EP1631631A1 - Materiaux de revetement exempts de pigments couvrants, contenant des solvants, thermodurcissables et/ou durcissables par un rayonnement actinique ; leur procede de production et leur utilisation - Google Patents

Materiaux de revetement exempts de pigments couvrants, contenant des solvants, thermodurcissables et/ou durcissables par un rayonnement actinique ; leur procede de production et leur utilisation

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Publication number
EP1631631A1
EP1631631A1 EP04734223A EP04734223A EP1631631A1 EP 1631631 A1 EP1631631 A1 EP 1631631A1 EP 04734223 A EP04734223 A EP 04734223A EP 04734223 A EP04734223 A EP 04734223A EP 1631631 A1 EP1631631 A1 EP 1631631A1
Authority
EP
European Patent Office
Prior art keywords
coating materials
actinic radiation
wax particles
polyamide wax
synthetic polyamide
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP04734223A
Other languages
German (de)
English (en)
Inventor
Cornelia Ketteler
Thomas Farwick
Vincent Cook
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
BASF Coatings GmbH
Original Assignee
BASF Coatings GmbH
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by BASF Coatings GmbH filed Critical BASF Coatings GmbH
Publication of EP1631631A1 publication Critical patent/EP1631631A1/fr
Withdrawn legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K3/00—Materials not provided for elsewhere
    • C09K3/10—Materials in mouldable or extrudable form for sealing or packing joints or covers
    • 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
    • C09D7/47—Levelling agents
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2200/00—Chemical nature of materials in mouldable or extrudable form for sealing or packing joints or covers
    • C09K2200/06—Macromolecular organic compounds, e.g. prepolymers
    • C09K2200/0615—Macromolecular organic compounds, e.g. prepolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C09K2200/0625—Polyacrylic esters or derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2200/00—Chemical nature of materials in mouldable or extrudable form for sealing or packing joints or covers
    • C09K2200/06—Macromolecular organic compounds, e.g. prepolymers
    • C09K2200/0645—Macromolecular organic compounds, e.g. prepolymers obtained otherwise than by reactions involving carbon-to-carbon unsaturated bonds
    • C09K2200/0667—Polyamides, polyimides

Definitions

  • Solvent-containing coating materials curable thermally and / or with actinic radiation and free from opaque pigments, processes for their production and their use
  • the present invention relates to new, solvent-containing, thermally and / or curable with actinic radiation, opaque pigments, free coating materials.
  • the present invention relates to a novel process for the production of solvent-borne coating materials which are curable thermally and / or with actinic radiation and are free from covering pigments.
  • the present invention relates to the use of the new, solvent-containing, thermally and / or actinic radiation-curable, coating pigments-free coating materials for the production of transparent, in particular clear, coatings, preferably clear coats and in particular clear coats of color and / or effect-giving multi-layer paintwork.
  • the present invention relates to the use of the new, solvent-containing, thermally and / or actinic radiation-curable, coating pigments-free coating materials as adhesives and sealants for the production of adhesive layers and seals.
  • Multi-layer paintwork As is known, these comprise an electro-dip coating, a filler coating,
  • Stone chip protection primer or functional layer a color and / or effect base coat and a clear coat.
  • the multicoat paint systems are produced with the aid of so-called wet-in-rass processes, in which a clear coat is applied to a dried but not hardened basecoat, after which at least the basecoat and clearcoat are thermally combined hardened. This process can also be used to manufacture the electrocoat and filler paint,
  • Stone chip protection primer or functional layer can be included.
  • the clear coats in particular shape such essential technological properties as
  • the quality of the clearcoats is therefore subject to particularly high requirements.
  • runners formation is the name for the sagging of applied coating materials on vertical or inclined surfaces, which results in an unsightly appearance of the resulting coatings. If this process phenomenon occurs in a larger area, it is also called “curtain formation”. In general, a distinction is made between runners at edges and corners and the large-scale sagging of coatings on surfaces, which is also known as “pushing". The formation of runners can be caused by an incorrect composition or an incorrect application of the coating material.
  • the “runner limit” is generally the wet film thickness of the applied coating material in ⁇ m, above which the first runners appear after spray application on a vertical, perforated sheet.
  • Craters are understood to be the always strictly circular depressions with or without ring bulge, which occur on paintwork, sometimes individually, sometimes in a heap, which hardly goes beyond the mm range, usually even lies below it. Despite the uniform appearance, there are very different causes for craters, making it particularly difficult to avoid crater formation in practice (cf. Römpp-Online 2002, "Crater (education)”).
  • the automobile manufacturers often reduce the layer thickness of the clearcoats, which, however, can significantly impair essential technical properties such as gloss, distinctness of images and weather and UV resistance and can lead to matting of the clearcoats.
  • the clearcoat manufacturers are attempting to solve the problems by adding larger amounts of conventional and known rheological aids or rheology-controlling additives, such as those from the applications WO 94/22968 A1, EP 0 276 501 A1, EP 0 249 201 A1 or WO 97 / 12945 A 1 known Sag Control Agents (SCA); the crosslinked polymeric microparticles, as disclosed, for example, in EP 0 008 127 A1; the inorganic layered silicates such as aluminum-magnesium-silicates, sodium-magnesium and
  • Montmorillonite type sodium magnesium fluorine lithium layered silicates such as aerosils; or the synthetic polymers with ionic and / or associative groups, such as polyvinyl alcohol, poly (meth) acrylamide, poly (meth) acrylic acid, polyvinyl pyrrolidone,
  • Ethylene-maleic anhydride copolymers and their derivatives or hydrophobically modified ethoxylated urethanes or polyacrylates to avoid.
