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WO2001083578A1 - Matieres a plusieurs composants pour l'enduction, le collage et l'etancheification, et leur utilisation - Google Patents

Matieres a plusieurs composants pour l'enduction, le collage et l'etancheification, et leur utilisation Download PDF

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Publication number
WO2001083578A1
WO2001083578A1 PCT/EP2001/004698 EP0104698W WO0183578A1 WO 2001083578 A1 WO2001083578 A1 WO 2001083578A1 EP 0104698 W EP0104698 W EP 0104698W WO 0183578 A1 WO0183578 A1 WO 0183578A1
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WO
WIPO (PCT)
Prior art keywords
isocyanate
adhesives
groups
coating materials
component coating
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.)
Ceased
Application number
PCT/EP2001/004698
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German (de)
English (en)
Inventor
Hubert Baumgart
Heinz-Peter Rink
Simone Bitter
Edeltraut Hagemeister
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BASF Coatings GmbH
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BASF Coatings GmbH
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Publication date
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Priority to AU58371/01A priority Critical patent/AU5837101A/en
Publication of WO2001083578A1 publication Critical patent/WO2001083578A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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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
    • C08G18/28—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
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/4291—Polycondensates having carboxylic or carbonic ester groups in the main chain prepared from polyester forming components containing monoepoxy 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
    • C08G18/2805—Compounds having only one group containing active hydrogen
    • C08G18/285—Nitrogen containing compounds
    • C08G18/2875—Monohydroxy compounds containing tertiary amino 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
    • C08G18/622—Polymers of esters of alpha-beta ethylenically unsaturated carboxylic acids
    • C08G18/6225—Polymers of esters of acrylic or methacrylic acid
    • C08G18/6229—Polymers of hydroxy groups containing esters of acrylic or methacrylic acid with aliphatic polyalcohols
    • 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 multi-component coating materials, adhesives and sealing compounds.
  • the present invention relates to the use of the new multi-component coating materials for the production of new clearcoats or color and effect-giving solid-color topcoats, base coats and multi-coat coats in automotive OEM painting and refinishing, painting indoor and outdoor structures, furniture, window and Door painting as well as industrial painting, including coil coating, container coating and the impregnation of electrical components.
  • the present invention relates to the use of the new multi-component adhesives and sealants for the production of new adhesive layers and seals, in particular in the fields of application listed above.
  • Two-component coating materials which - generally reactive components with isocyanate-reactive functional groups, customary and known polyisocyanates and adducts of diisocyanates and dioxolanes, dioxanes or oxazolidines, which have an isocyanate-reactive functional group, in a molar ratio of 1: 1, are known from German patent application DE 196 09 617 A 1 known.
  • the reactive components inter alia are hydroxy-functional polymers with a hydroxyl group content of 0.1 to 20% by weight (corresponding to 33 to 660 mg KOH / g) ,
  • the number average molecular weight of the polymers is preferably 1,000 to 100,000.
  • the polymers preferably contain more than 50 wt .-% C ⁇ Ca ö -Alky metl jacrylat, vinylaromatics having up to 20 Carbon atoms, vinyl esters of carboxylic acids containing up to 20 carbon atoms, vinyl halides, non-aromatic hydrocarbons with 4 to 8 carbon atoms and 1 or 2 double bonds, unsaturated nitriles and mixtures thereof.
  • Polymers are preferred which contain up to 60% by weight of C 1 -C 8 alkyl (meth) acrylates, styrene or mixtures thereof.
  • the polymers contain hydroxy-functional monomers, corresponding to the above hydroxyl group content, as well as other monomers such as unsaturated acids not specified, in particular carboxylic acids, acid anhydrides or acid amides.
  • the two-component coating materials known from DE 19609617 A 1 are, however, not as widely applicable as would actually be desirable.
  • their service life i.e. the time within which they can be processed without any problems after the two components have been mixed and deliver perfect coatings can be extended even further.
  • the object of the present invention is to further develop the known multicomponent coating materials while fully maintaining the property profile already achieved, so that new advantageous multicomponent coating materials result which have a high solids content with low viscosity and a long service life, and coatings, in particular clearcoats and color and or effect-giving solid-color coatings, Deliver basecoats and multi-coat paints that, in addition to high hardness, flexibility and chemical resistance, also have an excellent flow, very good interlayer adhesion, an excellent overall optical impression, very good weather resistance, very high scratch resistance and very good polishability.
  • the object of the present invention to further develop the previously known two-component adhesives and sealants, so that new multicomponent adhesives and sealants with a high solids content at low viscosity and a long service life result, the adhesive layers of particularly high adhesive strength and seals of particularly high sealability also deliver to chemically aggressive substances. Accordingly, the new multi-component coating materials, adhesives and sealants have been found to contain
  • At least one liquid mixture of at least one (co) polymer and at least one thermally curable reactive diluent can be prepared by at least one olefinically unsaturated monomer (al) with at least one isocyanate-reactive functional group in at least one thermally curable reactive diluent with at least two isocyanate-reactive functional parts Groups (co) polymerized,
  • R 3 alkylene radical having 1 to 5 carbon atoms
  • R 4 and R 5 independently of one another hydrogen atoms, isocyanate-reactive functional groups or
  • a radical R 4 , R. 5 or R 6 contains an isocyanate-reactive functional group or a radical R 4 or R 5 is an isocyanate-reactive functional group, the other radicals R 4 , R 5 or R 6 - if present - have no isocyanate-reactive functional groups;
  • the new multi-component coating materials, adhesives and sealing compounds are referred to below as "coating materials, adhesives and sealing compounds according to the invention".
  • coating materials adhesives and sealing compounds according to the invention.
  • the new process for producing a clearcoat by applying a clearcoat to a primed or unprimed substrate or a paint thereon was found, in which the coating material according to the invention is used as clearcoat.
  • a pigmented and a non-pigmented coating material according to the invention is used as the basecoat and as the clearcoat.
  • the coating materials, adhesives and sealants according to the invention are multi-component systems. This means that their highly reactive Ingredients divided into several components, which in themselves are stable in storage, are available and are only added comparatively shortly before use.
  • “comparatively short” means a period of 1 minute to 24 hours
  • “storage-stable” means that the component in question can be stored for at least 24 hours, preferably at least one week, without decomposition and or premature crosslinking.
  • the constituents are preferably present in two components, the binders and, if appropriate, the reactive diluents in one component and the crosslinking agents in the other component.
  • the first component of the coating materials, adhesives and sealants according to the invention is the liquid, (co) polymer-containing, i.e. binder-containing mixture (A).
  • the liquid mixture (A) to be used according to the invention can be obtained by at least one olefinically unsaturated monomer (al) which contains at least one, preferably one, isocyanate-reactive functional group in at least one thermally curable reactive diluent, which has at least two, preferably two, isocyanate-reactive contains functional groups, (co) polymerized, preferably radical (co) polymerized.
  • Suitable isocyanate-reactive functional groups are hydroxyl groups, thiol groups or primary or secondary amino groups, in particular hydroxyl groups.
  • Suitable olefinically unsaturated monomers (al) with an isocyanate-reactive functional group are hydroxyl group, thiol group and / or amine group-containing, preferably hydroxyl group and / or amine group-containing, especially hydroxyl group-containing monomers (al) such as Hydroxyalkyl esters of acrylic acid, methacrylic acid or another alpha, beta-ethylenically unsaturated carboxylic acid which (i) are derived from an alkylene glycol which is esterified with the acid, or (ii) can be obtained by reacting the acid with an alkylene oxide such as ethylene oxide or propylene oxide , in particular hydroxyalkyl esters
  • Acrylic acid methacrylic acid, crotonic acid or ethacrylic acid in which the hydroxyalkyl group contains up to 20 carbon atoms, such as 2-hydroxyethyl, 3-hydroxypropyl, 3-hydroxybutyl, 4-
  • higher-functional monomers (a1) are generally used only in minor amounts.
  • minor amounts of higher-functional monomers (a1) are to be understood as amounts which do not lead to crosslinking or gelling of the copolymers, unless they are intended to be in the form of crosslinked microgel particles;
  • Chemicals is sold, or 2-hydroxyalkyl allyl ether, especially 2-hydroxyethyl allyl ether; if used, they are preferably not used as sole monomers (al), but in an amount of 0.1 to 10% by weight, based on the (meth) acrylate copolymer (A); Reaction products from acrylic acid and / or methacrylic acid with the glycidyl ester of a monocarboxylic acid with 5 to 18 carbon atoms per molecule branched in the alpha position, in particular one Versatic® acid, or instead of the reaction products, an equivalent amount of acrylic and / or methacrylic acid, which then during or after
  • the monomer (al) or the monomers (al) are preferably chosen such that (meth) acrylate (co) polymers, in particular
  • the profile of properties of the (co) polymers and thus also that of the liquid mixtures (A) to be used according to the invention advantageously varied widely and can be optimally adapted to the respective purpose.
