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
  • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
  • C09D7/40—Additives
  • C09D7/60—Additives non-macromolecular
  • C09D7/63—Additives non-macromolecular organic
• • 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
  • C08G18/288—Compounds containing at least one heteroatom other than oxygen or nitrogen
  • C08G18/289—Compounds containing at least one heteroatom other than oxygen or nitrogen containing silicon
• • 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
  • C08G18/622—Polymers of esters of alpha-beta ethylenically unsaturated carboxylic acids
  • C08G18/6225—Polymers of esters of acrylic or methacrylic acid
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/49—Phosphorus-containing compounds
  • C08K5/51—Phosphorus bound to oxygen
  • C08K5/53—Phosphorus bound to oxygen bound to oxygen and to carbon only
  • C08K5/5317—Phosphonic compounds, e.g. R—P(:O)(OR')2
  • C08K5/5333—Esters of phosphonic acids
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/54—Silicon-containing compounds
  • C08K5/544—Silicon-containing compounds containing nitrogen
  • C08K5/5455—Silicon-containing compounds containing nitrogen containing at least one group
• • 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
  • C09D5/002—Priming paints
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/54—Silicon-containing compounds
  • C08K5/544—Silicon-containing compounds containing nitrogen
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T156/00—Adhesive bonding and miscellaneous chemical manufacture
  • Y10T156/10—Methods of surface bonding and/or assembly therefor

Definitions

• curable mixtures containing silane-containing compounds and phosphonic or Diphosphonklarediester as adhesion promoters
• the present invention relates to the novel use of curable mixtures comprising silane-containing compounds and phosphonic diesters and / or diphosphonic diesters as adhesion promoters, in particular as adhesion promoters in composites comprising at least one substrate, at least one coating, at least one adhesive layer and at least one pane.
• the present invention relates to a novel process for the preparation of novel composites, comprising at least one substrate, at least one coating, at least one adhesive layer and at least one disc, which is carried out using curable mixtures containing silane-containing compounds and phosphonic and / or Diphosphonklarediester ,
• the present invention relates to novel composites comprising at least one substrate, at least one coating, at least one adhesive layer and at least one disc, which can be produced using curable mixtures containing silane-containing compounds and phosphonic and / or Diphosphonklarediester.
• the present invention relates to novel thermally curable mixtures containing polyesters and curable mixtures containing silane-containing compounds and phosphonic and / or Diphosphonklarediester.
• Phosphonic diesters are esters of phosphonic acid [HP (O) (OH) 2 ], which is tautomeric with the phosphorous acid [P (OH) 3 ].
• the phosphonic diesters are often not correctly called secondary phosphites.
• the real derivatives are the Phosphorous acid only the triesters.
• Diphosphonic diesters are the diesters of diphosphonic acid:
• Curable mixtures in particular coating materials, especially clearcoats containing polyesters as binders, are known to be used in automotive finishing because they provide thermally cured mixtures, in particular coatings, especially clearcoats, which have surfaces with an excellent overall appearance (appearance).
• thermally cured mixtures in particular coatings, especially clearcoats, which have surfaces with an excellent overall appearance (appearance).
• composites comprising at least one substrate, at least one coating, at least one adhesive layer and at least one pane, they leave something to be desired in their adhesion effect.
• US Pat. No. 2005/0074617 describes the use of silane-containing acrylate copolymers which, in addition, may still have hydroxyl groups.
• OEM automotive OEM
• German patent applications DE 100 51 485 A1, DE 28 09 588 A or DE 25 59 259 A or the international patent application WO 2005/105938 the effect of these substances alone without additional activators is limited and is sufficient in particular for special applications in the field the polyester-containing two-component clearcoat for the automotive OEM is not enough.
• German patent application DE 10 2005 045 228.0-44 which is not prepublished, describes that silane-containing mixtures with suitable additives based on phosphonic acid derivatives can form particularly stable three-dimensional networks as reaction products. The use as a primer is not described.
