO 2003033605 A1 WO2003033605 A1 WO 2003033605A1 EP 0211396 W EP0211396 W EP 0211396W WO 03033605 A1 WO03033605 A1 WO 03033605A1
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Prior art keywords
coating material
component coating
material according
groups
actinic radiation
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PCT/EP2002/011396
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German (de)
English (en)
Inventor
Uwe Meisenburg
Hubert Baumgart
Original Assignee
Basf Coatings Ag
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Publication of WO2003033605A1 publication Critical patent/WO2003033605A1/fr

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Classifications

    • 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
    • C08G18/80—Masked polyisocyanates
    • C08G18/8061—Masked polyisocyanates masked with compounds having only one group containing active hydrogen
    • C08G18/8096—Masked polyisocyanates masked with compounds having only one group containing active hydrogen with two or more compounds having only one group containing active hydrogen
    • 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
    • C08G18/6229—Polymers of hydroxy groups containing esters of acrylic or methacrylic acid with aliphatic polyalcohols
    • 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
    • C08G18/80—Masked polyisocyanates
    • C08G18/8061—Masked polyisocyanates masked with compounds having only one group containing active hydrogen
    • C08G18/8093—Compounds containing active methylene groups
    • 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

Definitions

  • the present invention relates to a new, thermally and with actinic radiation curable, non-aqueous one-component coating material.
  • the present invention also relates to a new process for producing non-aqueous one-component coating materials which are curable thermally and with actinic radiation.
  • the present invention relates to the use of the new, non-aqueous coating material which is curable thermally and with actinic radiation for the production of single- and multi-layer coatings and seals, and as an adhesive and sealants for the production of adhesive layers and seals.
  • actinic radiation means electromagnetic radiation, such as near infrared (NiR), visible light, UV radiation and X-rays, in particular UV radiation, and corpuscular radiation, such as electron beams.
  • NiR near infrared
  • UV radiation visible light
  • UV radiation ultraviolet radiation
  • corpuscular radiation such as electron beams.
  • dual-cure The curing of coating materials with heat 20 and actinic radiation is also referred to by experts as dual-cure.
  • one-component coating material means that the components of the coating material in question can be present in a mixture at temperatures of up to 25 90 ° C. and do not have to be stored separately from one another until the coating material is used.
  • ingredients such as B.
  • (meth) acrylate copolymers which are mandatory in addition to isocyanate-reactive functional groups
  • constituents such as (eth) acrylate copolymers, which also have mandatory (meth) acryloyl groups in addition to complementary free isocyanate groups.
  • they can contain thermally curable constituents, such as (meth) acrylate copolymers, which are free of
  • the known dual-cure coating materials give coatings with very good chemical, gasoline and solvent resistance, high scratch resistance and good and quick sandability and in this respect the requirements for a multi-layer coating in the field of vehicle painting, in particular Vehicle refinishing, should suffice.
  • the coatings should be free of cracks and have good adhesion to the substrate. Overall, they should have a perfect visual appearance.
  • this property profile can be set and optimized in detail and which of the practically innumerable alternatives that can be derived from several lists work best is not specified in the description or using an example.
  • dual-cure coating materials are well suited for the coating of thermally sensitive substrates, since incomplete thermal curing at low temperatures can be compensated for by curing with actinic radiation, so that overall coatings with good application properties result.
  • dual-cure coating materials are good for coating more complex shapes suitable for three-dimensional substrates, since incomplete radiation curing in the shadow areas of the substrates can be compensated for by the thermal curing, so that overall coatings with good application properties also result here.
  • (c 2) at least one blocking agent selected from the group consisting of different from (c 1) and containing at least one active methylene group
