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WO1997025380A1 - Agents de revetement durcissables avec un faible retrait et comportant un bon pouvoir d'adherence sur des substrats metalliques - Google Patents

Agents de revetement durcissables avec un faible retrait et comportant un bon pouvoir d'adherence sur des substrats metalliques Download PDF

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Publication number
WO1997025380A1
WO1997025380A1 PCT/EP1996/005502 EP9605502W WO9725380A1 WO 1997025380 A1 WO1997025380 A1 WO 1997025380A1 EP 9605502 W EP9605502 W EP 9605502W WO 9725380 A1 WO9725380 A1 WO 9725380A1
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Prior art keywords
component
weight
structural units
coating agent
formula
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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
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PCT/EP1996/005502
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German (de)
English (en)
Inventor
Dietmar Chmielewski
Uwe Meisenburg
Rainer Blum
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BASF Farben und Fasern AG
PPG Industries Inc
Original Assignee
BASF Lacke und Farben AG
PPG Industries Inc
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Publication of WO1997025380A1 publication Critical patent/WO1997025380A1/fr
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    • 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
    • C09D167/00—Coating compositions based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Coating compositions based on derivatives of such polymers
    • C09D167/06—Unsaturated polyesters having carbon-to-carbon unsaturation
    • C09D167/07—Unsaturated polyesters having carbon-to-carbon unsaturation having terminal carbon-to-carbon unsaturated bonds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
    • C08F290/06—Polymers provided for in subclass C08G
    • 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
    • C09D171/00—Coating compositions based on polyethers obtained by reactions forming an ether link in the main chain; Coating compositions based on derivatives of such polymers
    • C09D171/02—Polyalkylene oxides
    • 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
    • C09D177/00—Coating compositions based on polyamides obtained by reactions forming a carboxylic amide link in the main chain; Coating compositions based on derivatives of such polymers
    • C09D177/12—Polyester-amides
    • 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
    • C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
    • C09D4/06—Organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond in combination with a macromolecular compound other than an unsaturated polymer of groups C09D159/00 - C09D187/00

Definitions

  • the invention relates to low-emission and low-shrinkage curable coating compositions with good adhesion to metal substrates, in particular tinplate, steel sheet and aluminum, which contain mixtures of prepolymers A) as binders, at least two ethylenically unsaturated double bonds, preferably at least two acrylic and / or methacrylic groups, as well as prepolymers B), which contain dihydrodicyclopentadiene and / or oligodihydicyclopentadiene structural units.
  • Radiation- and / or thermosetting lacquers for metal substrates are usually composed of binder systems, reactive diluents, solvents, pigments and auxiliaries.
  • binder systems are, for example, polyester (meth) acrylates, polyether (meth) acrylates, urethane (meth) acrylates, epoxy (meth) acrylates and similar (meth) acrylated polymers, which are generally used with reactive diluents, such as, for example, monomers and / or oligomeric (meth) acrylates can be adjusted to the processing viscosity.
  • the proportion of reactive diluents in customary paints is up to 50% by weight.
  • a disadvantage of the reactive diluent-containing systems is the surface inhibition by atmospheric oxygen and the health-damaging potential of the reactive diluents, such as, for example, styrene, vinyl toluene,
  • the high shrinkage is in particular the cause of adhesion problems of the paints on smooth, hard substrates.
  • An attempt is therefore made to improve the adhesion with so-called adhesion promoters, such as, for example, acrylates containing acid groups, dimethylaminopropyl acrylate, silanes, titanates or thio compounds.
  • adhesion promoters such as, for example, acrylates containing acid groups, dimethylaminopropyl acrylate, silanes, titanates or thio compounds.
  • DE-A-43 02 327 describes radiation-curable coating compositions containing oligomers with several ethylenically unsaturated end groups and several urea and optionally urethane groups per molecule, which are used for coating glass surfaces, in particular glass fibers.
  • the coating compositions contain at least one ethylenically unsaturated monomeric and / or oligomeric compound in an amount of 20 to 50% by weight, based on the total weight of the coating composition.
  • the monomers described are critical with regard to their toxicity.
  • DE-A-43 44 125 covers low-shrinkage, radiation-curable protective coatings containing at least one prepolymer with at least two ethylenically unsaturated double bonds, at least one cationically curing epoxy resin, at least one ketone and / or ketone / formaldehyde resin, 5 to 40% by weight .-% of at least one reactive diluent and a mixture of at least one initiator for initiating the cationic polymerization and at least one initiator for initiating the radical polymerization.
  • the coating compositions described are complex in their composition, in particular with regard to the initiator mixture.
  • Powder coatings As relatively low-emission systems, powder coatings, aqueous coating systems and liquid (UV) radiation-curable coatings are known as alternatives to the solvent-containing systems. Powder coatings have the disadvantage that the requirements for good storage stability, in particular for blocking resistance, and for a good flow when melting the powder coating are often opposing. Another disadvantage is that a relatively high energy is required for melting the powder coating particles in powder coatings.
  • the disadvantage of the aqueous systems is that the evaporation of the water is complex, in particular energy-intensive, and that the water mostly has a deleterious effect on the substrates to be coated.
