EP1828276A1 - Melanges durcissables a viscosite intrinseque, procede pour les produire et utilisation de ceux-ci - Google Patents

Melanges durcissables a viscosite intrinseque, procede pour les produire et utilisation de ceux-ci

Info

Publication number
EP1828276A1
EP1828276A1 EP05817210A EP05817210A EP1828276A1 EP 1828276 A1 EP1828276 A1 EP 1828276A1 EP 05817210 A EP05817210 A EP 05817210A EP 05817210 A EP05817210 A EP 05817210A EP 1828276 A1 EP1828276 A1 EP 1828276A1
Authority
EP
European Patent Office
Prior art keywords
mixtures according
mixtures
curable
group
thermally
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Withdrawn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
EP05817210A
Other languages
German (de)
English (en)
Inventor
Hubert Baumgart
Berthold Austrup
Günther OTT
Karl-Heinz Joost
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 EP1828276A1 publication Critical patent/EP1828276A1/fr
Withdrawn legal-status Critical Current

Links

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
    • C08G18/81—Unsaturated isocyanates or isothiocyanates
    • C08G18/8108—Unsaturated isocyanates or isothiocyanates having only one isocyanate or isothiocyanate group
    • C08G18/8116—Unsaturated isocyanates or isothiocyanates having only one isocyanate or isothiocyanate group esters of acrylic or alkylacrylic acid having only one isocyanate or isothiocyanate group
    • 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
    • C08G18/67—Unsaturated compounds having active hydrogen
    • C08G18/671—Unsaturated compounds having only one group containing active hydrogen
    • C08G18/672—Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen
    • C08G18/673—Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen containing two or more acrylate or alkylacrylate ester 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
    • 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