• the new adhesion promoters are said to provide excellent adhesion within the coatings, such that, in the mechanical stress of composites comprising at least one substrate, at least one coating, at least one adhesive layer and at least one wafer, not between the substrate and the coating, within the Coating and between coating and adhesive layer comes, but only to a cohesive failure within the adhesive layer.
• novel adhesion promoters should permit the simple and exactly reproducible production of composites comprising at least one substrate, at least one coating, at least one adhesive layer and at least one pane.
• the new adhesion promoters should be suitable for the production of thermally curable mixtures, in particular of coating materials, especially clearcoats, which are storage-stable or have a long pot life or processing time.
• the new thermally curable mixtures, especially the coating materials, especially the clearcoats, hardened materials, especially coatings, especially clearcoats provide that are particularly hard, abrasion resistant, highly scratch resistant, particularly resistant to chemicals and etch resistant and clearcoats are particularly high gloss and clear.
• novel clearcoats in the context of multicoat paint systems should have excellent adhesion properties, so that in composites comprising at least one substrate, at least one multicoat system having at least one new clearcoat, at least one adhesive layer and at least one pane, only a cohesive failure within the mechanical load the adhesive layer comes.
• adhesion promoter which is referred to below as "inventive use”.
• the new thermally curable mixtures were found which contain a curable mixture (A / B) according to the use according to the invention and at least one thermally curable polyester (C) and which are referred to below as "mixtures according to the invention".
• the adhesion promoters to be used according to the invention caused excellent adhesion within the coatings, so that it is not at least one coating, at least one adhesive layer and at least one disc in the mechanical stress of the composites of the invention comprising at least one substrate came to an abstention between substrate and coating, within the coating and between the coating and the adhesive layer, but only to a cohesive failure within the adhesive layer.
• the mixtures according to the invention in particular the Coating materials according to the invention, especially the clearcoats according to the invention, new hardened materials, in particular new coatings, especially new clearcoats, which were particularly hard, abrasion-resistant, highly scratch-resistant, particularly resistant to chemicals and etches and clearcoats with a particularly high gloss and clarity.
• the clearcoats of the invention in the context of new multicoat paint systems had outstanding adhesion properties, so that in the composites according to the invention comprising at least one substrate, at least one multicoat system comprising at least one clearcoat according to the invention, at least one adhesive layer and at least one pane under mechanical stress only a cohesive failure occurred within the adhesive layer.
• the use according to the invention relates to the use of curable mixtures (A / B) as adhesion promoters.
• Adhesive agent is the collective term for all substances which lead to an improvement in the adhesion of materials to be combined (eg coatings on various substrates such as metal, plastic, wood, glass etc.) (see Römpp Lexikon Lacke und Druckmaschine, Georg Thieme Verlag, Stuttgart, New York, 1998, "adhesion agent”).
• the curable mixtures (A / B) to be used according to the invention essentially contain or consist of components (A) and (B).
• the curable mixtures (A / B) contain only such additional substances and these only in such an amount that the adhesion-promoting effect is not impaired.
• the additional substances can be selected from the additives (D) described below
• Preference is given to using organic solvents and stabilizers Particular preference is given to using glycols, very particularly preferably propylene glycol, butylglycol and homologues having from 5 to 10 carbon atoms in the molecule and, in particular, propylene glycol and butylglycol as stabilizers Stabilizers in an amount of 5 to 50 wt .-%, in particular 10 to 40 wt .-%, each based on a curable mixture (A / B / D) used.
• the phosphonic diesters and the diphosphonic diesters (A) are preferably selected from the group consisting of acyclic phosphonic diesters, cyclic phosphonic diesters, acyclic
• Diphosphonic diesters and cyclic diphosphonic diesters selected.
• acyclic phosphonic diesters (A) are preferably selected from the group consisting of acyclic phosphonic diesters (A) of the general formula I:
• radicals R 1 and R 2 are identical or different from one another; preferably they are the same.
