EP1590399A1 - Melanges de matieres durcissables, leur procede de production et leur utilisation - Google Patents

Melanges de matieres durcissables, leur procede de production et leur utilisation

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Publication number
EP1590399A1
EP1590399A1 EP04701915A EP04701915A EP1590399A1 EP 1590399 A1 EP1590399 A1 EP 1590399A1 EP 04701915 A EP04701915 A EP 04701915A EP 04701915 A EP04701915 A EP 04701915A EP 1590399 A1 EP1590399 A1 EP 1590399A1
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EP
European Patent Office
Prior art keywords
curable
substance mixtures
mixtures according
coatings
acid
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.)
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Application number
EP04701915A
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German (de)
English (en)
Inventor
Hubert Baumgart
Annette Roters
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BASF Coatings GmbH
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BASF Coatings GmbH
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Filing date
Publication date
Application filed by BASF Coatings GmbH filed Critical BASF Coatings GmbH
Publication of EP1590399A1 publication Critical patent/EP1590399A1/fr
Withdrawn legal-status Critical Current

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/011—Nanostructured additives

Definitions

  • the present invention relates to new curable mixtures.
  • the present invention relates to a new method for producing curable mixtures.
  • the present invention relates to the use of the new curable substance mixtures and the curable substance mixtures produced by the new method for the production of scratch-resistant, self-supporting foils and scratch-resistant molded parts and as coating materials, adhesives and sealants for the production of scratch-resistant coatings, adhesive layers and seals, in particular as coating materials for the production of transparent, clear, scratch-resistant coatings.
  • Curable mixtures of substances which are suitable as coating materials for the production of scratch-resistant coatings are known. As is known, they contain components and nanoparticles curable thermally and / or with actinic radiation (cf. international
  • Vehicles especially cars, are used, they must have light stabilizers, especially sterically hindered amines (sterically hindered amines,
  • HALS HALS
  • the scratch-resistant nanoparticles cause considerable problems due to their inorganic nature, which are particularly noticeable with the broom sealants that are used to produce transparent, clear, scratch-resistant coatings, especially clear coats.
  • the broom sealants that are used to produce transparent, clear, scratch-resistant coatings, especially clear coats.
  • segregation often occurs, which in the coating materials in question leads to such a high level of turbidity that even complete gelling or coagulation that their use leads to Production of clear coats is no longer possible.
  • the state of the art takes the measure to modify the surface of the nanoparticles in a complex manner.
  • HALS light stabilizers used in the known coating materials apparently have no influence on the stability of the coating materials, since all types of HALS (unsubstituted, alkyl-substituted and ether-substituted HALS on the cyclic amino groups) are used without distinction.
  • the object of the present invention was to provide new curable substance mixtures which no longer have the disadvantages of the prior art, but which are also stable in storage when using economically producible, unmodified or largely unmodified, hydrophilic nanoparticles and no clouding and no increase in viscosity to complete gelling or coagulation.
  • the new curable material mixtures are said to be suitable for the economical production of scratch-resistant, self-supporting foils and scratch-resistant molded parts, and as coating materials, adhesives and sealants for the production of scratch-resistant coatings, adhesive layers and seals, in particular as coating materials for the production of transparent, clear, scratch-resistant coatings.
  • the new scratch-resistant, self-supporting foils as well as the scratch-resistant molded parts, coatings, adhesive layers and seals, especially the new transparent, clear, scratch-resistant coatings, should remain scratch-resistant and have an excellent overall appearance (appearance) even after many years of outdoor use.
  • the substance mixtures according to the invention no longer had the disadvantages of the prior art, but were also storage-stable when using economically producible, unmodified or largely unmodified, hydrophilic nanoparticles and no longer exhibited gelling or coagulation. In fact, there were no cloudiness and none Increase in viscosity to be observed.
  • the mixtures of substances according to the invention were outstandingly suitable for the economical production of scratch-resistant, self-supporting films and scratch-resistant molded parts, and as coating materials, adhesives and sealants for the economical production of scratch-resistant coatings, adhesive layers and seals, in particular as coating materials for the production of transparent, clear, scratch-resistant coatings.