Definitions

  • the present invention relates to new pseudoplastic curable mixtures. Moreover, the present invention relates to a novel process for the preparation of pseudoplastic curable mixtures. Last but not least, the present invention relates to the use of the novel pseudoplastic curable mixtures and the pseudoplastic curable mixtures prepared by the novel process for the production of films
  • Thermal and UV-curable (ie dual-cure) coating materials containing reaction products (A) of 3-acryloyloxy-2-hydroxypropyl methacrylate and polyisocyanates and unspecified thickener (B) are known from German Patent Application DE 198 60 041 A1 known.
  • the coating materials cure very quickly and provide coatings that
  • UV radiation is and - have high gloss and good adhesion to a wide variety of substrates.
  • Runner formation is the term for the sagging of applied coating materials on vertical or inclined surfaces, resulting in an unsightly appearance of the resulting coatings. If this process phenomenon occurs in a larger area, it is also called “curtain formation”. In general, a distinction is made between runners at edges, corners and holes (initiator points) and the large-scale sagging of coatings on surfaces, which is also referred to as “pushing". The formation of runners may be due to a wrong composition or incorrect application of the broom. In general, the dry film thickness of the applied coating material in ⁇ m is stated as the "runner limit”, above which the first runners appear after spray application on a vertical, perforated metal sheet (cf. also Römpp-Online 2002, "runner formation”, “runner limit «And» curtain formation «).
  • Object of the present invention is to provide new pseudoplastic curable mixtures which are suitable for the production of films moldings and as coating materials, adhesives and sealants or for their preparation, in particular the coating materials have an excellent profile and a very low tendency to form Runners have.
  • the new coatings produced from this are still intended
  • coating materials according to the invention were outstandingly suitable for the production of single-coat and multi-layer coatings, in particular as electrodeposition paints, fillers and primers, solid-color topcoats,
  • the adhesive layers produced from the adhesives according to the invention also had a particularly high bond strength in the long term during and after exposure to mechanical and chemical stress, radiation, temperature fluctuations and atmospheric moisture.
  • the gaskets produced from the sealants according to the invention seal the sealed substrates outstandingly even against aggressive chemicals, even during and after exposure to mechanical and chemical stress, radiation, temperature fluctuations and atmospheric humidity.
  • the mixtures according to the invention are structurally viscous. This means that the viscosity of the mixtures according to the invention is lower at higher shear stresses or higher velocity gradients than at low values (see Rompp Lacke and Druckmaschine, Georg Thieme Verlag, Stuttgart, New York, 1998, "Intrinsic Viscosity").
  • the mixtures according to the invention are curable. They can be cured oxidatively, thermally and / or with actinic radiation.
  • the oxidative curing is carried out under the influence of atmospheric oxygen by linking the film-forming constituents via oxygen bridges to aliphatic double bonds, accompanied by linkages through polymerization (see Rompp Lexikon Lacke and Druckmaschine, Georg Thieme Verlag, Stuttgart, New York, 1998, “Hardening", Pages 274 to 276, especially page 275, left column).
  • thermally curable mixtures according to the invention can be self-crosslinking and / or externally crosslinking.
  • self-crosslinking refers to the property of an existing binder (for the term cf., Rompp Lexikon Lacke und Druckmaschine, Georg Thieme Verlag, Stuttgart, New York, 1998, Binders, pages 73 and 74) to engage in self-crosslinking reactions.
  • the binders already contain both types of complementary reactive functional groups which are necessary for crosslinking, or reactive functional groups which react "with themselves".
  • such externally crosslinking mixtures are those according to the invention in which one type of the complementary reactive functional groups is present in the binder present and the other type is present in an existing hardener or crosslinking agent.
  • the mixtures according to the invention can be curable with actinic radiation.
  • the curing takes place via groups which contain bonds which can be activated with actinic radiation.
  • actinic radiation means electromagnetic radiation, such as near infrared (NIR) visible light, UV radiation, X-radiation or gamma radiation, in particular UV radiation, and corpuscular radiation such as electron radiation, alpha radiation, beta radiation or neutron radiation, in particular electron radiation.
  • NIR near infrared
  • UV radiation UV radiation
  • X-radiation or gamma radiation in particular UV radiation
  • corpuscular radiation such as electron radiation, alpha radiation, beta radiation or neutron radiation, in particular electron radiation.
  • suitable bindings activatable with actinic radiation are known from patent application DE 100 42 152 A1, page 3, paragraphs [0021] to [0027].
  • the mixtures according to the invention can be curable thermally and with actinic radiation. If thermal and curing with actinic light are used together in the mixtures according to the invention, this is also referred to as “dual cure” and “dual-cure mixtures”.
  • the mixtures according to the invention may also be physically curable.
  • the term "physical curing” means the hardening of a layer of a mixture according to the invention by film formation, wherein the linkage within the layer takes place via loop formation of the polymer molecules of the binders present. Or the filming takes place via the coalescence of binder particles (see Rompp Lexikon Lacke and printing inks, Georg Thieme Verlag, Stuttgart, New York, 1998, “Hardening", pages 274 and 275).
  • the physical cure may optionally assist curing of the mixtures of the invention by atmospheric oxygen, heat, or by exposure to actinic radiation.
  • the first essential constituent of the mixtures according to the invention is at least one reaction product (A)