  • the known one-component coating materials already have a number of application-related advantages, such as good hardness, good gloss, very good interlayer adhesion, high yellowing resistance and very good repaintability. However, they still leave a lot to be desired in terms of polishability, chemical resistance and scratch resistance. In particular, they do not achieve a memory module E 'of at least 10 7.6 Pa and a loss factor tan ⁇ of at most 0.1, as would be required for a particularly good scratch resistance (cf. German patent DE 197 09 467 C1, comparative example 1, Page 7, line 24, to page 8, line 26, in conjunction with page 11, table 2).
  • the object of the present invention is to provide a new one-component coating material which no longer has the disadvantages of the prior art, but is stable in storage and provides coatings, in particular clearcoats, which are polishable, scratch-resistant, chemical-resistant and resistant Moisture resistance is better than the coatings known from German patent application DE 42 04 518 A 1 and German patent DE 197 09 467 C 1, without losing their high gloss, very good interlayer adhesion, high yellowing stability and very good repaintability.
  • the new one-component coating materials should have the advantages of Duai-Cure coating materials.
  • the new thermally and actinic radiation-curable, non-aqueous one-component coating material was found to contain (A) at least one binder with at least two isocyanate-reactive functional groups which is free of reactive functional groups which contain at least one bond which can be activated with actinic radiation,
  • (c 2) at least one blocking agent selected from the group consisting of blocking agents and oximes different from (c 1) and containing at least one active methylene group,
  • coating material that is curable thermally and with actinic radiation.
  • Blocking agents (c 1) blocked isocyanate groups to form isocyanate groups blocked with blocking agents (c 2) is between 9: 1 and 1: 1, and
  • the new process for producing a non-aqueous coating material which is curable thermally and with actinic radiation is referred to as the “process according to the invention”.
  • the coating material of the invention is stable in storage and provides coatings, in particular clearcoats, which are better in polishability, scratch resistance, chemical resistance and moisture resistance than those known from German patent application DE 42 04 518 A 1 and German patent DE 197 09 467 C 1 Coatings are without losing their high gloss, very good interlayer adhesion, high yellowing stability and very good repaintability.
  • the coatings of the invention have the advantages associated with dual-cure coating materials.
  • the coating material of the invention could be used to produce seals for SMC (sheet molded compounds) and BMC (bulk molded compounds) and as an adhesive and sealant for the production of adhesive layers and seals.
  • the first essential constituent of the coating material of the invention is at least one binder (A), which is in the statistical means contains at least two, preferably at least three and in particular at least four isocyanate-reactive functional groups in the molecule. Otherwise, the binder (A) is free of reactive functional groups which contain at least one bond which can be activated with actinic radiation.
  • the term "free from reactive functional groups” means that the binders (A) are completely free from these groups or contain these groups in minor amounts which do not or only marginally influence the crosslinking properties of the binders (A).
  • the isocyanate-reactive functional groups are preferably selected from the group consisting of thiol groups, hydroxyl groups and primary and secondary amino groups.
  • the hydroxyl groups are preferred.
  • the binders (A) are preferably selected from the group consisting of (linear), branched and comb-like (co) polymers of olefinically unsaturated monomers, polyaddition resins and / or polycondensation resins that are soluble and dispersible in organic solvents, random, alternating and block-like, linear, branched and comb-like.
  • the binders (A) are preferably selected from the group consisting of (meth) acrylate polymers, partially saponified polyvinyl esters, polyesters, alkyds, polylactones, polycarbonates, polyethers, epoxy resin-amine adducts, polyureas, polyamides, polyimides and polyurethanes.
  • the binders (A) are (meth) acrylate copolymers.
  • the (meth) acrylate copolymers (A) are customary and known polymers. Examples of highly suitable (meth) acrylate copolymers (A) are described, for example, in German patent applications DE 42 04 518 A1, page 3, line 65, to page 4, line 43, or DE 43 10 414 A1, page 2, line 50, to page 4, line 41, or DE 199 24 171 A1, page 5, line 54, to page 7, line 37, described in detail.
  • the (meth) acrylate copolymers (A) to be used with preference have no special procedural features, but are carried out using the methods known and known in the plastics field of continuous or discontinuous radical-initiated copolymerization in bulk, solution, emulsion, miniemulsion or microemulsion under normal pressure or overpressure in stirred tanks, autoclaves, tubular reactors, loop reactors or Taylor reactors at temperatures of preferably 50 to 200 ° C.
