EP1242496A1 - Procede de production de revetements a base de substances de recouvrement durcissables par voie thermique et par rayonnement actinique - Google Patents

Procede de production de revetements a base de substances de recouvrement durcissables par voie thermique et par rayonnement actinique

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Publication number
EP1242496A1
EP1242496A1 EP00983217A EP00983217A EP1242496A1 EP 1242496 A1 EP1242496 A1 EP 1242496A1 EP 00983217 A EP00983217 A EP 00983217A EP 00983217 A EP00983217 A EP 00983217A EP 1242496 A1 EP1242496 A1 EP 1242496A1
Authority
EP
European Patent Office
Prior art keywords
agents
actinic radiation
carbon
coating material
meth
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Withdrawn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
EP00983217A
Other languages
German (de)
English (en)
Inventor
Uwe Meisenburg
Hubert Baumgart
Jorge Prieto
Roland STEINRÜCKEN
Ludger Dornieden
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 EP1242496A1 publication Critical patent/EP1242496A1/fr
Withdrawn legal-status Critical Current

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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
    • C09D175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
    • C09D175/16—Polyurethanes having carbon-to-carbon unsaturated bonds having terminal carbon-to-carbon unsaturated 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
    • C08G18/70—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
    • C08G18/8158—Polyisocyanates or polyisothiocyanates masked with unsaturated compounds having active hydrogen with unsaturated compounds having only one group containing active hydrogen
    • C08G18/8175—Polyisocyanates or polyisothiocyanates masked with unsaturated compounds having active hydrogen with unsaturated compounds having only one group containing active hydrogen with esters of acrylic or alkylacrylic acid having only one group containing active hydrogen

Definitions

  • the present invention relates to a new process for producing coatings from coating materials curable thermally and with actinic radiation.
  • Coating materials curable thermally and with actinic radiation which are also referred to as dual-cure coating materials, and processes for producing coatings therefrom are known from European patent specification EP-A-0 928 800.
  • the known coating material necessarily contains a urethane (meth) acrylate which has (meth) acrylate groups and free isocyanate groups, a UV polymer initiator (photoinitiator) which initiates the radical polymerisation and an isocyanate-reactive compound.
  • Possible isocyanate-reactive compounds are polyols such as polyesters from diols and triols and diacarboxylic acids, hindered amines from maleic esters and cycloaliphatic primary diamines, polyether polyols or hydroxyl-containing (meth) acrylate copolymers.
  • the known dual-cure coating material has the advantage that, on the one hand, an incomplete thermal hardening, which is consciously carried out, for example, to protect thermally sensitive substrates, with UV hardening, or an incomplete hardening, for example in the shadow areas of complex-shaped substrates can be compensated with UV light with the thermal hardening, so that overall a very good result results in both cases.
  • the object of the present invention is to find a new process for the production of coatings from dual-cure coating materials which, while preserving the advantages of the dual-cure systems described, delivers coatings which are non-yellowing and emission-free.
  • Crosslinking deaerating agents, slip additives, polymerization inhibitors. Defoamers, emulsifiers, wetting and diperging agents, adhesion promoters, leveling agents, film-forming aids, sag control agents (SCA), rheology-controlling additives (thickeners), flame retardants, siccatives, drying agents, skin-preventing agents,
  • the new process for producing coatings from coating materials curable thermally and with actinic radiation is referred to as the “process according to the invention”.
  • the method according to the invention is used to produce coatings, in particular single-layer and multi-layer clearcoats and color and / or effect coatings, on primed or unprimed substrates.
  • Suitable substrates are all surfaces to be painted which are not damaged by hardening of the paintwork thereon with combined use of heat and actinic radiation; these are e.g. B. metals, plastics, wood, ceramics, stone, textiles, fiber composites, leather, glass, glass fibers, glass and rock wool, mineral and resin-bound building materials, such as plaster and cement boards or roof tiles, as well as composites of these materials. Accordingly, the method according to the invention is also suitable for applications outside of automotive painting.
  • primers can be used which are produced in a customary and known manner from electrocoat materials (ETL). Both anodic (ATL) and cathodic (KTL) electrodeposition coatings, but especially KTL, come into consideration for this.
  • ETL electrocoat materials
  • ATL anodic
  • KTL cathodic
  • the substrate can also be subjected to a surface treatment, for example galvanizing or phosphating or anodizing. have undergone
  • a filler or a stone chip protection primer is applied to the fully cured or only dried electrodeposition coating (ETL).
  • ETL electrodeposition coating
  • This layer of paint is cured either on its own or together with the electrocoat layer below.