• radicals R 1 and R 2 are selected from the group consisting of:
• substituted and unsubstituted 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 with 5 to 20, preferably
• alkylaryl substituted and unsubstituted alkylaryl, arylalkyl, alkylcycloalkyl,
• substituted and unsubstituted radical of the type mentioned above containing at least one, in particular a, heteroatom selected from the group consisting of oxygen atom, sulfur atom, nitrogen atom, phosphorus atom and silicon atom, in particular oxygen atom, sulfur atom and nitrogen atom, wherein the stroke is the covalent bond between a carbon atom of the rest and the oxygen atom of the OP group symbolizes;
• the cyclic phosphonic diesters (A) are preferably selected from the group consisting of the cyclic phosphonic diesters (A) of the general formula II:
• radicals R 3 and R 4 are identical or different from one another; preferably they are the same.
• radicals R 3 and R 4 are selected from the group consisting of:
• alkylaryl substituted and unsubstituted, divalent alkylaryl, arylalkyl, Alkylcycloalkyl, cycloalkylalkyl, arylcycloalkyl, cycloalkylaryl, alkylcycloalkylaryl, alkylarylcycloalkyl, arylcycloalkylalkyl, arylalkylcycloalkyl, cycloalkylalkylaryl and cycloalkylarylalkyl, wherein the alkyl, cycloalkyl and aryl groups contained herein each contain the above-mentioned number of carbon atoms and wherein each stroke is the covalent bond between a carbon atom of the
• a divalent, linking group selected from the group consisting of oxygen atom, substituted, in particular oxygen-substituted, and unsubstituted sulfur atom, substituted, in particular alkyl-substituted, nitrogen atom, substituted, in particular oxygen-substituted, phosphorus atom and substituted, in particular with alkyl and Alkoxy-substituted silicon atom, in particular oxygen atom; or
• a divalent, linking group selected from the group consisting of substituted and unsubstituted, at least one heteroatom selected from
• the acyclic diphosphonic diesters (A) are preferably selected from the group consisting of the acyclic diphosphonic diesters (A) of the general formula III:
• the cyclic diphosphonic diesters (A) are preferably selected from the group consisting of the cyclic diphosphonic diesters (A) of the general formula IV:
• Suitable substituents for the radicals R 1, R 2, R 3 and R 4 are all the groups and atoms into account, which do not impair the effect of the phosphonic diesters and diphosphonic diesters (A), do not inhibit the curing reactions in the blends of this invention, no adverse In addition to 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.
• radicals R 1 , R 2 , R 3 and R 4 are unsubstituted.
• the radicals R 1 and R 2 are selected from the group consisting of phenyl, methyl and ethyl. More preferably, phenyl is used.
• the acyclic phosphonic diesters (A) of the general formula I are preferred used.
• the radicals R 1 and R 2 of the acyclic phosphonic diesters (A) of the general formula I are particularly preferably selected from the group consisting of phenyl, methyl and ethyl. In particular, phenyl is used.
• diphenylphosphonate which is sometimes referred to by the experts (not quite correctly) as diphenyl phosphite.
• the mixtures according to the invention comprise at least one, in particular one, compound (B) containing at least two, in particular at least three, condensable silane groups.
• a basic structure is linked to at least two, in particular at least three, condensable silane groups.
• the condensable silane groups have the general formula V:
• n is an integer from 1 to 3, in particular 3;
• R 5 is a monovalent, condensable atom or monovalent, condensable, organic radical
• R 6 monovalent, inert, organic radical.
• the monovalent condensable atoms are selected from the group consisting of hydrogen atoms, fluorine atoms, chlorine atoms and bromine atoms.
• the monovalent, condensable, organic radicals R 5 from the Group consisting of hydroxyl groups and the groups of general formula VI:
• variable R 7 is a divalent linking atom or a divalent linking, functional group and R 6 has the meaning given above.