  • Unsaturated polyester resins with dicyclopentadiene structural units as components of conventional UP resin systems are known.
  • UP resin systems also contain monomeric reactive thinners, in particular styrene, which cause the above-mentioned problems and emission problems when processing the UP resins.
  • DE-A-27 08 846 describes the partial replacement of the reactive thinner styrene in conventional UP resin systems by special polyesters with dicyclopentadiene structure units, and the use of such UP resin systems as materials.
  • the rest of the reactive thinner styrene is for the use of such resin systems, in particular as low-emission processable and curable printing inks from ecological Reasonable and for reasons of pollution in the workplace.
  • DE-A-31 07 450 covers unsaturated polyesters with oligomers of dicyclopentadiene as end groups, which are used as solutions in ethylenically unsaturated monomers for the production of moldings and coatings.
  • the ethyle ⁇ used as reactive diluents cally unsaturated monomers are generally pro- sion problems problematic because of their high vapor pressure at room and processing temperature ⁇ and the associated Emis ⁇ .
  • EP-A-0 101 585 describes unsaturated polyester resins which are modified by adding cyclopentadiene to the double bonds of the unsaturated units of the polyester and are then dissolved in vinyl monomers as reactive diluents.
  • binders for coating agents especially for metal substrates, which have low shrinkage, which are comparatively simple in their construction and which are largely free of solvents and / or reactive thinners.
  • binders should have the properties required for metal coating compositions, such as, for example, good absorption capacity for pigments and / or dyes, storage stability, sufficient processing times and good workability.
  • prepolymers A) with at least two ethylenically unsaturated double bonds, preferably at least two (meth) acrylic groups are used as binders.
  • the coating compositions according to the invention preferably contain 5 to 95% by weight, particularly preferably 10 to 80% by weight, of the prepolymers A) and 2 to 95% by weight, particularly preferably 10 to 80% by weight, of the prepolymers B), each based on the coating agent.
  • the following may preferably be present in the coating composition: C) 0 to 10% by weight, preferably 2 to 5% by weight, based on the coating agent, of at least one initiator for initiating the free-radical polymerization,
  • F 0 to 10% by weight, preferably 1 to 5% by weight, based on the coating agent, customary additives and / or auxiliaries.
  • the dihydrodicyclopentadienyl units and / or the oligodihydicyclopentadienyl units contained in component B) are preferably esters of dihydrodicyclopentadienol according to formula (III) or esters of oligodihydrodicyclopentadienol according to formula (IV):
  • dihydrodicyclopentadiene units and / or oligodihydrodicyclopentadiene units are half esters of dihydrodicyclopentadienol with maleic acid and / or fumaric acid according to formula (V) or half esters of oligodihydrodicyclopentadienol with maleic acid and / or fumaric acid:
  • Prepolymers B) are preferably saturated and / or unsaturated polyester resins which contain the structural units of the formulas (I) to (VI).
  • the saturated and / or unsaturated polyester resins B) further preferably contain mono- and / or polyols which are alkoxylated, preferably ethoxylated and / or propoxylated, for example derived from polyethylene oxide, polypropylene oxide or polytetrahydrofuran, as structural units.
  • the saturated and / or unsaturated polyester resins B) contain mono- and / or polyols which Have polyester units, for example polycaprolactone, as structural units.
  • the unsaturated polyester resins B) preferably contain ethylenically unsaturated polymer building blocks, such as preferably maleic acid and / or fumaric acid.
  • the saturated and / or unsaturated polyester resins B) preferably contain mono- and / or polyols which have imide groups as structural elements.
  • the saturated and / or unsaturated polyester resins B) further preferably contain mono- and / or polycarbonate acids which have imide groups as structural elements.
  • the prepolymers B) contain up to 100% by weight, based on the prepolymers B), of low molecular weight esterification products B ') with the (oligo) dihydrodicyclopentadiene structural units of the formulas (III) bis (VI), the esterification products having a low viscosity and a high boiling point.
  • the present invention also encompasses processes for producing coatings, in particular on metal containers, in which the previously described coating compositions are cured by radiation and / or thermally at temperatures between 80 and 300 degrees, optionally in the presence of initiators C).
  • the invention also encompasses the use of the coating compositions according to the invention for painting, coating and printing metal substrates, in particular metal containers, such as for example, metal cans, in particular made of aluminum, sheet steel or tinplate.
  • Suitable as component A) are prepolymers which have at least two ethylenically unsaturated groups per molecule.
  • a wide variety of resins can be used as the basic structure.
  • the double bonds are preferably derived from ethylenically unsaturated carboxylic acids, preferably from acrylic and / or methacrylic acid and particularly preferably from acrylic acid. Therefore, as component A), for example, polyester acrylates, polyether acrylates, epoxy acrylates, urethane acrylates or acrylate polymer acrylate groups are suitable.
  • the urethane acrylates which can be used as component A) are known and are described, for example, in EP-B-0 167 199 and EP-B-0 204 161.