  • Essentially acid group-free (meth) acrylic esters such as (meth) acrylic or alkyl cycloalkyl esters with up to 20 carbon atoms in the alkyl radical, in particular methyl, ethyl, propyl, n-butyl, sec-butyl, tert-butyl, Hexyl, ethylhexyl, stearyl and lauryl acrylate or methacrylate; cycloaliphatic (meth) acrylic acid esters, in particular cyclohexyl, isobornyl, dicyclopentadienyl, octahydro-4,7-methano-1H-indene methanol or tert-butylcyclohexyl (meth) acrylate; (Meth) acrylic acid oxaalkyl esters or oxacycloalkyl esters such as ethoxytriglycol (meth) acrylate and methoxyoligoglycol
  • Acrylic acid and / or methacrylic acid are particularly preferably used as component (a22).
  • other ethylenically unsaturated carboxylic acids with up to 6 carbon atoms in the molecule can also be used. Examples of such acids are ethacrylic acid, crotonic acid, maleic acid, fumaric acid and itaconic acid.
  • ethylenically unsaturated sulfonic or phosphonic acids or their partial esters can be used as component (a22).
  • Monomers (a22) furthermore include maleic acid mono (meth) acryloyloxyethyl ester, succinic acid mono (meth) acryloyloxyethyl ester and phthalic acid mono (meth) acryloyloxyethyl ester as well as vinylbenzoic acid (all isomers), alpha-methylvinylbenzoic acid (all isomers) or
  • Vinylbenzenesulfonic acid (all isomers). Further examples of monomers containing acid groups (a22) are known from published patent application DE 196 25 773 A1, column 2, line 58 to column 3, line 8, or from international patent application WO 98/49205, page 3, lines 23 to 34
  • the branched monocarboxylic acids can be obtained by reacting formic acid or carbon monoxide and water with olefins in the presence of a liquid, strongly acidic catalyst; the olefins can be cracked products of paraffinic hydrocarbons, such as mineral oil fractions, and can contain both branched and straight-chain acyclic and / or cycloaliphatic olefins.
  • paraffinic hydrocarbons such as mineral oil fractions
  • a mixture of carboxylic acids is formed in which the carboxyl groups are predominantly located on a quaternary carbon atom.
  • olefinic starting materials are, for example, propylene trimer, propylene tetramer and diisobutylene.
  • the vinyl esters can also be prepared from the acids in a manner known per se, for example, by allowing the acid to react with acetylene. Because of the good availability, vinyl esters of saturated aliphatic monocarboxylic acids having 9 to 11 carbon atoms which are branched on the alpha carbon atom are particularly preferably used. Vinyl esters of this type are sold under the VeoVa® brand (see also Römpp Lexikon Lacke und Druckmaschine, Georg Thieme Verlag, Stuttgart, New York, 1998, page 598).
  • Diarylethylenes in particular those of the general formula VII:
  • radicals R 13 , R 14 , R 15 and R 16 each independently represent hydrogen atoms or substituted or unsubstituted alkyl, cycloalkyl, alkylcycloalkyl, cycloalkylalkyl, aryl, alkylaryl, cycloalkylaryl, arylalkyl or arylcycloalkyl radicals with the proviso that at least two of the variables R 13 , R 14 , R 15 and R 16 are substituted or unsubstituted aryl, arylalkyl or arylcycloalkyl radicals, in particular substituted or unsubstituted aryl residues.
  • alkyl radicals examples include methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl, amyl, hexyl or 2-ethylhexyl.
  • suitable cycloalkyl radicals are cyclobutyl, cyclopentyl or cyclohexyl.
  • suitable alkylcycloalkyl radicals are methylenecyclohexane, ethylenecyclohexane or propane-1,3-diylcyclohexane.
  • Suitable cycloalkylalkyl radicals are 2-, 3- or 4-methyl-, ethyl-, propyl- or butylcyclohex-1-yl.
  • suitable aryl radicals are phenyl, naphthyl or biphenylyl, preferably phenyl and naphthyl and in particular phenyl.
  • suitable alkylaryl radicals are benzyl or ethylene or propane-1,3-diyl-benzene.
  • suitable cycloalkylaryl radicals are 2-, 3- or 4-phenylcyclohex-l-yl.
  • Suitable arylalkyl radicals are 2-, 3- or 4-methyl-, ethyl-, propyl- or butylphen-1-yl.
  • suitable arylcycloalkyl radicals are 2-, 3- or 4-cyclohexylphen-l-yl.
  • the aryl radicals R 13 , R 14 , R 15 and / or R 16 are preferably phenyl or naphthyl radicals, in particular phenyl radicals.
  • the substituents optionally present in the radicals R 13 , R 14 , R 15 and / or R ] 6 are electron-withdrawing or electron-donating atoms or organic radicals, in particular halogen atoms, nitrile, nitro, partially or fully halogenated alkyl, cycloalkyl, alkylcycloalkyl -, Cycloalkylalkyl, aryl, alkylaryl, cycloalkylaryl, arylalkyl and arylcycloalkyl radicals; Aryloxy, alkyloxy and cycloalkyloxy radicals; Arylthio, alkylthio and cycloalkylthio residues and / or primary, secondary and / or tertiary amino groups.
  • the monomers (a25) are used in order to regulate the copolymerization advantageously in such a way that a free-radical copolymerization in batch mode is also possible. If they have isoeyanate-reactive functional groups, they can also act as monomers (al).
  • Cyclic and / or acyclic olefins such as ethylene, propylene, but-1-ene, pent-1-ene, hex-1-ene, cyclohexene, cyclopentene, norbornene, butadiene, isoprene, cyclopentadiene and / or dicyclopentadiene.
  • Monido-containing monomers such as (meth) acrylic acid amides such as
  • (Meth) acrylic acid amide N-methyl, N, N-dimethyl, N-ethyl, N, N-diethyl, N-propyl, N, N-dipropyl, N-butyl, N, N- Dibutyl-, N-cyclohexyl-, N, N-cyclohexyl-methyl- and / or N-methylol-, N, N-dimethylol-, N-methoxymethyl-, N, N-di (methoxymethyl) -, N-ethoxymethyl- and / or N, N-di (ethoxyethyl) - (meth) acrylic acid amide; monomers containing carbamate groups such as
  • Monomers containing epoxy groups such as the glycidyl ester of acrylic acid, methacrylic acid, ethacrylic acid, crotonic acid, maleic acid, fumaric acid and / or itaconic acid.
  • Vinylaromatic hydrocarbons such as styrene, vinyltoluene, diphenylethylene or alpha-alkylstyrenes, especially alpha-methylstyrene;
  • Nitriles such as acrylonitrile and / or methacrylonitrile
  • Vinyl compounds especially vinyl and / or vinylidene dihalides such as vinyl chloride, vinyl fluoride, vinylidene dichloride or vinylidene difluoride; N-vinylamides such as vinyl-N-methylformamide, N-vinylcaprolactam or N-vinylpyrrolidone; 1-vinylimidazole; Vinyl ethers such as ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, isobutyl vinyl ether and / or vinylcyclohexyl ether; and / or vinyl esters such as vinyl acetate, vinyl propionate, vinyl butyrate, vinyl pivalate and / or the vinyl ester of 2-methyl-2-ethylheptanoic acid.
  • vinyl ethers such as ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether,
  • Allyl compounds especially allyl ethers and esters such as allyl methyl, ethyl, propyl or butyl ether or allyl acetate, propionate or butyrate.
  • Monomers (a213) polysiloxane macromonomers which have a number average molecular weight Mn of 1,000 to 40,000 and an average of 0.5 to 2.5 ethylenically unsaturated double bonds per molecule; in particular
  • Polysiloxane macromonomers which have a number average molecular weight Mn of 2,000 to 20,000, particularly preferably 2,500 to 10,000 and in particular 3,000 to 7,000 and on average 0.5 to 2.5, preferably 0.5 to 1.5, ethylenically unsaturated double bonds per molecule, such as it in DE 38 07 571 A1 on pages 5 to 7, DE 37 06 095 A1 in columns 3 to 7, EP 0 358 153 B1 on pages 3 to 6, in US 4,754,014 A1 in columns 5 to 9, in DE 44 21 823 A1 or in international patent application WO 92/22615 on page 12, line 18 to page 18, line 10.
  • hydroxyl-containing (meth) acrylate (co) polymers result which have an OH number of 40 to 240, preferably 60 to 210, acid numbers of 0 to 80, preferably 0 to 50, very particularly preferably 3.9 to 15.5, glass transition temperatures from -35 to +70
  • the monomers (a2) which contain reactive functional groups which are not isocyanate-reactive are selected by type and amount so that they crosslink the reactions of the isocyanate-reactive functional groups with the adducts (B) and / or crosslinking agents (D) described below in do not inhibit or completely prevent the second component.