• the monovalent, inert, organic radicals R 6 are selected from the group consisting of
• alkyl preferably having 1 to 20, preferably 2 to 16 and in particular 2 to 10 carbon atoms, cycloalkyl preferably having 3 to 20, preferably 3 to 16 and in particular 3 to 10 carbon atoms and aryl preferably having 5 to 20, preferably 6 to 14 and especially 6 to 10 carbon atoms;
• alkylaryl monovalent, substituted and unsubstituted alkylaryl, arylalkyl, alkylcycloalkyl, cycloalkylalkyl, arylcycloalkyl, cycloalkylaryl, alkylcycloalkylaryl, alkylarylcycloalkyl, arylcycloalkylalkyl, arylalkylcycloalkyl, cycloalkylalkylaryl and cycloalkylarylalkyl, wherein the alkyl, cycloalkyl and aryl groups contained herein preferably each contain the above-mentioned number of carbon atoms; and
• Phosphorus atom and silicon atom in particular oxygen atom, sulfur atom and nitrogen atom;
• the divalent, linking atoms R 7 are selected from the group consisting of oxygen atoms and sulfur atoms, in particular oxygen atoms.
• the divalent atoms R 8 are selected from the group consisting of oxygen atoms and sulfur atoms, in particular oxygen atoms.
• the divalent, linking atoms R 7 are used.
• silane groups of general formula V are selected from the group consisting of trimethoxysilyl and triethoxysilyl groups.
• the compounds (B) may be monomeric, oligomeric or polymeric, d. h., They may have a monomeric, an oligomeric or a polymeric basic structure.
• “Monomer” means that the relevant compound (B) or its basic structure consists essentially of one structural unit or of two structural units which may be the same or different.
• Olemer means that the relevant compound (B) or its basic structure is built up on a statistical average of 3 to 12 monomeric structural units, which may be the same or different.
• Polymer means that the relevant compound (B) or its basic structure is built up on a statistical average of at least 8 monomeric structural units which may be identical or different from each other:
• a compound (B) or its basic structure which is built up 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 such a compound (B) or basic structure. If the molecular weights are comparatively high, one will speak of a polymer, they are comparatively low, from an oligomer.
• the monomeric basic structures of the compounds (B) are derived from customary and known, low molecular weight, organic compounds.
• the oligomeric and polymeric basic structures of the compounds (B) are preferably derived from the customary and known, organic and organometallic oligomers and polymers. These 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 compound (B).
• the structures may have a statistical and / or block-shaped distribution of the monomeric structural units.
• the oligomeric and polymeric basic structures of the compounds (B) are preferably derived from the customary and known oligomers and polymers obtainable by free-radical, anionic or cationic polymerization of olefinically or acetylenically, preferably olefinically, unsaturated monomers, oligomers and polymers preparable by polycondensation or by polyaddition Oligomers and polymers from.
