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EP1922348A1 - Melanges durcissables exempts de composes molybdene et tungstene, a base de polyisocyanates inhibes et contenant des composes cesium, procedes permettant de les produire et leur utilisation - Google Patents

Melanges durcissables exempts de composes molybdene et tungstene, a base de polyisocyanates inhibes et contenant des composes cesium, procedes permettant de les produire et leur utilisation

Info

Publication number
EP1922348A1
EP1922348A1 EP06791710A EP06791710A EP1922348A1 EP 1922348 A1 EP1922348 A1 EP 1922348A1 EP 06791710 A EP06791710 A EP 06791710A EP 06791710 A EP06791710 A EP 06791710A EP 1922348 A1 EP1922348 A1 EP 1922348A1
Authority
EP
European Patent Office
Prior art keywords
mixtures according
mixtures
compounds
groups
isocyanate
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP06791710A
Other languages
German (de)
English (en)
Inventor
Marco Deyda
Hubert Baumgart
Bianca Giesen
Michael Tecklenborg
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 EP1922348A1 publication Critical patent/EP1922348A1/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Withdrawn legal-status Critical Current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
    • C08G18/08—Processes
    • C08G18/16—Catalysts
    • C08G18/22—Catalysts containing metal compounds
    • C08G18/225—Catalysts containing metal compounds of alkali or alkaline earth metals
    • 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
    • C08G18/2805—Compounds having only one group containing active hydrogen
    • C08G18/2815—Monohydroxy compounds
    • C08G18/283—Compounds containing ether groups, e.g. oxyalkylated monohydroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/62—Polymers of compounds having carbon-to-carbon double bonds
    • C08G18/6216—Polymers of alpha-beta ethylenically unsaturated carboxylic acids or of derivatives thereof
    • C08G18/625—Polymers of alpha-beta ethylenically unsaturated carboxylic acids; hydrolyzed polymers of esters of these acids
    • C08G18/6254—Polymers of alpha-beta ethylenically unsaturated carboxylic acids and of esters of these acids containing hydroxy groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
    • C08G18/78—Nitrogen
    • C08G18/79—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates
    • C08G18/791—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups
    • C08G18/792—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups formed by oligomerisation of aliphatic and/or cycloaliphatic isocyanates or isothiocyanates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/80—Masked polyisocyanates
    • C08G18/8061—Masked polyisocyanates masked with compounds having only one group containing active hydrogen
    • C08G18/807—Masked polyisocyanates masked with compounds having only one group containing active hydrogen with nitrogen containing compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes

Definitions

  • the present invention relates to new, free from molybdenum and tungsten compounds, cesium compounds containing curable mixtures based on blocked
  • the present invention relates to the use of the new, free of molybdenum and tungsten compounds, cesium compounds containing curable
  • German patent application DE 103 08 104 A1 discloses one-component baking systems based on blocked polyisocyanates which contain organic and / or inorganic compounds of molybdenum and / or tungsten of an oxidation state of at least +4, in particular +6. It is given a large number of suitable compounds, u. a. also lithium, sodium, potassium, rubidium and cesium molybdate. In the examples, only lithium and sodium and potassium molybdate are used. Thus, the German patent application for the expert no suggestions and hints that cesium compounds as such could have particular advantages in Einkomponenten- burn-in systems based on blocked polyisocyanates. On the contrary, the examples of the German patent application substantiate that it is precisely not the use of cesium that matters but the use of the molybdate anion - and this independently of the counterion.
  • molybdenum and / or tungsten are intended to allow a significant lowering of the baking temperatures.
  • molybdenum and tungsten are known to form, under a variety of conditions, intense colored compounds such as molybdenum blue, molybdophosphoric acid (yellow), tungsten blue or tungsten bronzes, some of which are of great importance to analytical chemistry, such as molybdenum blue as a sensitive molybdenum or molybdophosphoric acid sensitive evidence of phosphate.
  • aqueous polyurethane dispersions can be used for coating or bonding of
  • Objects are used in metals, plastics, paper, textile, leather or wood.
  • hydrophobic auxiliary agents such as polymer-based adhesion promoters, or commercially available auxiliaries and additives, such as propellants, defoamers,
  • Emulsifiers, thickeners and thixotropic agents and colorants, such as dyes and pigments, are added. It can not be inferred from the patent application, whether the catalyst residues, which may still be in the aqueous
  • Polyurethane dispersions are present, in addition to their original catalytic effect in addition, the performance properties of the coating materials and adhesives and the coatings produced therefrom influence adhesive layers or not.
  • German Patent Application DE 103 20 267 A1 discloses low-temperature curable polyurethane powder coating compositions containing uretdione groups. They contain metal hydroxides and alcoholates, u. a. also cesium hydroxide, which greatly accelerate the cleavage of uretdione groups, so that the curing temperatures can be considerably reduced.
  • European patent EP 0 447 074 B1 discloses that isocyanate trimerization and urethane formation can be accelerated by cesium fluoride as catalyst so that milder reaction conditions are possible. task
  • the present invention has for its object to find new, free of molybdenum and tungsten compounds, cesium compounds, curable mixtures based on blocked polyisocyanates (hereinafter called "new mixtures" called) to find that should no longer have the disadvantages of the prior art ,
  • the new mixtures should contain no other toxicologically and ecologically questionable metal compounds, such as organic tin compounds, in particular dibutyltin dilaurate, instead of molybdenum and tungsten compounds.
  • organic tin compounds in particular dibutyltin dilaurate, instead of molybdenum and tungsten compounds.
  • the new mixtures should be able to be cured at comparatively low temperatures. They should very well wet the surfaces of different substrates, d. h., they should have a particularly low wetting limit.
  • the new mixtures are to provide new hardened materials that show no signs of yellowing when overburning and long-term exposure in the atmosphere, even in high layer thicknesses no paint defects, such as cookers, specks, runners, craters or micro-disturbances (starry sky), have and a very good Course, a high gloss and a low haze, high chemical stability, high weathering stability and high hardness, high flexibility and high scratch resistance. Overall, they should easily reach the so-called automobile quality, as defined in European Patent EP 0 352 298 B1, page 15, lines 42, to page 17, line 40.
  • A a complementary reactive system containing blocked isocyanate groups (a1) and isocyanate-reactive functional groups (a2), and
  • mixtures according to the invention are hereinafter referred to as "mixtures according to the invention”.
  • novel process for the preparation of the mixtures according to the invention was found, in which at least the components (A) and (B) are mixed together and the resulting mixture is homogenized and hereinafter referred to as "inventive method”.
  • the mixtures of the invention contained no other toxicologically and ecologically questionable metal compounds, such as organic tin compounds, in particular dibutyltin dilaurate, in place of the molybdenum and tungsten compounds of the prior art. Nevertheless, they are infested, if at all, only to a small extent by microorganisms.
  • organic tin compounds in particular dibutyltin dilaurate