  • all customary and known olefinically unsaturated carboxylic acids (a11) and (a121) can be used for the preparation of the reaction product (a1) and the glycidyl esters (a12), as long as they contain no groups which can not be reacted with the olefinically unsaturated carboxylic acid (a11) with the glycidyl ester (a12) or the reaction of the resulting reaction product (a1) with the polyisocyanate (a2) in any way disturb, for example, inhibit or cause decomposition reactions and / or side reactions such as polymerization reactions.
  • the olefinically unsaturated carboxylic acids (a11) and (a121) may be the same or different from each other; preferably, they are different from each other.
  • the olefinically unsaturated carboxylic acids (a11) and (a121) are selected from the group consisting of di- and monocarboxylic acids; in particular they are monocarboxylic acids.
  • Examples of particularly suitable monocarboxylic acids (a11) and (a121) are acrylic acid, dimeric acrylic acid, methacrylic acid, crotonic acid and cinnamic acid. Especially suitable are acrylic acid and methacrylic acid.
  • the olefinically unsaturated carboxylic acid (a11) is acrylic acid and the olefinically unsaturated carboxylic acid (a121) is methacrylic acid.
  • An example of a particularly suitable reaction product (a1) is the reaction product of acrylic acid (a1) with glycidyl methacrylate (a12).
  • Very particularly suitable reaction products (a1) of this type in each case based on their respective total amount, at least 60, preferably at least 70 and in particular at least 80 wt .-% of a mixture of 3-acryloyloxy-2-hydroxy-propyl methacrylate and 2-acryloyloxy 3-hydroxy-propyl methacrylate.
  • the most suitable reaction products (a1) contain only oligomers obtained by the Michael analogous addition of the hydroxyl groups to the
  • the content of the reaction products (a1) determined by gel permeation chromatography is preferably based on oligomeric and polymeric constituents ⁇ 40, particularly preferably ⁇ 30 and in particular ⁇ 20% by weight, in each case based on a reaction product (a1).
  • the reaction is catalyzed, it being advantageous to add a smaller portion of the catalyst towards the end of the reaction in order to achieve the fullest possible reaction.
  • Suitable catalysts are all customary and known compounds which catalyze the reaction between glycidyl compounds and carboxylic acids.
  • suitable catalysts are tertiary amines, tertiary phosphines, ammonium or phosphonium thiodiglycol and tin, chromium, potassium and cesium compounds.
  • suitable catalysts are tetrabutylammonium hydroxide, tetrabutylphosphonium bromide,
  • Trimethylbenzylammonium chloride triethylamine, diazabicyclooctane,
  • the reaction is preferably carried out in the presence of stabilizers for acrylates and methacrylates.
  • stabilizers for acrylates and methacrylates In addition to oxygen-containing gas, in particular air, conventional and known stabilizers to prevent premature polymerization in an amount of 0.01 to 1 wt .-%, preferably 0.1 to 0.5 wt .-%, each based on the amount of olefinically unsaturated compounds. Suitable stabilizers are described for example in Houben-Weyl, Methods of Organic Chemistry, 4th Edition, Volume XIV / 1, Georg Thieme Verlag, Stuttgart, 1961, page 433 et seq.
  • Examples of well-suited stabilizers are sodium dithionite, sodium hydrosulfide, sulfur, hydrazine, phenylhydrazine, hydrazobenzene, N-phenyl-beta-naphthylamine, N-phenyl-ethanoldiamine, dinitrobenzene, picric acid, p-nitroso-dimethylaniline, diphenylnitrosamine, phenols, in particular p-methoxyphenol, 2,5-di-tert-butylhydroquinone, 2,6-di-tert-butyl-4-methylphenol, p-tert-butylcatechol or 2,5-di-tert-amyl-hydroquinone, tetramethylthiuram disulfide, 2-mercaptobenzothiazole, dimethyl-dithiocarbamic acid sodium salt, phenothiazine or N-oxyl compounds such as 2,2,6,6-tetramethylpiperidine-N-
  • the reaction can be carried out in the presence of an organic solvent which is inert towards the educts (a11) and (a12) and the products and which is preferably also inert toward isocyanates.
  • organic solvent which is inert towards the educts (a11) and (a12) and the products and which is preferably also inert toward isocyanates.
  • suitable solvents are paint solvents, such as butyl acetate, Solventnaphtha® from Exxon-Chemie, methoxypropyl acetate or hydrocarbons, such as cyclohexane, methylcyclohexane or isooctane.
  • the solvent can be removed, for example, by distillation or remain in the reaction product (a1).
  • the reaction is in bulk, i. H. without organic solvent.
  • the ducks (a11) and (a12) can be reacted in any order.
  • a starting material is initially charged, mixed with the main amount of the catalyst and with the stabilizer, after which the resulting mixture is heated with stirring.
  • the other starting material is then metered in at one time or preferably gradually, wherein preferably a constant reaction temperature is maintained.
  • the conversion during the reaction is determined by analysis. This can be done spectroscopically, for example by IR or NIR spectroscopy. However, it is also possible to carry out chemical analyzes on samples taken. In particular, both the acid and the epoxide content of the
  • Reaction mixture as a measure of sales.
  • reaction products (a1) can be immediately further reacted with the polyisocyanates (a2) to the reaction products (A). But they can also be stored and / or transported until their further use.
  • the reaction products (a1) are preferably used without further purification.
  • polyisocyanates (a2) the polyisocyanates can be used, as they are commonly used in the paint industry, d. h., The so-called paint polyisocyanates. These preferably have an average isocyanate functionality of 2 to ⁇ 6, in particular> 2 to ⁇ 6. Examples of suitable polyisocyanates (a2) are described, for example, in German patent application DE 100 42 152 A1, page 4, paragraph [0037], to page 6, 0063]. The isocyanate groups of the polyisocyanates (a2) may be partially blocked with customary and known blocking agents, as described, for example, in German Patent Application DE 100 42 152 A1, page 6, paragraph [0062].
  • reaction of the reaction products (a1) with the polyisocyanates (a2) to the reaction products (A) is preferably the urethanization.
  • the urethanization it is also possible, for example, to allophanatize polyisocyanates (a2) containing oxadiazinetrione groups with reaction products (a1) in which carbon dioxide is liberated under suitable analysis.
  • reaction products (A) Following the reaction of (a1) with (a2), it is possible with the resulting reaction products (A) to carry out further reactions known from polyisocyanate chemistry, such as further urethanization and / or allophanatization, biuretization, trimerization, urea formation and / or uretdionization, optionally with the addition of isocyanate-reactive compounds, such as hydroxyl or amino compounds.