  • this can lead to a deterioration in the level of the topcoat because the clearcoat is impaired.
  • the new solvent-containing coating materials which are curable thermally and / or with actinic radiation and are free from opacifying pigments have been found to contain
  • coating materials in the following, the new, solvent-based, thermally and with actinic radiation curable, coating pigments free coating pigments are referred to as "coating materials according to the invention".
  • additive (B) was extremely effective even in small amounts in terms of avoiding runners, craters and matting.
  • the coatings according to the invention produced from the coating materials according to the invention, preferably the clear coats according to the invention and in particular the clear coats according to the invention in color and / or effect multi-coat coatings, had the automotive quality described at the outset and thereby no longer showed runners, craters and matting.
  • actinic radiation includes electromagnetic radiation, such as near infrared (NIR), visible light, UV radiation, X-rays and gamma radiation, in particular UV radiation, and corpuscular radiation, such as electron radiation, beta radiation, proton radiation, neutron radiation and alpha radiation, in particular
  • NIR near infrared
  • UV radiation visible light
  • UV radiation X-rays
  • gamma radiation in particular UV radiation
  • corpuscular radiation such as electron radiation, beta radiation, proton radiation, neutron radiation and alpha radiation
  • Electron radiation understood. Combined curing with heat and actinic radiation is also known as dual-cure.
  • the coating materials of the invention curable thermally or thermally and with actinic radiation, can be any coating materials of the invention.
  • they can also be multi-component systems, in particular two-component systems, in which at least two of the components required for thermal curing have to be stored separately from one another because of their high reactivity, for example compounds containing hydroxyl groups and polyisocyanates.
  • the coating materials according to the invention are thermally curing one-component systems.
  • the essential component of the coating materials according to the invention is at least one, in particular one, additive (B).
  • the additive (B) is synthetic polyamide wax particles.
  • the synthetic polyamide wax particles (B) are preferably dispersed in the organic solvents (C) of the coating materials of the invention and are thereby swollen by them.
  • the synthetic polyamide wax particles (B) preferably have a melting point or melting range above 100 ° C., preferably above 120 ° C. and particularly preferably above 130 ° C.
  • the melting point or melting range is preferably below 200 ° C., preferably below 180 ° C. and particularly preferably below 160 ° C. In particular, you have a melting point or melting range from 132 to 136 ° C.
  • Their average particle size is preferably below the layer thickness of the coating according to the invention produced from the relevant coating material according to the invention.
  • the average particle size is preferably below 100 ⁇ m, particularly preferably below 80 ⁇ m, very particularly preferably below 60 ⁇ m and in particular below 50 ⁇ m. The range from 5 to 40 ⁇ m is particularly advantageous.
  • the additive (B) in the coating materials of the invention is in an amount of, based on the coating material, 0.01 to 3, preferably 0.02 to 3.8, preferably 0.03 to 3.6, particularly preferably 0, 04 to 3.4 and in particular 0.05 to 3.2 wt .-% contain.
  • the synthetic polyamide wax particles (B) to be used according to the invention can be added as such to the coating materials according to the invention. However, it is advantageous to add them in the form of a dispersion in organic solvents (C).
  • the solids content of the dispersion can vary widely; it preferably contains the additive (B) to be used according to the invention in an amount of 5 to 40, preferably 10 to 30 and in particular 15 to 25% by weight, based on their total amount.
  • additive (B) to be used according to the invention in the form of a paste (A / B), preferably containing, based on the paste (A / B), 20 to 60, preferably 25 to 55 and in particular 30 to 50% by weight of at least one, in particular one, of the binders (A) described below and 3 to 9, preferably 4 to 8 and in particular 5 to 7% by weight of the additive (B) and at least one organic solvent (C) , It is particularly advantageous if the binder (A) used in the paste (A / B) is identical to the binder (A) of the respective coating material according to the invention.
  • the solids content of the pastes (A / B) is preferably 30 to 80, preferably 35 to 70 and in particular 40 to 60% by weight, based on the paste (A / B).
  • Organic solvents (C) are preferably used which do not inhibit the crosslinking of the coating materials according to the invention and / or do not have any interfering interactions with the other constituents of the coating materials according to the invention.
  • suitable solvents are from D. Stoye and W. Freitag (Editors), "Paints, Coatings and Solvente", Second, Completely Revised Edition, Wiley-VCH, Weinheim, New York, 1998, »14.9. Solvent Groups «, pages 327 to 373.
  • the dispersions of the additives (B) in organic solvents (C) are commercially available products and are sold, for example, by C. H. Erbslöh under the brand Disparlon®, in particular Disparlon® 6900-20X.
  • the further essential constituent of the coating materials according to the invention is at least constituent (A), selected from the group consisting of low molecular weight, oligomeric and polymeric binders, crosslinking agents and reactive diluents which are curable thermally with actinic radiation and thermally and with actinic radiation.
  • constituent (A) selected from the group consisting of low molecular weight, oligomeric and polymeric binders, crosslinking agents and reactive diluents which are curable thermally with actinic radiation and thermally and with actinic radiation.
  • Components (A) which essentially consist only of a basic structure or a monomer unit are regarded as low molecular weight. In general, low molecular weight components have number average molecular weights below 1,000 daltons. Oligomeric components (A) generally contain 2 to 15 monomer units; polymeric components generally contain more than 10, in particular more than 15, monomer units (cf. also Römpp-Online 2002, “Oligomers", “Polymers”).