  • the production of the (co) polymers to be used according to the invention has no special procedural features, but is carried out using the methods of continuous or discontinuous copolymerization which are customary and known in the plastics field, in particular those initiated by free radicals Copolymerization, in solution under normal pressure or overpressure in stirred tanks, autoclaves, tube reactors, loop reactors or Taylor reactors at temperatures from 50 to 200 ° C.
  • Suitable free-radical initiators are dialkyl peroxides, such as di-tert-butyl peroxide or dicumyl peroxide; Hydroperoxides, such as cumene hydroperoxide or tert-butyl hydroperoxide; Peresters, such as tert-butyl perbenzoate, tert-butyl perpivalate, tert-butyl per-3,5,5-trimethyl hexanoate or tert-butyl per-2-ethyl hexanoate; peroxodicarbonates; Potassium, sodium or
  • ammonium peroxodisulfate ammonium peroxodisulfate
  • Azo initiators for example azo dinitriles such as azobisisobutyronitrile
  • CC-cleaving initiators such as benzpinacol silyl ether
  • a combination of a non-oxidizing initiator with hydrogen peroxide can also be used. Further examples of suitable initiators are described in German patent application DE 196 28 142 A1, page 3, line 49, to page 4, line 6.
  • Comparatively large amounts of free-radical initiator are preferably added, the proportion of the initiator in the reaction mixture, based in each case on the total amount of the monomers (a) and the initiator, particularly preferably 0.2 to 20% by weight, very particularly preferably 0.5 is up to 15 wt .-% and in particular 1.0 to 10 wt .-%.
  • the resulting (co) polymers especially the (meth) acrylate copolymers, selected by type and quantity that the inventive coating materials adhesives, and sealing compounds after curing has a storage modulus E 'in the rubber-elastic range of at least l ⁇ 7 5 6 p a and d have a loss factor tan ⁇ at 20 ° C of a maximum of 0.10, the memory module E 'and the loss factor having been measured using dynamic mechanical thermal analysis on free films with a layer thickness of 40 + 10 ⁇ m (cf. the German patent DE 197 09 467 C 2).
  • the (co) polymerization in particular the radical (co) polymerization, is carried out in at least one thermally curable reactive diluent with at least two isocyanate-reactive functional groups.
  • thermally curable reference is made to Römpp Lexicon Lacke und Druckmaschine, Georg Thieme Verlag, Stuttgart, New York, 1998, “Härtung”, pages 274 to 276.
  • the thermally curable reactive diluents to be used according to the invention contain at least two of the isocyanate-reactive agents described above functional groups. Accordingly, in principle all polyols, polythiols, polyamines, polyol polythiols, polythiol polyamines, amino alcohols and / or polyol polyamine polythiols are suitable as reactive diluents, provided that they do not inhibit or suppress the (co) polymerization of the monomers (al) or (al) and (a2) or do not lead to undesirable side reactions such as the precipitation of salts with monomers (a2) or the oligomers or polymers containing them, or the decomposition of the reactive diluents during the (co) polymerization.
  • the polyols are particularly advantageous and are therefore preferably used according to the invention.
  • Suitable polyols are hyperbranched compounds with a tetra-functional central group, derived from ditrimethylolpropane, diglycerol and / or ditrimethylolethane, or a tetrafunctional central group of the general formula V,
  • q, r, s and t an integer from 1 to 5, where q> r, s, t, in particular q> r, s, t;
  • X -O-, -S- or -NH-;
  • Alkanediyl and / or -Oxaalkandiylrest which has 2 to 5 carbon atoms and / or an oxygen atom -O-, which bridges 3 to 5 carbon atoms of the radical -A-.
  • the central groups V are advantageous and are therefore used with particular preference.
  • the indices q, r, s and t denote integers from 1 to 5.
  • the index q can be equal to the indices r, s and t.
  • symmetrical central groups V result.
  • Suitable symmetrical central groups V to be used according to the invention are derived from symmetrical tetrols such as pentaerythritol, tetrakis (2-hydroxyethyl) methane or tetrakis (3-hydroxypropyl) methane.
  • central groups V in which the index q is greater than the indices r, s and t and therefore have a value of at least 2 are advantageous and are therefore used with very particular preference. Under this framework, asymmetric central groups V result.
  • the indices m, n, o and p add up to 4.
  • the index m is always greater than 0 and stands for an integer from 1 to 3, in particular for 1.
  • the indices n, o and p have the value 0 in consideration of the above boundary condition or stand for an integer from 1 to 3. This means that not each of these indices can assume the value 0.
  • variable -X- in the general formula V denotes double-bonded oxygen atoms -O- or sulfur atoms -S- or a secondary amino group - NH-. According to the invention, it is advantageous if -X- stands for -O-.
  • the variable -A- in the formula V means a double-bond radical -C (R 7 ) 2 -.
  • the radical R 7 here stands for hydrogen atoms -H, fluorine atoms -F, chlorine atoms - Cl, bromine atoms -Br, nitrile groups -CN, nitro groups -NO 2 , CrCralkyl or - haloalkyl groups or CrC 3 -alkoxy groups.
  • suitable groups of this type are methyl, ethyl, propyl, trifluoromethyl, trichloromethyl, perfluoroethyl, perfluoropropyl, methoxy, ethoxy or propoxy groups.
  • hydrogen atoms or methyl groups are advantageous and are therefore preferably used.
  • hydrogen atoms are used.
  • the variables -A- which are particularly preferred according to the invention are accordingly methylene groups.
  • the radical R 7 can also be a C 2 -C -alkanediyl and / or oxaalkanediyl radical which has 2 to 5 carbon atoms the rest - A- cyclically bridged.
  • the radical -R 7 - can, however, also represent an oxygen atom - O-, which cyclically bridges 3 to 5 carbon atoms of the radical -A-.
  • cyclopentane-1, 2- or -1, 3-diyl groups tetrahydrofuran-2,3-, -2,4-, -2,5- or -3,4-diyl groups, cyclohexane-1, 2-, -1,3- or -1,4-diyl groups or tetrahydropyran-2,3-, 2,4-, 2,5- or 2,6-diyl groups, but no epoxy groups.
  • the tetrols of the general formula VA are of particular advantage for the preparation of the central group V or of the compounds to be used according to the invention and are therefore used with particular preference.
  • they are referred to below as "Tetrole VA”.
  • VA very particularly suitable tetrols
  • VA symmetrical tetrols pentaerythritol, tetrakis (2-hydroxyethyl) methane or tetrakis (3-hydroxypropyl) methane or the asymmetrical tetrols (VA 1) to (VA 10):
  • the tetrol (VA1) (2,2-bis-hydroxymethylbutanediol- (1,4); homopentaerythritol
  • VA1 2,2-bis-hydroxymethylbutanediol- (1,4); homopentaerythritol
  • the variables -X- described above are each connected to a hydroxyl group via spacer groups.
  • This also applies mutatis mutandis to the central groups which are derived from the tetrols ditrimethylolpropane, diglycerol or ditrimethylolethane, the oxygen atoms of which correspond to the variable -X-.
  • the following description of the spacer groups therefore also applies to these central groups, which are different from central groups V.
  • all double-bonded organic residues are suitable as spacer groups.
  • alkane alkene, cycloalkane, cycloalkene, alkylcycloalkane, alkylcycloalkene, alkenylcycloalkane, or alkenylcycloalkene, aromatics and heteroamates as well as an alkyl, alkenyl, cycloalkyl, cycloalkenyl, alkylcycloalkyl, alkylcycloalkenyl, alkenyl or alkenyl alkenyl or alkenyl alkenyl or alkenyl alkenyl or alkenyl Aromatics or heteroaromatics; or from
  • Suitable substituents to be used according to the invention for the divalent organic radicals are all organic radicals which are essentially inert, i.e. That is, they do not undergo any reactions with the compounds which are used for the construction of the reactive diluents which are particularly preferred according to the invention or for their further reaction with isocyanates (B) and (D), in particular halogen atoms, nitro groups, nitrile groups or alkoxy groups.
  • the spacer groups are connected in particular via carbonyl groups to the central groups V or to the central groups which are derived from the other tetrols mentioned.
  • organic compounds which are particularly suitable for the preparation of these spacer groups epsilon-caprolactone, hexahydrophthalic acid, hexahydrophthalic anhydride, phthalic acid, phthalic anhydride, hexahydroterephthalic acid, terephthalic acid, fumaric acid, maleic acid, maleic anhydride, itaconic acid, itaconic anhydride, oxalic acid, malonic acid, malonic acid, succinic acid , Succinic anhydride, glutaric acid, glutaric anhydride, adipic acid, adipic anhydride, pimelic acid, suberic acid, azelaic acid, sebacic acid or decanoic, undecanoic or dodecanedicarboxylic acid.