  • the applied filler layer can also only be dried or partially cured, after which it is coated with the lacquer layers above and, if necessary, with the electrocoat layer underneath is fully cured (extended wet-on-wet process).
  • the term primer also includes the combination of electro-dip coating and filler coating or stone chip protection primer.
  • primed or non-primed plastics such as B. 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 (short names according to DIN 7728T1) can be painted.
  • the plastics to be painted can of course also be polymer blends, modified plastics or fiber-reinforced plastics.
  • the plastics typically used in vehicle construction, in particular motor vehicle construction, can also be used.
  • non-functionalized and / or non-polar substrate surfaces these can be subjected to a pretreatment, such as with a plasma or with flame treatment, or provided with a hydro primer in a known manner before the coating.
  • the coating material described below, to be used according to the invention and curable thermally and with actinic radiation is applied to the primed or unprimed substrate, resulting in a layer of the dual-cure coating material to be used according to the invention.
  • This process variant is used in particular in the production of single-layer clearcoats or color and / or effect coatings.
  • the dual-cure coating material to be used according to the invention is applied to at least one basecoat layer located on the substrate.
  • the basecoat layer can also be a pigmented dual-cure coating material.
  • the base lacquer layer is preferably merely dried or partially cured, so that it can be cured together with the layer made of the dual-cure coating material (wet-on-wet method).
  • the pigmented dual-cure coating material to be used according to the invention is applied in the first process step and covered with a customary and known clearcoat, after which the two layers are cured together (wet-on-wet process).
  • the second and the third, but in particular the second, variant of the method according to the invention are used above all for the production of multi-layer color and / or effect coatings.
  • the application of the dual-cure coating material to be used according to the invention can be carried out by all customary application methods, such as e.g. Spraying, knife coating, painting, pouring, diving, watering. Dribbling or rolling take place.
  • 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.
  • Spray application methods are preferably used, such as compressed air spraying. Airless spray. High rotation, electrostatic spray application (ESTA), possibly combined with hot spray applications such as hot air - hot spraying.
  • the application can be carried out at temperatures of max. 70 to 80 ° C are carried out so that suitable application viscosities are achieved without a change or damage to the dual-cure coating material to be used according to the invention and its overspray, which may need to be reprocessed, occurring under the briefly acting thermal load.
  • hot spraying can be designed such that the dual-cure coating material to be used according to the invention is heated only very briefly in or shortly before the spray nozzle.
  • the spray booth used for the application can be operated, for example, with a circulation that can be tempered, if necessary, which is equipped with a suitable absorption medium for the overspray, e.g. B. the dual-cure coating material to be used according to the invention itself is operated.
  • the application is preferably carried out when illuminated with visible light of a wavelength of more than 550 ⁇ m or with exclusion of light if the water-based lacquer is curable thermally and with actinic radiation. This avoids a material change or damage to the dual-cure coating material to be used according to the invention and to the overspray.
  • the dual-cure coating materials to be used according to the invention are applied in a wet layer thickness such that, after they have hardened, coatings result in the layer thicknesses necessary and advantageous for their functions.
  • a base coat they are 5 to 50, preferably 5 to 40, particularly preferably 5 to 30 and in particular 10 to 25 ⁇ m
  • a clear coat they are 10 to 100, preferably 15 to 80, particularly preferably 20 to 75 and in particular 25 to 70 ⁇ m.
  • the application methods described above can also be used in the production of the other lacquer layers in the process according to the invention.
  • the layer of the dual-cure coating material to be used according to the invention is cured thermally and with actinic radiation after its application.
  • the methods of thermal curing described below and the methods of curing with actinic radiation described below are preferably used here.
  • electromagnetic radiation is like visible light
  • UV radiation and X-rays in particular UV radiation, or
  • UV radiation and or electron radiation are preferably used.
  • curing can take place immediately after the application of the layer made of the dual-cure coating material to be used according to the invention. If necessary, layers of paint that are not yet fully cured can also be cured. According to the invention, it is advantageous if the primer is already fully cured.
  • Curing can take place after a certain rest period or flash-off time. It can have a duration of 30 s to 2 h, preferably 1 min to 1 h and in particular 1 min to 45 min. The rest time is used, for example, for the course and degassing of the layers and for the evaporation of volatile constituents such as any solvent that may still be present.
  • a dose of 1,000 to 2,000, preferably 1,100 to 1,900, particularly preferably 1,200 to 1,800, very particularly preferably 1,300 to 1,700 and in particular 1,400 to 1,600 mJ / cm 2 is preferably used. If necessary, this hardening can be supplemented with actinic radiation from other radiation sources.
  • work is preferably carried out under an inert gas atmosphere. This can be ensured, for example, by supplying carbon dioxide and / or nitrogen directly to the surface of the clear lacquer layer I.