  • the component (A) is selected as such or the components (A) are selected in their entirety in such a way that the resulting coating materials according to the invention achieve the desired
  • the coating materials of the invention contain at least one binder and at least one crosslinking agent as constituents (A)
  • the binders (A) are preferably selected from the group consisting of physically, thermally or thermally and with actinic radiation, random, alternating and block-like, linear, branched and comb-like (co) polymers of ethylenically unsaturated monomers, polyaddition resins and / or Polycondensation resins selected.
  • Polycondensation resins (A) are polyesters, alkyds, polyurethanes, polylactones, polycarbonates, polyethers, epoxy resin-amine adducts, polyureas, polyamides, polyimides, polyester-polyurethanes, polyether-polyurethanes or polyester-polyether-polyurethanes, in particular polyester.
  • the binders (A) curable thermally and / or with actinic radiation can be used on average
  • variable R stands for an acyclic or cyclic aliphatic, an aromatic and / or an aromatic-aliphatic (araliphatic) radical; the variables R and R stand for identical or different aliphatic radicals or are linked to one another to form an aliphatic or heteroaliphatic ring.
  • the complementary reactive functional groups (i) are preferably selected from the group consisting of hydroxyl, thiol, amino, N-methylolamino, N-alkoxymethylamino, imino, carbamate, allophanate and / or carboxyl groups, and on the other hand from the group consisting of anhydride, carboxyl, epoxy, blocked and unblocked isocyanate, urethane, alkoxycarbonylamino, methylol, methylol ether, carbonate,.
  • Hydroxyalkylamide groups selected.
  • Self-crosslinking binders (A) in particular contain methylol, methylol ether and / or N-alkoxymethylamino groups (i).
  • Alkoxymethylamino groups on the other hand used as complementary reactive functional groups (i).
  • the reactive functional groups (ii) with at least one bond which can be activated with actinic radiation can also be present in the binders (A) in addition to the groups (i) (dual-cure binders) or they are the only groups capable of crosslinking (binders curable with actinic radiation).
  • a bond which can be activated with actinic radiation is understood to mean a bond which becomes reactive when irradiated with actinic radiation and which undergoes polymerization reactions and / or crosslinking reactions with other activated bonds of its kind which take place according to radical and / or ionic mechanisms.
  • suitable bonds are carbon-hydrogen single bonds or carbon-carbon, carbon-oxygen, carbon-nitrogen, carbon-phosphorus and / or carbon-silicon single bonds or double bonds or carbon-carbon triple bonds.
  • the carbon-carbon double bonds are particularly advantageous and are therefore used with very particular preference in accordance with the invention. For the sake of brevity, they are referred to below as "double bonds".
  • group (ii) preferred according to the invention contains one double bond or two, three or four double bonds. If more than one double bond is used, the double bonds can be conjugated. According to the invention, however, it is advantageous if the double bonds are isolated, in particular each individually in the group (ii) in question here. According to the invention, it is particularly advantageous to use two, in particular one, double bond.
  • the dual-cure binder or the binder (A) curable with actinic radiation contains on average at least one of the groups (ii) which can be activated with actinic radiation as described above.
  • the functionality of the binder in in this respect is an integer, that is, for example, is equal to two, three, four, five or more, or is not an integer, that is, is, for example, equal to 2.1 to 10.5 or more.
  • the groups (ii) are structurally different from one another or of the same structure.
  • Examples of suitable groups (ii) are (meth) acrylate, ethacrylate, crotonate, cinnamate, vinyl ether, vinyl ester, dicyclopentadienyl, norbornenyl, isoprenyl, isopropenyl, allyl or butenyl groups; Dicyclopentadienyl, norbornenyl, isoprenyl, isopropenyl, allyl or butenyl ether groups or dicyclopentadienyl, norbornenyl, isoprenyl, isopropenyl, allyl or butenyl ester groups, but especially acrylate groups.
  • the groups (ii) are preferably bonded to the respective basic structures of the binders (A) via urethane, urea, allophanate, ester, ether and / or amide groups, but in particular via ester groups.
  • This is usually done by customary and known polymer-analogous reactions such as the reaction of pendant glycidyl groups with the olefinically unsaturated monomers described below, which contain an acid group, of pendant hydroxyl groups with the halides of these monomers, of hydroxyl groups with double bonds
  • Isocyanates such as vinyl isocyanate, methacryloyl isocyanate and / or 1- (1-isocyanato-1-methylethyl) -3- (1-methylethenyl) benzene (TMI® from CYTEC) or isocyanate groups with the monomers described below which contain hydroxyl groups.
  • the (meth) acrylate copolymers and the polyesters in particular the (meth) acrylate copolymers, especially the hydroxyl-containing (meth) acrylate copolymers, have particular advantages and are therefore used with particular preference.
  • the preferred coating material to be used according to the invention accordingly preferably contains at least one, in particular one, hydroxyl-containing (meth) acrylate copolymer (A) as a binder.