  • isocyanate-reactive compounds such as hydroxyl or amino compounds.
  • free isocyanate groups can still be blocked with the blocking agents described above.
  • hydrophilicizing or potentially hydrophilizing groups such as, for example, polyoxyalkylene groups, in particular polyoxyethylene groups, can be introduced if the reaction products (A) are to be used in aqueous mixtures according to the invention.
  • reaction of the reaction products (a1) with the polyisocyanates (a2) to the reaction products (A) in the presence of suitable catalysts to accelerate the isocyanate addition reactions, such as tertiary amines, tin, zinc or bismuth compounds, in particular trimethylamine, 1, 4-diazabicycl- [2,2,2] -ooctane, bismuth octoate or dibutyltin dilaurate, which can be initially charged with the educts or metered in during the course of the reaction.
  • suitable catalysts to accelerate the isocyanate addition reactions, such as tertiary amines, tin, zinc or bismuth compounds, in particular trimethylamine, 1, 4-diazabicycl- [2,2,2] -ooctane, bismuth octoate or dibutyltin dilaurate, which can be initially charged with the educts or metered in during the course of the reaction.
  • the reaction takes place in the presence of stabilizers.
  • stabilizers are those described above as well as compounds which stabilize isocyanates against reactions other than those desired. Examples of suitable
  • Stabilizers of the latter type are acids or acid derivatives, such as
  • the addition of the stabilizers may occur before and / or after
  • the reaction may be carried out in organic solvents and / or reactive diluents that are inert to the starting materials and the products.
  • Suitable solvents are in particular paint solvents such as ethyl acetate, butyl acetate, Solventnaphta® Exxon-Chemie as an aromatic solvent, methoxypropyl acetate, acetone and / or methyl ethyl ketone. After completion of the reaction, the solvent can be removed by distillation, for example, or remain in the reaction product (A).
  • paint solvents such as ethyl acetate, butyl acetate, Solventnaphta® Exxon-Chemie as an aromatic solvent, methoxypropyl acetate, acetone and / or methyl ethyl ketone.
  • reaction products (a1) with the polyisocyanates (a2) to give the reaction products (A) all the isocyanate groups present in the respective polyisocyanate (a2) or only a part thereof can be reacted with the reaction product (a1).
  • the reaction of the reaction products (a1) with the polyisocyanates (a2) to give the reaction products (A) can be carried out continuously, for example in a static mixer, or batchwise, for example in a suitable stirred vessel. In the case of discontinuous procedure, (a1) or (a2) can be initially charged and the other starting material added at room temperature or elevated temperatures.
  • the reaction is preferably carried out at elevated temperature, in particular at 40 to 130 ° C., in particular 60 to 80 ° C., the temperature range being set by heating or being established by the exothermicity of the reaction.
  • the degree of conversion can be determined spectroscopically as described above. However, it is also possible to take samples and to analyze them chemically.
  • the isocyanate and optionally also the hydroxyl content of the reaction mixture are suitable as a measure of the conversion.
  • the resulting reaction products (A) ⁇ 0.5 wt .-%, in particular ⁇ 0.2 wt .-%, each based on (A), of monomeric diisocyanates.
  • the reaction products (A) may be free from isocyanate groups, i. That is, they have an isocyanate content ⁇ 0.1% by weight, preferably an isocyanate content below the detection limit.
  • reaction products (A) may also contain on statistical average at least one reactive functional group. These are preferably free and / or blocked isocyanate groups.
  • reaction products (A) are free from isocyanate groups.
  • the content of the mixtures according to the invention in the reaction products (A) to be used according to the invention can vary very widely and depends on the requirements of the individual case.
  • the content is preferably from 1 to 80, preferably from 5 to 70, particularly preferably from 5 to 60 and in particular from 5 to 50,% by weight, based in each case on the mixture according to the invention.
  • the further essential constituent of the mixtures according to the invention is at least one rheology-controlling additive (B).
  • Suitable rheology control additives (B) are the customary and known compounds and mixtures with the aid of which a substance mixture, preferably a coating material, an adhesive or a sealant, in particular a coating material, can be adjusted in a pseudoplastic manner.
  • the rheology controlling additives (B) are selected from the group consisting of urea derivatives; crosslinked polymeric microparticles; inorganic phyllosilicates; silicas; synthetic polymers having ionic and / or associative groups; Cellulose derivatives; Starch derivatives; hydrogenated castor oil; overbased sulphonates and polyurethane-based associative thickeners.
  • the inorganic phyllosilicates (B) are preferably selected from the group consisting of aluminum-magnesium silicates and sodium-magnesium and sodium-magnesium fluorine-lithium phyllosilicates of the montmorillonite type; the silicic acids (B) from the group consisting of the nanoscale pyrogenic silicon dioxides and silicon dioxides produced using the sol-gel technique; the synthetic polymers (B) from the group consisting of polyvinyl alcohol, poly (meth) acrylamide, poly (meth) acrylic acid, polyvinylpyrrolidone,
  • the content of the mixtures according to the invention in the rheology-controlling additives (B) can likewise vary very widely. The content depends on the nature of the respectively used rheology-controlling additive (B) and the strength of the pseudoplastic effect, which one wants to adjust.
  • rheology controlling additives (B) are employed in the conventional and known effective amounts described in the prior art. In general, these are from 0.1 to 40 and in particular 0.5 to 30 wt .-%, each based on the mixture according to the invention.
  • the mixtures according to the invention may also contain at least one further constituent (C). If the contents of the essential constituents (A) and (B) do not add up to 100% by weight, the mixtures according to the invention necessarily contain at least one constituent (C).