  • the amounts of chain extender, di- and / or polyisocyanate and hydroxyalkyl ester of an ethylenically unsaturated carboxylic acid are chosen so that the equivalent ratio of the NCO groups to the reactive groups of the chain extender (hydroxyl, amino or mercapto groups) is between 3: 1 and 1: 2, is preferably 2: 1 and that the hydroxyl groups of the hydroxylalkyl esters of the ethylenically unsaturated carboxylic acids are present in a stochiometric amount with respect to the still free NCO groups of the prepolymer of isocyanate and chain extender.
  • polyurethane acrylates A) by first reacting some of the NCO groups of a di- and / or polyisocyanate with at least one hydroxyalkyl ester of an ethylenically unsaturated carboxylic acid and then reacting the remaining isocyanate groups with the chain extender . In this case, too, the equivalent ratios given above apply.
  • part of the isocyanate groups of a diisocyanate can first be reacted with a diol, then another part of the isocyanate groups can be reacted with the hydroxylalkyl ester of an ethylenically unsaturated carboxylic acid and then the remaining isocyanate groups can be reacted with a diamine.
  • the epoxy acrylates suitable as component A) are also known and commercially available. They can be obtained by adding acrylic acid
  • Epoxy resins for example epoxy resins based on bisphenol-A or other commercially available epoxy resins.
  • component A ethylenically unsaturated, preferably acryloxy group-containing,
  • Copolymers can be obtained by reacting a copolymer with functional groups, such as, for example, hydroxyl, carboxyl, amino, thiol, epoxy and / or isocyanate groups, with compounds which have at least one ethylenically unsaturated double bond and one compared to the functional groups have a reactive group.
  • functional groups such as, for example, hydroxyl, carboxyl, amino, thiol, epoxy and / or isocyanate groups
  • Suitable ethylenically unsaturated acrylate copolymers can be obtained, for example, by adding an ethylenically unsaturated isocyanate, an anhydride of an ethylenically unsaturated carboxylic acid, an ethylenically unsaturated carboxylic acid or an equimolar addition product of an ethylenically unsaturated hydroxyl group-containing compound and a diisocyanate compound to a hydroxyl group-containing acrylate group.
  • Suitable ethylenically unsaturated acrylate copolymers A) can also be obtained, for example, by reacting an acrylate resin containing carboxyl groups with ethylenically unsaturated compounds which also have a group which is reactive towards carboxyl groups, such as, for example, hydroxyalkyl esters of ethylenically unsaturated carboxylic acids or epoxy group-unsaturated, ethylenically unsaturated compounds e.g. Glycidyl (meth) acrylate.
  • epoxy group-containing acrylate resins can also be reacted with ethylenically unsaturated compounds which have a group which is reactive towards epoxy groups, such as e.g. ethylenically unsaturated carboxylic acids.
  • Acrylic-modified polyesters are preferably used as component A). These polyesters can be produced by various methods. For example, acrylic acid or another ethylenically unsaturated
  • Carboxylic acid directly as an acid component in the construction of the Polyester are used.
  • hydroxyalkyl esters of (meth) acrylic acid or other ethylenically unsaturated carboxylic acids as alcohol components directly in the construction of the polyesters.
  • the acrylic-modified polyesters are preferably produced by acrylating polyesters.
  • hydroxyl-containing polyesters can first be built up, which are then reacted with acrylic and / or methacrylic acid.
  • 'E ⁇ can also be zunumble ⁇ t carboxyl Polye ⁇ ter workplace ⁇ constructs, which are then reacted with a Hydroxyalkyle ⁇ ter of acrylic and / or methacrylic acid.
  • Unreacted (meth) acrylic acid can be removed from the reaction mixture by washing, distilling or preferably by reacting with an equivalent amount of a mono- or diepoxide compound using suitable catalysts, such as triphenylphosphine.
  • polyester acrylates suitable as component A With regard to further details on the preparation of the polyester acrylates suitable as component A), reference is made in particular to DE-A-33 16 593 and DE-A-38 36 370 and also to EP-A-0 054 105, DE-AS -20 03 579 and EP-B-0 002 866.
  • polyester acrylates suitable as component A) are the products commercially available under the following brand names: various Laromer® types from BASF AG, such as Laromer® LR 8799, Laromer® LR 8828, Laromer® LR 8800, Laromer® PE 55F, Laromer® PE 46 and Laromer® E 55W, as well as oligomer AS-X95 and oligomer AS-X6 from Han ⁇ Rahn & Co., Zurich.
  • Laromer® types from BASF AG, such as Laromer® LR 8799, Laromer® LR 8828, Laromer® LR 8800, Laromer® PE 55F, Laromer® PE 46 and Laromer® E 55W, as well as oligomer AS-X95 and oligomer AS-X6 from Han ⁇ Rahn & Co., Zurich.
  • Component A) is used in the coating compositions according to the invention in an amount of 5 to 95% by weight, preferably 10 to 80% by weight, based on the coating composition.
  • prepolymers B which contain, as structural units, dihydrodicyclopentadienyl structural units of the formula (I) or oligodihydrodicyclopentadienyl structural units of the formula (II).