  • at least two, in particular two, hydroxyl-containing (meth) acrylate copolymers (A) which have a different property profile within the preferred ranges for OH number, glass transition temperature and number and mass average molecular weight given below ,
  • the (meth) acrylate copolymer (A) preferably has
  • the (meth) acrylate copolymer (A) preferably contains an amount corresponding to its OH number of hydroxyl-containing olefinically unsaturated monomers (a), of which
  • (a1) 20 to 90, preferably 22 to 85, preferably 25 to 80 and in particular 28 to 75% by weight, in each case based on the hydroxyl-containing monomers (a), from the group consisting of 4-hydroxybutyl (meth) acrylate and 2-alkyl-propane-1,3-diol-mono (meth) acrylates, and
  • Examples of suitable 2-alkyl-propane-1,3-diol-mono (meth) acrylates (a1) are 2-methyl, 2-ethyl, 2-propyl, 2-isopropyl or 2-n-butyl propane -1, 3-diol-mono (meth) acrylate, of which 2-methyl-propane-1,3-diol-mono (meth) acrylate is particularly advantageous and is preferably used.
  • Suitable other hydroxyl-containing olefinically unsaturated monomers (a2) are hydroxyalkyl esters of olefinically unsaturated carboxylic, sulfonic and phosphonic acids and acidic phosphoric and sulfuric acid esters, in particular carboxylic acids, such as acrylic acid, beta-carboxyethyl acrylate, methacrylic acid, ethacrylic acid and Crotonic acid, especially acrylic acid and methacrylic acid. They are derived from an alkylene glycol which is esterified with the acid, or they can be obtained by reacting the acid with an alkylene oxide such as ethylene oxide or propylene oxide.
  • the hydroxyalkyl esters in which the hydroxyalkyl group contains up to 20 carbon atoms are preferably used, in particular 2-hydroxyethyl or 3-hydroxypropyl acrylate or methacrylate; 1,4-bis (hydroxymethyl) cyclohexane or octahydro-4,7-methano-1H-indene-dimethanol monoacrylate or monomethacrylate; or reaction products from cyclic esters, such as, for example, epsilon-caprolactone and these hydroxyalkyl esters; or olefinically unsaturated alcohols such as allyl alcohol; or polyols, such as trimethylolpropane mono- or diallyl ether or pentaerythritol mono-, di- or triallyl ether; used.
  • higher-functional monomers (a2) are generally only used in minor amounts.
  • minor amounts of higher-functional monomers (a2) are to be understood as amounts which do not lead to the crosslinking or gelling of the (meth) acrylate copolymers (A), unless they should be in the form of crosslinked microgel particles ,
  • ethoxylated and / or propoxylated allyl alcohol which is sold by Arco Chemicals, or 2-hydroxyalkyl allyl ether, in particular 2-hydroxyethyl allyl ether, are suitable as monomers (a2). If used, they are preferably not used as sole monomers (a2), but in an amount of 0.1 to 10% by weight, based on the (meth) acrylate copolymer (A).
  • reaction products come from the olefinically unsaturated acids listed above, in particular acrylic acid and / or methacrylic acid, with the glycidyl ester of a monocarboxylic acid having 5 to 18 carbon atoms per molecule and branched in the alpha position, in particular a Versatic® acid, or instead of the reaction products, an equivalent amount of the olefinically unsaturated acids listed above, in particular acrylic and / or methacrylic acid, which are then used during or after the polymerisation reaction with the glycidyl ester of a monocarboxylic acid branched in the alpha position with 5 to 18 carbon atoms per molecule, in particular a Versatic® acid (cf. Römpp Lexikon Lacke und Druckmaschine, Georg Thieme Verlag, Stuttgart, New York, 1998, “Versatic® acids”, pages 605 and 606) becomes.
  • vinyl monomers containing acryloxysilane are suitable as monomers (a2), which are obtained by reacting hydroxy-functional silanes with epichlorohydrin and then reacting the reaction product with (meth) acrylic acid and / or hydroxyalkyl and / or cycloalkyl esters of (meth) acrylic acid and / or others hydroxyl-containing monomers (a1) and (a2) can be prepared.
  • the complementary reactive functional groups (i) can be introduced into the (meth) acrylate copolymers using the olefinically unsaturated monomers (a3) described below, which contain the reactive functional groups (i) in question, or by polymer-analogous reactions.
  • Acrylic acid beta-carboxyethyl acrylate, methacrylic acid
  • Ethacrylic acid crotonic acid, maleic acid, fumaric acid or itaconic acid
  • Vinylbenzoic acid (all isomers), alpha-methylvinylbenzoic acid (all isomers) or vinylbenzenesulfonic acid (all isomers); and or
  • epoxy groups such as the glycidyl ester of acrylic acid, methacrylic acid, ethacrylic acid, crotonic acid,
  • An example of the introduction of reactive functional groups (i) via polymer-analogous reactions is the reaction of some of the hydroxyl groups present in the binder (A) with phosgene, which results in resins containing chloroformate groups, and the polymer-analogous reaction of the resins containing chloroformate groups with ammonia and / or primary and / or secondary amines to binders (A) containing carbamate groups.
  • suitable methods of this type are described in US Pat 4,758,632 A 1, US 4,301,257 A 1 or US 2,979,514 A 1 known. It is also possible to introduce carboxyl groups by the polymer-analogous reaction of some of the hydroxyl groups with carboxylic anhydrides, such as maleic anhydride or phthalic anhydride.
  • the (meth) acrylate copolymers (A) may also contain at least one olefinically unsaturated monomer (a4) which are essentially or completely free of reactive functional groups, such as:
  • (Meth) acrylic acid derivatives (further examples of suitable monomers (a41) of this type are known from published patent application DE 196 25 773 A1, column 3, line 65, to column 4, line 20). These can be used in minor amounts of higher functional (meth) acrylic acid alkyl or cycloalkyl esters such as ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, butylene glycol, pentane-1,5-diol, hexane-1,6-diol, octahydro 4,7-methano-1H-indene-dimethanol or cyclohexane-1,2-, 1,3- or -1,4-diol-di (meth) acrylate; Trimethylolpropane di- or tri (meth) acrylate; or pentaerythritol di-, tri- or tetra (meth) acrylate. frame In the present invention, minor amounts of higher-functional mono
  • 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.