  • the mixtures according to the invention could be cured quickly and easily at comparatively low temperatures. They wet the surfaces of different substrates very well, d. they had a particularly low wetting limit.
  • the mixtures according to the invention provided new, hardened materials which no longer showed yellowing on overburning and long-term exposure to the atmosphere, even in high layer thicknesses no paint defects, such as stoves, specks, Runners, craters or micro-disturbances (starry sky), had and have a very good flow, a high gloss and a low haze, high chemical stability, high weathering stability and high hardness, high flexibility and high scratch resistance. Overall, they readily achieved the so-called automotive quality, as defined in European Patent EP 0 352 298 B1, page 15, lines 42 to page 17, line 40.
  • the mixtures according to the invention are free of molybdenum and tungsten compounds. This means that the mixtures according to the invention at most contain traces of molybdenum and tungsten compounds which are introduced by the constituents of the mixtures according to the invention. Preferably, the content of molybdenum and tungsten compounds is below the detection limits of the conventional and known methods of qualitative and quantitative detection of molybdenum and tungsten.
  • the mixtures of the invention are also free of metal compounds, especially compounds of toxicologically and ecologically questionable metals, especially tin compounds such as dibutyltin dilaurate.
  • the mixtures according to the invention are thermally curable. That is to say that they crosslink three-dimensionally via thermally initiated reactions of complementary, reactive, functional groups, isocyanate groups (a1) blocked according to the invention and isocyanate-reactive functional groups (a2), and give cured thermoset materials.
  • the thermal curing by the complementary, reactive, functional groups (a1) and (a2) can be supported by other conventional and known curing mechanisms.
  • other curing mechanisms are the thermal curing by other complementary, reactive, functional groups than the groups (a1) and (a2), the physical hardening by the filming of film-forming constituents, the air drying by the cross-linking of corresponding constituents with oxygen as well as the hardening with actinic radiation , in particular UV radiation or electron radiation.
  • These hardening mechanisms and methods are additionally used and serve to modify and optimize the thermal curing to be used according to the invention by the complementary, reactive, functional groups (a1) and (a2), which characterizes the performance property profile of the mixtures according to the invention and of the materials according to the invention produced therefrom.
  • the mixtures according to the invention contain a complementary reactive system (A) 1 which comprises blocked isocyanate groups (a1) and isocyanate-reactive functional groups (a2).
  • A complementary reactive system 1 which comprises blocked isocyanate groups (a1) and isocyanate-reactive functional groups (a2).
  • the complementary reactive system (A) at least one, in particular a self-crosslinking component (A1 / 2), the statistical average of at least two blocked isocyanate groups (a1) and at least one isocyanate-reactive functional group (a2) or at least one blocked isocyanate group ( a1) and contains at least two isocyanate-reactive functional groups (a2), comprising or consisting thereof.
  • the self-crosslinking component (A1 / 2) contains on statistical average 2 to 10, preferably 2.5 to 6.5 and in particular 3 to 6 blocked isocyanate groups (a1) and 2 to 10, preferably 2.5 to 6.5 and in particular 3 to 6 isocyanate-reactive functional groups (a2).
  • the complementary reactive functional groups (a1) and (a2) are in the self-crosslinking.
  • oligomers compounds or structural units understood, 'the monomeric statistical average of 3 to 12 structural units which may be the same or different, are constructed;
  • polymers are understood to mean compounds or structural units which are built up on a statistical average from more than 8 monomeric structural units, which may be the same or different from one another.
  • a self-crosslinking constituent (A1 / 2), which is constructed on a statistical average of 8 to 12 monomeric structural units, is regarded by the skilled person as an oligomer or as a polymer depends in particular on the number-average and mass-average molecular weight of the relevant constituent. If the molecular weights are comparatively high, one will speak of a polymer, they are relatively low from an oligomer.
  • the monomeric structural units of the self-crosslinking constituents (A1 / 2) are structural units which are derived from customary and known, low molecular weight, organic compounds.
  • the oligomers and polymeric structural units of the self-crosslinking constituents (A1 / 2) are derived from the customary and known, organic and organometallic oligomers and polymers. They are preferably derived from the oligomers and polymers customarily used as binders (see Rompp Lexikon Lacke and Druckmaschine, Georg Thieme Verlag, Stuttgart, New York, 1998, "Binders").