  • component (C) is selected from the group consisting of physically, thermally, actinic, and thermally and actinically curable binders, thermally and thermally curable with actinic radiation curable crosslinking agents, thermally curable with actinic radiation, and thermally and with actinic radiation , low molecular weight and oligomeric reactive diluents, and additives other than component (B).
  • the additive (C) from the group consisting of color and / or effect pigments, molecularly soluble dyes; Sunscreens, 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; Catalysts for thermal crosslinking; thermolabile radical initiators; Adhesion promoters; Leveling agents; film-forming aids; Flame retardants; Corrosion inhibitors; anti-caking agents; To grow; desiccants; Biocides and matting agents selected.
  • Sunscreens 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; Catalysts for thermal crosslinking; thermolabile radical initiators; Adhesion promoters;
  • the content of the mixtures of the components (C) according to the invention can vary extremely widely and depends on the nature of the constituents (C) used in each case.
  • the ingredients (C) are used in the usual and known, effective amounts.
  • the mixtures according to the invention are prepared by mixing their constituents (A) and (B) and optionally (C) together and homogenizing the resulting mixtures.
  • the resulting mixtures according to the invention are conventional mixtures containing organic solvents, aqueous mixtures, substantially or completely solvent- and water-free liquid mixtures (100% systems), substantially or completely solvent- and water-free solid powders or substantially or completely solvent-free powder suspensions ( powder slurries). Besides, they can
  • Binders and the crosslinking agents are present until shortly before the application separately.
  • the mixtures according to the invention can be used extremely widely. They are preferably used for the production of films and moldings and as coating materials, adhesives and sealants or for the production of coating materials, adhesives and sealants.
  • the mixtures according to the invention are preferably sweeteners.
  • the coating materials according to the invention are particularly preferably used as electrodeposition coatings, primer coatings, fillers or antistonechip primers, basecoats, solid-color topcoats and clearcoats for the production of electrodeposition coatings, primer coatings, surfacer coatings or antistonechip primers, basecoats, solid-color topcoats and clearcoats.
  • These coatings can be single-layered or multi-layered. With very particular preference they are multi-layered and may comprise at least two finishes, in particular at least one electrocoating, at least one surfacer or antistonechip primer and at least one basecoat and at least one clearcoat or at least one solid-color topcoat.
  • the multicoat paint systems comprise at least one basecoat and at least one clearcoat.
  • the clearcoats are the outermost layer of the multicoat paint systems, which substantially determines the overall appearance (appearance) and protects the color and / or effect basecoats from mechanical and chemical damage and radiation damage.
  • the clearcoats of the invention prove to be
  • the mixtures according to the invention are applied to customary and known temporary or permanent substrates.
  • conventional and known temporary substrates are preferably used, such as metal and plastic tapes or hollow bodies of metal, glass, plastic, wood or ceramic, which can be easily removed without damaging the films and moldings according to the invention ,
  • the mixtures according to the invention are used for the production of coatings, adhesives and gaskets, permanent substrates are used, such as bodies of locomotion, in particular motor vehicle bodies, and parts thereof, indoor and outdoor structures and parts thereof, doors, windows and furniture as well as in the frame the industrial coating hollow glass body, coils, containers, packaging, small parts, electrical, mechanical and optical components and components for white goods.
  • the films and moldings according to the invention can likewise serve as substrates.
  • the application of the mixtures according to the invention has no peculiarities, but can by all customary and known, suitable for the respective mixture application methods, such as. Electrocoating, fluid bed coating, spraying, spraying, knife coating, brushing, pouring, dipping, trickling or rolling occur. Preferably, spray application methods are used unless they are powders.
  • the application of the powder has no special features on, but takes place, for example, according to the usual and known fluidized bed processes, such as those from the company publications of BASF Coatings AG, "powder coatings for industrial applications," January 2000, or »Coatings Partner, powder coating special « , 1/2000, or Rompp Lexikon Lacke and printing inks, Georg Thieme Verlag, Stuttgart, New York, 1998, pages 187 and 188, "Electrostatic Powder Spraying", “Electrostatic Spraying” and “Electrostatic Whirling” are known.
  • the curing of the mixtures according to the invention generally takes place after a certain period of rest or flash-off time. It can last for 30 seconds to 2 hours, preferably
  • the rest period serves, for example, for the course and degassing of the applied mixtures according to the invention and for the evaporation of volatile constituents, if appropriate
  • the ventilation can be accelerated by an elevated temperature, which is not sufficient for curing, and / or by a reduced humidity.
  • the thermal curing of the applied mixtures 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 of microwave radiation, infrared light and / or near infrared light (NIR).
  • a gaseous, liquid and / or solid, hot medium such as hot air, heated oil or heated rollers, or of microwave radiation, infrared light and / or near infrared light (NIR).
  • the heating takes place in a circulating air oven or by irradiation with IR and / or NIR lamps.
  • the thermal curing can also take place in stages.
  • the thermal curing takes place at temperatures from room temperature to 200 ° C.
  • the curing with actinic radiation preferably is preferably 2x10 3 to 2x10 4, preferably 3x10 3 to 1, 5x10 4 and in particular 3 to 5x10 1, 2x10 4 Jm 2 used a radiation dose of 10 3 to 3x10. 4
  • the radiation intensity is at 1x10 ° to 3x10 5 , preferably 2x10 ° to 2x10 5 , preferably 3x10 ° to 1, 5x10 5 and in particular 5x10 ° to 1, 2x10 5 Wm second
  • the usual and known radiation sources and optical aids are used.
