EP1497387A1 - Melanges thixotropes thermodurcissables contenant des groupes carbamate et/ou allophanate - Google Patents

Melanges thixotropes thermodurcissables contenant des groupes carbamate et/ou allophanate

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Publication number
EP1497387A1
EP1497387A1 EP02732655A EP02732655A EP1497387A1 EP 1497387 A1 EP1497387 A1 EP 1497387A1 EP 02732655 A EP02732655 A EP 02732655A EP 02732655 A EP02732655 A EP 02732655A EP 1497387 A1 EP1497387 A1 EP 1497387A1
Authority
EP
European Patent Office
Prior art keywords
group
mixtures according
carbamate
mixtures
thixotropic
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Withdrawn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
EP02732655A
Other languages
German (de)
English (en)
Inventor
Hubert Baumgart
Vince Cook
Sandra Hasse
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 EP1497387A1 publication Critical patent/EP1497387A1/fr
Withdrawn legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/04—Thixotropic paints
    • 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
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
    • C08G18/3203—Polyhydroxy compounds
    • C08G18/3212—Polyhydroxy compounds containing cycloaliphatic 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
    • C08G18/28—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
    • C08G18/80—Masked polyisocyanates
    • C08G18/8061—Masked polyisocyanates masked with compounds having only one group containing active hydrogen
    • C08G18/8093—Compounds containing active methylene groups
    • C—CHEMISTRY; METALLURGY
    • 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
    • C08G71/00—Macromolecular compounds obtained by reactions forming a ureide or urethane link, otherwise, than from isocyanate radicals in the main chain of the macromolecule
    • C08G71/04—Polyurethanes
    • 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
    • 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
    • C09D201/00—Coating compositions based on unspecified macromolecular compounds
    • C09D201/02—Coating compositions based on unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups
    • C09D201/025—Coating compositions based on unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups containing nitrogen atoms

Definitions

  • the invention relates to new, thermally curable, thixotropic mixtures containing carbamate and / or AUophanat phenomenon.
  • the present invention relates to thermal processes for the preparation of the new, thermally curable, thixotropic mixtures containing carbamate and / or AUophanat phenomenon.
  • the present invention relates to the use of the new, thermally curable, thixotropic mixtures containing carbamate and / or AUophanat phenomenon as coating materials, adhesives and sealants.
  • the present invention relates to the use of the new, thermally curable, thixotropic coating materials containing carbamate and / or AUophanat phenomenon as clear lacquer, in particular for the production of clear lacquers in the context of color and / or effect multi-layer lacquers.
  • Thixotropic agents and coating materials containing them have long been known.
  • coating materials which contain urea and / or urea derivatives as thixotropic agents.
  • paint surfaces are obtained, at least at high solids contents, which are unsatisfactory in terms of their visual appearance (in particular leveling and gloss) and, moreover, also do not have sufficient condensation resistance (whitening through water storage).
  • Thixotropic agents based on silicas provide coating materials which are also unsatisfactory in terms of their flow.
  • thixotropic agents An essential feature of thixotropic agents is that the viscosity of a varnish produced with it depends on the history of the flow and / or that the thixotropic agents are structurally viscous, ie that the viscosity of the varnish decreases with increasing shear stress. Starting from a basic viscosity, the viscosity decreases during a shear stress and only gradually returns to the initial value after the shear stress has ended.
  • a thixotropic gel for example, liquefies when mechanical energy is added (stirring or the like) and only gradually solidifies again after the energy input has ended. Structurally viscous or thixotropic properties are advantageous for paint processing.
  • thixotropic agents must not adversely affect the optical and chemical properties of a finished coating produced with them.
  • thixotropic agents are particulate and dispersed in a coating material, be it aqueous or non-aqueous.
  • these are needle-shaped, partly helically twisted crystals, preferably a particle size distribution between 0.1 ⁇ m and 6 ⁇ m (95-99% of the particles, based on the volume) and 80% of the particles Crystals (based on the number) are smaller than 2 ⁇ m.
  • the fineness of the finished coating material is typically less than 10 ⁇ m in accordance with DIN ISO 1524.
  • the primary particle size of pyrogenic silicas is usually in the range from 5 to 20 nm.