  • the process according to the invention made it possible in a simple manner to select suitable essential starting products and to produce mixtures of substances according to the invention, the resulting mixtures of substances according to the invention for the economical production of scratch-resistant, self-supporting films and scratch-resistant moldings and as coating materials, adhesives and sealants for the production of scratch-resistant coatings , Adhesive layers and seals, particularly as coating materials for the production of transparent, clear, scratch-resistant coatings, were outstandingly suitable.
  • the term “physical hardening” means the hardening of a layer of a hardenable substance mixture by filming by solvent release from the hardenable substance mixture, the connection within the layer via loop formation of the polymer molecules of the binders (for the term see Römpp Lexikon Lacke and printing inks, Georg Thieme Verlag, Stuttgart, New York, 1998, “Binders", pages 73 and 74. Or the filming takes place via the coalescence of binder particles (cf. Römpp Lexikon Lacke und Druckmaschine, Georg Thieme Verlag, Stuttgart, New York, 1998, “Hardening", pages 274 and 275. Usually no crosslinking agents are required for this purpose. If necessary, physical hardening can be supported by atmospheric oxygen, heat or by exposure to actinic radiation.
  • the thermally curable constituents (A) in turn can be self-crosslinking or externally crosslinking.
  • electromagnetic radiation such as near infrared (NIR), visible light, UV radiation, X-rays and gamma radiation, in particular UV radiation, and corpuscular radiation such as electron radiation, beta radiation, alpha radiation and neutron radiation, in particular electron radiation, are included under actinic radiation understand.
  • NIR near infrared
  • UV radiation visible light
  • UV radiation UV radiation
  • X-rays and gamma radiation in particular UV radiation
  • corpuscular radiation such as electron radiation, beta radiation, alpha radiation and neutron radiation, in particular electron radiation
  • the substance mixtures according to the invention preferably contain at least one binder (A).
  • the binders (A) are oligomeric and polymeric resins.
  • suitable polyaddition resins and polycondensation resins (A) are polyesters, alkyds, polyurethanes, polylactones, polycarbonates, polyethers, epoxy resin-amine adducts, polyureas, polyamides, polyimides, polyester-polyurethanes, polyether-polyurethanes or polyester-polyether-polyurethanes, in particular polyester polyurethanes.
  • the (meth) acrylate (co) polymers (A) have advantages and are therefore used with preference.
  • the self-crosslinking binders (A) of the thermally curable substance mixtures and dual-cure substance mixtures according to the invention contain reactive functional groups which can undergo crosslinking reactions with groups of their type or with complementary reactive functional groups.
  • the externally crosslinking binders (A) contain reactive functional groups which can undergo crosslinking reactions with complementary reactive functional groups which are present in crosslinking agents (A). Examples of suitable complementary reactive functional groups to be used according to the invention are summarized in the following overview.
  • variable R stands for an acyclic or cyclic aliphatic, an aromatic and / or an aromatic-aliphatic (araliphatic) radical; the variables R and R stand for identical or different aliphatic radicals or are linked to one another to form an aliphatic or heteroaliphatic ring.
  • the selection of the respective complementary groups is based on the one hand on the fact that they do not undergo any undesired reactions, in particular no premature crosslinking, during the production, storage and application and, if appropriate, during the melting of the substance mixtures according to the invention and / or if necessary curing with actinic radiation must not disturb or inhibit, and on the other hand according to the temperature range in which the crosslinking should take place.
  • crosslinking temperatures of the thermally curable or dual-cure curable material mixtures according to the invention crosslinking temperatures of
  • the functionality of the binders (A) with respect to the reactive functional groups described above can vary very widely and depends in particular on the crosslinking density that is to be achieved and / or on the functionality of the crosslinking agent (A) used in each case.
  • the acid number is preferably included 10 to 100, preferably 15 to 80, particularly preferably 20 to 75, very particularly preferably 25 to 70 and in particular 30 to 65 mg KOH / g.