  • olefins When such olefins are reacted with formic acid or with carbon monoxide and water, a mixture of carboxylic acids is formed in which the carboxyl groups are predominantly located on a quaternary carbon atom.
  • olefinic starting materials are e.g. Propylene trimer, propylene tetramer and diisobutylene.
  • the vinyl esters can also be prepared from the acids in a manner known per se, e.g. 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).
  • radicals R 1 , R 2 , R 3 and R 4 each independently represent hydrogen atoms or substituted or unsubstituted alkyl, cycloalkyl, alkylcycloalkyl, cycloalkylalkyl, aryl, alkylaryl, cycioalkylaryl, arylalkyl or arylcycloalkyl radicals with the proviso that at least two of the variables R 1 , R 2 , R 3 and R 4 stand for substituted or unsubstituted aryl, arylalkyl or arylcycloalkyl radicals, in particular substituted or unsubstituted aryl radicals.
  • 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-1-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-1-yl.
  • the aryl radicals R 1 , R 2 , R 3 and / or R 4 are preferably phenyl or naphthyl radicals, in particular phenyl radicals.
  • the substituents optionally present in the radicals R 1 , R 2 , R 3 and / or R 4 are electron-withdrawing or electron-donating atoms or organic radicals, in particular halogen atoms, nitrile, nitro, partially or completely halogenated alkyl, cycloalkyl, alkylcycloalkyl , Cycloalkylalkyl, aryl, alkylaryl, cycioalkylaryl, arylalkyl and arylcycloalkyl radicals; Aryloxy, alkyloxy and cycloalkyloxy radicals; and / or arylthio, alkylthio and cycloalkylthio radicals.
  • Diphenylethylene is particularly advantageous, Dinaphthaleneethylene, eis or trans-stilbene or vinylidene bis (4-nitrobenzene), in particular diphenylethylene (DPE), which is why they are preferably used.
  • the monomers (a43) are used in order to regulate the copolymerization advantageously in such a way that a free-radical copolymerization in batch mode is also possible.
  • Vinyl aromatic hydrocarbons such as styrene, vinyl toluene,
  • 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-vinylpyrrolidori; 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 vinyl cyclohexyl 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 and / or vinylidene dihalides such as vinyl chloride, vinyl fluoride, vinylidene dichloride or vinylidene difluoride; N-vin
  • Allyl compounds especially allyl ethers and esters such as allyl methyl, ethyl, propyl or butyl ether or allyl acetate, propionate or butyrate.
  • 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 Have 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, as in DE 3807 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 4421 823 A1 or in international patent application WO 92/22615 on page 12, line 18, to page 18, line 10.
  • the monomers (a1) and (a2) and (a3) and / or (a4) are selected so that the OH numbers and glass transition temperatures given above result.
  • the type and amount of the monomers (a3) which contain reactive functional groups (i) are selected such that they do not inhibit or completely prevent the crosslinking reactions of the hydroxyl groups with the compounds (C) described below.
  • Tg glass transition temperature of the poly (meth) acrylate
  • W n weight fraction of the nth monomer
  • Method (Meth) acrylate copolymers (A) has no special procedural features, but takes place with the aid of the methods known and known in the plastics field of continuous or discontinuous radical-initiated copolymerization in bulk, solution, emulsion, miniemulsion or microemulsion under normal pressure or overpressure in stirred tanks, autoclaves , Tubular reactors, loop reactors or Taylor reactors at temperatures of preferably 50 to 200 ° C.
  • copolymerization processes are described in the patent applications DE 197 09 465 A1, DE 197 09 476 A1, DE 28 48 906 A1, DE 195 24 182 A1, DE 198 28 742 A1, DE 196 28 143 A1, DE 196 28 142 A1, EP 0 554 783 A1, WO 95/27742 A1, WO 82/02387 A1 or WO 98/02466 A1.
  • the copolymerization can, however, also be carried out in polyols (thermally curable reactive diluents) as the reaction medium, as is described, for example, in German patent application DE 198 50 243 A1.
  • Suitable free-radical initiators are dialkyl peroxides, such as di-tert-butyl peroxide or dicumyl peroxide; Hydroperoxides, such as cumene hydroperoxide or te .- 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; Azo initiators, for example azo dinitriles such as azobisisobutyronitrile; CC-splitting initiators like benzpinacol silyl ether; or a combination of a non-oxidizing initiator with hydrogen peroxide. Combinations of the initiators described above can also be used.
  • 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 .-%.
  • thiocarbonylthio compounds or mercaptans such as dodecyl mercaptan can be used as chain transfer agents or molecular weight regulators.
  • the (meth) acrylic copolymers (A) are preferably selected according to their type and quantity so that the coating materials according to the invention, after they have hardened, have a storage modulus E 'in the rubber-elastic range of at least 107.5 p a and j a loss factor tan ⁇ at 20 ° C. of a maximum of 0 , 10, the storage module E ' and the loss factor having been measured with 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 content of the binders (A) in the coating materials according to the invention can vary widely and depends primarily on the functionality of the binders (A) on the one hand and the possibly present, Compounds (A) described below, on the other hand.