  • thixotropic agents known hitherto have since been further developed in a variety of ways.
  • German patent application DE 199 24 170 A1 discloses thixotropic agents which can be prepared by reacting monoamines with special polyisocyanates in the presence of, for example, hydroxyl-containing polyacrylates.
  • the clear lacquers in which they are contained provide, after the wet-on-wet process, coloring and / or effect-giving multi-layer lacquers which, owing to the very good intercoat adhesion, show no delamination of the lacquers, have excellent optical properties and do not tarnish after exposure to condensation water demonstrate.
  • the thixotropic agents and the relevant thixotropic coating materials contain no carbamate and / or AUophanat phenomenon.
  • German patent application DE 199 24 172 A 1 discloses thixotropic agents which comprise a mixture of silica and urea and / or urea derivatives.
  • the urea derivatives are prepared by reacting monoamines with polyisocyanates in the presence of binders, such as hydroxyl-containing polyacrylates.
  • binders such as hydroxyl-containing polyacrylates.
  • the coating materials in question have a reduced tendency to run and are stable in storage.
  • the clear coats or color and / or effect multi-coat coats produced from them are stable against condensation and have excellent optical properties.
  • Neither the thixotropic agents nor the coating materials contain carbamate and / or AUophanat phenomenon.
  • German patent application DE 199 24 171 A 1 discloses thixotropic agents which are a mixture of at least one wetting agent (wetting agent; cf. Römpp Lexikon Lacke und Druckmaschine, Georg Thieme Verlag, Stuttgart, New York, page 409, "Netzstoff") and Urea and / or urea derivatives and optionally include silicas.
  • the urea derivatives are also produced here by reacting monoamines with polyisocyanates in the presence of binders, such as hydroxyl-containing polyacrylates.
  • the coating materials in question also have a reduced tendency to run and are stable in storage.
  • the clearcoats or color and / or effect multi-layer coatings produced from them are also stable against condensation and have a very good flow, a very good surface smoothness and excellent optical properties. Because of the very good interlayer adhesion, there is no delamination of the paintwork. Neither the thixotropic agents nor the coating materials contain carbamate and / or AUophanat weakness.
  • Coating materials which contain constituents containing AUophanate groups are known from German patent application DE 198 39 453 A1. These coating materials can be used widely and are outstandingly suitable for the wet-on-wet process for producing color and / or effect multi-layer coatings.
  • the paints made from the coating materials have a high level of compatibility with other paints and are scratch-resistant and weather-resistant.
  • the equipment of these known coating materials with thixotropic agents is not described in the German patent application.
  • thixotropic agents which contain urea derivatives and polymers with pendant or terminal carbamate groups.
  • the Urea derivatives can be prepared by reacting monoamines with polyisocyanates in the presence of these polymers.
  • the coating materials equipped with the thixotropic agents can also contain surface-active or surface-active substances (surfactants; cf. Römpp Lexikon Lacke und Druckmaschine, Georg Thieme Verlag, Stuttgart, New York, page 271, “surface-active substances”).
  • surfactants cf. Römpp Lexikon Lacke und Druckmaschine, Georg Thieme Verlag, Stuttgart, New York, page 271, “surface-active substances”.
  • a silicone-glycol copolymer (Worlee ® 315) is used.
  • the thixotropic agents improve the thixotropic behavior of the coating materials treated with them and effectively suppress the tendency to run.
  • the coatings produced from this have a high gloss and high hardness.
  • the thixotropic agents known from the international patent application do not include silicas.
  • coating materials which, as binders, can produce at least one pendant and / or terminal resin containing carbamate groups, by reacting a resin containing at least one hydroxyl group with phosgene to form a resin containing at least one chloroformate group, after which this resin is reacted with ammonia, primary amines and / or secondary amines.
  • the coating materials can also contain numerous different additives.
  • transparent fillers based on silicon dioxide, aluminum oxide or zirconium oxide are also mentioned (in addition, reference is made to Römpp Lexikon Lacke und Druckmaschine, Georg Thieme Verlag, Stuttgart, 1998, pages 250 to 252); Sag control agents (thixotropic agents), such as ureas and / or modified ureas or silicas, as described, for example, in the literature references EP 0 192 304 A1, DE 23 59 923 A1, DE 18 05 693 A1, WO 94/22968 , DE 27 51 761 C 2, WO 97/12945 and "färbe + lack", 11/1992, pages 829 ff.