• the oligomeric and polymeric basic structures of the compounds (B) are particularly preferably derived from the customary and known polyolefins, polystyrenes, polyacrylonitriles, (meth) acrylate (co) polymers, polyesters, polyamides,
• the basic structures of the compounds (B) particularly preferably contain at least one group and in particular at least two groups selected from the group consisting of the groups of the general formulas (VII 1), (VII 2) and (VII 3):
• n 0 or 1
• o 1, 2 or 3;
• R 10 in the first alternative group -NH-, with the proviso that
• Bonds are linked to the radicals R 14 or R 14 and R 13 ;
• R 13 monovalent, inert, organic radical R 6 or group of the general formula VIII:
• R 14 is at least divalent, inert, organic radical
• the at least monovalent radicals R 9 are selected from the group consisting of at least monovalent, substituted and unsubstituted alkyl preferably having 1 to 20, preferably 2 to 16 and in particular 2 to 10 carbon atoms, cycloalkyl preferably having 3 to 20, preferably 3 to 16 and in particular 3 to 10 carbon atoms and aryl preferably having 5 to 20 , preferably 6 to 14 and especially 6 to 10 carbon atoms;
• alkylaryl at least monovalent, substituted and unsubstituted alkylaryl, arylalkyl, alkylcycloalkyl, cycloalkylalkyl, arylcycloalkyl, cycloalkylaryl, alkylcycloalkylaryl, alkylarylcycloalkyl, arylcycloalkylalkyl, arylalky ⁇ cycloalkyl, cycloalkylalkylaryl and
• Cycloalkylarylalkyl wherein the alkyl, cycloalkyl and aryl groups contained herein preferably each contain the above-mentioned number of carbon atoms;
• radicals R 12 are selected from the group consisting of trivalent
• the at least divalent, in particular divalent, radicals R 14 are selected from the group consisting of
• alkyl preferably having 1 to 20, preferably 2 to 16 and especially 2 to 10 carbon atoms, cycloalkyl preferably having 3 to 20, preferably 3 to 16 and especially 3 to 10 carbon atoms and aryl preferably having 5 to 20 , preferably 6 to 14 and especially 6 to 10 carbon atoms;
• alkylaryl at least divalent, substituted and unsubstituted alkylaryl, arylalkyl, alkylcycloalkyl, cycloalkylalkyl, arylcycloalkyl, cycloalkylaryl, alkylcycloalkylaryl, alkylarylcycloalkyl, arylcycloalkylalkyl, arylalkylcycloalkyl, cycloalkylalkylaryl and cycloalkylarylalkyl, wherein the alkyl, cycloalkyl and aryl groups herein preferably each contain the number of carbon atoms listed above ; and
• At least divalent, 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, nitrogen atom, phosphorus atom and silicon atom, in particular oxygen atom, sulfur atom and nitrogen atom;
• the compounds (B) described above can be prepared by the conventional and known methods of organosilicon chemistry.
• they can be produced by
• the first alternative (a) is used.
• Monoisocyanates such as ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, lauryl, cyclohexyl or phenyl isocyanate;
• 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-2,4-di (isocyanato-methyl) benzene, 1, 5- Di-methyl-2,4-di (isocyanatoethyl) benzene, 1, 3,5-trimethyl-2,4-di (isocyanatomethyl) benzene, 1, 3,5-triethyl-2,4-di (isocyanatomethyl) -benz
• Isophorone diisocyanate dicyclohexyldimethylmethane-4,4'-diisocyanate, 2,4-
• Tolylene diisocyanate 2,6-tolylene diisocyanate, diphenylmethane-4,4'-diisocyanate;
• Polyisocyanates such as triisocyanates such as nonane triisocyanate (NTI) and polyisocyanates based on the diisocyanates and triisocyanates described above, in particular oligomers containing isocyanurate, biuret, allophanate, iminooxadiazinedione, urethane, carbodiimide, urea and / or uretdione for example from patents and patent applications CA 2,163,591 A 1,
• Examples of suitable compounds of general formula XI are N, N-bis (3-trimethoxysilylpropan-1-yl) amine, N, N-bis (3-triethoxysilylpropan-1-yl) amine, N- (3-trimethoxysilylpropan-1-yl ) -Nn-butylamine or N- (3-triethoxysilylpropan-1-yl) -Nn-butylamine.
• Examples of suitable compounds of general formula XII are the customary and known, aliphatic, cycloaliphatic, aromatic, aliphatic-cycloaliphatic, aliphatic-aromatic or aliphatic-cycloaliphatic-aromatic, at least one hydroxyl group, at least one thiol group and / or? at least one primary and / or secondary amino group-containing alcohols, thiols, thio alcohols, phenols, amines, amino alcohols, aminothiols or Aminothioalkohole.
• Examples of suitable compounds of general formula XIII are 3-trimethoxysilylpropane-1-yl-isocyanate or 3-triethoxysilylpropane-1-yl-isocyanate.
• the content of the curable mixtures (A / B) to be used according to the invention of phosphonic diesters and / or diphosphonic diesters (A) can vary very widely and depends on the requirements of the individual case, so that it can be optimally adapted to them.