  • inert gas in order to avoid the formation of ozone.
  • 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.
  • the areas (shadow areas) which are not directly accessible to radiation, such as cavities, folds and other undercuts due to construction can be combined with point, small area or all-round emitters, combined with an automatic movement device for irradiating cavities or Edges to be (partially) cured.
  • the curing can take place in stages, ie by multiple exposure or irradiation with actinic radiation. This can also be done alternately, ie alternately curing with UV radiation and electron radiation.
  • the thermal curing also has no special features in terms of method, but is carried out according to the customary and known methods, such as heating in a forced air oven or irradiation with IR lamps. As with curing with actinic radiation, thermal curing can also be carried out in stages. The thermal curing advantageously takes place at temperatures below 100 ° C., in particular 90 ° C.
  • Thermal curing and curing with actinic radiation are used simultaneously or in succession. If the two curing methods are used in succession, 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. Particular advantages result if the layer of the dual-cure coating material to be used according to the invention is first cured thermally in two separate process steps and then with actinic radiation.
  • the single- or multi-layer clearcoat or color and / or effect coating resulting from the process according to the invention can also be coated with a layer of an organically modified ceramic material, as it is commercially available, for example, under the brand Ormocer®.
  • the dual-cure coating material to be used for the process according to the invention consists of the two components (A) and (B) or the three components (A), (B) and (C).
  • Constituent (A) is at least one compound which contains on average at least one, in particular at least two, free isocyanate group (s) and at least one, in particular at least two, bonds which can be activated with actinic radiation per molecule.
  • Compound (A) is preferably free from aromatic structures.
  • a bond which can be activated with actinic radiation is understood to mean a bond which becomes reactive when irradiated with actinic radiation and which undergoes polymerization reactions and / or crosslinking reactions with other activated bonds of its type which take place according to radical and / or ionic mechanisms.
  • suitable bonds are carbon-hydrogen single bonds or carbon-carbon, carbon-oxygen, carbon-nitrogen, carbon-phosphorus or carbon-silicon single bonds or double bonds.
  • the carbon-carbon double bonds are particularly advantageous and are therefore used with very particular preference in accordance with the invention. For the sake of brevity, they are referred to below as "double bonds".
  • Particularly suitable double bonds are, for example, in (meth) acrylate,
  • the acrylate groups offer very special advantages, which is why they are used according to the invention in a particularly preferred manner.
  • Suitable isocyanate-reactive functional groups are thio, hydroxyl, amino and / or imino groups, in particular thio, hydroxyl and / or amino groups, especially hydroxyl groups.
  • the compound (A) can be obtained by reacting polyisocyanates which contain on average at least 2.0, preferably more than 2.0 and in particular more than 3.0 isocyanate groups per molecule with compounds which have at least one, in particular one, contain bond which can be activated with actinic radiation and contain at least one, in particular one, isocyanate-reactive group.
  • the number of isocyanate groups in the polyisocyanates there is basically no upper limit to the number of isocyanate groups in the polyisocyanates; According to the invention, however, it is advantageous if the number does not exceed 15, preferably 12, particularly preferably 10, very particularly preferably 8.0 and in particular 6.0.
  • polyisocyanates examples include polyurethane prepolymers containing isocyanate groups, which can be prepared by reacting polyols with an excess of preferably aliphatic and cycloaliphatic diisocyanates and are preferably of low viscosity.
  • cycloaliphatic diisocyanate denotes a diisocyanate in which at least one isocyanate group is bonded to a cycloaliphatic radical.
  • Diisocyanatocyclopentane 1,2-diisocyanatocyclohexane, 1,3-diisocyanatocyclohexane, 1,4-diisocyanatocyclohexane, dicyclohexylmethane-2,4'-diisocyanate or dicyclohexylmethane-4,4'-diisocyanate, especially isophorone diisocyanate.
  • Suitable acyclic aliphatic diisocyanates to be used according to the invention are trimethylene diisocyanate, tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, ethyl ethylene diisocyanate,
  • hexamethylene diisocyanate is of particular advantage and is therefore used with very particular preference in accordance with the invention.
  • polyisocyanates are used which are prepared in a customary and known manner from the diisocyanates described above.
  • Examples of suitable production processes and polyisocyanates are, for example, from the patents CA-A-2,163,591, US-A-4,419,513, US-A-4,454,317, EP-A-0 646 608, US-A-4,801,675, EP-A-0 183 976, DE-A-40 15 155, EP-A-0 303 150, EP-A-0 496 208, EP-A-0 524 500, EP-A-0 566 037, US-A-5,258,482, US- A-5,290,902, EP-A-0 649 806, DE-A-42 29 183 or EP-A-0 531 820.