  • suitable radiation sources are flash lamps of the company VISIT, high or low pressure mercury vapor lamps, which are optionally doped, or electron beam sources.
  • Their arrangement is known in principle and can be adapted to the circumstances of the workpiece and the process parameters.
  • at complicated shaped workpieces, such as those provided for automobile bodies, may include the non-direct radiation accessible areas (shadow areas), such as cavities, folds and other constructional undercuts, with spot, small area or omnidirectional radiators coupled with an automatic moving device for irradiating cavities or edges, to be cured.
  • the equipment and conditions of these curing methods are described, for example, in R. Holmes, U.V. and E.B. Curing Formulations for Printing Inks, Coatings and Paints, SITA Technology, Academic Press, London, United Kindom 1984, in German Patent Application DE 198 18 735 A1, column 10, line 31, to column 11, line 16, in R. Stephen Davidson, "Exploring the Science, Technology and Applications of UV and E.B. Curing, Sita Technology Ltd., London, 1999, or Dipl.-Ing. Peter Klamann, "eltosch System Competence, UV Technology, User Guide", page 2, October 1998.
  • the curing with actinic radiation is particularly preferably carried out under an oxygen-depleted atmosphere.
  • Oxygen depleted means that the oxygen content of the atmosphere is less than the oxygen content of air (20.95% by volume).
  • the maximum oxygen depleted atmosphere content is 18, preferably 16, more preferably 14, most preferred 10 and in particular 6.0% by volume.
  • Both thermal curing and curing with actinic radiation can be carried out in stages. They can be done consecutively (sequentially) or simultaneously. According to the invention, the sequential curing is advantageous and is therefore preferred. It is of particular advantage to carry out the thermal curing after curing with actinic radiation.
  • thermoset materials according to the invention in particular the films, moldings, coatings, adhesive layers and seals according to the invention are outstandingly suitable for coating, bonding, sealing, wrapping and packaging
  • the substrates according to the invention which are coated with coatings according to the invention, bonded to adhesive layers according to the invention, sealed with gaskets according to the invention and / or enveloped or packed with films and / or molded parts according to the invention have outstanding performance properties combined with a particularly long service life.
  • the resulting solution of the Methacrylatcopolymerisats (C1) had a solids content of 66 wt.% (One hour convection oven / 130 0 C) on.
  • the methacrylate copolymer (A 1) had an OH number of 95 mg KOH / g solids, a Glass transition temperature Tg of +22 0 C, a number average molecular weight of 3,336 daltons, a mass-average molecular weight of 7,975 daltons and a nonuniformity of the molecular weight of 2.4.
  • a 2 l beaker was charged with 485 parts by weight of the solution of the methacrylate copolymer (C1) of preparation example 1, 2.24 parts by weight of ethylenediamine and 3.33 parts by weight of methoxypropylamine.
  • a solution of 9.43 parts by weight of hexamethylene diisocyanate in 100 parts by weight of butyl acetate was metered in over the course of 5 minutes with vigorous stirring with a laboratory dissolver. The reaction mixture was stirred vigorously for 15 minutes.
  • the resulting rheology control additive (B) had a solids content of 55%, determined in a circulating air oven (1 h at 130 0 C).
  • the resulting solution of the methacrylate copolymer (C2) had a solids content of 66 wt.% (One hour forced-air oven / 130 0 C).
  • the methacrylate copolymer (C2) had an OH number of 175 mg KOH / g solids, a glass transition temperature Tg of -22 0 C, a number average molecular weight of 3,908 daltons, a weight average molecular weight of 10,170 daltons and a molecular weight polydispersity of 2.6 to ,
  • Clearcoats 1 and 2 were prepared by mixing the ingredients listed in Table 1 in the order given and homogenizing the resulting mixtures.
  • Table 1 The material composition of the clearcoats 1 and 2 of Examples 1 and 2
  • Component example (parts by weight): 1 2
  • UV absorber substituted hydroxyphenyltriazine 1, 0 1, 0
  • HALS N-methyl-2,2,6,6-tetramethylpiperidinyl ester 1, 0 1, 0
  • Irgacure ® 184 commercial photoinitiator of
  • Isocyanatoacrylate Roskydal® UA VPLS 2337 from Bayer AG (based on trimeric hexamethylene diisocyanate, content of isocyanate groups: 12% by weight) 22.54 22.54
  • the clearcoats 1 and 2 had a very good pot life and a very good application behavior. In particular, they showed an excellent course and a very low tendency to form runners, so that they could be applied easily in high film thicknesses.
  • Clearcoats 1 and 2 were used to produce free films applied by means of polypropylene with a layer thickness of 40 + 10 ⁇ m and by means of Dynamic Mechanical Thermal Analysis (DMTA) (cf., for this purpose, Murayama, T., Dynamic Mechanical Analysis of Polymeric Materials, Vol. Elsevier, New York, 1978, and Loren W. Hill, Journal of Coatings Technology, Vol. 64, No. 808, May 1992, pp. 31-33; Th. Frey, K.-H. persistente Brinkhaus and U. Röckrath in Cure Monitoring Of Thermoset Coatings, Progress In Organic Coatings 27 (1996), 59-66, German Patent Application DE 44 09 715 A1 or German Patent DE 197 09 467 C2).
  • DMTA Dynamic Mechanical Thermal Analysis
  • the curing of the films was carried out by irradiation with UV light of a dose of 1,000 mJc ⁇ r 2 and a radiation intensity of 83 Wm 2 with an iron-doped mercury vapor lamp from IST and a final thermal curing for 30 minutes at 120 0 C. From the homogeneous, cured free film, the viscoelastic characteristics and the glass transition temperature Tg were determined by means of DMTA measurements under the following conditions:
  • Example 3 For the preparation of the white multi-layer coating of Example 3, the clearcoat 1 of Example 1 was used.
  • Example 4 For the preparation of the white multi-layer coating of Example 4, the clearcoat 2 of Example 2 was used.
  • the curing of the aqueous basecoat films and the clearcoat layers 1 and 2 was carried out for 5 minutes at room temperature, for 10 minutes at 80 0 C, followed by irradiation with UV light in a dose of 10 4 Jm 2 (1000 mJc ⁇ r 2) and a radiation intensity of 83 Wm 2 with an iron-doped mercury vapor lamp from IST, and finally for 20 minutes at 140 0 C. This gave the white multi-layer coatings. 1 and 2
  • Multicoat paint systems 1 and 2 were excellent, as well as their condensation resistance, determined by means of the customary and known