  • the dihydrodicyclopentadienyl and the oligodihydrodicyclopentadienyl structural units of the formulas (I) to (VT) are all derived from the starting material dicyclopentadiene, which in turn is a dimerization product of cyclopentadiene (for the synthesis of the cyclopentadiene, compare the chemistry of the en .conoml., Volume 9, pages 699 to 704, Verlag Chemie, Weinheim, 1975).
  • the cyclopentadiene dimerizes spontaneously at room temperature to dicyclopentadiene.
  • cyclopentadiene reacts with itself via dicyclopentadiene as an intermediate to oligodicyclopentadiene by the mechanism of the Diels-Alder reaction.
  • catalysts such as the halides of aluminum, antimony, boron, egg, hermitage or tin, are added, cyclopentadiene polymerizes in the absence of oxygen to polycyclopentadiene with molecular weights of up to 10,000 daltons.
  • the dihydrodicyclopentadiene and / or oligodihydrodicyclopentadiene units used in component B) can be derived from the corresponding dihydrodicyclopentadienol of the formula (VII):
  • the compounds of the formulas (VII) and (VIII) are accessible, for example, from dicyclopentadiene or oligodicyclopentadiene by, if appropriate, acid-catalyzed addition of water and are commercially available.
  • the (oligo) dihydrodicyclopentadienols of the formulas (VII) and (VIII) can also be used on their own as a synthesis unit.
  • the structural units of the formulas (III) to (IV) are preferably obtainable by reacting the dicyclopentadiene or the oligodicyclopentadiene with acids or their anhydrides, preferably with carboxylic acids, particularly preferably with polycarboxylic acids or their anhydrides. Is very particularly preferred as an acid Maleic and / or fumaric anhydride is used in such amounts that the corresponding half esters of formulas (V) and (VI) are obtained as structural units.
  • the dicyclopentadiene or the oligodicyclopentadiene is preferably reacted with the (poly) carboxylic anhydride in the presence of water at preferably elevated temperature.
  • the structural units (III) to (VI) containing ester groups can also be reacted by reacting the corresponding dihydrodicyclopentadienol (VII) or the corresponding oligodihydrodicyclopentadienol (VIII) with acids, preferably with carboxylic acid, particularly preferably with polycarboxylic acids and very particularly preferably with Maleic and / or fumaric acid or in particular their anhydrides can be obtained.
  • Suitable polycarboxylic acids which can also be involved as the sole structural element in addition to the structural elements according to the invention in the construction of the unsaturated and / or saturated polyesters preferred as component B), are, in addition to the preferably used maleic and / or fumaric acid, for example: phthalic acid, isophthalic acid , Terephthalic acid, tetrahydro- and / or hexahydrophthalic acid, endomethylenetetrahydrophthalic acid, malonic acid, succinic acid, glutaric acid, sebacic acid, azelaic acid, trimellitic acid, pyromelitic acid, di- and / or polycarboxylic acid with ethylenically unsaturated acidic acid units, such as contaconic acid, such as aconconic acid, , mono- or polyunsaturated fatty acids, such as coconut oil, peanut oil, castor oil, wood oil, soybean oil, linseed oil, cottonseed oil or saf
  • the synthesis of the saturated and unsaturated polyesters preferred as component B) is carried out according to the known processes of the prior art, generally by polycondensation of di- and / or polyols and di- and / or polycarboxylic acids or their anhydrides at elevated temperature . Furthermore, it can be advantageous to use the esters with lower alcohols instead of the di- and / or polycarboxylic acids and to produce the polyesters by transesterification at higher temperatures, because in some cases such transesterifications run faster than the comparable veresterification reaction.
  • polyesters with amide groups can also be used as component B) be preserved.
  • amide or imide structures into the preferred polyesters B) is known, for example, from DE-A-15 70 273 and DE-A-17 20 323.
  • Such polyester amides or polyester imides can meet special requirements, such as increased heat resistance, better in some cases than polyester B), which exclusively have polyol and polycarbonate units.
  • Di- and / or polyols suitable for the synthesis of the polyesters preferred as component B) are, for example: ethylene glycol, 1,2-and 1,3-propanediol, 1,2-1,3 and 1,4-butanediol , 2-Ethylpropanediol-1, 3, 2-ethylhexanediol-1,6, 1,3-neopentylglycol, 2,2-dimethylpentanediol-1,3, hexanediol-1,6, cyclohexanediol-1,2 and -1, 4, 1,2- and l, 4-Bi ⁇ (hydroxymethyl) cyclohexane, adipic acid bis (ethylene glycol) ester, ether alcohols, such as di- and triethylene glycol or dipropylene glycol, bisphenols, perhydrogenated bisphenols, butanetriol-1,2,4 , Hexanetriol-1,2,6, trimethylolethane, trimethyl
  • oligomeric and / or polymeric diols and / or polyols can be used as di- and / or polyol building blocks, such as, for example: hydroxyl-group-modified polybutadienes, hydroxyl-group-containing polyurethanes or hydroxyl-group-containing epoxy resins.
  • alkoxylated diols and / or polyols such as, for example, the ethoxylation or propoxylation products of the diols and / or polyols mentioned.