  • - Hydroxyalkyl esters of acrylic acid or methacrylic acid especially acrylic acid, which are obtainable by esterification of aliphatic diols, for example the low-molecular diols B) described above, with acrylic acid or methacrylic acid or by reaction of acrylic acid or methacrylic acid with an alkylene oxide, in particular hydroxyalkyl esters of acrylic acid or methacrylic acid in which the
  • Hydroxyalkyl group contains up to 20 carbon atoms, such as 2-hydroxyethyl, 2-hydroxypropyl, 3-hydroxypropyl, 3-hydroxybutyl, 4-hydroxybutyl, bis (hydroxymethyl) cyclohexane acrylate or methacrylate; Of these, 2-hydroxyethyl acrylate and 4-hydroxybutyl acrylate are particularly advantageous and are therefore used with particular preference in accordance with the invention; or
  • Reaction products from cyclic esters such as epsilon-caprolactone, and these hydroxyalkyl or cycloalkyl esters.
  • the polyisocyanates are reacted with the compounds which contain at least one bond which can be activated with actinic radiation and at least one isocyanate-reactive group in a molar ratio such that, on average, at least one free isocyanate group remains per molecule.
  • the content of compounds (A) in the dual-cure coating materials to be used according to the invention can vary very widely. It depends in particular on the functionality and the amount of component (B) and any reactive diluent (C) present.
  • the dual-cure coating material of the invention further consists of at least one hydroxyl-containing (meth) acrylate copolymer (B).
  • the (meth) acrylate copolymers (B) containing hydroxyl groups contain primary and / or secondary hydroxyl groups. It is a very important advantage of the process according to the invention that both types of hydroxyl groups can be used. This enables the reactivity of the (meth) acrylate copolymers (B) containing hydroxyl groups to be controlled in a targeted manner via steric effects.
  • Highly suitable hydroxyl-containing (meth) acrylate copolymers (B) are obtained by copolymerizing the olefinically unsaturated monomers (b) described below, at least one of which contains at least one hydroxyl group and is essentially free of acid groups.
  • Suitable monomers containing hydroxyl groups (b1) are hydroxyalkyl esters of acrylic acid, methacrylic acid of another alpha, beta ethylenically unsaturated carboxylic acid which is derived from an alkylene glycol which is esterified with the acid, or can be obtained by reacting the acid with an alkylene oxide, in particular hydroxyalkyl esters of acrylic acid, methacrylic acid or ethacrylic acid in which the hydroxyalkyl group contains up to 20 carbon atoms, such as 2 -Hydroxyethyl, 2-hydroxypropyl, 3-hydroxypropyl, 3-hydroxybutyl, 4-hydroxybutyl acrylate, methacrylate, ethacrylate or crotonate; 1,4-bis (hydroxymethyl) cyclohexane, octahydro-4,7-methano-1H-indene-dimethanol or methyl propanediol monoacrylate, monomethacrylate, monoethacrylate or monocro
  • Monomers (bl) are generally only used in minor amounts. In the context of the present invention, minor amounts of higher-functional monomers are understood to mean amounts which do not lead to crosslinking or gelling of the polyacrylate resins.
  • the proportion of trimethylolpropane diallyl ether can thus be 2 to 10% by weight, based on the total weight of the monomers (b1) to (b6) used to prepare the (meth) acrylate copolymers (B) containing hydroxyl groups. be.
  • the monomers (bl) can be used as the sole monomers (b) using at least one (meth) acrylate (bl). According to the invention, however, it is advantageous to use them in combination with other monomers (b).
  • Suitable further monomers (b) are:
  • These can be used in minor amounts of higher functional (meth) acrylic acid alkyl or cycloalkyl esters such as ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, butylene glycol, pentane-1, 5-diol, hexane, 1,6-diol, octahydro 4,7-methano-1H-indene-dimethanol or cyclohexane-1,2-, 1,3- or -1,4-diol-di (meth) acrylate; Trimethylolpropane di- or tri (meth) acrylate; or pentaerythritol di, tri or tetra (meth) acrylate; contain.
  • Monomers (b3) At least one acid group, preferably a carboxyl group, ethylenically unsaturated monomer carrying per molecule or a mixture of such monomers.
  • Acrylic acid and / or methacrylic acid are particularly preferably used as component (b3).
  • other ethylenically unsaturated carboxylic acids with up to 6 carbon atoms in the molecule can also be used. Examples of such acids are ethacrylic acids, crotonic acid, maleic acid, fumaric acid and itaconic acid.
  • ethylenically unsaturated sulfonic or phosphonic acids or their partial esters can be used as component (b3).