  • copolymerization processes are described in patent applications DE 197 09 465 A1, DE 197 09 476 A1, DE 28 48 906 A1, DE 195 24 182 A1, DE 198 28 742 A1, DE 196 28 143 A1, DE 196 28 142 A1, EP 0 554 783 A1, WO 95/27742, WO 82/02387 or WO 98/02466.
  • the copolymerization can also be carried out in polyols (thermally curable reactive diluents) as the reaction medium, as is described, for example, in German patent application DE 198 50 243 A1.
  • the content of the binder (A) in the coating material of the invention can vary widely and depends primarily on the functionality of the binder (A) on the one hand and the constituents (B), (C) and (D) described below on the other hand.
  • the content, based on the solids content of the coating material of the invention is preferably 20 to 80, preferably 25 to 75, particularly preferably 30 to 70, very particularly preferably 35 to 65 and in particular 35 to 60% by weight.
  • Solid is to be understood as the proportion of the coating material of the invention that builds up the coating after curing.
  • the further essential component of the coating material according to the invention is at least one aminoplast resin (B).
  • the aminoplast resins (B) are preferably selected from the group consisting of non-functionalized and defunctionalized, non-etherified, partially etherified and fully etherified condensation products of aldehydes with urea, melamine, guanamine and benzoguanamine. Formaldehyde is preferred as the aldehyde.
  • suitable amino resins are from 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.
  • the content of aminoplast resins (B) in the coating material of the invention can vary widely and depends primarily on the functionality of the other constituents (A) and (C) of the coating material of the invention.
  • the content is preferably 5 to 40, preferably 6 to 35, particularly preferably 7 to 30, very particularly preferably 8 to 25 and in particular 10 to 25% by weight, in each case based on the solids of the coating material of the invention.
  • the essential constituent of the coating material of the invention is at least one, especially one, blocked polyisocyanate (C).
  • the blocked polyisocyanates (C) are preferably selected from the group consisting of blocked polyisocyanates containing isocyanurate, biuret, allophanate, iminooxadiazinedione, urethane, carbodiimide, urea and uretdione groups.
  • the precursor of the blocked polyisocyanates (C) are preferably prepared from diisocyanates.
  • the polyisocyanates (C) with at least one, in particular one, dialkyl malonate (c 1) and at least one, in particular one blocking agent are selected from the group consisting of blocking agents which differ from (c 1) and contain at least one, in particular one, active methylene group and oximes, blocked.
  • dialkyl malonates (c 1) are preferably selected from the group consisting of dimethyl, diethyl, dipropyl, dibutyl, dipentyl and dihexyl malonate; diethyl malonate is preferably used.
  • the blocking agents (c 2) which differ from (c 1) and contain at least one active methylene group are preferably selected from the group consisting of acetoacetic acid ethyl, ethyl, propyl, butyl, pentyl, hexyi, -heptyl-, -octyl-, -nonyl-, -decyl-, -undecyl- and - dodecyiester, and the oximes (c 2) from the group consisting of acetone oxime, methyl ethyl ketoxime, formal doxime, acetaldoxime, acetoxime, diisobutyiketoxime, diacetylmonoxime, Benzophenone oxime and the positionally isomeric chlorohexanone oximes, selected; ethyl acetoacetate and methyl ethyl ketoxime are preferably used.
  • the equivalent ratio of isocyanate groups blocked with blocking agents (c 1) to blocked with blocking agents (c 2) is preferred Isocyanate groups between 4: 1 and 1.5: 1 and in particular between 3: 1 and 1.85: 1.
  • the fourth essential constituent of the coating material according to the invention is at least one, in particular one, compound (D) with at least one, preferably at least two, particularly preferably at least three and in particular at least four reactive (n) functional group (s) with at least one, in particular a bond that can be activated with actinic radiation.
  • the compound (D) can be low molecular weight, oligomeric or polymeric.
  • bonds which can be activated with actinic radiation are preferably selected from the group consisting of carbon-hydrogen single bonds or carbon-carbon, carbon-oxygen, carbon-nitrogen, carbon-phosphorus or carbon-silicon single bonds or double bonds ,
  • bonds which can be activated with actinic radiation are preferably carbon-carbon double bonds (“double bonds”).
  • bonds which can be activated with actinic radiation can be formed via carbon-carbon bonds or ether, thioether,