  • the oligomers and polymers can have a wide variety of structures. For example, they may be linear, star-shaped, comb-shaped or irregularly branched, dendrimeric or ring-shaped, with more than one of these structures being present in a self-crosslinking component (A1 / 2).
  • the structures may have a statistical and / or block-shaped distribution of the monomeric structural units.
  • the complementary reactive system (A) is externally crosslinking, d. h., It comprises at least one blocked polyisocyanate (A1) containing at least two blocked isocyanate groups (a1), and at least one component (A2), containing on statistical average at least two isocyanate-reactive functional groups (a2), or it consists thereof. More preferably, the complementary reactive system (A) consists of a blocked polyisocyanate (A1) and a component (A2).
  • the equivalent ratio of blocked isocyanate groups (a1) to isocyanate-reactive functional groups (a2) can vary widely.
  • the equivalent ratio (a1): (a2) is close to 1, preferably from 1.5: 1 to 1: 1.5, more preferably from 1.3: 1 to 1: 1.3 and especially from 1.2: 1 to 1: 1, 2.
  • the blocked polyisocyanate (A1) contains on average 2 to 10, preferably 2.5 to 6.5 and in particular 3 to 6 blocked isocyanate groups (a1).
  • the blocked polyisocyanate (A1) is low molecular weight or oligomeric in the above sense.
  • its blocked isocyanate groups (a1) are prepared by the reaction of isocyanate groups with blocking agents.
  • the isocyanate groups are preferably present in the customary and known polyisocyanates.
  • Diisocyanates such as tetramethylene-1,4-diisocyanate, hexamethylene-1,6-diisocyanate, 2,2,4-trimethylhexamethylene-1,6-diisocyanate, omega, omega-dipropyl-ether-diisocyanate, cyclohexyl-1, 4- diisocyanate, cyclohexyl-1, 3-diisocyanate, cyclohexyl-1, 2-diisocyanate, dicyclohexylmethane-4,4'-diisocyanate, 1, 5-dimethyl 1-2,4-di (isocyanato-methyl) -benzene, 1, 5 -Di-methyl-2,4-di (isocyanatoethyl) benzene, 1, 3.5-
  • Polyisocyanates such as triisocyanates such as nonane triisocyanate (NTl) and polyisocyanates based on the diisocyanates and triisocyanates described above, in particular oligomers containing isocyanurate, biuret, allophanate, iminooxadiazinedione, urethane, carbodiimide, urea and / or uretdione
  • Nl nonane triisocyanate
  • oligomers containing isocyanurate, biuret, allophanate, iminooxadiazinedione, urethane, carbodiimide, urea and / or uretdione for example, from the patents and
  • Phenols such as phenol, cresol, xylenol, nitrophenol, chlorophenol, ethylphe ⁇ ol, tert-butylphenol, hydroxybenzoic acid, esters of this acid or 2,5-di-tert-butyl-4-hydroxytoluene;
  • Lactams such as ⁇ -caprolactam, ⁇ -valerolactam, ⁇ -butyrolactam or ⁇ -propiolactam;
  • active methylenic compounds such as diethyl malonate, dimethyl malonate, ethyl or methyl acetoacetate or acetylacetone;
  • Alcohols such as methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, t-butanol, n-amyl alcohol, t-amyl alcohol, lauryl alcohol,
  • Ethylene glycol monomethyl ether ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether,
  • Methoxymethanol glycolic acid, glycolic acid ester, lactic acid, lactic acid ester, methylolurea, methylolmelamine, diacetone alcohol, ethylene chlorohydrin, ethylene bromohydrin, 1,3-dichloro-2-propanol, 1,4-cyclohexyldimethanol or acetocyanohydrin;
  • Mercaptans such as butylmercaptan, hexylmercaptan, t-butylmercaptan, t-dodecylmercaptan, 2-mercaptobenzothiazole, thiophenol, methylthiophenol or ethylthiophenol;
  • Acid amides such as acetoanilide, acetoanisidine amide, acrylamide, methacrylamide, acetic acid amide, stearic acid amide or benzamide;
  • Imides such as succinimide, phthalimide or maleimide
  • Amines such as diphenylamine, phenylnaphthylamine, xylidine, N-phenylxylidine, carbazole, aniline, naphthylamine, butylamine, dibutylamine or butylphenylamine;
  • Imidazoles such as imidazole or 2-ethylimidazole
  • Ureas such as urea, thiourea, ethyleneurea, ethylene thiourea or 1,3-diphenylurea; Carbamates such as N-phenylcarbamic acid phenyl ester or 2-oxazolidone;
  • Imines such as ethyleneimine
  • Oximes such as acetone oxime, formaldoxime, acetaldoxime, acetoxime, methyl ethyl ketoxime, diisobutyl ketoxime, diacetyl monoxime, benzophenone oxime or chlorohexanone oximes;
  • Salts of sulfurous acid such as sodium bisulfite or potassium bisulfite
  • Hydroxamic acid esters such as benzyimethacrylohydroxamate (BMH) or allyl methacrylohydroxamate;
  • the constituent (A2) preferably contains on statistical average at least 2, preferably at least 3 and in particular at least 4 isocyanate-reactive, functional groups (a2).
  • the isocyanate-reactive functional groups (a2) are selected from the group consisting of hydroxyl groups, thiol groups, primary and secondary amino groups, primary and secondary amide groups, and primary and secondary carbamate groups.
  • hydroxyl groups (a2) are used.
  • the hydroxyl groups (a2) in the constituents (A2) are preferably present in an amount such that hydroxyl numbers of 50 to 500, preferably 80 to 300 and in particular 100 to 250 mg KOH / g result.
  • constituents (A2) may contain other, non-isocyanate-reactive, reactive, functional groups which may undergo thermal crosslinking reactions with complementary, reactive, functional groups. Examples of suitable pairs of complementary, non-isocyanate-reactive, reactive, functional groups are known from international patent application WO 03/010247, page 18, line 12, to page 21, line 15.