  • Suitable monomers (b3) are maleic acid mono (meth) acryloyloxyethyl ester, succinic acid mono (meth) acryloyloxyethyl ester and phthalic acid mono (meth) acryloyloxyethyl ester.
  • the branched monocarboxylic acids can be obtained by reacting formic acid or carbon monoxide and water with olefins in the presence of a liquid, strongly acidic catalyst; the olefins can be cracked products of paraffinic hydrocarbons, such as mineral oil fractions, and can contain both branched and straight-chain acyclic and / or cycloaliphatic olefins.
  • paraffinic hydrocarbons such as mineral oil fractions
  • a mixture of carboxylic acids is formed in which the carboxyl groups are predominantly located on a quaternary carbon atom.
  • olefinic starting materials are e.g. Propylene trimer, propylene tetramer and diisobutylene.
  • the vinyl esters can also be prepared from the acids in a manner known per se, e.g. by allowing the acid to react with acetylene. Because of the good availability, vinyl esters of saturated aliphatic monocarboxylic acids having 9 to 11 carbon atoms which are branched on the alpha carbon atom are particularly preferably used.
  • Reaction product of acrylic acid and / or methacrylic acid with the glycidyl ester of a monocarboxylic acid with 5 to 18 carbon atoms per molecule branched in the alpha position The reaction of acrylic or methacrylic acid with the glycidyl ester of a carboxylic acid with a tertiary alpha carbon atom can be carried out before, during or after the polymerization reaction.
  • the reaction product of acrylic and / or methacrylic acid with the glycidyl ester of Versatic® acid is preferably used as component (b5). This glycidyl ester is commercially available under the name Cardura® E10. In addition, reference is made to Römpp Lexikon Lacke und Druckmaschine, Georg Thieme Verlag, Stuttgart, New York, 1998, pages 605 and 606. Monomers (b6):
  • Olefins such as ethylene, propylene, but-1-ene, pent-1-ene, hex-1-ene,
  • (Meth) acrylic saxaxides such as (meth) acrylic acid amide, N-methyl, N, N-dimethyl, N-ethyl, N, N-diethyl, N-propyl, N, N-dipropyl, N-butyl,
  • Monomers containing epoxy groups such as the glycidyl ester of acrylic acid, methacrylic acids, ethacrylic acids, crotonic acid, maleic acid,
  • vinyl aromatic hydrocarbons such as styrene, alpha-alkylstyrenes, in particular alpha-methylstyrene, arylstyrenes, in particular diphenylethylene, and / or vinyltoluene:
  • Nitriles such as acrylonitrile and / or methacrylonitrile:
  • Vinyl compounds such as vinyl chloride, vinyl fluoride, vinylidene dichloride, vinylidene difluoride; N-vinylpyrrolidone; Vinyl ethers such as ethyl vinyl ether. n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether,
  • Mn from 1,000 to 40,000, preferably from 2,000 to 20,000, particularly preferably 2,500 to 10,000 and in particular 3,000 to 7,000 and on average 0.5 to 2.5, preferably 0.5 to 1.5, ethylenically unsaturated double bonds per molecule, such as they in DE-A-38 07 571 on pages 5 to 7, DE-A 37 06 095 in columns 3 to 7, the
  • hydroxyl-containing (meth) acrylate copolymers (B) which preferably have an OH number of 100 to 250, preferably 130 to 210, preferably acid numbers of 0 to 80, preferably 0 to 50, very particularly preferably 0 to 15, preferably glass transition temperatures Tg from -25 to +80
  • the glass transition temperature Tg of the (meth) acrylate copolymers (B) containing hydroxyl groups is determined by the type and amount of those used Monomers (bl) and optionally (b2), (b3), (b4), (b5) and or (b6) determined.
  • the person skilled in the art can select the monomers (b) with the aid of the following formula from Fox, with which the glass transition temperatures Tg of (co) polymers, in particular polyacrylate resins, can be approximately calculated:
  • Tg glass transition temperature of the hydroxyl group
  • the preparation of the hydroxyl-containing (meth) acrylate copolymers (B) has no special features, but is carried out according to the customary and known methods of radical polymerization in the presence of at least one polymerization initiator in bulk or in solution.
  • suitable polymerization initiators are free radical initiators such as dialkyl peroxides such as di-tert-butyl peroxide or dicumyl peroxide; Hydroperoxides such as cumene hydroperoxide or tert-butyl hydroperoxide; Peresters, such as tert-butyl perbenzoate, tert-butyl perpivalate, tert-butyl per-3,5,5-trimethyl hexanoate or tert-butyl per-2-ethyl hexanoate; Azodinitriles such as azobisisobutyronitrile; CC-cleaving initiators such as benzpinacol silyl ether. Oil-soluble initiators are preferably used. The initiators will preferably in an amount of 0.1 to 25% by weight, particularly preferably from 0.75 to 10% by weight, based on the total weight of the monomers (b).