  • the tetrols VA or the other tetrols mentioned are reacted with the above-mentioned difunctional compounds to form an intermediate into which the hydroxyl groups can be introduced.
  • Examples of highly suitable organic compounds of this type are compounds containing epoxy groups, in particular those containing glycidyl groups.
  • Examples of highly suitable compounds containing epoxy groups are ethylene oxide, propylene oxide, Epichlorohydrin, glycidol, glycidyl ether, in particular aryl and alkyl glycidyl ether, or glycidyl ester, in particular the glycidyl ester of tertiary, highly branched, saturated monocarboxylic acids, which are sold under the trade name Versatic® acids by Deutsche Shell Chemie.
  • the Versatic ® acid glycidyl esters are particularly advantageous and are therefore used with very particular preference.
  • the reactive diluents described above are liquid at room temperature. Either single liquid hyperbranched compounds or liquid mixtures of these compounds can thus be used. This is particularly the case when hyperbranched compounds are used which are solid as individual compounds because of their high molecular weight and / or their symmetry. The person skilled in the art can therefore select the corresponding hyperbranched connections in a simple manner.
  • the reactive diluents which are particularly preferred according to the invention can be prepared by the customary and known methods of producing hyperbranched and dendrimeric compounds. Suitable synthetic methods are described, for example, in patent applications WO 93/17060 or WO 96/12754 or in the book by GR Newkome, CN Moorefield and F. Vögtle, "Dendritic Molecules, Concepts, Syntheses, Perspectives", VCH, Weinheim, New York, 1996 , described.
  • suitable polyols are the cyclic and / or acyclic C 9 -C 16 alkanes, which are functionalized with at least two hydroxyl groups and, for the sake of brevity, are referred to below as "functionalized alkanes".
  • Advantageous functionalized alkanes are derived from branched acyclic alkanes with 9 to 16 carbon atoms, which each form the basic structure.
  • suitable alkanes of this type with 9 carbon atoms are 2-methyloctane, 4-methyloctane, 2,3-dimethyl-heptane, 3,4-dimethyl-heptane, 2,6-dimethyl-heptane, 3,5-dimethyl-heptane, 2 -Methyl-4-ethylhexane or isopropylcyclohexane.
  • alkanes of this type with 10 carbon atoms are 4-ethyloctane, 2,3,4,5-tetramethyl-hexane, 2,3-diethyl-hexane or l-methyl-2-n-propyl-cyclohexane.
  • alkanes of this type with 11 carbon atoms examples include 2,4,5,6-tetramethyl-heptane or 3-methyl-6-ethyl-octane.
  • alkanes of this type with 12 carbon atoms are 4-methyl-7-ethyl-nonane, 4,5-diethyl-octane, r-ethyl-butyl-cyclohexane, 3,5-diethyl-octane or 2,4-diethyl-octane ,
  • alkanes of this type with 13 carbon atoms are 3,4-dimethyl-5-ethyl-nonane or 4,6-dimethyl-5-ethyl-nonane.
  • An example of a suitable alkane of this type with 14 carbon atoms is 3,4-dimethyl-7-ethyl-decane.
  • alkanes of this type with 15 carbon atoms are 3,6-diethyl-undecane or 3,6-dimethyl-9-ethyl-undecane.
  • alkanes of this type with 16 carbon atoms are 3,7-diethyl-dodecane or 4-ethyl-6-isopropyl-undecane.
  • alkanes with 10 to 14 and in particular 12 carbon atoms are particularly advantageous and are therefore used with preference.
  • the octane derivatives are particularly advantageous.
  • the functionalized alkanes which are derived from these branched, cyclic or acyclic alkanes as basic frameworks, are liquid at room temperature. Either single liquid functionalized alkanes or liquid mixtures of these compounds can thus be used. This is particularly the case when functionalized alkanes are used which are solid as individual compounds due to their high number of carbon atoms in the alkane backbone. The person skilled in the art can therefore select the corresponding functionalized alkanes or the reactive diluents in a simple manner.
  • the functionalized alkanes have a boiling point of over 200, preferably 220 and in particular 240 ° C. In addition, they are said to have a low evaporation rate.
  • the functionalized alkanes are acyclic.
  • the functionalized alkanes have primary and / or secondary hydroxyl groups or primary and / or secondary hydroxyl groups and thiol groups. According to the invention, it is advantageous if primary and secondary groups of this type are present in a functionalized alkane.
  • the functionalized alkanes can be used individually or together as mixtures. Particular advantages arise when the polyols are diols and / or triols, but especially diols. They are therefore used with particular preference.
  • the positionally isomeric dialkyloctanediols in particular diethyloctanediols, are very particularly advantageous diols. Of these, 2,4-diethyl-octanediol-1,5 is particularly noteworthy.
  • the reactive diluents described above are compounds known per se and can be prepared using customary and known synthetic methods of organic chemistry, such as base-catalyzed aldol condensation, or they are obtained as by-products of large-scale chemical syntheses, such as the preparation of 2-ethylhexanol.
  • R 8 - (- CH 2 -) W -, where the index w is an integer from 1 to 6, or
  • the index v in formula VI stands for the number of divalent radicals R 8 .
  • the value v and thus the degree of the ring-opening metathesis can be determined by the activity of the
  • 20 used metathesis catalyst can be influenced.
  • radicals R 9 , R 10 , R 11 and R 12 independently of one another represent hydrogen or alkyl, the term “alkyl” encompassing straight-chain and branched alkyl groups.
  • alkyl groups are in particular methyl, ethyl, propyl, 1-methylethyl, butyl, 1-methylpropyl, 2-methylpropyl, 1,1-dimethylethyl. n-
  • the degree of branching and the number of carbon atoms of the terminal alkyl radicals R 9 , R 10 , R 11 and R 12 depend on the structure of the acyclic monoolefins of the hydrocarbon mixture used and the activity of the catalyst, which underlies the degree of cross-metathesis (self-metathesis) of the acyclic olefins Formation of structurally new olefins is influenced, in which cyclopentene is then formally inserted in the sense of a ring-opening metathesis polymerization.
  • Oligomer mixtures are preferably used which have an increased proportion of oligomers with only one terminal double bond.
  • the oligomer is preferably prepared by using a hydrocarbon mixture containing acyclic monoolefins such as cyclopropene, cyclobutene, cyclopentene, cyclohexene, cycloheptene, cyclooctene, norbones or 7-oxanorbones and also acyclic monoolefins from petroleum processing by cracking (C 5 cut) in a homogeneous or heterogeneous metathesis reaction implemented.
  • acyclic monoolefins such as cyclopropene, cyclobutene, cyclopentene, cyclohexene, cycloheptene, cyclooctene, norbones or 7-oxanorbones
  • C 5 cut acyclic monoolefins from petroleum processing by cracking (C 5 cut) in a homo
  • the metathesis reaction includes formal
  • steps a) and or b) and / or c) can be carried out several times alone or in combination.
  • Oligomers affected. For example, at the previously described
  • the average number of insertions of the cyclic monoolefin in the growing chain in the sense of a ring-opening metathesis polymerization determines the average molecular weight of the oligomer mixture VI formed.
  • Oligomer mixtures VI having an average molecular weight of at least 274 g per mole are preferably formed by the process according to the invention, which corresponds to an average number of three units of a cyclic monoolefin per oligomer.
  • the chain termination takes place by reacting oligomers which still have an active chain end in the form of a catalyst complex (alkylidene complex) with an acyclic olefin, ideally recovering an active catalyst complex.
  • acyclic olefin can originate unchanged from the hydrocarbon mixture originally used for the reaction or can have been modified beforehand in a cross metathesis according to step a).
  • the process is generally suitable for the preparation of oligomers VI from hydrocarbon mixtures which contain acyclic and cyclic monoolefins.
  • Mono-olefins such as Cyclobutene, cyclopentene, cyclohexene,
  • Cyclohepten, norbonen or 7-oxanorbonen, in particular cyclopentene is particularly useful.
  • a hydrocarbon mixture obtained on a large industrial scale in petroleum processing is preferably used, which, if desired, can be subjected to a catalytic partial hydrogenation beforehand to remove dienes.
  • a mixture enriched in saturated and unsaturated C 5 hydrocarbons (C 5 cut ) is particularly suitable for use in the present process.
  • pyrolysis gasoline obtained in the steam cracking of naphtha can first be subjected to a selective hydrogenation in order to selectively convert the dienes and acetylenes contained into the corresponding alkanes and alkenes and then subjected to a fractional distillation, one of which is used for further distillation chemical syntheses important C 6 -C 8 cut, which contains the aromatic hydrocarbons, as well as the Cs cut used for the process according to the invention.
  • the Cs cut generally has a total olefin content of at least 30% by weight, preferably at least 40% by weight, in particular at least 50% by weight.