• the content of the curable mixtures (A / B) to be used according to the invention in compounds (B) can vary very widely and can be optimally adapted to the requirements of the individual case.
• the solid is equal to the sum of all components of a curable mixture (A / B), which form the nonvolatile residue after the removal of the volatile constituents, for example a hardened material.
• the curable mixtures (A / B)) can be used in the context of the use according to the invention for improving the adhesion between a wide variety of materials.
• they are used as adhesion promoters in the composites according to the invention, comprising at least one substrate, at least one coating, at least one adhesive layer and at least one pane.
• slice is a planar, substantially planar, or three-dimensionally shaped, optically transparent, d. H.
• d. H Preferably understood for visible Lcht permeable, especially clear, optionally tinted molding, which may consist of a variety of materials, in particular of plastic or glass.
• the molded parts are laminated glass panes.
• the laminated glass panes are used in particular in the windows of locomotion means, preferably motorized road vehicles, preferably passenger cars.
• the adhesive layer For the production of the adhesive layer, a wide variety of adhesives can be used. Examples of suitable adhesives, their application forms and the methods for their curing are known from German patent DE 102 02 819 C1, page 5, paragraphs [0058] and [0059].
• the adhesives are preferably moisture-curing.
• the adhesives contain polyisocyanates.
• the coating is preferably a coating which consists of a Layer or consists of at least two layers.
• the coating is preferably a multicoat system, in particular a multicoat system, as is customarily used in automotive OEM finishing (cf, German Patent Application DE 199 38 758 A1, page 10, line 65, to page 12, line 51, and DE 199 48 004 A1, page 17, line 37, to page 19, line 22).
• the substrate may be made of any suitable material.
• the substrate is made of a material selected from the group consisting of metals, glasses, plastics, natural or artificial minerals, ceramics, concrete, cement, clay, wood, paper, leather, textile and composites of these materials, in particular of metals and plastics.
• the substrate is a motor vehicle body or a part thereof.
• the adhesion promoter to be used according to the invention is present in the coating according to the invention in the coating. If the coating is a multi-layer coating, the adhesion promoter is preferably present in the layer which directly adjoins the adhesive layer.
• the composite according to the invention can be prepared by means of customary and known processes. Preferably, it is prepared by the process according to the invention by
• the coating material layer is cured by itself or together with at least one layer of another coating material underneath, thereby resulting in a coating
• curable mixtures (A / B), substrates and adhesives are those described above.
• the coating material is preferably a conventional coating material based on organic solvents, an aqueous coating material, a substantially or completely anhydrous and solvent-free liquid coating material (100% system) or finely divided solid coating material (powder coating) or an aqueous suspension of finely divided, solid particles ( Powder slurry), preferably a conventional coating material based on organic solvents, in particular a conventional coating material which can be produced from a multicomponent system, in particular a two-component system.
• the coating material is a clearcoat and the coating is a clearcoat. Examples of suitable coating materials of this type and the methods for their application and curing are known from German patent DE 102 02 819 C1, page 4, paragraph [0040], to page 5, paragraph [0055].
• the layers of the other coating materials are preferably selected from the group consisting of primers, electrodeposition coating layers, surfacer basecoats, preferably primers, electrodeposition coating layers, primer surfacer primer surfacers, as are customarily used for the production of multilayer automotive OEM finishes.
• the coatings made from layers of the other coating materials are selected from the group consisting of primers, electrocoats, surfacers or antistonechip primers, and basecoats.
• the mixture according to the invention contains one of the curable ones described above Mixtures (A / B) and at least one thermally curable polyester (C).
• the thermally curable polyester (C) is hydrophobic (see Rompp Lexikon Lacke and printing inks, Georg Thieme Verlag, Stuttgart, New York, 1998, "hydrophobicity") and contains hydroxyl groups as reactive functional groups for thermal curing.