  • the polyesters preferred as component B) are produced as follows: In a first stage, a polyester resin, polyester amide resin or polyester imide resin (prepolyester) is synthesized, which does not have structural units of formula (I) and formula (II) but an excess of free acid groups due to a specific ratio of hydroxyl to acid groups during the polyester synthesis.
  • the prepolyester is reacted with dicyclopentadiene, optionally in the presence of catalysts, polymer-analogously to the polyesters B) with the structural units of the formula (I) and / or (II).
  • the side reaction is the addition of cyclopentadiene to the double bonds, which leads, for example in the case of maleic acid units, to the formation of endomethylene tetrahydrophthalic acid structural units.
  • polyesters B) which meet special requirements, such as hardness, elasticity or processing viscosity, is carried out according to rules known to the person skilled in the art.
  • the elasticity of the polyesters can be varied by the chain length of the degraded polyols and / or polycarboxylic acids between the ester linkage points: for example, polyesters with hexanediol and / or adipic acid components are elastic as polyesters with ethylene glycol and / or phthalic acid Building blocks.
  • component B) contains, in addition to the ' prepolymers B) described, up to 100% by weight, based on B), of low molecular weight esterification products B') with (oligo) dihydrodicyclopentadiene structural units of the formulas (III) and / or (IV) and / or half esters of the formulas (V) and / or (VI), the esterification products having a low viscosity and a high boiling point.
  • the low molecular weight esterification products B ') can be prepared, for example, by reacting the (oligo) dihydrodicyclopentadiene compounds of the formulas (V) or (VI) with monofunctional and / or polyfunctional alcohols.
  • butanol, hexanol, polyethylene glycol monoalkyl ether or polypropylene glycol monoalkyl ether can be used as monofunctional alcohols (monools).
  • polyfunctional alcohols polyols
  • polyols are the polyols already mentioned above in the synthesis of polyester, in particular butanediol, hexanediol, trimethylolpropane, pentaerythritol or compounds with even higher hydroxy functionality.
  • polyol components are the alkoxylation products, especially the ethoxy lation products and / or the propoxylation products, such polyols, and also polyester polyols, for example polycaplactone, or polyether polyols, for example based on polyethylene oxide, polypropylene oxide or polytetrahydrofuran, their esterification with the (oligo) dihydrodicyclopentadiene compounds of the formulas (V) and (VI) leads to esters with low viscosity.
  • the type of alkoxylating agent and the degree of alkoxylation also allow properties of the resulting hardened films, such as hardness, abrasion resistance, flexibility and lubricity, to be controlled.
  • the polyols can also be exclusively esterified with the (oligo) dihydrodicyclopentadiene compounds of the formulas (V) and (VI), the remaining hydroxyl groups of the polyol remaining free or esterified, etherified or with other substances which react with hydroxyl groups, such as for example isocyanates or epoxides.
  • the low molecular weight esterification products B ') can be prepared, for example, by reacting the (oligo) dihydrodicyclopentadienol of the formula (VII) or (VIII) with mono- and / or polycarboxylic acids.
  • moncarboxylic acids are: acetic acid, propionic acid, hexanoic acid, benzoic acid and preferably monofunctional mono- or polyunsaturated fatty acids, as mentioned above, or other mono- and polyunsaturated monofunctional carboxylic acids, or their esters and / / or their anhydride.
  • Polycarboxylic acids suitable for the esterification are, for example: phthalic acid, isophthalic acid, terephthalic acid, tetrahydro- and / or hexahydrophthalic acid, endomethylene tetrahydrophthalic acid, malonic acid, Bern- succinic acid, glutaric acid, sebacic acid, azelaic acid, trimellitic acid, pyromellitic acid, and preferably di- and / or polycarboxylic acids with ethylenically unsaturated double bonds, such as itaconic acid, aconitic acid, mono- and polyunsaturated compounds with at least two carboxyl groups and particularly preferably maleic and / or maleic, ⁇ as well as the esters and anhydrides of the compounds mentioned.
  • the low molecular weight esterification products used can be used on their own as component B 1 ) or in a mixture with the preferred polyesters B) mentioned above which preferably contain (oligo) dihydrodicyclopentadiene structural units and which generally have a high melt viscosity exhibit.
  • the low molecular weight esterification products B 1 When mixed with high molecular weight polyesters B), the low molecular weight esterification products B 1 ) lower the processing viscosity and at the same time act as an additional highly effective crosslinking agent. Compared to the usual reactive diluents, the low molecular weight esterification products B ') have the advantage of the high boiling point and thus the low volatility combined with high crosslinking activity.
  • Component B) is used in the coating compositions according to the invention in an amount of 2 to 95% by weight, preferably 10 to 80% by weight, based on the coating composition.
  • the radiation-curable coating compositions according to the invention contain as component C) from 0 to 10% by weight, preferably 2 to 5% by weight, based on the coating agent, initiators for catalyzing the radical polymerization.
  • the initiators are generally compounds which form photolytically and / or thermally free radicals for initiating the radical polymerization.