  • Carboxylic acid ester, thiocarboxylic acid ester, carbonate, thiocarbonate, phosphoric acid ester, thiophosphoric acid ester, phosphonic acid ester, thiophosphonic acid ester, phosphite, thiophosphite, sulfonic acid ester, amide, amine, thioamide, phosphoric acid amide, thiophosphonic acid amide, , Thiophosphonic acid amide, sulfonic acid amide, imide, Ureihan, hydrazide, urea, thiourea, carbonyl, thiocarbonyl, sulfone or sulfoxide groups can be connected to the basic structure of the compound (D). They are preferably connected to the basic structure of the compound (D) via carbon-carbon bonds, carboxylic ester groups and ether groups.
  • the basic structure of the compound (D) can be low molecular weight, oligomeric or polymeric.
  • the basic structure is preferably of low molecular weight. It can be aliphatic, cycloaliphatic or aromatic or aliphatic-cycloaliphatic, aliphatic-aromatic, cycloaliphatic-aromatic or aliphatic-cycloaliphatic-aromatic.
  • the basic structure is preferably aliphatic, cycloaliphatic or aliphatic-cycloaliphatic, in particular aliphatic.
  • the groups containing double bonds are particularly preferably selected from the group consisting of (meth) acrylate, ethacrylate, crotonate, cinnamate, vinyl ether, vinyl ester, dicyclopentadienyl, norbomenyl, isoprenyl, isoprenyl, isopropenyl and allyl - or butenyl groups; Dicyclopentadienyl, norbomenyl, isoprenyl, isopropenyl, allyl or butenyl ether groups or dicyclopentadienyl, norbomenyl, isoprenyl, isopropenyl, allyl or butenyl ester groups.
  • (Meth) acrylate groups are very particularly preferably used.
  • Suitable low molecular weight, oligomeric and / or polymeric compounds (D) with at least one acrylate group or methacrylate group are described in detail in Römpp Lexikon Lacke und Druckmaschine, Georg Thieme Verlag, Stuttgart, New York, 1998, "Reaktiwerschreibner” pages 491 and 492, in the German patent application DE 199 08 013 A1, column 6, line 63, to column 8, line 65, in German patent application DE 199 08 018 A1, page 11, lines 31 to 33, in German patent application DE 198 18 735 A. 1 , Column 7, lines 1 to 35, or the German patent DE 197 09 467 C1, page 4, line 36, to page 5, line 56. Pentaerythritol tetraacrylate and / or aliphatic urethane acrylates with six acrylate groups in the molecule are preferably used.
  • the compounds (D) may also contain at least one, in particular one, isocyanate-reactive functional group, in particular a hydroxyl group.
  • isocyanate-reactive functional group in particular a hydroxyl group. Examples of suitable compounds (D) of this type are described in German patent application DE 198 18 735 A1, column 3, line 16 to column 6, line 33. Trimethylol propane diacrylate, pentaerythritol triacrylate and
  • Dipentaerythritol pentaacrylate is used.
  • the content of compounds (D) in the coating material of the invention can vary widely. It is preferably 2 to 50, preferably 3 to 45, particularly preferably 4 to 40, very particularly preferably 5 to 35 and in particular 5 to 30% by weight, in each case based on the solids of the coating material of the invention.
  • the coating material of the invention preferably contains at least one photoinitiator and preferably two photoinitiators (E) in an amount of 0.2 to 5, preferably 0.3 to 4.8, preferably 0.4 to 4.6, particularly preferably 0.5 to 4 , 5 and in particular 0.5 to 4.3% by weight, in each case based on the solid of the coating material of the invention.
  • photoinitiators (E) examples include UVinitiators (E) and UV-IRIN® or by Ciba Specialty Chemicals under the brand IRGACURE®.
  • the coating materials of the invention can also contain at least one additive (F) selected from the group consisting of thermally curable reactive diluents; molecularly dispersible dyes; Light stabilizers, such as UV absorbers and reversible radical scavengers (HALS); antioxidants; low and high boiling ("long") organic solvents; Venting means; Wetting agents; emulsifiers; slip additives; polymerization inhibitors; Thermal crosslinking catalysts; thermolabile free radical initiators; Adhesion promoters; Leveling agents; film-forming aids; Rheology aids such as thickeners and pseudoplastic Sag controi agents, SCA; nanoparticles; Flame retardants; Corrosion inhibitors; anti-caking agents; To grow; driers; Biocides and matting agents.
  • F additive
  • the coating material of the invention can contain nanoparticles (F).
  • the nanoparticles (F) can be unmodified or surface-modified.
  • the nanoparticles (F) are preferably selected from the group consisting of compounds of main and subgroup metals.
  • the main and subgroup metals are preferably selected from the metals of the third to fifth main group and the third to sixth and the second subgroup of the periodic table of the elements.
  • Boron, aluminum, gallium, silicon, germanium, tin, arsenic, antimony, zinc, titanium, zirconium, hafnium, vanadium, niobium, tantalum, molybdenum and tungsten, in particular aluminum, silicon, titanium and zirconium, are particularly preferably used.