  • the OH number is preferably 15 to 300, preferably 20 to 250, particularly preferably 25 to 200, very particularly preferably 30 to 150 and in particular 35 to 120 mg KOH / g.
  • the epoxy equivalent weight is preferably 400 to 2,500, preferably 420 to 2,200, particularly preferably 430 to 2,100, very particularly preferably 440 to 2,000 and in particular 440 to 1,900 equivalent / g.
  • the complementary reactive functional groups described above can be incorporated into the binders (A) by the customary and known methods of polymer chemistry. This can be done, for example, by incorporating monomers which carry the corresponding reactive functional groups and / or using polymer-analogous reactions.
  • (a3) monomers containing epoxy groups such as the glycidyl ester of acrylic acid, methacrylic acid, ethacrylic acid, crotonic acid,
  • suitable monomer units for introducing reactive functional groups into polyester or polyester-polyurethane (A) are 2,2-dimethylolethyl- or propylamine, which are blocked with a ketone, the resulting ketoxime group being hydrolyzed again after incorporation; or compounds which have two hydroxyl groups or two primary and / or secondary amino groups and at least one acid group, in particular at least one carboxyl group and / or contain at least one sulfonic acid group, such as
  • Dimethylolbutyric acid 2,2-dimenthylolpentanoic acid, alpha.omega-diaminovaleric acid, 3,4-diaminobenzoic acid, 2,4-diaminotoluenesulfonic acid or 2,4-diamino-diphenylether sulfonic acid.
  • the binders (A) of the dual-cure substance mixtures according to the invention or of the substance mixtures according to the invention curable purely with actinic radiation furthermore contain on average at least one, preferably at least two, group (s) with at least one bond which can be activated with actinic radiation per molecule.
  • 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 kind 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 and carbon-carbon triple 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".
  • the group preferred according to the invention which can be activated with actinic radiation, contains one double bond or two, three or four double bonds. If more than one double bond is used, the double bonds can be conjugated. According to the invention, however, it is advantageous if the double bonds are isolated, in particular each individually in the group in question here. According to the invention, it is particularly advantageous to use two, in particular one, double bond.
  • the dual-cure binder (A) or the binder (A) curable purely with actinic radiation contains on average at least one of the groups described above which can be activated with actinic radiation.
  • the functionality of the binder in this respect is an integer, i.e., for example two, three, four, five or more, or non-integer, i.e., for example 2.1 to 10.5 or more. Which functionality is chosen depends on the requirements placed on the respective dual-cure substance mixtures according to the invention or the substance mixtures according to the invention curable with actinic radiation.
  • the groups are structurally different from one another or of the same structure. If they are structurally different from one another, this means within the scope of the present invention that two, three, four or more, but in particular two, groups which can be activated with actinic radiation and which differ from two, three, four or more, in particular two, are used. Derive monomer classes.
  • the groups are preferably via urethane, urea, allophanate, ester, ether and / or amide groups, but in particular via
  • binders (A) which are purely thermally curable and curable purely with actinic radiation can also be used.
  • the material composition of the binders (A) basically has no peculiarities, but comes
  • Reactors for the copolymerization are the customary and known stirred tanks, stirred tank cascades, tubular reactors, loop reactors or Taylor reactors, as described, for example, in the patents and patent applications DE 1 071 241 B1, EP 0 498 583 A1 or DE 198 28 742 A1 or in the article by K. Kataoka in Chemical Engineering Science, Volume 50, Issue 9, 1995, pages 1409 to 1416.
  • polyesters and alkyd resins are described, for example, in the standard work Ulimanns Encyklopadie der Technische Chemie, 3rd edition, volume 14, Urban & Schwarzenberg, Kunststoff, Berlin, 1963, pages 80 to 89 and pages 99 to 105, as well as in the books: "Resines Alkydes-Polyesters” by J. Bourry, Paris, Dunod Verlag, 1952, "Alkyd Resins” by CR Martens, Reinhold Publishing Corporation, New York, 1961, and "Alkyd Resin Technology” by TC Patton, Intersience Publishers, 1962, described.