  • constituents (A2) may also contain ion-forming, functional groups which can be converted into salt groups by neutralization and can thus assume ionic stabilization in water.
  • suitable ion-forming functional groups are also known from international patent application WO 03/010247, page 12, line 9, to page 13, line 11.
  • constituents (A2) may also contain reactive, functional groups which can be activated with actinic radiation, in particular UV radiation and electron radiation.
  • suitable groups of this kind are also known from international patent application WO 03/010247, page 23, line 29, to page 26, line 4.
  • the constituents (A2) are preferably oligomers or polymers in the abovementioned sense. They are preferably selected from the group of customary and known binders. Examples of suitable binders (A2) are known from international patent application WO03 / 010247, page 13, line 13, to page 15, line 8. In particular, (meth) acrylate copolymers (A2) are used.
  • the mixtures according to the invention contain at least one cesium compound, in particular at least one cesium salt (B).
  • the anions of the cesium salts are selected from the group consisting of F “ , he, CiO-, CiO 3 ' , CiO 4 " , Br, r, JO 3 “ , CN ⁇ , OCN ⁇ , SCN “ , NO 2 -, NO 3 " , HCO 3 -, CO 3 2 -, SiO 4 2 " ,
  • organic radicals R are selected from the group consisting of:
  • alkyl having 1 to 20, preferably 2 to 16 and especially 2 to 10 carbon atoms, cycloalkyl having 3 to 20, preferably 3 to 16 and especially 3 to 10 carbon atoms and aryl having 5 to 20, preferably 6 to 14 and especially 6 to 10 carbon atoms;
  • alkylaryl substituted and unsubstituted alkylaryl, arylalkyl, alkylcycloalkyl, cycloalkylalkyl, arylcycloalkyl, cycloalkylaryl,
  • n-linked, substituted and unsubstituted radical of the type mentioned above containing at least one, in particular one, heteroatom selected from the group consisting of oxygen atom, sulfur atom,
  • Suitable substituents for the radicals R are all groups and atoms which are inert, d. H. do not affect the effect of the cesium salts (B), do not inhibit the curing reactions in the mixtures of the invention, do not lead to undesirable side reactions and cause no toxic effect.
  • suitable substituents are halogen atoms, nitrile groups or nitro groups, preferably halogen atoms, in particular fluorine atoms, chlorine atoms and bromine atoms.
  • the anions are selected from the group consisting of bicarbonate, carbonate, formate, acetate, propionate, butyrate, pentanoate, hexanoate and 2-ethylhexanoate.
  • the content of the mixtures according to the invention on the cesium compounds (B) can vary widely and depends on the requirements of the individual case.
  • the mixtures of the invention contain the cesium compounds (B) in an amount of 0.01 to 10 wt .-%, preferably 0.05 to 5 wt .-% and in particular 0.1 to 3 wt .-%, each based on the Solid body of the relevant mixture according to the invention.
  • solid is understood to mean the sum of all constituents of a mixture according to the invention minus any organic and inorganic solvents (C) which may be present. Accordingly, the term “solids content” of a mixture according to the invention means the percentage fraction of the solid in the total amount of the mixture according to the invention.
  • the solids content of the mixtures according to the invention can be 100% by weight. If the mixtures according to the invention contain organic and / or inorganic solvents (C), the solids content is preferably from 10 to 90% by weight, preferably from 15 to 80% by weight, particularly preferably from 20 to 70% by weight and in particular from 20 to 60% by weight .-%.
  • the mixtures according to the invention may contain at least one additive (C) in effective amounts.
  • the additive (C) is selected from the group consisting of reactive and inert, oligomeric and polymeric, film-forming binders other than the components (A); Crosslinking agents other than components (A); Water; reactive and inert, organic and inorganic solvents; with actinic radiation, in particular UV radiation and electron radiation, activatable compounds; organic and inorganic, colored and achromatic, optically effecting, electrically conductive, magnetically shielding and fluorescent pigments; transparent and opaque, organic and inorganic fillers; nanoparticles; UV absorbers; Light stabilizers; Radical scavengers; Photoinitiators; Initiators of radical polymerization; Driers; Venting means; slip additives;
  • the additive (C) is selected from the group consisting of reactive and inert, oligomeric and polymeric, film-forming binders other than the components (A); Crosslinking agents other than components (A); Water; reactive and inert, organic and inorganic solvents; with actinic radiation, in
  • mixtures according to the invention can be present in a wide variety of physical states and three-dimensional forms.
  • the mixtures according to the invention can be solid or liquid or flowable at room temperature. However, they may also be solid at room temperature and flowable at higher temperatures, preferably exhibiting thermoplastic behavior. In particular, they may contain 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, aqueous powder suspensions ( Puiverslurries).