  • the compounds of the metals are preferably the oxides, oxide hydrates, sulfides, selenides or phosphates, in particular oxides and oxide hydrates.
  • Silicon dioxide aluminum oxide, aluminum oxide hydrate, titanium dioxide, zirconium oxide and mixtures thereof, particularly preferably silicon dioxide and aluminum oxide hydrate, are used.
  • the nanoparticles preferably have a primary particle size ⁇ 50 nm, preferably 5 to 50 nm, in particular 10 to 30 nm.
  • the coating materials of the invention which contain the above-described components (A) (B) (C) and (D) and, if appropriate, (E) and / or (F), are preferably used as clearcoats of the invention for the production of clearcoats. They are particularly preferred for the production of clear coats within the scope of Production of coloring and / or effect-giving multi-layer coatings used according to the wet-on-wet method.
  • the coating material according to the invention can be present as a solvent-containing liquid coating material, as a largely or completely solvent-free, solid, powdery coating material, in particular powder coating, or as a largely or completely solvent-free liquid coating material (100% system). It is preferably in the form of a solvent-based, liquid coating material.
  • the production of the coating materials according to the invention has no special features, but instead takes place by mixing and homogenizing the constituents described above with the aid of customary and known mixing methods and devices such as stirred kettles, agitator mills, extruders, kneaders, Ultraturrax, in-line dissolvers, static mixers, Gear rim dispersers, pressure relief nozzles and / or microfluidizers, preferably with the exclusion of actinic radiation (method according to the invention).
  • mixing methods and devices such as stirred kettles, agitator mills, extruders, kneaders, Ultraturrax, in-line dissolvers, static mixers, Gear rim dispersers, pressure relief nozzles and / or microfluidizers, preferably with the exclusion of actinic radiation (method according to the invention).
  • the application of the coating material of the invention has no special features, but can be done by everyone customary and known application methods suitable for the respective coating material, such as, for example, electrocoating, spraying, spraying, knife coating, brushing, pouring, dipping, trickling or rolling.
  • Spray application methods are preferably used, such as, for example, compressed air spraying, airless spraying, high rotation, electrostatic spray application (ESTA), possibly combined with hot spray application, for example! Hot air hot spraying, unless it is powder coating.
  • powder coatings also has no special features in terms of method, but is carried out, for example, using the customary and known fluidized bed processes, such as those found in the company publications of BASF Coatings AG, "Powder coatings for industrial applications", January 2000, or “Coatings Partner, special powder coating” , 1/2000, or Römpp Lexikon Lacke und Druckmaschine, Georg Thieme Verlag, Stuttgart, New York, 1998, pages 187 and 188, "Electrostatic Powder Spraying", “Electrostatic Spraying” and “Electrostatic Whirl Bath Process”.
  • the coating materials of the invention are generally cured after a certain resting time or flash-off time. It can have a duration of 5 s to 2 h, preferably 1 min to 1 h and in particular 1 to 45 min.
  • the idle time is used, for example, for the course and degassing of the paint layers and for the evaporation of volatile constituents such as any solvent that may still be present.
  • the ventilation can be caused by an increased temperature, which leads to hardening not sufficient, and / or accelerated by reduced humidity.
  • this process measure can also be used for drying further applied lacquer layers, in particular electro-dipping lacquer layers, filler layers and / or basecoat layers, which should not or only partially be hardened.
  • the thermal curing takes place, for example, with the aid of a gaseous, liquid and / or solid, hot medium, such as hot air, heated oil or heated rollers, or using microwave radiation, infrared light and / or near infrared light (NIR).
  • the heating is preferably carried out in a forced air oven or by irradiation with IR and / or NIR lamps.
  • thermal curing can also be carried out in stages.
  • the thermal curing advantageously takes place at temperatures from room temperature to 200.degree.
  • a dose of 500 to 4,000, preferably 1,000 to 2,900, particularly preferably 1,200 to 2,800, very particularly preferably 1,300 to 2,700 and in particular 1,400 to 2,600 mJ / cm 2 is preferably used.
  • the usual and known radiation sources and optical auxiliary measures are used for curing with actinic radiation.
  • suitable radiation sources are flash lamps from VISIT, high-pressure or low-pressure mercury vapor lamps, which may be doped with lead to open a radiation window up to 405 nm, or electron beam sources.