  • Sag control agents thixotropic agents
  • additives such as siloxanes, fluorine-containing compounds, carboxylic acid semiesters, Phosphoric acid esters, polyacrylic acids and their copolymers or polyurethanes; called.
  • wetting agents such as siloxanes, fluorine-containing compounds, carboxylic acid semiesters, Phosphoric acid esters, polyacrylic acids and their copolymers or polyurethanes; called.
  • thermally and with actinic radiation curable substance mixtures are known which contain at least one constituent, which is a statistical average of at least one primary or secondary carbamate group and at least one with actinic Has radiation-activatable bond.
  • the known dual-cure substance mixtures can also contain the fillers, transparent fillers and thixotropic agents mentioned above.
  • the dual-cure mixtures can be used as coating materials, adhesives and sealants.
  • the object of the present invention is to provide new, thermally curable, thixotropic mixtures containing carbamate and / or AUophanat phenomenon, which are used as coating materials, adhesives and sealants can be used, which achieve, if not exceed, the high technological level of the prior art.
  • the new carbamate and / or AUophanat phenomenon containing, thermally curable, thixotropic coating materials, adhesives and sealants should provide coatings that reach, if not exceed, the high technological level of the prior art and at the same time also have high stone chip resistance.
  • At least one thixotropic agent selected from the group consisting of urea or urea derivatives, which can be prepared by reacting at least one amine and / or water with at least one polyisocyanate.
  • the thixotropic agent (B) in an amount of 0.1 to 5% by weight
  • polymers are understood to mean substances which on average contain at least 10 monomer units in the molecule.
  • Oligomers are understood to mean substances which, on a statistical average, contain 3 to 15 monomer units in the molecule.
  • the mixtures according to the invention contain at least one oligomer and / or polymer (A) selected from the group consisting of AUophanate groups or AUophanate groups and carbamate group-containing oligomers and polymers.
  • Oligomers and / or polymers (A) are preferably used which contain on average at least one allophanate group and preferably at least two, particularly preferably at least three and in particular at least four AUophanate groups in the molecule.
  • oligomers and or polymers (A) are preferably used which on average contain at least one allophanate group and at least one carbamate group and preferably at least two, particularly preferably at least three and in particular at least four AUophanate groups and at least one carbamate group, in particular at least two carbamate groups, in the molecule
  • the mixtures according to the invention according to the first variant contain at least one thixotropic agent (B) selected from the group consisting of urea and urea derivatives, which can be prepared by reacting at least one amine and / or water, in particular an amine, with at least one polyisocyanate, of which the Urea derivatives are advantageous and are therefore used with preference.
  • the mixtures according to the invention can contain at least one, in particular one, silica as the thixotropic agent (C).
  • the mixtures according to the invention in accordance with the second variant according to the invention contain at least one, in particular one, carbamate group-free oligomer and / or polymer (A) free from AUophanate groups, at least one thixotropic agent (B) and at least one thixotropic agent (C).
  • the oligomers and / or polymers (A) containing carbamate groups preferably contain on average at least one carbamate group and preferably at least two, particularly preferably at least three and in particular at least four carbamate groups in the molecule.
  • the mixtures according to the invention of the first and second variants according to the invention can also contain at least one wetting agent (D).
  • the content of the oligomers and polymers (A) in the mixtures according to the invention can vary very widely and depends on the requirements of the particular intended use.
  • the mixtures according to the invention preferably contain the oligomers and polymers (A) in an amount of 10 to 98, based in each case on the solids of the mixture according to the invention, preferably 12 to 95, particularly preferably 14 to 92, very particularly preferably 16 to 90 and in particular 18 to 88% by weight.
  • solid means the sum of the constituents of the respective mixture according to the invention which build up the coatings, adhesive layers or seals after the thermal hardening.
  • the content of the thixotropic agents (B) in the mixtures according to the invention can vary very widely. It also depends on the requirements of the respective purpose.