  • Cs-hydrocarbon mixtures with a total cyclopentene content of at least 5% by weight, preferably at least 10% by weight, in particular at least 12% by weight, and generally not more than 30% by weight, preferably not more than 20, are suitable wt .-%.
  • suitable Cs-hydrocarbon mixtures have a pentene isomer content of the acycyclic monoolefins of at least 70% by weight, preferably at least 80% by weight, in particular at least 90% by weight.
  • the production process can also be a large-scale Cs cut with a total olefin content of, for example, 50 to 60% by weight Cyclopentene content of, for example, 10 to 20% by weight and a content of pentene isomers of, for example, 33 to 43% by weight are carried out, the weight percentages adding up to 100% by weight.
  • a hydrocarbon mixture is used in the production process, which comprises the Cs cut and an oil fraction (raffonate-2) containing acyclic C -olefins.
  • a hydrocarbon mixture which comprises the Cs cut and ethene.
  • Oligomer mixtures VI with an increased double bond content are obtained. This is achieved, on the one hand, by ethenolysis of the acyclic n- and iso-pentenes contained in the Cs cut to give shorter-chain ⁇ -olefins, such as propene and 1-butene, which react with cyclopentene in a ring-opening metathesis reaction to form oligomers VI, each with a terminal one Double bond react.
  • the self-metathesis of the acyclic olefins with formation of further ethene e.g.
  • oligomer mixtures VI with increased functionality density preferably result.
  • Suitable catalysts for metathesis are known in the prior art and include homogeneous and heterogeneous catalyst systems.
  • the catalysts suitable for the production process are based on a transition metal of the 6th, 7th or 8th subgroup of the periodic table, preferably catalysts based on Mo, W, Re and Ru are used.
  • Suitable homogeneous catalyst systems are e.g. by RH Grubbs in Comprehensive Organometallic Chemistry, Pergamon Press, Ltd., New York, Volume 8, page 499 ff. (1982), by RR Schrock in Accounts of Chemical Research, Volume 23, page 158 ff. (1990), in Angewandte Chemie, volume 107, pages 2179 ff. (1995), in Journal of the American Chemical Society, volume 118, pages 100 ff. (1996) and in Journal of the Chemical Society, Chemical Communications, page 1127 ff. (1995) ,
  • Suitable heterogeneous catalyst systems generally include one
  • Transition metal compound on an inert support that is capable without
  • Re O and CH 3 ReO 3 are preferably used.
  • Suitable inorganic carriers are the oxides customary for this, in particular silicon and aluminum oxides, aluminosilicates, zeolites, carbides, nitrides, etc. and mixtures thereof. Al O 3 , SiO and mixtures thereof, optionally in combination with BO 3 and Fe 2 O 3 , are preferably used as carriers.
  • the reaction temperature of the metathesis is from -20 to 200 ° C, preferably 0 to 100 ° C, in particular 20 to 80 ° C.
  • the metathesis can be carried out at an increased pressure of up to 20 bar, preferably up to 10 bar, or in particular at ambient pressure.
  • Suitable reaction apparatuses are known to the person skilled in the art and are described, for example, in Ullmanns Encyclopedia of Industrial Chemistry, Volume 1, page 743 ff. (1951). These include, for example, stirred tanks for the batch process and, for example, tubular reactors for the continuous process.
  • the metathesis mixture is separated using customary methods. This includes e.g. the fractional distillation, if appropriate under reduced pressure, or the separation at elevated temperatures and normal pressure in a falling film evaporator. Low-boiling fractions which contain unreacted olefins can, if desired, be returned to the reaction apparatus.
  • a further conversion of the olefins contained in the Cs cut to oligomers VI is achieved in the production process, so that the separated low boilers comprise a C5 hydrocarbon mixture with predominantly saturated cyclic and acyclic compounds.
  • the iodine number of the oligomer VI is at least 250 g I 2/100 g oligomers VI, preferably at least 300 g I 2/100 g VI oligomers.
  • the average molecular weight of these oligomers VI derived from cyclic monoolefins, in particular cyclopentene, is at least 274 g / mol, which corresponds to an average conversion of three cyclopentene units per oligomer VI, in which case chain termination by an acyclic pentene (and not by a Cross metathesis product) is assumed.
  • the oligomers VI described in detail above are hydroformylated in a customary and known manner.
  • the oligomers VI in the presence of suitable transition metal-containing catalysts with hydrogen and carbon monoxide under normal pressure or implemented under elevated pressure at temperatures of 50 to 150 ° C to products VI containing aldehyde groups.
  • An example of a suitable transition metal is rhodium.
  • the polyaldehydes VI thus obtained are isolated and reduced in a customary and known manner to the reactive diluents to be used according to the invention. All reducing agents with which aldehyde groups can be reduced to hydroxyl groups are suitable for this. Examples of suitable reducing agents are borohydrides such as sodium tetrahydroboranate or hydrogen in the presence of hydrogenation catalysts.
  • the polyols VI can be partially or completely hydrogenated in a customary and known manner. This includes the above-mentioned reducing agents.
  • the particularly advantageous polyols VI have a hydroxyl number (OHZ) of 200 to 650, in particular 250 to 450.
  • the number average molecular weight M n determined with the aid of gel permeation chromatography with polystyrene as the internal standard is in the range from 400 to 1,000, in particular 400 to 600.
  • the mass average molecular weight M w determined with the aid of gel permeation chromatography and polystyrene as the internal standard is in the range from 600 to 2,000 , in particular 600 to 1,100.
  • the inconsistency M n / M w is 1.4 to 3, in particular 1.7 to 1.9.
  • the thermally curable reactive diluents described above can be added to the liquid mixture (A) after their preparation as additives (C).
  • the content of (co) polymers, in particular (meth) acrylate (co) polymers, on the one hand and reactive diluents on the other hand in the liquid mixtures (A) to be used according to the invention can vary very widely. It depends primarily on the intended use of the liquid mixture (A) and the viscosity required for this and on whether additives (C) are still present.
  • the content of reactive diluent, based in each case on the sum of (co) polymer and reactive diluent, is 1.0 to 50, preferably 2.0 to 45, particularly preferably 3.0 to 40, very particularly preferably 4.0 to 35 and in particular 5.0 to 30% by weight.
  • the content of the liquid mixtures (A) described above in the coating materials, adhesives and sealants according to the invention can likewise vary very widely.
  • the content depends in particular on the functionality of the binders on the one hand and the functionality of the adducts (B) and the crosslinking agents (D) described below on the other.
  • the content is preferably 5.0 to 80, preferably 6.0 to 75, particularly preferably 7.0 to 70, very particularly preferably 8.0 to 65 and in particular 9.0 to 60% by weight, in each case based on the Solids content of the coating materials, adhesives and sealants according to the invention.
  • the binder component to be used according to the invention ie the liquid mixture (A)
  • suitable additives are color and or effect pigments, organic and inorganic, transparent or opaque fillers, nanoparticles, thermally and or with actinic radiation reactive diluents, low-boiling organic solvents and high-boiling organic solvents ("long solvents"), water , UV absorbers, light stabilizers, radical scavengers, thermolabile free radical initiators, photoinitiators and coinitiators, other additional binders, crosslinking agents, such as are used in one-component systems, catalysts for thermal crosslinking, deaerating agents, slip additives, polymerization inhibitors, defoamers, emulsifiers, wetting agents Detergents, adhesion promoters, leveling agents, film-forming aids, sag control agents (SCA), rheology control additives (thickeners), flame retardants, siccatives, drying agents,
  • Skin prevention agents corrosion inhibitors, waxes, matting agents, precursors of organically modified ceramic materials or additional binders.
  • the type and amount of additives (C) depend on the intended use of the coatings produced using the coating materials of the invention.
  • a coating material according to the invention is used to produce solid-color top coats or basecoats, it usually contains color and / or effect pigments (C) and optionally opaque fillers. If a coating material according to the invention is used, for example, to produce clearcoats or sealers - which is the preferred use - these additives (C) are naturally not present in the coating material in question.
  • suitable effect pigments (C) are metal plate pigments such as commercially available aluminum bronzes, chromated according to DE 36 36 183 A1 Aluminum bronzes, and commercially available stainless steel bronzes as well as non-metallic effect pigments, such as pearlescent or interference pigments.
  • metal plate pigments such as commercially available aluminum bronzes, chromated according to DE 36 36 183 A1 Aluminum bronzes, and commercially available stainless steel bronzes as well as non-metallic effect pigments, such as pearlescent or interference pigments.
  • non-metallic effect pigments such as pearlescent or interference pigments.
  • suitable inorganic color pigments (C) are titanium dioxide, iron oxides, Sicotrans yellow and carbon black.
  • suitable organic color pigments (C) are thioindigo pigments indanthrene blue, cromophthal red, irgazine orange and heliogen green.