  • the content of binders (A) in the substance mixtures according to the invention can vary very widely and depends primarily on whether they are physically curable, thermally self-crosslinking curable and / or curable with actinic radiation.
  • the content can preferably be 20 to 99.9, preferably 25 to 99.7, particularly preferably 30 to 99.5, very particularly preferably 35 to 99.3 and in particular 40 to 99.1% by weight, in each case based on the solids of the mixtures according to the invention.
  • beta-hydroxyalkylamides such as N, N, N ', N'-T ⁇ trakis (2-hydroxyethyl) adipamide or N, N, N', N , -Tetrakis (2-hydroxypropyl) - adipamide and / or
  • Tris (alkxycarbonylamino) triazines are preferably used.
  • the content of the crosslinking agents (A) in the substance mixtures according to the invention can likewise vary very widely and depends on the requirements of the individual case, in particular on the number of reactive functional groups present. It is preferably 1.0 to 50, preferably 2.0 to 45, particularly preferably 3.0 to 40, very particularly preferably 4.0 to 35 and in particular 5.0 to 30% by weight, in each case based on solids mixtures of substances according to the invention.
  • the substance mixtures according to the invention contain at least one, in particular one, type of inorganic nanoparticles (B) with an electrophoretic mobility ⁇ e ⁇ - 0.5, preferably ⁇ - 1 and in particular ⁇ - 1.5 ( ⁇ m / s) / (V / cm) at a pH of 3 to 7.
  • the electrophoretic mobility can be determined with the aid of laser Doppler electrophoresis.
  • the Zetasizer ® 3000 from Malvern can be used as the measuring device. However, microelectrophoretic (microscopic) measurement methods can also be used.
  • the nanoparticles (B) are preferably selected from the group consisting of main and subgroup metals and their compounds.
  • the main and subgroup metals are preferably selected from metals of the third to fifth main group, the third to sixth and the first and second subgroups of the periodic table of the elements and the lanthanides.
  • the compounds of the metals are preferably the oxides, oxide hydrates, sulfates or phosphates, in particular oxides.
  • pyrogenic silicon dioxide is pyrogenic silicon dioxide.
  • the agglomerates and aggregates of its primary particles have a chain structure and are produced by flame hydrolysis of silicon tetrachloride in a detonating gas flame.
  • the pyrogenic silicon dioxide as such is hydrophilic and can be used without further notice Modification or after only a minor modification of its surface can be used as nanoparticles (B).
  • “Minor” means that when the surface is modified, only a small part, in particular ⁇ 50 equivalent%, of the silanol groups present on the surface of the nanoparticles are reacted with customary and known modifiers.
  • the nanoparticles (B) to be modified preferably have a primary particle size ⁇ 50 nm, preferably 5 to 50 nm, in particular 10 to 30 nm.
  • the substance mixtures according to the invention further contain at least one, in particular one, light stabilizer (C) based on sterically hindered amines (HALS) with a pKe value of at least 9.0, in particular at least 9.5.
  • the light stabilizers (C) are preferably selected from the group of aminoether-functionalized HALS.
  • the amino ether functionalized 2,2,6,6-tetramethylpiperidine derivatives are used, such as bis (1-octyloxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate, which is available from Ciba Specialty Chemicals under the brand name Tinuvin ⁇ 123 is distributed.
  • aminoether-functionalized HALS which have at least one reactive molecule which is complementary to the reactive functional groups of the crosslinking agent and / or binder (A) contain functional group so that they are immobilized during the thermal crosslinking of the substance mixtures according to the invention.
  • the substance mixtures according to the invention preferably contain the light stabilizers (C) in an amount of 0.1 to 5, preferably 0.2 to 4 and in particular 0.3 to 3% by weight, based in each case on the solids of the substance mixtures according to the invention.
  • the mixtures of substances according to the invention can further contain at least one additive (D).