  • Their arrangement is known in principle and can be adapted to the conditions of the workpiece and the process parameters. For complicated shaped workpieces like those for If car bodies are provided, areas that are not directly accessible to radiation (shadow areas), such as cavities, folds and other undercuts due to construction, can be cured with spotlights, small area or all-round emitters, combined with an automatic movement device for irradiating cavities or edges.
  • the curing can take place in stages, i. H. by multiple exposure or exposure to actinic radiation. This can also take place alternately, i. that is, for example, curing alternately with UV radiation and electron radiation.
  • Thermal curing and curing with actinic radiation can be used simultaneously or in succession. If the two curing methods are used one after the other, thermal curing can be started, for example, and curing with actinic radiation can be ended. In other cases, it may prove advantageous to start and end the curing with actinic radiation.
  • Curing with actinic radiation is preferably carried out under inert gas in order to avoid the formation of ozone.
  • an oxygen-depleted atmosphere can be used “Oxygen-depleted” means that the content of oxygen in the atmosphere is less than the oxygen content of air (20.95% by volume).
  • the maximum content of the oxygen-depleted atmosphere is preferably 18, preferably 16, particularly preferably 14, very particularly preferably 10 and in particular 6.0% by volume, preferably the minimum oxygen content is 0.1, preferably 0.5, particularly preferably 1.0, very particularly preferably 1.5 and in particular 2.0% by volume.
  • the oxygen-depleted atmosphere can be provided in different ways.
  • a corresponding gas mixture can be produced and made available in pressure bottles.
  • the depletion is preferably achieved by introducing at least one inert gas in the amounts required in each case into the air cushion located above the surface of the clear lacquer layer to be hardened according to the invention.
  • the oxygen content of the atmosphere above the surface in question can be continuously measured using conventional and known methods and devices for determining elemental oxygen and, if necessary, automatically set to the desired value.
  • Inert gas is understood to be a gas which, under the curing conditions used, is not decomposed by the actinic radiation, does not inhibit curing and / or does not react with the coating material of the invention.
  • Coating materials such as electrocoat materials, fillers or basecoats, are used, which are used together with the coating materials of the invention for the production of clearcoats and color and / or effect multi-layer coatings.
  • Suitable fillers which are also referred to as stone chip protection primers or functional layers, are known from the patents and applications US 4,537,926 A1, EP 0529335 A1, EP 0595186 A1, EP 0639660 A1, DE 4438504 A1, DE 4337961 A1, WO 89, / 10387, US 4,450,200 A1, US 4,614,683 A1 or WO 94/26827.
  • Suitable basecoats in particular waterborne basecoats, are known from patent applications EP 0089497 A1, EP 0256540 A1, EP 0260447 A1, EP 0297576 A1, WO 96/12747, EP 0523610 A1, EP 0228003 A1, EP 0397806 A1, EP 0574417 A1, EP 0531510 A1, EP 0581211 A1, EP 0708788 A1, EP 0593454 A1, DE 4328092 A1, EP 0299148 A1, EP 0394737 A1, EP 0590484 A1, EP 0234362 A1, EP 0234 361 A1, EP 0543817 A1, WO 95/14721, EP 0521928 A1, EP 0522 420 A1, EP 0522419 A1, EP 0649865 A1, EP 0536712 A1, EP 0 596460 A1, EP 0596461 A1, EP 0584818 A 1, EP 0669356 A 1, EP 0634431 A 1, EP 0678536 A 1, EP 0354261 A
  • the coatings according to the invention obtained, in particular the one- or multi-layer, color and / or effect coatings and clearcoats according to the invention are simple to produce and have excellent optical properties and very high overburning stability, polishability, over-paintability and light, chemicals, water and condensation water -, weather, yellowing and etch resistance.
  • the clearcoats according to the invention are free from turbidity and inhomogeneities. They have a very good reflow behavior and excellent scratch resistance with high hardness.
  • the layer thicknesses within the coatings according to the invention are preferably in the customarily used ranges:
  • Clear coating Preferably 10 to 00, preferably 15 to 80 and in particular 20 to 70 ⁇ m;
  • coating materials according to the invention are that they also provide coatings in the shadow zones of complex three-dimensional substrates, such as bodies, radiators or electrical winding goods, even without optimal, in particular complete, illumination of the shadow zones with actinic radiation, the application properties of which match those of the coatings beyond the shadow zones at least.