  • the content, based on the solids content of the coating material according to the invention, is preferably 10 to 99.8, preferably 15 to 95, particularly preferably 15 to 90, very particularly preferably 15 to 85 and in particular 15 to 80% by weight.
  • the coating materials of the invention preferably also contain at least one constituent selected from the group consisting of low molecular weight, oligomeric and polymeric compounds (A) which are different from the binders (A) and which are on average
  • Suitable purely thermally curable crosslinking agents (A) are, for example, from German patent application DE 199 24 171 A1, page 7, line 38, to page 8, line 46, in conjunction with page 3, line 43, to page 5, Line 31, known. Blocked, partially blocked or unblocked polyisocyanates and aminoplast resins are preferably used.
  • suitable, purely thermally curable reactive diluents (A) are low molecular weight polyols, such as diethyloctanediols.
  • the coating materials according to the invention can replace at least one, in particular at least two, low molecular weight, oligomeric and / or polymeric compound (s) (A) with at least one, in particular at least two, group (s) instead of or in addition to the compounds (A) (i) and at least one, in particular at least two, group (s) (ii).
  • These compounds (A) are both dual-cure crosslinking agents and dual-cure reactive thinners.
  • Suitable dual-cure crosslinking agents / reactive diluents (A) of this type are described in detail in European patent application EP 0 928 800 A1, page 3, lines 17 to 54, and page 4, lines 41 to 54, or in the German patent application DE 198 18 735 A 1, column 3, line 16, to column 6, line 33.
  • Isocyanatoacrylates which can be prepared from polyisocyanates and the above-described hydroxyl-containing monomers (a1) and / or (a2) are preferably used.
  • the coating materials of the invention contain at least one organic solvent (C).
  • suitable organic solvents are the organic solvents described above in connection with the additive (B) to be used according to the invention.
  • the coating materials of the invention can also contain at least one customary and known additive (D) in the customary and known effective amounts, preferably selected from the group consisting of molecularly dispersible dyes; Light stabilizers, such as UV absorbers and reversible radical scavengers (HALS); antioxidants; Wetting agents; emulsifiers; slip additives;
  • D customary and known additive
  • Corrosion inhibitors ; anti-caking agents; To grow; driers; Biocides and matting agents.
  • the coating materials according to the invention can contain opaque, transparent pigments (E), in particular nanoparticles (E).
  • the solids content of the coating materials according to the invention can vary very widely. It depends in particular on the ingredients used, the application behavior and the intended use of the coating materials. If the coating materials according to the invention are adjusted in their composition, for example, so that they are curable thermally or thermally and with actinic radiation, their solids content during application is preferably above 40 and in particular above 45% by weight, in each case based on the coating material according to the invention.
  • the coating materials according to the invention as one-component systems, they preferably contain, based in each case on the solid of a coating material according to the invention
  • binder (A) 10 to 80, preferably 20 to 75 and in particular 25 to 70% by weight of binder (A),
  • additive (B) 0.01 to 6, preferably 0.02 to 5, and in particular 0.0 3 to 4% by weight of additive (B) and
  • the coating materials according to the invention also contain 5 to 30, preferably 7 to 25 and in particular 10 to 20% by weight of at least one rheology aid, preferably a sag control agent (SCA) (D).
  • SCA sag control agent
  • the production of the coating materials according to the invention has no special features, but takes place by mixing and homogenizing the constituents described above with the aid of customary and known mixing methods and devices such as stirred kettles, agitator mills, extruders, kneaders, Ultraturrax, in-line dissolvers, static mixers, Gear rim dispersers, pressure relief nozzles and / or microfluidizers, possibly with the exclusion of actinic radiation.
  • the application of the coating materials according to the invention has no special features, but can be carried out by all customary and known application methods suitable for the respective coating material, such as, for example, Spraying, spraying, knife coating, brushing, pouring, dipping, trickling or rolling. Spray application methods are preferably used
  • the coating materials of the invention generally harden after a certain resting time or flash-off time. It can last from 5 s to 2 h, preferably 1 min to 1 h and in particular 1 to Have 45 min.
  • the rest period is used, for example, for the course and degassing of the wet layers and for the evaporation of the organic solvents present.
  • the ventilation can be accelerated by an elevated temperature, which is not yet sufficient for hardening.
  • this process measure can also be used to dry the applied paint layers, in particular electrocoat layers, filler layers and / or basecoat layers, which are not intended to be cured or only to be partially cured.
  • the thermal curing takes place, for example, with the aid of a gaseous, liquid and / or solid, hot medium, such as hot air, heated oil or heated rollers, or using microwave radiation, infrared light and / or near infrared light (NIR).
  • the heating is preferably carried out in a forced air oven and / or by irradiation with IR and / or NIR lamps.
  • thermal curing can also be carried out in stages, for example by moving at least one temperature ramp.
  • the thermal curing advantageously takes place at temperatures from room temperature to 200.degree.
  • a dose of 500 to 4,000, preferably 1,000 to 2,900, particularly preferably 1,200 to 2,800, very particularly preferably 1,300 to 2,700 and in particular 1,400 to 2,600 mJ / cm 2 is preferably used.
  • the usual and known radiation sources and optical auxiliary measures are used for curing with actinic radiation.
  • suitable radiation sources are flash lamps from VISIT, high-pressure or low-pressure mercury vapor lamps, which, if appropriate are doped with lead to open a beam window up to 405 nm, or electron beam sources.
  • Their arrangement is known in principle and can be adapted to the conditions of the workpiece and the process parameters.