• polyesters (C) are customary and known compounds and can be prepared by the usual and known polycondensation of the starting materials commonly used. Examples of suitable starting materials are known from German patent application DE 199 48 004 A1, page 5, line 11, to page 6, line 21.
• mixtures according to the invention may additionally contain at least one additive (D) which is different from the constituents (A), (B) and (C) described above.
• the additive (D) is selected from the group consisting of reactive and inert, oligomeric and polymeric, film-forming binders; Crosslinking agents; reactive and inert, organic and inorganic solvents; with actinic radiation, in particular UV 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; stabilizers; UV absorbers; Light stabilizers; Radical scavengers; Photoinitiators; Initiators of radical polymerization; Driers; Venting means; slip additives; polymerization inhibitors; defoamers; Emulsifiers and wetting agents; Adhesion promoters; Leveling agents; Coalescing agents; rheology-controlling additives and flame retardants selected.
• actinic radiation in particular UV radiation, activatable compounds
• the additive (D) is selected from the group consisting of thermally curable, oligomeric and polymeric film-forming binders and crosslinking agents.
• the solids content of the mixtures according to the invention can vary very widely and can therefore be optimally adapted to the requirements of the individual case.
• the solids content may be 100% by weight, ie, the mixture according to the invention contains no volatile Components that escape during thermal curing. If such volatile constituents are present, the solids content, in each case based on the mixture according to the invention, is preferably from 20 to 80% by weight, preferably from 25 to 70% by weight and in particular from 30 to 65% by weight.
• the content of the mixture of the curable mixture (A / B) according to the invention can vary widely and therefore be perfectly adapted to the requirements of the individual case.
• the mixture according to the invention preferably contains from 0.1 to 10% by weight, in particular from 0.5 to 8% by weight, based in each case on the solids of the mixture according to the invention, of the curable mixtures (A / B).
• the content of the mixture according to the invention on the polyester (C) can vary widely and therefore also be perfectly adapted to the requirements of the individual case.
• the mixture according to the invention preferably contains from 1 to 40% by weight, in particular from 2 to 30% by weight, based in each case on the solids of the mixture according to the invention, of polyester (C).
• the mixtures according to the invention are anhydrous. This means that at most they contain traces of water which are inadvertently introduced during their preparation via the constituents and / or during their production and / or handling via the atmospheric moisture.
• the water content is below the detection limits of the usual and known, qualitative and quantitative methods of water determination.
• the preparation of the mixtures according to the invention has no special features, but takes place by mixing and homogenizing the constituents described above by means of customary and known mixing methods and
• Dissolvers static mixers, micromixers, sprocket dispersers,
• Pressure relief nozzles and / or Microfluidizer optionally with the exclusion of actinic radiation.
• the mixtures according to the invention can serve numerous uses, such as the production of coatings, adhesive layers, gaskets, molded parts and films. In particular, they are used in the context of the process according to the invention for the production of clearcoats of multicoat paint systems.
• the mixtures according to the invention are applied to the substrates described above.
• 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 any solvent present.
• the ventilation can be accelerated by an elevated temperature, which is not sufficient for curing, and / or by a reduced humidity.
• 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 circulating air 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 180 0 C and in particular from room temperature to 160 0 C.
• the thermal curing can be supported by additional curing methods, including, where appropriate, the usual and known devices, such as for curing be used with actinic radiation, in particular UV radiation.
• the composite according to the invention in particular the composite according to the invention, which is produced by means of the process according to the invention, especially the composite according to the invention, which is produced by means of the process according to the invention using the mixture according to the invention has numerous advantages.
• its performance properties are largely independent of the conditions prevailing in its production conditions, especially as regards temperature and humidity. It is also durable under extreme conditions and suffers no damage, such as cracks or delaminations.