  • Römpp Lexikon Lacke und Druckmaschine, Georg Thieme Verlag, 1998 pages 180 and 181, "Iron Blue Pigments” to "Iron Oxide Black”, pages 451 to 453 "Pigments” to “Pigment Volume Concentration”, page 563 "Thioindigo Pigments” and Page 567 “Titanium dioxide pigments”.
  • organic and inorganic fillers are chalk, calcium sulfates, barium sulfate, silicates such as talc or kaolin, silicas, oxides such as aluminum hydroxide or magnesium hydroxide or organic fillers such as textile fibers, cellulose fibers, polyethylene fibers or wood flour.
  • silicates such as talc or kaolin
  • silicas oxides such as aluminum hydroxide or magnesium hydroxide
  • organic fillers such as textile fibers, cellulose fibers, polyethylene fibers or wood flour.
  • thermally curable reactive diluents (C) examples are those described in detail above.
  • Suitable reactive thinners (C) curable with actinic radiation are those described in Römpp Lexikon Lacke und Druckmaschine, Georg Thieme Verlag, Stuttgart, New York, 1998, on page 491 under the keyword “reactive diluents”.
  • suitable low-boiling organic solvents (C) and high-boiling organic solvents (C) (“long solvents”) are ketones such as methyl ethyl ketone or methyl isobutyl ketone, esters such as ethyl acetate or butyl acetate, ethers such as dibutyl ether or ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, Butylene glycol or
  • thermolabile free-radical initiators are organic peroxides, organic azo compounds or C-C-cleaving initiators such as dialkyl peroxides, peroxocarboxylic acids, peroxodicarbonates, peroxide esters, hydroperoxides, ketone peroxides, azodinitriles or benzpinacol silyl ethers.
  • Suitable catalysts (C) for crosslinking are dibutyltin dilaurate, lithium decanoate or zinc octoate.
  • Suitable other additional binders are oligomeric and polymeric, linear and / or branched and / or block-like, comb-like and or randomly structured (co) polymers of ethylenically unsaturated monomers, or polyaddition resins and or or thermally and / or with actinic radiation
  • Polycondensation resins such as those in Römpp Lexikon Lacke und Druckmaschine, Georg Thieme Verlag, Stuttgart, New York, 1 98, page 457: “Polyaddition” and “Polyadditionharze (Poly adducts)", pages 463 and 464: "Polycondensates”, “Polycondensation” and “Polycondensation Resins", as well as pages 73 and 74: "Binder”.
  • Suitable additional binders (C) are the poly (meth) acrylates or acrylate copolymers described in the patent DE 197 36 535 A1, polyesters, in particular the alkyds described in the patents DE 40 09 858 A1 or DE 44 37 535 A1 Acrylated polyesters, polylactones, polycarbonates, polyethers, epoxy resin-amine adducts, (meth) acrylate diols, partially saponified polyvinyl esters, polyurethanes and acrylated polyurethanes, such as those in the patents EP 0 521 928 A 1, EP 0 522420 A 1, EP 0 522419 A 1, EP
  • Suitable additional crosslinking agents are aminoplast resins, as described, for example, 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., The 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-B-0 245 700 A1 as well as in the article by B.
  • Suitable deaerating agents (C) are diazadicycloundecane or benzoin.
  • emulsifiers (C) are nonionic emulsifiers, such as alkoxylated alkanols and polyols, phenols and alkylphenols or anionic emulsifiers such as alkali metal salts or ammonium salts of alkane carboxylic acids, alkane sulfonic acids, and sulfonic acids of alkoxylated alkanols and polyols, phenols and alkylphenols.
  • nonionic emulsifiers such as alkoxylated alkanols and polyols, phenols and alkylphenols
  • anionic emulsifiers such as alkali metal salts or ammonium salts of alkane carboxylic acids, alkane sulfonic acids, and sulfonic acids of alkoxylated alkanols and polyols, phenols and alkylphenols.
  • Suitable wetting agents (C) are siloxanes, fluorine-containing compounds, carboxylic acid half-esters, phosphoric acid esters, polyacrylic acids and their copolymers or polyurethanes.
  • An example of a suitable adhesion promoter (C) is tricyclodecanedimethanol.
  • Suitable film-forming aids are cellulose derivatives such as cellulose acetobutyrate (CAB).
  • Suitable transparent fillers (C) are those based on silicon dioxide, aluminum oxide or zirconium oxide; In addition, reference is made to the Römpp Lexicon Lacke und Druckmaschine, Georg Thieme Verlag, Stuttgart, 1998, pages 250 to 252.
  • Sag control agents are ureas, modified ureas and / or silicas, as described, for example, in references EP 0 192 304 A1, DE 23 59 923 A1, DE 18 05 693 A1, WO 94/22968, DE 27 51 761 C 1, WO 97/12945 or "färbe + lack", 11/1992, pages 829 ff.
  • rheology control additives are those known from the patent specifications WO 94/22968, EP 0 276 501 A1, EP 0 249 201 A1 or WO 97/12945; crosslinked polymeric microparticles, as disclosed, for example, in EP 0 008 127 A1; inorganic layered silicates such as aluminum-magnesium silicates, sodium-magnesium and
  • Montmorillonite type sodium magnesium fluorine lithium layered silicates Silicas such as aerosils; or synthetic polymers with ionic and / or associative groups such as polyvinyl alcohol, poly (meth) acrylamide, poly (meth) acrylic acid, polyvinyl pyrrolidone, styrene-maleic anhydride or ethylene-maleic anhydride copolymers and their derivatives or hydrophobically modified ethoxylated urethanes or polyacrylates;
  • An example of a suitable matting agent (C) is magnesium stearate.
  • Suitable precursors (C) for organically modified ceramic materials are hydrolyzable organometallic compounds, in particular of silicon and aluminum.
  • additives (C) listed above examples of suitable UV absorbers, free radical scavengers, leveling agents,
  • the preparation of the binder component containing additives (C) to be used according to the invention has no peculiarities, but is carried out in a customary and known manner by mixing the mixtures (A) and additives (C) described above in suitable mixing units such as stirred kettles, dissolvers, stirrer mills or extruders ,
  • suitable mixing units such as stirred kettles, dissolvers, stirrer mills or extruders .
  • the second component of the coating materials, adhesives and sealants according to the invention contains at least one adduct (B).
  • the adduct (B) can be prepared from a diisocyanate (bl) and a compound I (b2).
  • the compounds I have an isocyanate-reactive functional group.
  • suitable isocyanate-reactive functional groups are hydroxyl groups, thiol groups and primary or secondary amino groups.
  • the compounds I have the general formula I:
  • R 1 and R 2 independently of one another represent hydrogen atoms or alkyl radicals having 1 to 10 carbon atoms, preferably methyl, ethyl.
  • U and V independently of one another represent oxygen atoms, sulfur atoms or residues> NR 6 , in which R 6 is an aliphatic residue with 1 to 30 carbon atoms, the carbon chain of which can be interrupted by one or more oxygen atoms, such as the residues R 1 and R 2 described above , Undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl or eicosanyl or OHgo (ethylene glycol) -l-yl, oligo (propylene glycol) -l-yl or Oligo (butylene glycol) -l-yl or the corresponding mixed oligomers with a degree of oligomerization of up to 15.
  • R 6 can be an aromatic radical with 6 to 30 carbon atoms, such as phenyl, naphthyl or
  • R 3 stands for an alkylene radical with 1 to 5 carbon atoms such as methylene, eth-1,2-ylene, trimethylene, tetramethylene or pentamethylene.
  • R 4 and R 5 independently of one another represent hydrogen atoms, isocyanate-reactive functional groups or radicals R 6 .
  • a radical R 4 , R 5 or R 6 contains an isocyanate-reactive functional group or a radical R 4 or R 5 is an isocyanate-reactive functional group, the other radicals R 4 , R 5 or R 6 - if present - have no isocyanate-reactive functional groups.
  • radicals R 1 , R 2 , R 4 , R 5 and R 6 have the meaning given above, the radicals R 4 or R 6 containing an isocyanate-reactive functional group.
  • oxazolidines (IV) have particular advantages, which is why they are used with particular preference according to the invention.
  • particularly suitable oxazolidines (IV) are N- (2-hydroxyethyl) -1, 3-oxazolidine or N- (2-hydroxyethyl) -2-isopropyl-1,3-oxazoHdin, as described on page 6, Table 1, No. 5a and No. 5b, the German patent application DE 196 09 617 A1 are described.
  • the molar ratio of isocyanate groups in the dusocyanates (b1) to the isocyanate-reactive functional groups in the compound I (b2) is 0.8: 1.2 to 1.2: 0, 8, preferably 0.9: 1.1 to 1.1: 0.9 and in particular 1: 1.