  • the mixtures according to the invention, the oligomers and polymers (A) which contain AUophanat phenomenon, preferably contain the thixotropic agents (B) in an amount of 0.1 to 5, preferably 0.2 to 4, based on the solids of the mixture according to the invention, 5, particularly preferably 0.3 to 4, very particularly preferably 0.4 to 3.5 and in particular 0.5 to 3% by weight.
  • the mixtures according to the invention, which contain oligomers and polymers (A) which are free from AUophanat tendency have this content of thixotropic agents (B).
  • the content of the thixotropic agent (C) in the mixtures according to the invention can also vary very widely. It also depends on the requirements of the respective purpose.
  • the mixtures according to the invention preferably contain the thixotropic agents (C) in an amount of, based on the mixture according to the invention, 0.1 to 10, preferably 0.2 to 9, particularly preferably 0.3 to 8, very particularly preferably 0.4 to 7 and in particular 0.5 to 6 wt .-%.
  • the wetting agents (D) in the mixtures according to the invention are preferably in a quantity of 0.01 to 5, preferably 0.02 to 4, particularly preferably 0.03 to 3, based on the solids of the mixture according to the invention particularly preferably contain 0.04 to 2, in particular 0.05 to 1% by weight.
  • Suitable oligomers and polymers (A) come from the polymer classes of the random, alternating and / or block-like linear and / or branched and / or comb-like (co) polymers of ethylenically unsaturated monomers, or polyaddition resins and / or polycondensation resins.
  • Examples of highly suitable (co) polymers (A) are (meth) acrylate copolymers and partially saponified polyvinyl esters, in particular (meth) acrylate copolymers.
  • Examples of highly suitable polyaddition resins and / or polycondensation resins (A) are polyesters, alkyds, polyurethanes, polylactones, polycarbonates, polyethers, epoxy resin-amine adducts, polyureas, polyamides or polyimides.
  • the oligomers and / or polymers (A) very particularly preferably originate from the polymer classes of the (meth) acrylate copolymers.
  • Oligomers and polymers (A) containing AUophanate groups and which originate from the abovementioned polymer classes are described in German patent application DE 198 39 453 A1, page 2, line 65, to page 6, line 34, and page 7, lines 25 to 53, known.
  • EP 0 594 142 A 1 page 3, line 1, to page 4, line 37, page 5, line 49, to page 6, line 12, and page 7, lines 5 to 26,
  • EP 0 675 141 B1 page 2, line 44, to page 5, line 15, page 8, line 5, to page 10, line 41, and
  • the oligomers and / or polymers (A) are preferably prepared by using a monomer mixture which contains at least one olefinically unsaturated carboxylic acid, for example methacrylic acid, in the presence of a glycidyl ester of Versatic® acid (cf.Römpp Lexikon Lacke und Druckmaschine, Georg Thieme Verlag, Stuttgart New York, 1998 "Versatic ® acids", pages 605 and 606) copolymerized, after which the resulting hydroxyl-containing (meth) acrylate copolymer is reacted with at least one alkyl urethane.
  • a monomer mixture which contains at least one olefinically unsaturated carboxylic acid, for example methacrylic acid
  • the oligomers and polymers (A) preferably have a number average molecular weight of 600 to 20,000, preferably 800 to 15,000, particularly preferably 1,000 to 10,000, very particularly preferably 1,200 to 8,000 and in particular 1,200 to 6,000 daltons.
  • the oligomers and polymers (A) can be made water-soluble or water-dispersible by incorporating dispersing groups.
  • suitable dispersing groups are anion-forming groups, such as carboxylic acid, sulfonic acid or phosphonic acid groups, or anionic groups, such as carboxylate, sulfonate or phosphonate groups, cation-forming groups such as primary, secondary or tertiary amino groups, or cationic groups, for example ammonium groups, such as primary secondary, tertiary or quaternary ammonium groups, sulfonium groups and phosphononium groups, or polyalkylene oxide groups, such as polyethylene oxide groups, which can be incorporated in the oligomers and polymers (A) in the lateral, terminal and / or chain positions (cf.Römpp Lexikon Lacke und Druckmaschinetechnik, Georg Thieme Verlag , Stuttgart, New York, 1998, "Water-dispersible binders", page 619, and "Water-soluble
  • the thixotropic agents (B) are selected from the group consisting of urea or urea derivatives, which can be prepared by reacting at least one amine and / or water with at least one polyisocyanate, in particular in the presence of at least one oligomer and / or polymer (A).