  • shadow areas such as cavities, folds and other undercuts due to construction, can be connected to spotlights, small areas or all-round emitters, combined with an automatic movement device for the irradiation of Cavities or edges, are cured.
  • the curing can take place in stages, i. H. by multiple exposure or exposure to actinic radiation. This can also take place alternately, i. that is, for example, alternately curing with UV radiation and electron radiation.
  • Thermal curing and curing with actinic radiation can be used simultaneously or in succession. If the two curing methods are used one after the other, thermal curing can be started, for example, and curing with actinic radiation can be ended. In other cases, it may prove advantageous to start with the end of curing with actinic radiation.
  • Curing with actinic radiation is preferably carried out under inert gas in order to avoid the formation of ozone.
  • inert gas instead of one pure inert gas, an oxygen-depleted atmosphere can be used
  • Oxygen-depleted means that the content of oxygen in the atmosphere is less than the oxygen content of air (20.95% by volume).
  • the maximum content of the oxygen-depleted atmosphere is preferably 18, preferably 16, particularly preferably 14, very particularly preferably 10 and in particular 6.0% by volume.
  • the minimum oxygen content is preferably 0.1, preferably 0.5, particularly preferably 1.0, very particularly preferably 1.5 and in particular 2.0% by volume.
  • the above-described methods and device for application and curing can also be used for coating materials, such as electrocoating materials, fillers and / or basecoats, which are not used according to the invention and are used for producing color and / or effect multi-layer coatings according to the invention.
  • Suitable fillers which are also referred to as stone chip protection primers or functional layers, can be found in 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 89J10387 A1, US 4,450,200 A1 , US 4,614,683 A1 or WO 94/26827 A1.
  • Suitable basecoats are known from patent applications EP 0 089 497 A1, EP 0 256 540 A1, EP 0 260 447 A1, EP 0 297 576 A1, WO 96/12747, EP 0 523 610 A1, EP 0 228 003 A1, EP 0 397 806 A1, EP 0 574 417 A1, EP 0 531 510 A1, EP 0 581 211 A1, EP 0 708 788 A1, EP 0 593 454 A1, DE 43 28 092 A1, EP 0 299 148 A1, EP 0 394 737 A1, EP 0 590 484 A1, EP 0 234 362 A1, EP 0 234 361 A1, EP 0 543 817 A1, WO 95 / 14721, EP 0 521 928 A1, EP 0 522 420 A1, EP 0 522 419 A1, EP 0 649 865 A1, EP 0 536 712 A1, EP 0 596
  • the layer thicknesses of the coatings according to the invention and not according to the invention are preferably in the customarily used ranges:
  • Basislackierunq Preferably 5 to 30, preferably 7.5 to 25 and in particular 10 to 20 ⁇ m;
  • the color and / or effect multi-layer coatings obtained according to the invention are simple to produce and have excellent automotive quality. In addition, they are free of runners, craters and dents. They can easily be painted over for repairs.
  • the coating materials according to the invention can also be used as adhesives and sealants for the production of adhesive layers and seals according to the invention and are used for coating, gluing and / or sealing primed or unprimed substrates made of metal, plastic, glass, wood, textile, leather, natural and artificial stone , Concrete, cement or composites of these materials.
  • the substrates can be primed.
  • customary and known primer layers or adhesive layers can be used as primers, or the plastic surfaces can be provided with reactive compounds such as fluorine by flame treatment or etching.
  • primers can be used as primers, as described in Römpp Lexikon Lacke und Druckmaschine, Georg Thieme Verlag, Stuttgart, New York, 1998, "Primer”, page 473, "Wash Primer", page 618 , or "Production Coating", page 230, is described.
  • Primer preferably uses an aluminum oxide layer produced by anodic oxidation.
  • the coating materials, adhesives or sealing compounds according to the invention are therefore outstanding for painting, gluing and sealing bodies of locomotion from locomotion means, including aircraft, rail vehicles, water vehicles and floating bodies, vehicles and motor vehicles powered by muscle power, indoors and outdoors and parts thereof, structures inside - and outdoors, doors, windows and furniture as well as for painting, gluing and sealing in the context of industrial painting of small parts, coils, containers, packaging, electrotechnical, mechanical and optical components as well as white goods.
  • the substrates which are coated, glued and / or sealed with them are of particularly long service life and are therefore economically, ecologically and technically particularly valuable for the users.
  • the coating materials of Examples 1 to 6 (see Table 1) and the non-inventive coating materials of Comparative Experiments V 1 to V 5 (see Table 2) were prepared by mixing their constituents and homogenizing the resulting mixtures.
  • the test panels had holes. These were arranged in the form of a row of holes parallel to the layer thickness gradient and close to an edge parallel to it.
  • the coated test sheets with a parallel row of holes were fixed in a vertical position in which the vector of gravity forms an angle of 0 ° with a contour line and an angle of 90 ° with the layer thickness gradient.
  • the applied wedge-shaped layers were then dried at room temperature for 10 minutes and cured at 140 ° C. for 30 minutes.
  • Tables 1 and 2 show the wet layer thicknesses from which runners formed below the holes due to the layer thickness, gravity and insufficient adhesion to the test sheet.