  • the content of the adducts (B) described in the coating materials, adhesives and sealants according to the invention can vary very widely. It depends in particular on the functionality of the crosslinking agent (D) and the liquid mixture (A) and on the viscosity of the coating materials, adhesives and sealants according to the invention.
  • the content is preferably 10 to 90, preferably 15 to 85, particularly preferably 20 to 80, very particularly preferably 22 to 75 and in particular 25 to 70% by weight, in each case based on the solids content of the coating materials, adhesives and sealants according to the invention, where the content of (B) up to twice as high as the content of (A) can be chosen.
  • the second component to be used according to the invention also contains at least one reactive crosslinking agent (D).
  • this crosslinking agent (D) can also be contained in a third component to be used according to the invention.
  • a reactive crosslinking agent (D) is understood to mean a crosslinking agent which, in contrast to the crosslinking agents (C) described above, for one-component systems is already below 90, preferably below 70, preferably below 60, particularly preferably below 50, particularly preferably below 40, very particularly preferably below 30 ° C. and in particular at room temperature, react with the liquid mixtures (A) described above, the adducts (B) after the ketone is split off and with any additional reactive diluents (C) which are present for the thermal curing.
  • Suitable reactive crosslinking agents (D) are polyisocyanates which, on a statistical average, have more than two isocyanate groups in the molecule and are, if appropriate, modified hydrophilically or hydrophobically.
  • the Polyisocyanates (D) are liquid and preferably of low viscosity, so that they can easily be incorporated into the second component or into the mixture of the first and second components.
  • Polyisocyanates (D) with 2 to 5 isocyanate groups per molecule and with viscosities at 23 ° C. of 100 to 2000 mPa.s are particularly preferably used.
  • organic solvents (C) preferably 1 to 25% by weight, based on pure polyisocyanate (D)
  • C organic solvents
  • D pure polyisocyanate
  • polyisocyanates (D) are polyurethane prepolymers containing isocyanate groups, which can be prepared by reacting polyols with an excess of the above-described diisocyanates (b1) and are preferably low-viscosity.
  • Polyisocyanates (D) containing isocyanurate, biuret, AUophanat, iminooxadiazindone, urethane, urea and / or uretdione groups can also be used.
  • Polyisocyanates containing urethane groups are obtained, for example, by reacting some of the isocyanate groups with polyols, e.g. Trimethylolpropane and glycerin.
  • Aliphatic or cycloaliphatic diisocyanates (b1) in particular hexamethylene diisocyanate, dimerized and trimerized hexamethylene diisocyanate, isophorone diisocyanate, 2-isocyanatopropylcyclohexyl isocyanate, dicyclohexylmethane-2,4'-diisocyanate or
  • Dicyclohexylmethane-4,4'-diisocyanate or mixtures of these dusocyanates are used.
  • uretdione and / or isocyanurate groups and / or allophanate groups containing polyisocyanates (D) based on hexamethylene diisocyanate or isophorone diisocyanate, such as those obtained by catalytic oligomerization of hexamethylene diisocyanate or Isophorone diisocyanate are formed using suitable catalysts.
  • the content of the crosslinking agents (D) described above in the coating materials, adhesives and sealants according to the invention can also vary very widely. In particular, it depends on the functionality of the crosslinking agent (D) and the (meth) acrylate copolymer (A) and the amount of adduct (B).
  • the content is preferably 10 to 70, preferably 15 to 65, particularly preferably 17 to 60, very particularly preferably 20 to 55 and in particular 22 to 50% by weight, in each case based on the solids content of the coating materials, adhesives and sealants according to the invention.
  • the second component to be used according to the invention or - if used - also or only the third component to be used according to the invention may contain at least one of the additives (C) described above, provided that these are not combined with the adducts (B) and / or the crosslinking agents (D ) enter undesirable reactions such as decomposition reactions or premature crosslinking reactions.
  • additives (C) described above which are used in the coating materials, adhesives and sealants according to the invention, may also be present as a separate, separate, third or fourth component.
  • the production of the coating materials, adhesives and sealants according to the invention from the components described above does not offer any special features in terms of method, but rather is carried out with the aid of the customary and known mixing devices and methods described above or by means of conventional two- or multi-component metering and mixing systems.
  • the mixing should ideally be done by hand.
  • the coating materials, adhesives and sealants according to the invention are used to produce coatings, adhesive layers and seals on and / or in primed and unprimed substrates.
  • the coating materials according to the invention are used to produce solid-color top coats, clear coats and basecoats and clear coats in multi-coat paint and / or effect coatings.
  • the application of the coating materials according to the invention has no peculiarities, but can be carried out by all the usual application methods, such as Spraying, knife coating, brushing, pouring, dipping, trickling or rolling.
  • Spraying a spraying, knife coating, brushing, pouring, dipping, trickling or rolling.
  • spraying a spraying, knife coating, brushing, pouring, dipping, trickling or rolling.
  • Spray application methods are used, such as compressed air spraying, airless spraying, high rotation, electrostatic spray application (ESTA), if appropriate combined with hot spray application such as hot air - hot spraying.
  • compressed air spraying airless spraying
  • high rotation high rotation
  • electrostatic spray application ESTA
  • hot spray application such as hot air - hot spraying.
  • Suitable substrates are surfaces which are not damaged by hardening of the coating materials, adhesives and / or sealing compounds located thereon using heat and, if appropriate, actinic radiation; these are e.g. B. metals, plastics, wood, ceramics, stone, textiles, fiber composites, leather, glass, glass fibers, glass and rock wool, mineral and resin-bound building materials, such as plaster and cement boards or roof tiles, as well as composites of these materials.
  • the coating materials, adhesives and sealants according to the invention are also suitable for applications outside the automotive industry. They are particularly suitable for painting, gluing and / or sealing furniture, windows, doors, structures indoors and outdoors and industrial painting, including coil coating, container coating and the impregnation or coating of electrical components.
  • primers can be used which are produced in a customary and known manner from electrocoat materials (ETL). Both anodic (ATL) and cathodic (KTL) electrodeposition coatings, but especially KTL, come into consideration for this.
  • ETL electrocoat materials
  • the electrodeposition coating or the electrodeposition coating layer can be covered with a filler which is cured either on its own or together with the electrodeposition coating layer (wet-on-wet method).
  • the overlay with a filler takes place in particular in areas that are exposed to strong mechanical stress, such as stone chips.
  • suitable fillers especially aqueous fillers, are also available as
  • Stone chip protection primers or functional layers are referred to, from the patents and applications US 4,537,926 A1, EP 0 529 335 A1, EP 0 595 186 A1, EP 0 639 660 A1, DE 44 38 504 A1, DE 43 37 961 A1, WO 89/10387, US 4,450,200 A1, US 4,614,683 A1 or WO 490/26827.
  • Primed or unprimed plastic parts made of e.g. B. ABS, AMMA, ASA, CA, CAB, EP, UF, CF, MF, MPF, PF, PAN, PA, PE, HDPE, LDPE, LLDPE, UHMWPE, PC, PC / PBT, PC / PA, PET, PMMA, PP, PS, SB, PUR, PVC, RF, SAN, PBT, PPE, POM, PUR-RIM, SMC, BMC, PP-EPDM and UP (short names according to DIN 7728T1) can be painted, glued or sealed. In the case of non-functionalized and / or non-polar substrate surfaces, these can be subjected to a pretreatment, such as with a plasma or with flame treatment, or provided with a hydro primer in a known manner before the coating.
  • a pretreatment such as with a plasma or with flame treatment, or provided with a hydro primer in a known manner before the coating.
  • the coating materials of the suitable composition according to the invention are applied to the substrates described above, after which the resulting clearcoat and solid-color lacquer layers are cured.
  • the adhesives and sealants according to the invention are applied to and / or in the substrates described above.
  • the surfaces to be bonded of two or more substrates are preferably coated with the adhesive according to the invention, after which the surfaces in question may be brought into contact under pressure and the resulting adhesive layers are cured.
  • the production of a multi-layer paint and / or effect coating according to the invention is carried out on a primed or unprimed substrate (1) applying a basecoat to the substrate,
  • a basecoat known per se and a clearcoat according to the invention are used as the clearcoat.
  • a clear lacquer known per se and a basecoat according to the invention are used as the basecoat.
  • a basecoat 20 according to the invention and a clearcoat according to the invention are used.