  • the urea derivatives are preferably used.
  • the amines are preferably used for their preparation.
  • the amines are preferably selected from the group consisting of acyclic aliphatic, aliphatic-aromatic, cycloaliphatic, aliphatic-cycloaliphatic and cycloaliphatic-aromatic primary and secondary monoamines.
  • suitable monoamimes are from the patent applications and patents mentioned at the outset, in particular from German patent applications DE 199 24 172 A1, page 3, lines 3 to 10, or DE 199 24 171 A1, page 3, lines 35 to 42, or international Patent application WO 00/31194, page 11, lines 14 to 29, known.
  • Methoxypropylamine, benzylamine and / or n-hexylamine are particularly preferably used.
  • Polyisocyanates are preferably used which have a statistical average of at least 1.8, preferably at least 2 and in particular 2 isocyanate groups in the molecule.
  • suitable polyisocyanates and diisocyanates are described in international patent application WO 00/31194, page 11, line 30, to page 12, line 26, or German patent applications DE 199 24 172 A1, page 3, lines 11 to 23, DE 199 24 170 A 1, column 3, line 61, to column 6, line 68, or DE 199 24 171 A 1, page 3, lines 43, to page 5, line 34, described in detail.
  • Hexamethylene diiosocyanate and its oligomers, in particular trimers, are particularly preferably used.
  • the silicas used as thixotropic agents (C) are selected from the group consisting of modified pyrogenic, hydrophilic and hydrophobic, transparent silicas.
  • Hydrophilic and hydrophobic fumed silicon dioxides are particularly preferably used, the agglomerates and aggregates of which have a chain-like structure and which can be produced by flame hydrolysis of silicon tetrachloride in a detonating gas flame. These are sold, for example, by Degussa under the brand Aerosil ®.
  • Suitable silicas are known from German patent application DE 199 24 172 A1, page 3, lines 28 to 32.
  • Another example of suitable hydrophilic, transparent silicas is Aerosil ® 380 with an inner surface area of 380 m 2 / g (measured according to BET according to DIN 66131).
  • the wetting agents (D) are selected from the group consisting of siloxanes, fluorine-containing compounds, semi-carboxylic acids, phosphoric esters, polyacrylic acids and their copolymers and polyurethanes. Polyurethanes are preferably used.
  • the wetting agents (D) described in German patent application DE 199 24 171 A1, page 2, line 63, to page 3, line 24 have particular advantages.
  • Other highly suitable wetting agents are sold under the trade names Disperbyk® 361 by Byk, Borchigen® by Bayer AG and Tego Disperse® 710 by Tego Chemie Services.
  • the mixtures according to the invention can contain at least one crosslinking agent which, on statistical average, has at least two reactive functional groups in the molecule which are complementary to carbamate and AUophanat phenomenon.
  • the relevant mixtures according to the invention are then cross-linking.
  • oligomers and polymers (A) which, on statistical average, have at least one, in particular at least two, reactive functional groups in the molecule which are complementary to carbamate and AUophanat groups.
  • the relevant mixtures according to the invention are then partially or completely self-crosslinking.
  • suitable complementary reactive functional groups are N-methylol groups and N-methylol ether groups, preferably the methyl, ethyl, n-propyl and or n-butyl ether.
  • the oligomers and polymers (A) may contain further reactive functional groups which can enter into complementary reactive functional groups other than the crosslinking reactions mentioned above.
  • suitable reactive functional groups are isocyanate-reactive functional groups, such as thiol, hydroxyl and / or primary and / or secondary amino groups, in particular hydroxyl groups, or epoxy-reactive groups such as the amino groups or carboxyl groups. Hydroxyl groups are preferably used.
  • the content of the further reactive functional groups in the oligomers and / polymers (A) can vary very widely.
  • Their hydroxyl number is preferably 20 to 120, preferably 25 to 110, particularly preferably 30 to 100, very particularly preferably 35 to 90 and in particular 40 to 80 mg KOH / g.
  • the acid number or amine number are preferably 5 to 100, preferably 10 to 95, particularly preferably 15 to 90, very particularly preferably 20 to 85 and in particular 25 to 80 mg KOH / g.