  • the polymerization is expediently carried out at a temperature of 80 to 200 ° C., preferably 110 to 180 ° C.
  • organic solvents (C) described below which are inert to isocyanate groups, in particular mixtures of aromatic hydrocarbons or esters, ethers and or ketones, or reactive diluents (C) for thermal crosslinking are preferably used as solvents.
  • the solvents can serve as additive (C) in the dual-cure coating material to be used according to the invention.
  • the (meth) acrylate copolymers (B) containing hydroxyl groups can be prepared by a two-stage process or a one-stage process.
  • the monomers (b4) and / or (b5) can also be added only partially together with at least part of the solvent and the rest of these monomers can be added as described above. For example, at least 20% by weight of the solvent and about 10% by weight of the monomers (b4) and (b5) and, if appropriate, parts of the monomers (bl) and (b6) are preferably introduced.
  • the initiator feed be started some time, generally about 1 to 15 minutes, before the monomers feed.
  • a method is further preferred in which the initiator addition begins at the same time as the addition of the monomers and is terminated about half an hour after the addition of the monomers has ended.
  • the initiator is preferably added in a constant amount per unit of time. After the addition of the initiator has ended, the reaction mixture is kept at the polymerization temperature (as a rule 1.5 hours) until all of the monomers used have essentially been completely reacted.
  • Substantially completely converted is intended to mean that preferably 100% by weight of the monomers used have been reacted, but it is also possible that a low residual monomer content of at most up to about 0.5% by weight, based on the Weight of the reaction mixture can remain unreacted.
  • the monomers (b) for the preparation of the hydroxyl-containing (meth) acrylate copolymers (B) are preferably polymerized with a not too high polymerization solid, preferably with a polymerization solid of 80 to 50% by weight, based on the monomers (b) ,
  • the preparation of the (meth) acrylate copolymers (B) containing hydroxyl groups also has no particular features in terms of apparatus, but takes place with the help of the methods known and known in the plastics field of continuous or discontinuous copolymerization under normal pressure or overpressure in stirred tanks, autoclaves, tubular reactors or Taylor reactors.
  • Suitable hydroxyl-containing (meth) acrylate copolymers (B) are commercially available and are sold, for example, by Bayer AG under the Desmophen® A brand, DSM under the Uracron® brand and Synthopol under the Synthalat® brand.
  • the content of hydroxyl-containing (meth) acrylate copolymers (B) in the dual-cure coating materials to be used according to the invention can vary very widely. It depends in particular on the functionality and the amount of component (A) and any reactive diluent (C) that is present.
  • the constituents (A) and (B) or (B) and (C) and (A) are preferably used in a quantitative ratio (B): (A) or [(B) + (C)]: (A) that the molar ratio of hydroxyl groups to isocyanate groups is 3: 1 to 1: 2, preferably 2: 1 to 1: 1, 5 and in particular 1.5: 1 to 1: 1.
  • the third component of the dual-cure coating material to be used according to the invention is at least one additive (C), selected from the group consisting of color and or effect pigments, organic and inorganic, transparent or opaque fillers, nanoparticles.
  • C additive
  • the type and amount of the additives (C) depend on the intended use of the coatings produced using the process according to the invention.
  • the dual-cure coating material to be used according to the invention is used to produce solid-color top coats or basecoats, it contains color and / or effect pigments (C) and, if appropriate, opaque fillers. If the dual-cure coating material to be used according to the invention is used for the production of clearcoats, these additives (C) are naturally not contained therein.
  • suitable effect pigments (C) are platelet pigments such as commercially available aluminum bronzes, aluminum bronzes chromated according to DE-A-36 36 183, and commercially available stainless steel bronzes as well as non-metallic effect pigments, such as pearlescent or interference pigments.
  • platelet pigments such as commercially available aluminum bronzes, aluminum bronzes chromated according to DE-A-36 36 183, and commercially available stainless steel bronzes as well as non-metallic effect pigments, such as pearlescent or interference pigments.
  • non-metallic effect pigments such as pearlescent or interference pigments.
  • suitable inorganic color pigments (C) are titanium dioxide, iron oxides, Sicotrans yellow and carbon black.
  • Suitable organic coloring pigments are thioindigo pigments indanthrene blue, chromophot, irgazine orange and heliogen green.
  • thioindigo pigments indanthrene blue, chromophot, irgazine orange and heliogen green.