  • Suitable for the photolytic initiation of radical polymerization are, for example, benzoin, benzoin ethers, substituted benzoin, alkyl ether of substituted benzoin, such as e.g. alpha-methylbenzoic alkyl ether or alpha-hydroxymethylbenzoic alkyl ether; Benziles, benzil ketals, e.g. Benzil dimethyl ketal or benzilmethylbenzyl ketal; Initiators based on ketones, e.g.
  • Acetophenone and its derivatives such as diethoxyacetophenone or m-chloroacetophenone, benzophenone and its derivatives, such as 4,4'-dimethylaminobenzophenone or 4,4'-diethylaminobenzophenone, propiophenone, hydroxycyclohexylphenyl ketone, 2-hydroxy-2-methyl-l- phenylpropan-1-one; Antrachinone and its derivatives as well as thioxanone and its derivatives as well as mixtures of different initiators.
  • Suitable for the thermal initiation of radical polymerization are, for example, peroxides, hydroperoxides, azo compounds or thermolabile C-C compounds known per se, such as highly substituted ethanes.
  • the coatings can also be cured thermally and / or by means of UV or electron radiation, preferably UV radiation, without using photoinitiators.
  • thermo and photo-lytic initiators can be used in the curing of the coating compositions according to the invention.
  • the coating agents according to the invention optionally contain minor amounts from 0 to 30% by weight, preferably from 5 to 25% by weight, based on the coating agent, at least one reactive diluent D) which is used, for example, to adjust the viscosity of the coating agent and / or to increase the reactivity of the coating agent can.
  • Component D) is preferably used in amounts such that the coating compositions according to the invention remain harmless with regard to their toxicological and ecological effects.
  • Suitable as component D) are acrylates and methacrylates which can be polymerized by free radicals and which have at least one ethylenically unsaturated group, vinyl and allyl monomers, vinyl ethers, N-vinyl monomers, epoxidized 1,2-olefins and / or saturated, low-viscosity compounds which have at least one group which is reactive towards the functional groups of the binder (component A) and / or component B)).
  • Suitable monomers D) are ethoxyethoxyethyl acrylate, N-vinylpyrrolidone, phenoxyethyl acrylate, dimethylaminoethyl acrylate, hydroxyethyl acrylate, butoxyethyl acrylate, isobornyl acrylate, dimethylacrylamide, 2-acetoxyethyl methacrylate, glycyl acrylate, glycyl acrylate, glycyl acrylate, glycyl acrylate, glycyl acrylate, glycyl acrylate, glycyl acrylate, glycyl acrylate, glycyl acrylate, glycyl acrylate, glycyl acrylate, glycyl acrylate, glycyl acrylate, glycyl acrylate, glycyl acrylate,
  • di-, tri- and / or polyacrylates such as, for example, butanediol diacrylate, trimethylolpropane triol di- and triacrylate, pentaerythritol di-, tri- and tetraacrylate, glycerol di- and triacrylate, 1,6-hexanediol diacrylate, tetraethylene glycol, tetraethylene glycol Diethylene glycol dimethacrylate, ethylene glycol diacrylate, neopentyl glycol diacrylate, trimethylolethane triacrylate and triacrylate oligomers, for example propoxylated glycerol esterified with acrylic acid, for example with 3 dopers in the static agent Pel bonds per molecule, a double bond equivalent of 160 daltons and a number average molecular weight Mn of 480 daltons, which is commercially available under the name "OTA 480" from UCB Chemie GmbH, Drugsbo, Belgium, and, for
  • Suitable al ⁇ component D are further described in EP-a-0250631, long chain linear diacrylates with a number average molecular weight Mn of 400 to 4000 daltons, preferably from 600 to 2500 daltons.
  • the two acrylate groups can be separated by a polyoxybutylene structure.
  • Also usable are 1,12-dodecanediol diacrylate and the reaction product of 2 mol acrylic acid with 1 Mol a dimer fatty alcohol, which generally has 36 carbon atoms
  • Component D) is also suitable for saturated, low-viscosity compounds which have at least one group which is reactive toward the functional groups of components A) and / or B), such as, for example, alcohols, diols, lactones or other cyclic esters, and straight-chain diepoxides and the like. These can also be used in combination with unsaturated monomers and / or oligomers as component D).
  • compositions of the invention may contain conventional components as component E)
  • Pigments and / or fillers in amounts from 0 to 45% by weight, preferably from 0 to 40% by weight, based on the coating agent.
  • color-imparting pigments and / or fillers are for example Anorganica such as titanium dioxides, Eisen ⁇ oxide, S iliciumdioxide, aluminum silicate, lead and Chromate compounds, barium sulfate, mica, talc, kaolin or chalk, as well as organics, such as carbon blacks, azo dye pigments or phthalocyanine dye pigments.
  • Anorganica such as titanium dioxides, Eisen ⁇ oxide, S iliciumdioxide, aluminum silicate, lead and Chromate compounds, barium sulfate, mica, talc, kaolin or chalk, as well as organics, such as carbon blacks, azo dye pigments or phthalocyanine dye pigments.
  • the coating compositions according to the invention optionally contain additives and / or auxiliaries F) in amounts of 0 to 10% by weight, preferably 1 to 5% by weight, based on the coating composition.