  • they are substantially or completely solvent-free, aqueous powder suspensions (Puiverslurries), in particular powder slurry clearcoats, as they - except for the inventive use of the cesium compounds (B) - from the international patent application WO 03/010247 or the German patent DE 198 41 842 C2 are known.
  • the preparation of the mixtures according to the invention has no special features, but takes place in the context of the process according to the invention by mixing and homogenizing the above-described constituents by means of customary and known mixing methods and devices such as stirred tank, stirred mills, extruders, kneaders, Ultraturrax, In-line Dissolvers, static mixers, micromixers, sprocket dispersers, pressure relief nozzles and / or microfluidizers optionally with the exclusion of actinic radiation.
  • the selection of the optimum method for a given individual case depends above all on the physical state and the three-dimensional shape which the mixture according to the invention is intended to have. For example, if a thermoplastic invention Mixture in the form of a film or a laminate, in particular the extrusion through a slot die for the production of the mixture according to the invention and its shaping into consideration.
  • the powder slurries according to the invention can be produced by means of secondary dispersion methods, as described, for example, in International Patent Application WO 03/010247, page 35, line 4, to page 38, line 19, or in German Patent DE 198 41 842 C2, page 5, line 43, to page 6, line 3 described.
  • the mixtures according to the invention are used for the production of new hardened materials, in particular new thermosetting materials, which serve a very wide variety of purposes and are referred to below as "materials according to the invention”.
  • the mixtures according to the invention are preferably starting materials for molded parts and films or coating materials, adhesives and sealants, in particular coating materials.
  • novel materials are preferably new moldings, films, coatings, adhesive layers and seals, in particular new coatings.
  • novel coating materials are preferably novel electrocoating lacquers, fillers, antistonechip primers, solid-color topcoats, water-based lacquers and / or clearcoats, more preferably clearcoats, in particular powder clearcoats, for the production of new color and / or effect, electrically conductive, magnetically shielding or fluorescent multi-layer finishes, in particular color and / or effect Multicoat paint systems used.
  • the customary and known wet-on-wet processes and / or extrusion processes as well as the customary and known paint or film structures can be used.
  • the mixtures according to the invention are applied to conventional and known temporary or permanent substrates.
  • conventional and known temporary substrates are preferably used, such as metal and plastic tapes and films or hollow bodies made of metal, glass, plastic, wood or ceramic, which can be easily removed without leaving the products according to the invention Mixtures produced inventive films and Fo ⁇ nmaschine be damaged.
  • permanent substrates such as bodies of locomotion, in particular motor vehicle bodies, and parts thereof, interior and exterior structures and parts thereof, doors, windows, furniture, hollow glass body , Coils, containers, packaging, small parts, optical, mechanical and electrotechnical components as well as components for white goods.
  • the films and moldings according to the invention can likewise serve as permanent substrates.
  • the application of the mixtures according to the invention has no special features, but can by all customary and known, suitable for the respective mixture according to the invention application methods, such as.
  • extrusion and spray application methods in particular spray application methods, are used.
  • the mixtures according to the invention are thermally cured in a conventional manner.
  • the thermal curing generally takes place after a certain rest period or ventilation time. It may have a duration of 30 seconds to 2 hours, preferably 1 minute to 1 hour and especially 1 to 45 minutes.
  • the rest period serves, for example, for the course and degassing of layers of the mixtures according to the invention and for the evaporation of volatile constituents, such as optionally present solvent and / or water.
  • the ventilation can be accelerated by an elevated temperature, which is not sufficient for curing, and / or by a reduced humidity.
  • This process measure is also used for drying the applied mixtures according to the invention, in particular the layers of the coating materials of the invention, especially the layers of the ⁇
  • Coating layers according to the invention applied, which are not or only partially cured.
  • the thermal curing takes place, for example, with the aid of a gaseous, liquid and / or solid, hot medium, such as hot air, heated oil or heated rollers, or 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 convection oven or by irradiation with IR and / or NIR
  • Lamps. Curing can also be done gradually.