  • Table 1 The composition of the coating materials according to the invention from Examples 1 to 6 and the performance properties of the clearcoats produced therefrom
  • Tinuvin ® 123 h 0.6 0.6 0.6 0.6 0.6 0.6 0.6
  • Solids content (% by weight) 46.6 45 46.2 48.3 47.6 46.1
  • Table 2 The composition of the coating materials of the comparative tests V 1 to V 5 and the application properties of the clearcoats produced therefrom Comparative tests:
  • Crosslinking agent 1 G 6.1 6.1 6.1 6.1 6.1
  • Tinuvin®123 h 0.6 0.6 0.6 0.6 0.6
  • Solids content (% by weight) 48.8 49.9 49.8 50.1 50.4

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Paints Or Removers (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Processes Of Treating Macromolecular Substances (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Sealing Material Composition (AREA)

Abstract

L'invention concerne des matériaux de revêtement exempts de pigments couvrants, contenant des solvants, thermodurcissables et/ou durcissables par un rayonnement actinique. Ces matériaux contiennent: (A) au moins un composant sélectionné dans le groupe constitué d'oligomères et polymères à faible poids moléculaire, des liants thermodurcissables et durcissables par un rayonnement actinique, des agents de réticulation et des diluants réactifs ; et (B) 0,01 à 4 % en poids, par rapport à la matière de revêtement, de particules de polyamide-cire synthétiques en dispersion . L'invention concerne également leur procédé de production et leur utilisation pour la production de vernis clair monocouche et multicouche et de peintures multicouches chromophore et/ou à effet ou comme colles et masses d'étanchéité.
EP04734223A 2003-06-12 2004-05-21 Materiaux de revetement exempts de pigments couvrants, contenant des solvants, thermodurcissables et/ou durcissables par un rayonnement actinique ; leur procede de production et leur utilisation Withdrawn EP1631631A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE10326353A DE10326353A1 (de) 2003-06-12 2003-06-12 Lösemittelhaltige, thermisch und/oder mit aktinischer Strahlung härtbare, von deckenden Pigmenten freie Beschichtungsstoffe, Verfahren zu ihrer Herstellung und ihre Verwendung
PCT/EP2004/005467 WO2004111139A1 (fr) 2003-06-12 2004-05-21 Materiaux de revetement exempts de pigments couvrants, contenant des solvants, thermodurcissables et/ou durcissables par un rayonnement actinique ; leur procede de production et leur utilisation

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EP (1) EP1631631A1 (fr)
JP (1) JP2006527287A (fr)
KR (1) KR20060020673A (fr)
CN (1) CN1806019A (fr)
CA (1) CA2526207A1 (fr)
DE (1) DE10326353A1 (fr)
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CA2487916A1 (fr) * 2003-12-04 2005-06-04 Rohm And Haas Company Revetement transparent flexible a un composant, resistant a l'attaque chimique
DE102005057245A1 (de) * 2005-11-29 2007-06-06 Bayer Materialscience Ag Lackierte Folien
DE102007015261A1 (de) * 2007-03-27 2008-10-02 Aacure Aadhesives Gmbh Reaktivmasse und Verfahren zur Aufbringung hierfür
US20080280061A1 (en) * 2007-05-07 2008-11-13 Roger Questel Method for sealing natural stone
DE102007031349A1 (de) * 2007-07-05 2009-01-08 Bayerische Motoren Werke Aktiengesellschaft Hybridbauteil mit haftvermittelnder Beschichtung sowie Verfahren zu dessen Herstellung
EP2697320B1 (fr) 2011-04-12 2015-11-25 BASF Coatings GmbH Composition de revêtement de vernis transparent contenant un solvant, procédé de fabrication et utilisation
EP2782966B1 (fr) * 2011-11-25 2016-09-28 BASF Coatings GmbH Composition de revêtement de peinture vernie contenant un solvant, procédé de préparation et utilisation de ladite composition
CN103102786A (zh) * 2012-11-13 2013-05-15 益阳祥瑞科技有限公司 一种脂肪族聚脲涂料
DE102018133035A1 (de) * 2018-12-20 2020-06-25 Pfinder Kg Lichtinduzierte Kaltapplikation einer dickschichtigen Korrosionsschutzbeschichtung mit kontrollierbarer Kinetik

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US5348998A (en) * 1989-08-04 1994-09-20 Kansai Paint Co., Ltd. Coating composition comprising particles of an emulsion polymerized gelled polymer
US5743946A (en) * 1995-12-18 1998-04-28 Asahi Glass Company Ltd. Water-color ink composition and process for forming an inorganic coating film
JPH11114489A (ja) * 1997-10-09 1999-04-27 Nippon Paint Co Ltd 積層塗膜形成方法及び塗料組成物
JPH11169783A (ja) * 1997-12-09 1999-06-29 Nippon Paint Co Ltd 積層塗膜の形成方法及び塗料組成物
DE10047290A1 (de) * 2000-09-25 2002-04-11 Bayer Ag Verfahren zur Herstellung einer Beschichtung auf porösen und/oder saugfähigen Materialien
US6433091B1 (en) * 2001-05-10 2002-08-13 Henkel Loctite Corporation Adhesive composition
DE10129899A1 (de) * 2001-06-21 2003-01-09 Basf Coatings Ag Physikalisch, thermisch oder thermisch und mit aktinischer Strahlung härtbarer wäßriger Beschichtungsstoff und seine Verwendung
JP4063715B2 (ja) * 2003-05-30 2008-03-19 本田技研工業株式会社 塗膜形成方法

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CN1806019A (zh) 2006-07-19
MXPA05012866A (es) 2006-02-22
KR20060020673A (ko) 2006-03-06
US20070054999A1 (en) 2007-03-08
WO2004111139A1 (fr) 2004-12-23
CA2526207A1 (fr) 2004-12-23
JP2006527287A (ja) 2006-11-30

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