  • Römpp Lexikon Lacke und Druckmaschine, Georg Thieme Verlag, 1998 pages 180 and 181, "iron blue pigments” to "iron oxide black”, pages 451 to 453 “pigments” to “pigment volume concentration”, page 563 "thioindigo pigments” and See page 567 “Titanium dioxide pigments”.
  • organic and inorganic fillers are chalk, calcium sulfates, barium sulfate, silicates such as talc or kaolin, silicas, oxides such as aluminum hydroxide or magnesium hydroxide or organic fillers such as textile fibers, cellulose fibers, polyethylene fibers or wood flour.
  • silicates such as talc or kaolin
  • silicas oxides such as aluminum hydroxide or magnesium hydroxide
  • organic fillers such as textile fibers, cellulose fibers, polyethylene fibers or wood flour.
  • pigments and fillers (C) can also be incorporated into the dual-cure coating materials using pigment pastes.
  • the hydroxyl-containing (meth) acrylate copolymers (B) described above are suitable.
  • binders (C) are thermally curable hydroxyl-containing or curable with actinic radiation, linear and / or branched and or block-like, comb-like and / or randomly constructed poly (mefh) acrylates or acrylate copolymers, polyesters, alkyds, polyurethanes, acrylated polyurethanes, acrylated polyesters Polylactones, polycarbonates, polyethers, epoxy resin-amine adducts, (meth) acrylate diols, partially saponified polyvinyl esters or polyureas or (me) acrylic functional (meth) acrylate copolymers curable with actinic radiation.
  • thermally curable reactive diluents are positionally isomeric diethyloctanediols or hydroxyl group-containing hyperbranched compounds or dendrimers.
  • Suitable reactive thinners (C) curable with actinic radiation are those described in Römpp Lexikon Lacke und Druckmaschine, Georg Thieme Verlag, Stuttgart, New York, 1998, on page 491 under the keyword “reactive diluents”.
  • Suitable crosslinking agents (C) for thermal curing are amino resins, compounds or resins containing anhydride groups, compounds or resins containing epoxy groups,
  • Suitable low-boiling organic solvents (C) and high-boiling organic solvents (C) (“long solvents”) are ketones such as methyl ethyl ketone or methyl isobutyl ketone, esters such as ethyl acetate or butyl acetate, ethers such as dibutyl ether or ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, Butylene glycol or
  • Suitable light stabilizers are HALS compounds, benzotriazoles or oxalanilides.
  • thermolabile free radical initiators (C) are the initiators described above, which are used in the preparation of the hydroxyl-containing (metha) acrylate copolymers (B).
  • Suitable catalysts (C) for crosslinking are dibutyltin dilaurate, lifhium decanoate or zinc octoate;
  • C deaerating agent
  • emulsifiers (C) are nonionic emulsifiers, such as alkoxylated alkanols and polyols, phenols and alkylphenols or anionic emulsifiers such as alkali metal salts or ammonium salts of alkane carboxylic acids, alkane sulfonic acids, and sulfonic acids of alkoxylated alkanols and polyols, phenols and alkylphenols.
  • nonionic emulsifiers such as alkoxylated alkanols and polyols, phenols and alkylphenols
  • anionic emulsifiers such as alkali metal salts or ammonium salts of alkane carboxylic acids, alkane sulfonic acids, and sulfonic acids of alkoxylated alkanols and polyols, phenols and alkylphenols.
  • Suitable wetting agents (C) are siloxanes, fluorine-containing compounds, carboxylic acid half-esters, phosphoric acid esters, polyacrylic acids and their copolymers or polyurethanes.
  • An example of a suitable adhesion promoter (C) is tricyclodecanedimethanol
  • suitable film-forming aids (C) are cellulose derivatives.
  • suitable transparent fillers (C) are those based on silicon dioxide, aluminum oxide or zirconium oxide; In addition, reference is made to the Römpp Lexicon Lacke und Druckmaschine, Georg Thieme Verlag, Stuttgart, 1998, pages 250 to 252.
  • Sag control agents are ureas, modified ureas and or silicas, as described, for example, in references EP-A-192 304, DE-A-23 59 923, DE-A-18 05 693, WO 94/22968 , DE-C-27 51 761, WO 97/12945 or "färbe + lack", 11/1992, pages 829 ff.
  • rheology-controlling additives are those known from the patents WO 94/22968, EP-A-0 276 501, EP-A-0 249 201 or WO 97/12945; crosslinked polymeric microparticles, such as are disclosed, for example, in EP-A-0 008 127; inorganic layered silicates such as aluminum magnesium silicates, sodium magnesium and
  • Montmorillonite type sodium magnesium fluorine lithium layered silicates Silicas such as aerosils; or synthetic polymers with ionic and / or associative groups such as polyvinyl alcohol, poly (meth) acrylamide, poly (meth) acrylic acid, polyvinyl pyrrolidone, styrene-maleic anhydride or ethylene-maleic anhydride copolymers and their derivatives or hydrophobically modified ethoxylated urethanes or polyacrylates;
  • An example of a suitable matting agent (C) is magnesix stearate.