  • the coatings located in the shadow zones are no longer easily damaged by mechanical and / or chemical action, which can occur, for example, in the line when additional components of motor vehicles are installed in the coated bodies.
  • the coatings according to the invention are notable for excellent wettability, which makes it possible to apply large-area refinish coatings and double coats without the need for physical, mechanical and / or chemical treatments to be carried out beforehand.
  • Clearcoats of the invention can be applied to the clearcoats or basecoats of the invention and clearcoats of the invention can be applied to the clearcoats of the invention.
  • the fillers can also be included in the repair painting or double painting.
  • the coating materials according to the invention can also be used as adhesives and sealants for the production of adhesive layers and seals according to the invention and are used for coating, gluing and / or sealing primed or unprimed substrates made of metal, plastic, glass, wood, textile, leather, natural and artificial stone , Concrete, cement or composites of these materials, such as SMC or BMC.
  • the coating materials, adhesives or sealing compounds according to the invention can therefore be used for painting, sealing, gluing and sealing motor vehicle bodies and parts thereof, motor vehicles inside and outside, buildings inside and outside, doors, windows and furniture, SMC, BMC and glass bodies as well as in the context of industrial painting for painting, sealing, gluing and sealing small parts, coils, containers, packaging, electrical components and white goods with great success.
  • the substrates can be primed.
  • primer layers or adhesive layers can be used as primers, or the plastic surfaces can be provided with reactive compounds such as fluorine by flame treatment or etching.
  • primers can be used as primers, as are found in Römpp Lexikon Lacke und Druckmaschine, Georg Thieme Verlag, Stuttgart, New York, 1998, "Primer”, page 473, “Wash Primer”, page 618 , or "Production Coating", page 230.
  • the SMC and BMC can contain the seal known from German patent application DE 19920 799 A1.
  • an aluminum oxide layer produced by anodic oxidation is preferably used as the primer.
  • the substrates which are coated, sealed, glued and / or sealed with them are of particularly long service life and are therefore particularly economical, ecological and technically valuable for users.
  • the clear lacquer according to the invention was produced with the exclusion of actinic radiation by mixing the following constituents and homogenizing the resulting mixture:
  • Irgacure® 184 commercially available photoinitiator from Ciba Specialty Chemicals
  • Lucirin ® TPO commercially available photoinitiator of
  • HALS radical scavenger
  • the clear lacquer according to the invention was homogeneous, free of specks and stable in storage. For the application, it was adjusted to a spray viscosity of 20 seconds in a DIN 4 flow cup with organic solvents.
  • steel panels were coated in succession with a cathodically deposited electrodeposition coating baked at 170 ° C. for 20 minutes and having a dry layer thickness of 18 to 22 ⁇ m.
  • the steel panels were then coated with a commercially available two-component water filler from BASF Coatings AG, as is usually used for plastic substrates.
  • the resulting filler layer was baked at 90 ° C. for 30 minutes, so that a dry layer thickness of 35 to 40 ⁇ m resulted.
  • a commercial black waterborne basecoat from BASF Coatings AG was then applied with a layer thickness of 12 to 15 ⁇ m, after which the resulting waterborne basecoat films were flashed off at 80 ° C. for ten minutes.
  • the clear lacquer with a layer thickness of 40 to 45 ⁇ m was applied pneumatically in a cloister with a gravity cup gun.
  • the water-based lacquer layers and the clear lacquer layers were cured for 5 minutes at room temperature, for 10 minutes at 80 ° C., followed by irradiation with UV light at a dose of 1,500 mJ / cm 2 , and finally for 20 minutes at 140 ° C.
  • the multi-layer coating had a very good property profile in terms of gloss, hardness and scratch resistance.
  • micro penetration hardness (universal hardness at 25.6 mN, Fisc erscope 100V with diamond pyramid according to Vickers) was 145.
  • the scratch resistance was assessed using the sand test (cf. German patent application DE 198 39 453 A 1, page 9, lines 1 to 63) using the test panels described above.
  • the loss of gloss was 11.9 units (20 °).
  • the first damage to the multilayer coatings according to the invention by sulfuric acid was only found at a temperature of 52 ° C., by tree resin only at 63 ° C. and water only at 80 ° C.
  • the etch resistance was also excellent.
  • the multi-layer coating had a very good flow and a surface free of faults without a stove.
  • the interlayer adhesion was very good (cross cut test according to DIN EN ISO 2409: GT0-1).