  • additives are preferably selected from the group consisting of photoinitiators; molecularly dispersible dyes; low and high boiling ("long") organic solvents; Venting means; Wetting agents; emulsifiers; Slip additives polymerization inhibitors; Catalysts for the thermal crosslinking of thermolabile free radical initiators; Adhesion promoters; Leveling agents film-forming aids; Rheology aids such as thickeners and pseudoplastic Sag control agents, SCA; Triazine and benzotriazole based light stabilizers; Flame retardants; Corrosion inhibitors; anti-caking agents; To grow; driers; Biocides and matting agents.
  • the substance mixtures according to the invention which contain the additives (D) described above, are used for the production of clear, transparent, hardened substance mixtures, in particular for the production of clear, transparent coatings, adhesive layers, seals, films and moldings.
  • the mixtures of substances according to the invention can, however, also be pigmented. They then preferably contain, as an additive or as one of the additives (D), at least one customary and known pigment selected from the group consisting of organic and inorganic, transparent and opaque, color and / or effect, electrically conductive, magnetically shielding and fluorescent Pigments and fillers.
  • the pigmented substance mixtures according to the invention are used in particular as coating materials, such as electrical smoke coatings, fillers, basecoats and solid-color topcoats, for the production of pigmented coatings, such as electrical smoke coatings, filler coatings or stone chip protection primers, basecoats and
  • Solid color finishes or used to manufacture pigmented adhesive layers, seals, foils and molded parts.
  • the pigmented substance mixtures according to the invention can also be used for the production of pigmented, transparent hardened substance mixtures, in particular of transparent coatings, adhesive layers, seals, foils and molded parts.
  • the substance mixtures according to the invention are preferably produced by mixing the constituents described above in suitable mixing units such as stirred kettles, agitator mills, extruders, kneaders, Ultraturrax, in-line dissolvers, static mixers, micromixers, gear rim dispersers,
  • Pressure relief nozzles and / or microfluidizers Preference is given to excluding light of a wavelength ⁇ ⁇ 550 nm or to completely excluding light in order to prevent premature crosslinking of the compositions according to the invention if the compositions according to the invention are curable with actinic radiation or with dual-cure.
  • customary and known temporary or permanent substrates are preferably used for the production of the films and molded parts according to the invention, such as metal and plastic strips or hollow bodies made of metal, glass, plastic, wood or ceramic, which can be easily removed without damaging the films and molded parts according to the invention ,
  • the substance mixtures according to the invention are used for the production of coatings, adhesive layers, primers and seals, permanent substrates are used, such as means of transportation, including aircraft, watercraft, rail vehicles, muscle-powered vehicles and motor vehicles, and parts thereof, structures indoors and outdoors and Parts thereof, doors, windows, furniture, hollow glass bodies, coils, containers, packaging, small industrial parts, optical components, electrotechnical components, mechanical components and components for white would.
  • the films and moldings according to the invention can also serve as substrates.
  • the application of the powdery mixtures of substances according to the invention 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 from BASF Coatings AG, “Powder coatings for industrial applications”, January 2000, or “Coatings Partner, powder coating Spezial «, 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 «.
  • compositions according to the invention are curable with actinic radiation or with dual-cure.
  • the applied substance mixtures according to the invention are preferably cured with UV radiation.
  • a radiation dose of 100 to 6,000, preferably 200 to 3,000, preferably 300 to 2,000 is preferred for the irradiation and particularly preferably 500 to 1,800 mJcm "2 are used, the range ⁇ 1,700 mJcm " 2 being very particularly preferred.
  • the radiation intensity can vary widely. It depends in particular on the radiation dose on the one hand and the radiation duration on the other. For a given radiation dose, the irradiation time depends on the belt or feed speed of the substrates in the irradiation system and vice versa.
  • UV lamps can be used as radiation sources for the UV radiation. Flash lamps can also be used.
  • Mercury vapor lamps preferably mercury low, medium and high pressure vapor lamps, are preferred as UV lamps, in particular
  • Unmodified mercury vapor lamps plus suitable filters or modified, in particular doped, mercury vapor lamps are particularly preferably used.