  • the thermal curing is carried out at temperatures from room temperature to 200 0 C, preferably from room temperature to 18O 0 C and in particular from room temperature to 160 -, ° OQ
  • the thermal curing can be further supported by the additional curing methods described above, including, if appropriate, the customary and known devices, for example for curing with actinic radiation, in particular UV radiation or Elektronenstrahiung be used.
  • the resulting materials according to the invention are outstandingly suitable for coating, bonding, sealing, wrapping and packaging bodies of vehicles, in particular motor vehicle bodies, and parts thereof, buildings in the interior and Exterior and parts thereof, doors, windows, furniture, glass hollow bodies, coils, containers, packaging, small parts, such as nuts, screws, rims or hubcaps, optical components, mechanical components, electrical components, such as windings (coils, stators, rotors), and Components for white goods, such as radiators, appliances, refrigerator covers or washing machine covers.
  • mixtures according to the invention offer very particular advantages when they are used as powder slurry clearcoats according to the invention for the production of novel clearcoats.
  • the clearcoats of the invention are usually the outermost layers of multicoat paint systems or films or laminates which essentially determine the overall visual appearance (appearance) and the substrates and / or the color and / or effect layers of multicoat paint systems or films or laminates protect against mechanical and chemical damage and radiation damage. That's why deficits in hardship, -
  • the clearcoats of the invention produced have only a slight yellowing. They are highly scratch-resistant and show only very slight gloss loss after scratching. In particular, the loss of gloss in the car wash simulation test according to Amtec / Kistler is very low. At the same time they have a high hardness and a particularly high chemical resistance. Last but not least, they have excellent substrate adhesion and intercoat adhesion. In addition, they have excellent recoatability.
  • Desmodur® N 3300 commercial isocyanurate of hexamethylene diisocyanate from Bayer AG
  • 200 parts by weight of methyl ethyl ketone were placed in a reaction vessel and heated to 40 ° C.
  • To the solution was added, with cooling, 100 parts by weight of 3,5-dimethylpyrazole, waiting for the exothermic reaction to disappear. Thereafter, with continued cooling, 100 parts by weight of 3,5-dimethylpyrazole were added again. After renewed decay of the exothermic reaction, an additional 66 parts by weight of 3,5-dimethylpyrazole were added. Thereafter, the cooling was turned off, causing the reaction slowly heated to 80 0 C. It was held at this temperature until its isocyanate content had dropped below 0.1%. Thereafter, the reaction mixture was cooled and discharged.
  • the resulting solution of the blocked polyisocyanate had a solids content of 81% by weight (1 h at 130 ° C.) and a viscosity of 3.4 dPas (70% in methyl ethyl ketone, plate and cone viscometer at 23 ° C.).
  • the resulting aqueous emulsion was diluted with 739 parts by weight of deionized water. Thereafter, it was removed on a rotary evaporator under vacuum, the same amount of a mixture of volatile organic solvents and water until the solids content was 37 wt .-% (1 h at 13O 0 C).
  • test panels were used, which had been coated with a conventional and known, cathodically deposited and thermally cured electrodeposition coating BASF Coatings AG.
  • the electrodeposition coatings were each wet-on-wet coated with a commercial water filler from BASF Coatings AG and a commercial black water-based paint from BASF Coatings AG. After each application, the respective wet layers were predried.
  • the predried, black aqueous basecoat films were coated in a wedge shape with the powder slurry clearcoat 1 of Example 1 pneumatically.
  • the wet film thicknesses of the clearcoat films 1 were selected such that dry film thicknesses of 15 to 70 ⁇ m resulted.
  • the clearcoat films 1 were each predried at 80 ° C. for 10 minutes. Subsequently, the surfacer layers, the aqueous basecoat films and the clearcoat films 1 were baked at 150 ° C. for 23 minutes. 1
  • the powder slurry clearcoat 1 was applied in a constant wet layer thickness, so that a dry layer thickness of 40 microns resulted.
  • Chemical resistance was determined in a conventional manner with a DC gradient oven. Visible damage occurred when loaded with 1% - percent sulfuric acid from 46 0 C, with 1% by percent NaOH from 55 ° C, with tree resin from 38 0 C and with deionized water from 41 0 C. This underpinned that the clearcoat 1 also had a high chemical resistance.
  • the mechanical dynamic properties of the clearcoat 1 were determined using self-supporting films with a layer thickness of 40 ⁇ m using Dynamic Mechanical Thermal Analysis (DMTA).
  • the measuring frequency was 1 Hz, the amplitude at 0.2% and the heating rate at 2 ° C / min from - 30 ° C to + 200 0 C (see also the German patent application DE 102 24 381 A1, page 5, paragraph [0047]).
  • the following values were measured:
  • Loss factor tangent delta 0.1 at 48 ° C
  • the measured values underpin the excellent hardness, flexibility, crosslinking density and scratch resistance of the clearcoat 1.