  • additives and / or auxiliaries F are: leveling agents, such as silicone oils, plasticizers, such as phosphoric acid or phthalic acid esters with long-chain alkyl substituents, matting agents or light protection agents.
  • An important feature of the present invention is the setting of the temperature-dependent viscosity of the coating compositions, which is achieved by the specific selection of the binders mentioned. Due to the low viscosity and the high crosslinking reactivity of the (oligo) dihydrodicyclopentadiene structural units of the binders, coating agents are made available which do not have the usual reactive diluents, such as styrene, vinyltoluenes, alpha-methylstyrene, allyl esters or (Meth) acrylates, or only small amounts thereof, either already
  • the low molecular weight esterification products B ') are mono- and / or polyols with (oligo) dihydrodicyclopentadiene structural units of the formulas (III) to (VI) or au ⁇ Mono- and / or polycarboxylic acids with (oligo) dihydrodicyclopentadienols of the formulas (VII) and (VIII) are suitable.
  • binders according to the invention consisting of components A) and B), are preferably first prepared, component B) being
  • polyesters according to the invention with (oligo) dihydrodicyclopentadiene structural units, it is possible to produce the low molecular weight esterification products with (oligo) dihydrodicyclopentadiene structural units by specifically selecting the stoichiometric ratios of the reactants in situ.
  • the coating compositions according to the invention can be applied to the metallic substrate by means of known application methods, for example by means of Spraying, rolling, flooding, dipping, knife coating, brushing or spin coating.
  • the coating agents are cured thermally and / or by means of UV or electron radiation, preferably by means of UV radiation.
  • Thermal curing generally takes place at temperatures between 80 and 300 degrees C.
  • the wavelength of the steel used for curing the coating agent varies depending on the absorption maximum of the photopolymerization initiator.
  • the wavelength of the radiation is usually in the range between 170 and 600 nanometers.
  • Suitable sources of radiation are, for example, carbon arcs, mercury vapor lamps, tungsten lamps, argon and xenon glow discharge lamps, photographic flood lamps, fluorescent tubes with ultraviolet-emitting phosphor compounds, and eximer, argon fluoride and xenon fluoride.
  • the exposure time is generally dependent on the type of radiation-sensitive resin mixture used and on other factors, such as the thickness of the polymer layer applied and the photo initiator selected, the type of radiation source and its distance from the coating film. The respective radiation duration can easily be determined by routine tests. In order to be able to cure the films economically, the shortest possible curing times should be feasible.
  • polyfunctional reagents such as, for example, polyisocyanates, aminoplast resins, urea or Benzoguanamine formaldehyde resins, polyfunctional epoxies and the like.
  • cover networks can result in the formation of mutually penetrating networks in the coatings, as a result of which specific, desired properties, such as, for example, particularly high chemical resistance, can be achieved.
  • the coating compositions according to the invention are used in particular for coating metal substrates, preferably aluminum, sheet steel and tinplate substrates.
  • the coating compositions of the invention are used as printing inks in decorative and protective printing, in particular of metal containers and closures of all kinds, especially in two-part and three-part cans.
  • a special feature of the coating compositions according to the invention is their good adhesion both to metal substrates and to substrates that have already been coated with the coating composition according to the invention, that is to say, for example, when printing cans several times. It is possible without any problems to deform the metal substrates in the production process in the partially or finished lacquered state, without the formation of cracks or delamination of the coating.
  • the viscosity and reactivity of the coating compositions according to the invention can be adjusted such that they can be processed using the customary painting devices of the prior art.
  • Example 1 Production of a UV clearcoat
  • the resulting lacquer has a viscosity at room temperature of 600 mPas and is applied to the metal substrate using a doctor blade 2 (12 micrometer wet film) which had previously been briefly flamed with the non-illuminating part of a Bun ⁇ en burner flame.
  • the UV lamp F450 from Fu ⁇ ion with a power of 120 W is used, the energy density being 3 x 0.18 J / cm 2.
  • titanium dioxide pigment titanium dioxide 2057 from Krono ⁇
  • the paint is completed with stirring: 13.00 parts by weight of tripropylene glycol diacrylate, 8.00 parts by weight of adduct of maleic anhydride and dicyclopentadiene according to formula (V), 1.80 parts by weight of benzophenone as UV absorber, 3.10 parts by weight of UV initiator (Darocur® 4265 the
  • the resulting lacquer has a viscosity at room temperature of approximately 1000 mPas and is applied to the metal substrate using a doctor blade 3 (24 micrometer wet film), since the non-luminous part of a Bunsen burner flame had been briefly flamed beforehand.
  • the UV lamp F450 from Fusion with a power of 120 W is used to harden the lacquer, the energy density being 3 x 0.18 J / cm2.
  • the paint pi-mentions, a diazo dye (yellow) and a perylene tetracarboxylic acid derivative (red), are first in a polyester acrylate with tripropylene glycol diacry- grated lat and milled on a laboratory three-roller to an average grain size ⁇ 10 microns,
  • the gold lacquer is mixed from the following components at room temperature using a laboratory stirrer:
  • the resulting coating has a viscosity at room temperature of approx. 1000 mPas and is applied with a
  • Squeegee 3 (24 microns wet film) mounted on the metal substrate, which had previously been briefly flamed with the non-illuminating part of a Bunsen burner flame.