  • Gallium-doped and / or iron-doped, in particular iron-doped, mercury vapor lamps are preferably used, as described, for example, in R. Stephen Davidson, "Exploring the Science, Technology and Applications of UN. and E.B. Curing «, Sita Technology Ltd., London, 1999, Chapter I,» An Overview «, page 16, Figure 10, or Dipl.-Ing. Peter Klamann, “eltosch system competence, UV technology, guidelines for users”, page 2, October 1998.
  • Suitable flash lamps are flash lamps from VISIT.
  • the distance of the UV lamps from the applied compositions according to the invention can vary surprisingly widely and therefore very well on the The requirements of the individual case can be set.
  • the distance is preferably 2 to 200, preferably 5 to 100, particularly preferably 10 to 50 and in particular 15 to 30 cm.
  • Their arrangement can also be adapted to the conditions of the substrate and the process parameters.
  • the areas which are not accessible to direct radiation (shadow areas), such as cavities, folds and other design-related undercuts can be combined with point, small area or all-round emitters, combined with an automatic movement device for the irradiation of Cavities or edges, are cured.
  • the irradiation can be carried out under an oxygen-depleted atmosphere.
  • Oxygen-depleted means that the content of oxygen in the atmosphere is lower than the oxygen content of air (20.95% by volume).
  • the atmosphere can basically also be oxygen-free, ie it is an inert gas. Because of the lack of However, the inhibiting effect of oxygen can cause a strong acceleration of radiation curing, which can result in inhomogeneities and stresses in the hardened compositions according to the invention. It is therefore advantageous not to reduce the oxygen content of the atmosphere to zero% by volume.
  • the thermal curing can be carried out, for example, with the aid of a gaseous, liquid and / or solid, hot medium, such as hot air, heated oil or heated rollers, or with the aid of 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 used done gradually. The thermal curing advantageously takes place at temperatures from room temperature to 200.degree.
  • Both thermal curing and curing with actinic radiation can be carried out in stages. They can take place one after the other (sequentially) or simultaneously. Sequential curing is advantageous according to the invention and is therefore used with preference. It is particularly advantageous to carry out the thermal hardening after the hardening with actinic radiation.
  • the resulting films, moldings, coatings, adhesive layers and seals according to the invention are outstandingly suitable for coating, gluing, sealing, wrapping and packaging of means of transportation, including aircraft, watercraft, rail vehicles, muscle-powered vehicles and motor vehicles, and parts thereof, structures inside - and outdoor areas and parts thereof, doors, windows and furniture as well as in the context of industrial painting of hollow glass bodies, coils, containers, packaging, small industrial parts such as nuts, screws or hubcaps, optical components, electrical components, such as winding materials, including coils and stators and rotors for electric motors, mechanical components and components for white goods, including household appliances, boilers and radiators.
  • the substance mixtures according to the invention are used as coating materials for the production of clear, transparent coatings, preferably clearcoats, preferably clearcoats of color and / or effect-giving, electrically conductive, magnetically shielding or fluorescent multi-layer coatings, particularly preferably of clearcoats of color and / or or effect-giving multi-layer coatings and in particular of clear coats of coloring and / or effect-giving multi-coat coats which have the so-called automotive quality (cf. also European patent EP 0 352 298 B1, page 15, line 42, to page 17, line 40).
  • the multicoat paint systems according to the invention are preferably applied by the customary and known wet-on-wet processes (see, for example, German patent applications DE 199 14 896 A1, column 16, line 54 to column 18, line 57, or DE 199 30 067 A1) , Page 15, line 25, to page 16, line 36).
  • the resulting coatings, moldings and films according to the invention are simple to produce and have excellent optical properties (appearance) and very high resistance to light, chemicals, water, condensation, weather and etching , In particular, they are free from cloudiness and inhomogeneities. They have excellent scratch resistance and abrasion resistance with excellent surface hardness and acid resistance.