  • the crosslinking agents are aminoplast resins, in particular melamine resins.
  • suitable aminoplast resins are found in Römpp Lexikon Lacke und Druckmaschine, Georg Thieme Verlag, 1998, page 29, “Aminoharze”, the textbook “Lackadditive” by Johan Bieleman, Wiley-VCH, Weinheim, New York, 1998, pages 242 ff., Dem Book “Paints, Coatings and Solvents", second completely revised edition, Edit. D. Stoye and W. Freitag, Wiley-VCH, Weinheim, New York, 1998, pages 80 ff., The patents US 4,710,542 A1 or EP 0 245 700 A1 as well as in the article by B. Singh and co-workers " Carbamylmethylated Melamines, Novel Crosslinkers for the Coatings Industry ", in Advanced Organic Coatings Science and Technology Series, 1991, Volume 13, pages 193 to 207.
  • crosslinking agents can be used, in particular if the oligomers and / or polymers also contain the further reactive functional groups described above.
  • suitable further crosslinking agents are from German patent applications DE 199 24 170 A1, column 10, line 51, to column 12, line 68, DE 199 24 171 A1, page 7, line 38, to page 8, line 35, and Page 8, lines 43 to 47, or DE 199 24 172 A1, page 5, line 22, to page 6, line 50, and page 6, lines 58 to 61.
  • the blocked, partially blocked and unblocked polyisocyanates described there are used. Partially blocked and unblocked polyisocyanates are mainly used in two- or multi-component systems.
  • the crosslinking agents are preferably present in the mixtures according to the invention in an amount of 5 to 70, preferably 10 to 65, particularly preferably 15 to 60, very particularly preferably 20 to 55 and in particular 20 to 50% by weight, based on the mixture according to the invention . It is also advisable to select the amounts of crosslinking agent and oligomers and / or polymers (A) so that the ratio of reactive functional groups in the crosslinking agent and complementary reactive functional groups in the oligomers and / or polymers (A ) is between 2: 1 to 1: 2, preferably 1.5: 1 to 1: 1.5, particularly preferably 1.2: 1 to 1: 1.2 and in particular 1.1: 1 to 1: 1.1 , In addition, it is advantageous if the additional crosslinking agent is used in smaller amounts than the crosslinking agent.
  • the quantitative ratio of crosslinking agent to additional crosslinking agent is preferably 10: 1, preferably 8: 1, particularly preferably 6: 1, very particularly preferably 5: 1 and in particular 4: 1.
  • the mixtures according to the invention may also contain at least one additive.
  • these pigments and fillers selected from the group consisting of customary and known organic and inorganic coloring and / or effect-giving, electrically conductive, magnetically shielding and fluorescent pigments and conventional and known organic and inorganic fillers, contain those of the thixotropic agents (C) are different.
  • pigments and fillers are used when the mixtures according to the invention are used as pigmented adhesives and sealants and also coating materials, such as fillers, basecoats or solid-color topcoats.
  • Additives which can be used both in the pigmented and in the unpigmented mixtures according to the invention are from German patent applications DE 199 24 170 A1, column 13, page 6, to column 14, line 2, or DE 198 39 453 A. 1, page 6, line 68, to page 7, page 6, the wetting agents and the transparent fillers based on silicon dioxide being excluded here.
  • Suitable additives are oligomers and / or polymers which are free from carbamate and / or AUophanat phenomenon, come from the polymer classes described above, in particular the class of (meth) acrylate copolymers, and contain the above-described additional reactive functional groups, especially hydroxyl groups .
  • Suitable oligomers or polymers are described in detail in the above-mentioned patent applications relating to the oligomers and polymers (A) or in the German patent application DE 139 08 018 A1, page 9, line 31 to page 11, line 37.
  • the mixtures according to the invention have no special features in terms of method, but instead are carried out by mixing the constituents (A) and (B) or (A), (B) and (C) described above and, if appropriate, the crosslinking agents and / or additives described above.
  • Mixing units such as stirred kettles, dissolvers, in-line dissolvers, agitator mills, static mixers, gear rim dispersers or extruders can be used.