Landscapes

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

Abstract

La présente invention concerne des mélanges durcissables à viscosité intrinsèque comprenant (A) au moins un produit de réaction entre (a1) un produit réactionnel entre (a11) au moins un acide carboxylique oléfiniquement insaturé et (a12) au moins un ester de glycidyle d'un acide carboxylique insaturé (a121) et (a2) au moins un polyisocyanate présentant une teneur en groupes époxyde (calculé avec M = 42 daltons) < 0,2 % en poids et un indice d'acide < 10 mg KOH/g, ainsi que (B) au moins un additif commandant les propriétés rhéologiques. Cette invention concerne également un procédé pour produire ces mélanges, ainsi que leur utilisation.
EP05817210A 2004-12-17 2005-12-08 Melanges durcissables a viscosite intrinseque, procede pour les produire et utilisation de ceux-ci Withdrawn EP1828276A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102004060966A DE102004060966A1 (de) 2004-12-17 2004-12-17 Strukturviskose härtbare Gemische, Verfahren zu ihrer Herstellung und ihre Verwendung
PCT/EP2005/056687 WO2006063976A1 (fr) 2004-12-17 2005-12-08 Melanges durcissables a viscosite intrinseque, procede pour les produire et utilisation de ceux-ci

Publications (1)

Publication Number Publication Date
EP1828276A1 true EP1828276A1 (fr) 2007-09-05

Family

ID=36011710

Family Applications (1)

Application Number Title Priority Date Filing Date
EP05817210A Withdrawn EP1828276A1 (fr) 2004-12-17 2005-12-08 Melanges durcissables a viscosite intrinseque, procede pour les produire et utilisation de ceux-ci

Country Status (5)

Country Link
US (1) US20090069465A1 (fr)
EP (1) EP1828276A1 (fr)
JP (1) JP2008524359A (fr)
DE (1) DE102004060966A1 (fr)
WO (1) WO2006063976A1 (fr)

Families Citing this family (19)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102005045228A1 (de) 2005-09-22 2007-04-05 Basf Coatings Ag Verwendung von Phosphonsäurediestern und Diphosphonsäurediestern sowie silangruppenhaltige, härtbare Gemische, enthaltend Phosphonsäurediester und Diphosphonsäurediester
DE102005045150A1 (de) 2005-09-22 2007-04-05 Basf Coatings Ag Verwendung von Phosphonsäurediestern und Diphosphonsäurediestern sowie thermisch härtbare Gemische, enthaltend Phosphonsäurediester und Diphosphonsäurediester
EP1844917A3 (fr) 2006-03-24 2008-12-03 Entex Rust &amp; Mitschke GmbH Procédé pour traiter des produits qui doivent être dégazés
DE102006024823A1 (de) 2006-05-29 2007-12-06 Basf Coatings Ag Verwendung von härtbaren Gemischen, enthaltend silangruppenhaltige Verbindungen sowie Phosphonsäurediester oder Diphosphonsäurediester, als Haftvermittler
FR2910877B1 (fr) 2006-12-28 2009-09-25 Eurocopter France Amelioration aux rotors de giravions equipes d'amortisseurs interpales
DE102007014720A1 (de) 2007-03-23 2008-09-25 Basf Coatings Japan Ltd., Yokohama Phosphonat-haltiges Zweikomponenten-Lacksystem, dessen Herstellung und Verwendung
EP2289687A1 (fr) 2007-05-16 2011-03-02 Entex Rust & Mitschke GmbH Procédé de traitement de produits de dégazage
MX342510B (es) * 2007-08-31 2016-10-03 The Sherwin-Williams Company Aductos funcionales de amina y composiciones curables que comprenden la misma.
JP2011171710A (ja) * 2010-01-12 2011-09-01 Rohm & Haas Co 光起電モジュールの製造方法
JP2011171709A (ja) * 2010-01-12 2011-09-01 Rohm & Haas Co 光起電モジュールの製造方法
DE102011112081A1 (de) 2011-05-11 2015-08-20 Entex Rust & Mitschke Gmbh Verfahren zur Verarbeitung von Elasten
MX342023B (es) * 2011-12-09 2016-09-12 Basf Coatings Gmbh Revestimiento con alto contenido de sólidos y proceso de revestimiento.
WO2014056553A1 (fr) 2012-10-11 2014-04-17 Entex Gmbh Rust & Mitschke Gmbh Extrudeuse de transformation de matières plastiques ayant tendance à coller
DE102015001167A1 (de) 2015-02-02 2016-08-04 Entex Rust & Mitschke Gmbh Entgasen bei der Extrusion von Kunststoffen
DE102017001093A1 (de) 2016-04-07 2017-10-26 Entex Rust & Mitschke Gmbh Entgasen bei der Extrusion von Kunststoffen mit Filterscheiben aus Sintermetall
DE102015008406A1 (de) 2015-07-02 2017-04-13 Entex Rust & Mitschke Gmbh Verfahren zur Bearbeitung von Produkten im Extruder
DE102016002143A1 (de) 2016-02-25 2017-08-31 Entex Rust & Mitschke Gmbh Füllteilmodul in Planetwalzenextruderbauweise
DE102017006638A1 (de) 2017-07-13 2019-01-17 Entex Rust & Mitschke Gmbh Füllteilmodul in Planetwalzenextruderbauweise
CN109722148B (zh) * 2019-01-03 2020-12-22 珠海市威旗防腐科技股份有限公司 一种触变型无溶剂环氧涂料及其制备方法