• the composite according to the invention is stable even at high and low temperatures, high and low humidity and rapidly changing conditions between these extremes, as prevail in the tropical climate and desert climate, high radiation intensity and intensive mechanical and chemical stress and suffers no damage , It is therefore particularly suitable as a component of motor vehicle bodies, in particular of bodies of commercial vehicles and cars. Because of its particularly high quality, it is suitable above all as a component of passenger cars of the upper class.
• base stocks 1 and 2 were prepared by mixing the constituents listed in Table 1 and homogenizing the resulting mixtures.
• Methacrylate copolymer (D) according to
• Tinuvin® 5248 (light stabilizer D of the
• Adhesive 1 according to Preparation Example 3 - 2.5
• the clearcoats 1 (Example 1) or 2 (Example 2) were obtained by mixing in each case 100 parts by weight of the masterbatches 1 or 2 with 33 parts by weight of a hardener solution consisting of 89.6% by weight of a commercially available polyisocyanate (Basonat Hl 190 from BASF Aktiengesellschaft), 5.2% by weight of butyl acetate and 5.2% by weight of Solventnaphtha®, and homogenizing the resulting mixtures.
• a hardener solution consisting of 89.6% by weight of a commercially available polyisocyanate (Basonat Hl 190 from BASF Aktiengesellschaft), 5.2% by weight of butyl acetate and 5.2% by weight of Solventnaphtha®, and homogenizing the resulting mixtures.
• the clearcoats 1 and 2 were applied to test panels, each with a conventional and well-known, cathodically deposited and thermally cured electrodeposition coating, a conventional and known, thermally cured surfacer and a 10 min at 8O 0 C pre-dried layer of a commercially available black water-based paint BASF Coatings AG were applied, applied.
• the basecoat films and the clearcoat films were each cured together. The following conditions were applied:
• the resulting basecoats each had a layer thickness of 7.5 microns and the Klariackmaschineen a layer thickness of 40 microns.
• the resulting multicoat systems 1 (Example 1) and 2 (Example 2) were highly lustrous and had an excellent overall appearance (appearance).
• the disc adhesion was determined as follows. Adhesive strips were applied on all the test panels across the narrow side.
• a commercial disk adhesive (EFTEC DA 300 from EFTEC, Switzerland) in a width of 10 mm and a length of 150 mm was applied in a caterpillar shape with a triangular nozzle.
• the caterpillars were allowed to dry for one minute under normal climatic conditions. Subsequently, the caterpillars were transferred to the test panels.
• Each end of a bead was placed on the adhesive tape, so that after curing the beads were easy to grasp with a pair of needle nose pliers and could be deducted to carry out the peel adhesion test. After applying the beads were placed on both sides of the caterpillar spacers. Bonding sheets were placed on the polyethylene film backs and spacers.
• the beads were adjusted to a layer thickness of 5 mm.
• the polyethylene films and the bond panels remained for seven days at 23 ° C and 50% relative humidity in Normtierraum for curing. After seven days, the polyethylene films and the bondboards were removed.
• the cured caterpillars were grasped 'head', ie, where they rested on the adhesive tape with a pair of needle-nose pliers and peeled off the adhesive surface at an angle of 90 ° After each 10 mm take-off length, the material was cut in the fracture zone with a knife Surface of the clearcoats trimmed and then further deducted.
• the interfaces were assessed visually. It is crucial that as complete as possible a cohesive break occurred in the caterpillar, corresponding to a complete adhesion of the caterpillar on the multi-layer coating.
• the liability was graded as follows:
• the glass bonding (3 x 20 min at 14O 0 C and 30 min at 160 0 C) was found to overbaking and subsequent aging for 2 weeks, a score of each of 3, whereas the corresponding results of the formulations on the basis of the millbases 1 and 2 were rated 5 as described. This underpinned the surprisingly high influence of the diphenyl phosphite on the pane bonding.

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

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• 2006
  • 2006-05-29 DE DE200610024823 patent/DE102006024823A1/de not_active Withdrawn
• 2007
  • 2007-01-26 WO PCT/EP2007/000660 patent/WO2007137632A1/de not_active Ceased
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