Landscapes

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

Abstract

L'invention concerne des mélanges durcissables exempts de composés molybdène et tungstène, contenant (A) au moins un constituant contenant des groupes isocyanates inhibés (a1) et des groupes fonctionnels (a2) isocyanate-réactifs, ainsi que (B) au moins un composé césium. L'invention concerne également des procédés permettant de les produire et leur utilisation.
EP06791710A 2005-08-31 2006-08-29 Melanges durcissables exempts de composes molybdene et tungstene, a base de polyisocyanates inhibes et contenant des composes cesium, procedes permettant de les produire et leur utilisation Withdrawn EP1922348A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102005041246A DE102005041246A1 (de) 2005-08-31 2005-08-31 Von Molybän- und Wolframverbindungen freie, Cäsiumverbindungen enthaltende, härtbare Gemische auf der Basis blockierter Polyisocyanate, Verfahren zu ihrer Herstellung und ihre Verwendung
PCT/EP2006/008445 WO2007025716A1 (fr) 2005-08-31 2006-08-29 Melanges durcissables exempts de composes molybdene et tungstene, a base de polyisocyanates inhibes et contenant des composes cesium, procedes permettant de les produire et leur utilisation

Publications (1)

Publication Number Publication Date
EP1922348A1 true EP1922348A1 (fr) 2008-05-21

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Country Status (5)

Country Link
US (1) US20080319111A1 (fr)
EP (1) EP1922348A1 (fr)
JP (1) JP2009506178A (fr)
DE (1) DE102005041246A1 (fr)
WO (1) WO2007025716A1 (fr)

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US7833692B2 (en) * 2007-03-12 2010-11-16 Brewer Science Inc. Amine-arresting additives for materials used in photolithographic processes
JP5304339B2 (ja) * 2009-03-11 2013-10-02 東洋インキＳｃホールディングス株式会社 粘着剤組成物及びそれを用いてなる粘着積層体
EP2604616A1 (fr) 2011-12-12 2013-06-19 Sika Technology AG Composés à base de complexes de dioxomolybdène (VI) comme catalyseurs de compositions de polyuréthane
CN103740315A (zh) * 2013-12-24 2014-04-23 上海邦中高分子材料有限公司 一种耐高温反应型热熔胶
KR101613245B1 (ko) 2015-04-27 2016-04-18 주식회사 대웅제약 신규의 4-메톡시 피롤 유도체 또는 이의 염 및 이를 포함하는 약학 조성물
PT3291986T (pt) * 2015-05-06 2019-06-04 Basf Se Processo para a produção de materiais compósitos
JP6484268B2 (ja) * 2017-03-09 2019-03-13 三洋化成工業株式会社 ブロックイソシアネートの製造方法
US11254784B2 (en) * 2017-08-31 2022-02-22 The University Of Massachusetts Method for deblocking a blocked isocyanate and method of making a polyurethane

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JP3195787B2 (ja) * 1990-03-12 2001-08-06 旭電化工業株式会社 イソシアネート三量化またはウレタン化触媒
JP5027962B2 (ja) * 2000-10-19 2012-09-19 Ｄｉｃ株式会社 液状ウレタンプレポリマーの製造方法および樹脂組成物
DE10161156A1 (de) * 2001-12-12 2003-06-18 Basf Ag Wässrige Polyurethan-Dispersionen, erhältlich mit Hilfe von Cäsiumsalzen
DE10308104A1 (de) * 2003-02-26 2004-09-09 Bayer Ag Polyurethan-Beschichtungssysteme
DE10309204A1 (de) * 2003-02-28 2004-09-09 Basf Ag Verfahren zur Herstellung wässriger Polyurethan-Dispersionen
DE10320267A1 (de) * 2003-05-03 2004-11-18 Degussa Ag Bei niedriger Temperatur härtbare feste uretdiongruppenhaltige Polyurethan-Pulverlackzusammensetzungen

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Title
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Also Published As

Publication number Publication date
DE102005041246A1 (de) 2007-03-08
JP2009506178A (ja) 2009-02-12
US20080319111A1 (en) 2008-12-25
DE102005041246A8 (de) 2007-06-28
WO2007025716A1 (fr) 2007-03-08

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