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19860041A1 (de) * 1998-12-23 2000-06-29 Basf Ag Durch Addition an Isocyanatgruppen als auch durch strahlungsinduzierte Addition an aktivierte C-C-Doppelbindungen härtbare Beschichtungsmittel
US6410635B1 (en) * 1999-02-22 2002-06-25 Ppg Industries Ohio, Inc. Curable coating compositions containing high aspect ratio clays
DE19919826A1 (de) * 1999-04-30 2000-11-02 Basf Ag Verfahren zur Herstellung von Polyurethanschaumstoffen
DE19924172A1 (de) * 1999-05-25 2000-11-30 Basf Coatings Ag Beschichtungsstoff mit einer Mischung aus Kieselsäuren und Harnstoff und/oder Harnstoffderivaten
DE10126647A1 (de) * 2001-06-01 2002-12-12 Basf Coatings Ag Rheologiehilfsmittel, Verfahren zu seiner Herstellung und seine Verwendung
DE10139262C1 (de) * 2001-08-09 2003-01-02 Basf Coatings Ag Rheologiehilfsmittel, Verfahren zu seiner Herstellung und seine Verwendung
DE10357712A1 (de) * 2003-12-09 2005-07-14 Bayer Materialscience Ag Härter

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO2006063976A1 *

Also Published As

Publication number Publication date
WO2006063976A1 (fr) 2006-06-22
US20090069465A1 (en) 2009-03-12
JP2008524359A (ja) 2008-07-10
DE102004060966A1 (de) 2006-06-29

Similar Documents

Publication Publication Date Title
EP1828276A1 (fr) Melanges durcissables a viscosite intrinseque, procede pour les produire et utilisation de ceux-ci
EP1828274A1 (fr) Systemes multicomposants, leur procede de production et leur utilisation
DE10048849A1 (de) Verfahren zur Herstellung eines thermisch und mit aktinischer Strahlung härtbaren Mehrkomponentensystems und seine Verwendung
DE10055549A1 (de) Farb- und/oder effektgebende Mehrschichtlackierung, Verfahren zu ihrer Herstellung und ihre Verwendung
EP1322689B1 (fr) Systeme a plusieurs composants contenant des solvants et durcissable par action thermique et par rayonnement actinique, et son utilisation
DE10048275C1 (de) Thermisch und mit aktinischer Strahlung härtbares Mehrkomponentensystem und seine Verwendung
EP1311575B1 (fr) Agent thixotrope activable par rayonnement actinique, son procede de preparation et son utilisation
EP1322690B1 (fr) Systeme d&#39;agents de revetement permettant la realisation de peintures multicouches de coloration et/ou a effets, se basant sur des agent de revetement a constituants multiples
EP1469951B1 (fr) Materiaux durcis, leur procede de fabrication et leur utilisation
WO2004090057A1 (fr) Melanges contenant des amorceurs activables par rayonnement actinique et systemes a deux ou plusieurs composants, procede de production et utilisation associes
EP1926783B1 (fr) Utilisation de diesters d&#39;acide phosphonique et de diesters d&#39;acide diphosphonique, ainsi que melanges a durcissement thermique contenant des diesters d&#39;acide phosphonique et des diesters d&#39;acide diphosphonique
EP1720923B1 (fr) Systemes a plusieurs constituants, procede pour produire ces systemes et leur utilisation
EP3034569B1 (fr) Systèmes réticulables par durcissement ultérieur au moyen de rayonnement actinique
EP1616925A1 (fr) Sytème aqueux à plusieurs composants, sa préparation et son utilisation
EP1470448B1 (fr) Melange de matieres durcissable par la chaleur et par rayonnement actinique, et procede de production et d&#39;utilisation dudit melange
DE102005057925A1 (de) Radikalisch polymerisierbare Gemische, Verfahren zu ihrer Herstellung und ihre Verwendung
DE102004018014A1 (de) Mindestens drei Komponenten enthaltendes Mehrkomponentensystem, Verfahren zu seiner Herstellung und seine Verwendung
DE10128885A1 (de) Härtbare Stoffgemische, Verfahren zu ihrer Herstellung und ihre Verwendung
DE10150088A1 (de) Thermisch und mit aktinischer Strahlung härtbarer, nicht wässriger Einkomponenten-Beschichtungsstoff, Verfahren zu seiner Herstellung und seine Verwendung
WO2001051537A1 (fr) Agent thixotrope, son procede de production et son utilisation
DE10011644A1 (de) Die Verwendung von Silanen, die eine Azidogruppe enthalten, als Vernetzungsmittel in Beschichtungsstoffen

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 20070713

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IS IT LI LT LU LV MC NL PL PT RO SE SI SK TR

DAX Request for extension of the european patent (deleted)
17Q First examination report despatched

Effective date: 20080902

RAP1 Party data changed (applicant data changed or rights of an application transferred)

Owner name: BASF COATINGS GMBH

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE APPLICATION IS DEEMED TO BE WITHDRAWN

18D Application deemed to be withdrawn

Effective date: 20120702