  • the mixtures according to the invention can be dissolved and / or dispersed in organic solvents (non-aqueous dispersions, NAD) or as essentially or completely solvent-free mixtures.
  • the essentially or completely solvent-free mixtures can be in liquid forms (100% system) or powder form.
  • the mixtures according to the invention can be dissolved or dispersed in water.
  • the powdery mixtures according to the invention can be present in the form of so-called powder slurries dispersed in water.
  • the mixtures according to the invention are preferably present in dissolved and / or dispersed form in organic solvents.
  • the mixtures according to the invention are outstandingly suitable as dual-cure coating materials, adhesives and sealing compounds or for their production.
  • the coating materials of the invention are outstandingly suitable for the production of single- or multi-layer, color and / or effect-giving, electrically conductive, magnetically shielding or fluorescent coatings, such as filler coatings, basecoats or solid-color coatings, or single- or multi-layer clearcoats.
  • the adhesives of the invention are excellent for Production of adhesive layers, and the sealing compounds according to the invention are outstandingly suitable for the production of seals.
  • the clearcoats according to the invention are used for the production of color and / or effect multi-layer coatings by the wet-on-wet method, in which a basecoat, in particular a water-based basecoat, is applied to the surface of a substrate, after which the resulting basecoat film is applied without it harden, dry and covered with a clear coat. The two layers are then hardened together.
  • the application of the coating materials, adhesives and sealants according to the invention has no peculiarities, but can be achieved using all customary application methods, such as Spraying, knife coating, brushing, pouring, dipping, trickling or rolling.
  • Spray application methods are preferably used in the coating materials according to the invention, such as, for example, compressed air spraying, airless spraying, high rotation, electrostatic spray application (ESTA), if appropriate combined with hot spray application such as hot air hot spraying.
  • Suitable substrates are all those whose surface is not damaged by the application of heat in the hardening of the layers thereon.
  • the substrates preferably consist of metals, plastics, wood, ceramics, stone, textiles, fiber composites, leather, glass, glass fibers, glass and rock wool, mineral and resin-bound building materials, such as gypsum and cement boards or roof tiles, as well as composites of these materials.
  • the coating materials, adhesives and sealants according to the invention are not only for applications in the fields of Motor vehicle serial painting and automotive refinishing are excellently suitable, but also come for the coating, gluing and sealing of buildings indoors and outdoors and of doors, windows and furniture, for industrial painting, including coil coating, container coating and impregnation and / or Coating of electrotechnical components, as well as for painting white goods, including household appliances, boilers and radiators.
  • industrial painting they are suitable for painting, gluing or sealing practically all parts and objects for private or industrial use such as household appliances, small parts made of metal, such as screws and nuts, hub caps, rims, packaging, or electrical components, such as motor windings or transformer windings.
  • primers can be used which are produced in a customary and known manner from electrocoat materials. Both anodic and cathodic electrocoat materials, but in particular cathodic electrocoat materials, are suitable for this.
  • non-functionalized and / or non-polar plastic surfaces these can be subjected to a pretreatment in a known manner, such as with a plasma or with flame treatment, or can be provided with a hydro primer before coating.
  • the curing of the applied mixtures according to the invention has no special features in terms of method, but instead takes place in accordance with the customary and known thermal methods, such as heating in a forced air oven or irradiation with IR lamps.
  • the resulting coatings according to the invention in particular the single- or multi-layer color and / or effect coatings and clear coats according to the invention are easy to produce and have excellent optical properties and a very high light, chemical, Resistance to water, condensation and water. In particular, they are free from cloudiness and inhomogeneities. They are also hard, flexible and scratch-resistant. They have an excellent interlayer adhesion between basecoat and clearcoat and good to very good adhesion to conventional and well-known car refinishes.
  • 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 at extreme temperatures and / or temperature fluctuations.
  • the seals according to the invention permanently seal the substrates, and they even have high chemical and mechanical stability even in the case of extreme temperatures and / or temperature fluctuations. V. m. exposed to aggressive chemicals.
  • the coatings according to the invention have a high resistance to stone chips, which is why they can be used with particular advantage in the field of motor vehicle coatings.