  • Clearcoats known per se are one- or multi-component clearcoats, powder clearcoats, powder slurry clearcoats, UV-curable clearcoats or sealers, as described in patent applications, patent specifications and publications DE 4204 518 A1, EP 0 594 068 A1, EP 0 594 071 A1, EP 0 594 142 A1, EP 0 604 992 A1, EP 0 596 460 A1, WO 94/10211, WO 94/10212, WO 94/10213, WO 94/22969 or WO 92/22615, US 5,474,811 A1 , US 5,356,669 A 1 or US 5,605,965 A 1, DE 42 22 194 A 1, product information from BASF Lacke + Weg, “Powder Coating”, 1990, company lettering from BASF Coatings AG “Powder Coating, Powder Coating for Industrial Applications”, January 2000, US 4,268,542 A1, DE
  • EP 0 650 978 A1 , EP 0 650 979 A1, EP 0 650
  • the curing of the applied coating materials, adhesive layers and sealants according to the invention is also not methodologically peculiar, but generally takes place at room temperature in the course of 30 minutes to several days, for example 4 to 10 days. Hardening can be supported by the application of heat and / or actinic radiation. This is particularly the case when the inventive Coating materials, adhesive layers and sealants contain constituents (C) which can be activated with actinic radiation and / or constituents (C) which are thermally curable, such as the crosslinking agents (C) for one-component systems. This is also the case if customary and known thermally and / or actinic radiation-curable clearcoats or basecoats are used in the production of the multi-layer paint and / or effect paint system according to the invention. Curing with heat and actinic radiation is also referred to by experts as "dual cure".
  • xinter actinic radiation is understood to mean electromagnetic radiation such as near infrared, visible light, UV light or X-rays, but especially UV light, and corpuscular radiation, in particular electron radiation.
  • the appropriate radiation sources, such as UV lamps, are used for curing.
  • the coating materials, adhesives and sealants according to the invention have a high solids content with low viscosity and a long service life.
  • the resulting coatings according to the invention in particular the solid-color top coats, clear coats and color and / or effect multi-layer lacquers, have high hardness, flexibility and chemical resistance, an excellent flow, a very good interlayer adhesion, an excellent overall optical impression, one very good weather resistance, very high scratch resistance and very good polishability.
  • the adhesive layers according to the invention are permanently adhesive, even under extreme and / or very strongly and rapidly changing climatic conditions.
  • the seals according to the invention completely seal against chemically aggressive substances.
  • primed and unprimed substrates according to the invention 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 service life in addition to the advantages listed above, which makes them particularly economical makes you valuable.
  • a monomer mixture of 225 parts by weight of styrene, 150 parts by weight of tert-butylcyclohexyl acrylate, 450 parts by weight of n-butyl methacrylate and 600 parts by weight of hydroxypropyl methacrylate was metered in uniformly over a period of 4 hours.
  • the resulting reaction mixture was diluted with 285 parts by weight of a solvent mixture (n-butyl acetate, xylene and methyl amyl ketone in a weight ratio of 8: 1: 1).
  • the resulting liquid mixture (A) had a solids content of 67.8% by weight (lg / 1 h / 130 ° C.) and a viscosity of 18 dPas.
  • N- (2-hydroxyethyl) -2-isopropyl-l, 3-oxazolidine was, as on page 9, lines 7 to 17, "V4 - Monourethane from HDI", which is described in DE 196 09 617 A1, with HDI in a molar ratio Converted 1: 1 to the adduct (B).
  • Example 1 was repeated for example 2, except that instead of 14.02 parts by weight, 49.8 parts by weight of the adduct (B) from preparation example 2 was used, so that a clear lacquer with a solids content of 80% by weight resulted (lg / lh / 130 ° C).
  • the clearcoats of Examples 1 and 2 were applied to glass panels with a wet layer thickness of 150 ⁇ m.
  • the clear lacquer layers were fully cured after heating for 45 minutes at 90 ° C.
  • the clear coats were hard, clear and transparent and free from stoves. They had a smooth, structure-free and tack-free surface.
  • the clearcoats were outstandingly suitable as automotive refinish paints or for the production of color and / or effect multi-layer coatings by the wet-on-wet process.

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  • 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)
  • Adhesives Or Adhesive Processes (AREA)
  • Sealing Material Composition (AREA)
  • Polyurethanes Or Polyureas (AREA)
  • Paints Or Removers (AREA)

Abstract

L'invention concerne des matières à plusieurs composants pour l'enduction, le collage et l'étanchéification, contenant (A) des mélanges liquides de (co)polymères et de diluants réactifs thermodurcissables, que l'on obtient par (co)polymérisation de monomères (a1) oléfiniques insaturés avec des groupes réagissant à l'isocyanate dans des diluants réactifs thermodurcissables avec des groupes réagissant à l'isocyanate; et (B) un produit d'addition, obtenu à partir (b1) d'un diisocyanate et (b2) d'un composé de formule générale (I) avec un groupe réagissant à l'isocyanate: où R<1> et R<2> représentent des atomes d'hydrogène ou des restes alkyle, X et Y signifient des atomes d'oxygène, des atomes de soufre ou <N-R?6> avec R<6> = reste alkyle ou reste aryle, R<3> est un reste alkyle, et R<4> et R<5> représentent des atomes d'hydrogène, des groupes réagissant à l'isocyanate ou des restes R<6>; R<4>, R<5> ou R<6> contenant un groupe réagissant à l'isocyanate ou bien R<4> ou R<5 > étant un groupe fonctionnel réagissant à l'isocyanate; R<4>, R<5> ou R<6> - s'ils sont existants ne comportant pas de groupes réagissant à l'isocyanate, et la relation molaire des groupes réagissant à l'isocyanate dans (b1) par rapport aux groupes réagissant à l'isocyanate dans le composé I étant de 1,0.
PCT/EP2001/004698 2000-04-28 2001-04-26 Matieres a plusieurs composants pour l'enduction, le collage et l'etancheification, et leur utilisation Ceased WO2001083578A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU58371/01A AU5837101A (en) 2000-04-28 2001-04-26 Multicomponent coating, adhesive and sealing materials and the utilization thereof

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE2000120969 DE10020969A1 (de) 2000-04-28 2000-04-28 Mehrkomponentenbeschichtungsstoffe, -klebstoffe und -dichtungsmassen und ihre Verwendung
DE10020969.6 2000-04-28

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2003074620A1 (fr) * 2002-03-07 2003-09-12 Akzo Nobel Coatings International B.V. Composition d'enrobage comprenant un liant a fonction acetal

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE10047989A1 (de) 2000-09-28 2002-04-18 Basf Coatings Ag Thermisch und mit aktinischer Strahlung härtbare Mehrkomponentenbeschichtungsstoffe, -klebstoffe und -dichtungsmassen und ihre Verwendung
DE10153645A1 (de) 2001-10-31 2003-05-22 Basf Coatings Ag Härtbares Stoffgemisch, Verfahren zu seiner Herstellung und seine Verwendung

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4342793A (en) * 1977-01-14 1982-08-03 Henkel Corporation Interpenetrating dual cure resin compositions
EP0752433A2 (fr) * 1995-07-01 1997-01-08 BASF Aktiengesellschaft Compositions de revêtement à base de polyuréthane à un ou deux composants
DE19609617A1 (de) * 1996-03-12 1997-09-18 Basf Ag Einkomponenten- und Zweikomponenten-Polyurethanbeschichtungsmassen
EP0908479A1 (fr) * 1997-10-10 1999-04-14 Basf Aktiengesellschaft Systèmes de polyuréthane à deux composants comprenant des diluants réactifs
WO2000026312A1 (fr) * 1998-10-31 2000-05-11 Basf Coatings Ag Melanges de substances liquides et (co)polymeres, leur procede de production et leur utilisation pour la production de melanges reactifs a plusieurs substances

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4342793A (en) * 1977-01-14 1982-08-03 Henkel Corporation Interpenetrating dual cure resin compositions
EP0752433A2 (fr) * 1995-07-01 1997-01-08 BASF Aktiengesellschaft Compositions de revêtement à base de polyuréthane à un ou deux composants
DE19609617A1 (de) * 1996-03-12 1997-09-18 Basf Ag Einkomponenten- und Zweikomponenten-Polyurethanbeschichtungsmassen
EP0908479A1 (fr) * 1997-10-10 1999-04-14 Basf Aktiengesellschaft Systèmes de polyuréthane à deux composants comprenant des diluants réactifs
WO2000026312A1 (fr) * 1998-10-31 2000-05-11 Basf Coatings Ag Melanges de substances liquides et (co)polymeres, leur procede de production et leur utilisation pour la production de melanges reactifs a plusieurs substances
DE19850243A1 (de) * 1998-10-31 2000-05-11 Basf Coatings Ag Flüssige Stoffgemische und (Co)Polymerisate, Verfahren zu ihrer Herstellung und ihre Verwendung zur Herstellung von reaktiven Mehrstoffmischungen

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2003074620A1 (fr) * 2002-03-07 2003-09-12 Akzo Nobel Coatings International B.V. Composition d'enrobage comprenant un liant a fonction acetal
US7045579B2 (en) 2002-03-07 2006-05-16 Akzo Nobel N.V. Coating composition comprising an acetal-functional binder

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AU5837101A (en) 2001-11-12

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