  • additives (C) listed above examples of suitable UV absorbers, radical scavengers, leveling agents,
  • Water can also be used as additive (C) if aqueous dual-cure coating materials are to be produced.
  • the additives (C) are used in customary and known, effective amounts.
  • the production of the dual-cure substance mixtures according to the invention has no special features, but is carried out in a customary and known manner by mixing the constituents (A), (B) and (C) described above in suitable mixing units such as stirred kettles, dissolvers, agitator mills or extruders the methods suitable for the production of the respective dual cure substance mixtures according to the invention.
  • suitable mixing units such as stirred kettles, dissolvers, agitator mills or extruders the methods suitable for the production of the respective dual cure substance mixtures according to the invention.
  • the dual-cure coating material to be used according to the invention is a two-component system in which the component (A) must be stored separately from the component (B) until it is used because of its high reactivity, the components ( A) and (C) a component I and from component (A) and optionally an additive which is inert to isocyanate groups (C), in particular an organic solvent (C), a component II. Components I and II are then combined shortly before the dual-cure coating materials are used.
  • the coatings produced with the aid of the method according to the invention are of the highest optical quality in terms of color, effect, gloss and DOI (distinctiveness of the reflected image), have a smooth, structureless, hard, flexible and scratch-resistant surface, are odorless and weather, chemical and etch resistant, do not yellow and show no cracking and delamination of the layers.
  • coated or unprimed substrates coated with these coatings therefore have a particularly long service life and a particularly high utility value, which makes them technically and economically particularly attractive for manufacturers, users and end users.
  • Table 1 The composition of the clearcoats to be used according to the invention (Examples 1 to 3 and of the clearcoats not to be used according to the invention (comparative experiments VI and V2)

Abstract

L'invention concerne un procédé permettant de produire des revêtements à base de substances de recouvrement durcissables par voie thermique et par rayonnement actinique sur des substrats munis ou non d'un apprêt. Ce procédé comprend les étapes suivantes : (1) appliquer au moins une substance de recouvrement durcissable par voie thermique ou par rayonnement actinique sur le substrat muni ou non d'un apprêt, de manière à former une couche de substance de recouvrement, et (2) durcir ladite couche par apport de chaleur et de rayonnement actinique. Ce procédé se caractérise en ce qu'on utilise une substance de recouvrement comprenant : A) des composés comprenant en moyenne statistique au moins un groupe isocyanate libre et au moins une liaison activable par rayonnement actinique, par molécule, et B) des (méth)acrylate-copolymérisats contenant des groupes hydroxyle, ainsi qu'éventuellement C) des additifs sélectionnés dans le groupe comprenant : pigments, charges, nanoparticules, liants, diluants réactifs, agents de réticulation pour le durcissement thermique, solvants, eau, absorbeurs d'U.V., agents stabilisants contre l'effet de la lumière, agents capteurs de radicaux, initiateurs, catalyseurs pour la réticulation thermique, agents de ventilation, agents glissants, inhibiteurs de polymérisation, agents antimoussants, émulsifiants, agents mouillants et dispersants, agents adhésifs, agents d'écoulement, auxiliaires filmogènes, agents de neutralisation d'affaissement (sag control agents (SCA)), additifs rhéologiques (épaississants), agents ignifuges, siccatifs, agents déshydratants, agents antipeau, inhibiteurs de corrosion, cires et agents de matage.
EP00983217A 1999-12-20 2000-12-05 Procede de production de revetements a base de substances de recouvrement durcissables par voie thermique et par rayonnement actinique Withdrawn EP1242496A1 (fr)

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DE19961402 1999-12-20
DE19961402A DE19961402A1 (de) 1999-12-20 1999-12-20 Verfahren zur Herstellung von Beschichtungen aus thermisch und mit aktinischer Strahlung härtbaren Beschichtungstoffen
PCT/EP2000/012188 WO2001046286A1 (fr) 1999-12-20 2000-12-05 Procede de production de revetements a base de substances de recouvrement durcissables par voie thermique et par rayonnement actinique

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CA (1) CA2394543A1 (fr)
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BR0015550A (pt) 2002-07-09
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MXPA02003931A (es) 2002-10-23
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US20030036604A1 (en) 2003-02-20
DE19961402A1 (de) 2001-07-05
AU2004501A (en) 2001-07-03

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