  • the coatings, in particular the clearcoats only experience a difference in gloss before and after exposure to less than 30, preferably less than 27 and in particular less than 25 units, which underpins their particularly high scratch resistance.
  • the adhesive layers according to the invention permanently bond a wide variety of substrates to one another and have high chemical and mechanical stability even in the case of extreme temperatures and / or temperature fluctuations.
  • the seals according to the invention permanently seal the substrates, and they also have high chemical and mechanical stability even in the case of extreme temperatures and / or temperature fluctuations. V. m. exposed to aggressive chemicals.
  • Binder solution (A 1) according to preparation example 1 31, 32 31, 32
  • Binder solution (A 1) according to Preparation Example 1 36.137 30.047
  • Baysilon ® OL 44 (commercially available leveling agent based on a modified polysiloxane from Bayer AG) 0.063
  • Tinuvin ® 400 (commercially available light stabilizer based on triazine from Ciba Specialty Chemicals) 1.1 0.9 Highlink ® OG 502-31 (dispersion of unmodified
  • the commercially available water-based lacquer "Starsilber" from BASF Coatings AG was applied with wet layer thicknesses, which resulted in dry layer thicknesses of 12 to 15 ⁇ m after curing, after which the resulting water-based lacquer layers were flashed off at 80 ° C. for ten minutes.
  • the clear coats 2 and 3 were applied pneumatically in a cloister with a gravity cup gun oil.
  • the wet layer thicknesses of the clear lacquer layers were set in such a way that dry layer thicknesses of 40 to 45 ⁇ m each resulted after curing.
  • the water-based lacquer layers and the clear lacquer layers were cured for 5 minutes at room temperature, for 10 minutes at 80 ° C. and finally for 20 minutes at 140 ° C. The result was the multi-layer paintwork 4 and 5.
  • micro penetration hardness was determined as universal hardness at 25.6 mN using a Fischerscope 100V with a diamond pyramid according to Vickers.
  • the chemical resistance was determined according to BART (BASF ACID RESISTANCE TEST).
  • the multicoat paint systems 4 and 5 were exposed to temperature loads on a gradient oven (30 min, 50 ° C, 60 ° C and 70 ° C and 80 ° C).
  • the test substances sulfuric acid 1%, 10%, 36%; sulfuric acid 5%, hydrochloric acid 10%, sodium hydroxide solution 5%, demineralized water - 1, 2, 3 or 4 drops
  • Table 3 Hardness, scratch resistance, condensation resistance and acid resistance of the multi-layer coatings 4 and 5
  • Gloss before mechanical stress 85.2 80.3 Gloss difference after mechanical stress 2.3 1.1 Gloss difference after reflow (2 h / 40 ° C) - 0.7 0.9 Gloss difference after reflow (2 h / 80 ° C) - 0.8 1.0

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Abstract

L'invention concerne des mélanges de matières durcissables, contenant : (A) au moins un constituant pouvant être durci physiquement ou thermiquement et/ou sous l'effet d'un rayonnement actinique, (B) au moins un type de nanoparticules inorganiques présentant une mobilité électrophorétique µe = - 0,5 (µm/s)/(V/cm) à un pH compris entre 3 et 7, et (C) au moins un photostabilisant à base d'amines stériquement encombrées (HALS) présentant une valeur pKB d'au moins 9,0. L'invention concerne également un procédé pour la production desdits mélanges et l'utilisation de ces derniers.
EP04701915A 2003-02-03 2004-01-14 Melanges de matieres durcissables, leur procede de production et leur utilisation Withdrawn EP1590399A1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
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DE10304127A DE10304127A1 (de) 2003-02-03 2003-02-03 Härtbare Stoffgemische, Verfahren zu ihrer Herstellung und ihre Verwendung
PCT/EP2004/000180 WO2004069910A1 (fr) 2003-02-03 2004-01-14 Melanges de matieres durcissables, leur procede de production et leur utilisation

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US20060148944A1 (en) 2006-07-06
DE10304127A1 (de) 2004-08-12

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