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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)
  • Paints Or Removers (AREA)
  • Polyurethanes Or Polyureas (AREA)

Abstract

L'invention concerne une substance de revêtement non aqueuse constituée d'un composant unique, durcissable thermiquement et par rayonnement actinique et comprenant : (A) au moins un liant comportant au moins deux groupes fonctionnels réactifs aux isocyanates et dépourvu de groupes fonctionnels réactifs comportant au moins une liaison pouvant être activée par rayonnement actinique ; (B) au moins une résine aminoplaste ; (C) au moins un polyisocyanate bloqué par (c1) au moins un malonate de dialkyle et (c2) au moins un agent de blocage sélectionné dans le groupe comprenant des agents de blocage, différents de (c1) et pourvus d'au moins un groupe méthylène actif, et des oximes, le rapport d'équivalence entre les groupes isocyanates bloqués par les agents de blocage (c1) et les groupes isocyanates bloqués les agents de blocage (c2) étant compris entre 9:1 et 1:1 ; et (D) au moins un composé comportant au moins un groupe fonctionnel réactif comprenant au moins une liaison pouvant être activée par rayonnement actinique. L'invention se rapporte en outre à un procédé de production et à l'utilisation de cette substance de revêtement.
PCT/EP2002/011396 2001-10-11 2002-10-11 Susbtance de revetement non aqueuse constituee d'un composant unique, durcissable thermiquement et par rayonnement actinique, son procede de production et son utilisation WO2003033605A1 (fr)

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DE10150088.2 2001-10-11
DE2001150088 DE10150088A1 (de) 2001-10-11 2001-10-11 Thermisch und mit aktinischer Strahlung härtbarer, nicht wässriger Einkomponenten-Beschichtungsstoff, Verfahren zu seiner Herstellung und seine Verwendung

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Cited By (1)

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Publication number Priority date Publication date Assignee Title
WO2006024885A1 (fr) * 2004-09-02 2006-03-09 Polinvent Fejleszto, Kivitelezo És Értékesíto Kft Procede de preparation de resines de polyaddition et de resines hybrides a base de polyisocyanate/acide polysilicique au moyen de polyisocyanates bloques et polyisocyanates bloques utilises selon ce procede

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6891012B2 (en) * 2003-05-23 2005-05-10 Bayer Materialscience Llc Powder coatings produced with crosslinkers capable of curing at low temperatures and coated articles produced therefrom

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US4634602A (en) * 1986-01-02 1987-01-06 Ppg Industries, Inc. Primer composition
DE4204518A1 (de) * 1992-02-15 1993-08-19 Basf Lacke & Farben Verfahren zur herstellung einer zweischichtigen lackierung und fuer dieses verfahren geeignete nicht-waessrige lacke
US5770347A (en) * 1994-11-11 1998-06-23 Taiyo Ink Manufacturing Co., Ltd. Photocurable and thermosetting coating composition and method for formation of solder mask for printed circuit board
US6228919B1 (en) * 1988-03-02 2001-05-08 E. I. Du Pont De Nemours And Company Solvent dispersible interpenetrating polymer networks
DE10004726A1 (de) * 2000-02-03 2001-08-16 Basf Coatings Ag Thermisch und/oder mit aktinischer Strahlung härtbarer wäßriger Beschichtungsstoff und seine Verwendung

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Publication number Priority date Publication date Assignee Title
DE4310414A1 (de) * 1993-03-31 1994-10-06 Basf Lacke & Farben Verfahren zur Herstellung einer zweischichtigen Decklackierung auf einer Substratoberfläche
DE19961402A1 (de) * 1999-12-20 2001-07-05 Basf Coatings Ag Verfahren zur Herstellung von Beschichtungen aus thermisch und mit aktinischer Strahlung härtbaren Beschichtungstoffen

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4634602A (en) * 1986-01-02 1987-01-06 Ppg Industries, Inc. Primer composition
US6228919B1 (en) * 1988-03-02 2001-05-08 E. I. Du Pont De Nemours And Company Solvent dispersible interpenetrating polymer networks
DE4204518A1 (de) * 1992-02-15 1993-08-19 Basf Lacke & Farben Verfahren zur herstellung einer zweischichtigen lackierung und fuer dieses verfahren geeignete nicht-waessrige lacke
US5770347A (en) * 1994-11-11 1998-06-23 Taiyo Ink Manufacturing Co., Ltd. Photocurable and thermosetting coating composition and method for formation of solder mask for printed circuit board
DE10004726A1 (de) * 2000-02-03 2001-08-16 Basf Coatings Ag Thermisch und/oder mit aktinischer Strahlung härtbarer wäßriger Beschichtungsstoff und seine Verwendung

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2006024885A1 (fr) * 2004-09-02 2006-03-09 Polinvent Fejleszto, Kivitelezo És Értékesíto Kft Procede de preparation de resines de polyaddition et de resines hybrides a base de polyisocyanate/acide polysilicique au moyen de polyisocyanates bloques et polyisocyanates bloques utilises selon ce procede

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