  • the primed or unprimed substrates which are usually used in the above-mentioned technological fields and which are coated with at least one coating according to the invention, bonded with at least one adhesive layer according to the invention and / or sealed with at least one seal according to the invention, have a particularly long profile with a particularly advantageous application properties Service life on what makes them economically particularly attractive.
  • the resulting solution of the carbamate groups containing methacrylate copolymer (A) had a solids content of 70 wt .-% (60 minutes convection oven / 130 ° C), an acid number of 1 to 4 mg KOH / g solids and a color number of 4 to 5 (Gardner).
  • regrind consisting of 592 parts by weight of the methacrylate copolymer solution (A) from preparation example 1, 80 parts by weight of butyl acetate, 64 parts by weight of xylene and 64 parts by weight of Aerosil® 972 (average primary particle sizes: 16 nm; in the surface according to BET according to DIN 66131: 110 +20 m 2 / g; Degussa AG, Hanau), weighed in together with 1100 parts by weight of quartz sand (grain size 0.7 - 1 mm) and rubbed under water cooling for 30 minutes. The quartz sand was then separated off.
  • the clear lacquer according to the invention was produced by mixing and homogenizing the following constituents:
  • Preparation example 2 41 parts by weight of the thixotropy paste (C) from preparation example 3
  • Resimene ® BM-9539 commercially available methyl- and butyl-etherified melamine resin from Monsanto
  • Tinuvin® 384 commercially available UV absorber from Ciba Specialty Chemicals, Inc.
  • Tinuvin® 123 commercially available reversible free radical scavenger, sterically hindered amine (HALS) from Ciba Specialty Chemicals, Inc.
  • Nacure ® 5528 commercially available catalyst (sulfonic acid derivative blocked with amines) from King
  • the clearcoat was adjusted to a viscosity of 25 seconds in the DIN 4 flow cup with the mixture of the solvents mentioned. This had a solids content of 48% by weight (one hour convection oven / 130 ° C).
  • the resulting water filler layer was baked at 160 ° C. for 20 minutes, so that a filler coating with a dry layer thickness of 35 to 40 ⁇ m resulted.
  • the filler coating was then coated with a black waterborne basecoat from BASF Coatings AG in a layer thickness of 12 to 15 ⁇ m.
  • the resulting waterborne basecoats were flashed off at 80 ° C for 10 minutes.
  • the clear varnish of Example 1 was then pneumatically applied in a layer thickness of 40 to 45 ⁇ m in a cloister with a flow gun.
  • the clear lacquer layers were then flashed off for 10 minutes at room temperature and 10 minutes at 80 ° C. and baked together with the water-based lacquer layers at 140 ° C. for 20 minutes in a forced-air oven.
  • the resulting multi-layer coating was very brilliant and had a gloss (20 °) according to DIN 67530 of 91.
  • the chemical resistance was determined with the help of the gradient oven test according to DaimlerChrysler PBODDC371, which is known in the technical field.
  • the temperatures from which the applied chemicals left visible damage in the multi-layer paints were recorded. In the case of sulfuric acid, damage was only registered at 61 ° C, which underpinned the chemical resistance.

Abstract

La présente invention concerne des mélanges thixotropes thermodurcissables contenant des groupes carbamate et/ou allophanate, lesdits mélanges comprenant: (A) au moins un oligomère et/ou polymère choisi dans le groupe constitué par les oligomères et les polymères qui contiennent des groupes allophanate, des groupes carbamate ou des groupes carbamate et allophanate; (B) au moins un agent de thixotropation choisi dans le groupe constitué par l'urée ou les dérivés d'urée, produit par conversion d'au moins une amine et/ou d'eau avec au moins un polyisocyanate. Selon l'invention, les mélanges, par rapport au corps solide du mélange, comprennent de plus au moins un acide silique qui sert d'agent de thixotropation (C), et l'agent de thixotropation (B) en une quantité qui va de 0,1 à 5 % en poids, lorsque les oligomères et polymères (A) ne comprennent pas de groupes allophanate. L'invention a également pour objet un procédé pour produire les mélanges et leur utilisation comme substances de revêtement, adhésifs et masses d'étanchéification.
EP02732655A 2002-04-24 2002-04-24 Melanges thixotropes thermodurcissables contenant des groupes carbamate et/ou allophanate Withdrawn EP1497387A1 (fr)

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