  • the UV lamp F450 from Fusion with a power of 120 W is used to harden the lacquer, the energy density being 3 x 0.18 J / cm2.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Paints Or Removers (AREA)
  • Macromonomer-Based Addition Polymer (AREA)
  • Bag Frames (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

L'invention concerne des agents de revêtement exempts de solvants, durcissables avec un faible retrait et une émission réduite, qui présentent un bon pouvoir d'adhérence sur des substrats métalliques. Ces agents de revêtement contiennent comme constituant A) des prépolymères ayant au moins deux liaisons doubles insaturées éthyléniquement et comme constituant B) des prépolymères comportant pour unités structurales des unités dihydrodicyclopentadiène de la formule (I) et/ou des unités oligodihydrodicyclopentadiène de la formule (II) dans laquelle n vaut entre 1 et 10. L'invention concerne des procédés de réalisation de revêtements à l'aide des agents de revêtement obtenus selon le procédé, ainsi que l'utilisation de ces agents de revêtement pour recouvrir des récipients métalliques, notamment des boîtes de conserve.
PCT/EP1996/005502 1996-01-04 1996-12-10 Agents de revetement durcissables avec un faible retrait et comportant un bon pouvoir d'adherence sur des substrats metalliques Ceased WO1997025380A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19600136.6 1996-01-04
DE1996100136 DE19600136A1 (de) 1996-01-04 1996-01-04 Schrumpfarm härtbare Beschichtungsmittel mit guter Haftung auf Metallsubstraten

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WO1997025380A1 true WO1997025380A1 (fr) 1997-07-17

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Publication number Priority date Publication date Assignee Title
DE19711410A1 (de) 1997-03-19 1998-09-24 Beck & Co Ag Dr Tränk-, Verguß- und Überzugsmassen für elektrotechnische und/oder elektronische Bauteile sowie für Trägermaterialien für flächige Isolierstoffe
DE19903725A1 (de) 1999-01-30 2000-08-10 Basf Coatings Ag Bindemittelgemische und ihre Verwendung in mit aktinischer Strahlung und/oder thermisch härtbaren Beschichtungsstoffen
DE19940855A1 (de) * 1999-08-27 2001-03-01 Basf Coatings Ag Lösemittelhaltiger Beschichtungsstoff und seine Verwendung
DE10002805A1 (de) * 2000-01-24 2001-07-26 Basf Coatings Ag Strahlenhärtbare Pulverlacke
KR20040030485A (ko) 2001-01-11 2004-04-09 디에스엠 아이피 어셋츠 비.브이. 방사선 경화성 코팅 조성물
DE10213971A1 (de) * 2002-03-28 2003-10-23 Basf Coatings Ag Pfropfmischpolymerisate, Verfahren zu ihrer Herstellung und ihre Verwendung

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2708846A1 (de) * 1976-03-02 1977-09-08 Hitachi Chemical Co Ltd Harzzusammensetzung
EP0237312A2 (fr) * 1986-03-10 1987-09-16 Canon Kabushiki Kaisha Composition de résine durcissable par un rayonnement actif
DE3807931A1 (de) * 1987-03-18 1988-09-29 Basf Ag Elastomermodifizierte ungesaettigte polyesterharze
JPS6485209A (en) * 1987-09-25 1989-03-30 Kemitetsuku Kk Ultraviolet ray curable adhesive composition
EP0355334A2 (fr) * 1988-07-22 1990-02-28 BASF Aktiengesellschaft Masser à mouler durcissables, obtenues à partir de polyesters insaturés
US4966928A (en) * 1986-06-05 1990-10-30 Somar Corporation Epoxy resin based powder coating composition
US5128387A (en) * 1987-07-28 1992-07-07 Borden, Inc. Extensible and pasteurizable radiation curable coating for metal
JPH0748422A (ja) * 1993-08-06 1995-02-21 Denki Kagaku Kogyo Kk 活性エネルギー線硬化性樹脂組成物

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2708846A1 (de) * 1976-03-02 1977-09-08 Hitachi Chemical Co Ltd Harzzusammensetzung
EP0237312A2 (fr) * 1986-03-10 1987-09-16 Canon Kabushiki Kaisha Composition de résine durcissable par un rayonnement actif
US4966928A (en) * 1986-06-05 1990-10-30 Somar Corporation Epoxy resin based powder coating composition
DE3807931A1 (de) * 1987-03-18 1988-09-29 Basf Ag Elastomermodifizierte ungesaettigte polyesterharze
US5128387A (en) * 1987-07-28 1992-07-07 Borden, Inc. Extensible and pasteurizable radiation curable coating for metal
JPS6485209A (en) * 1987-09-25 1989-03-30 Kemitetsuku Kk Ultraviolet ray curable adhesive composition
EP0355334A2 (fr) * 1988-07-22 1990-02-28 BASF Aktiengesellschaft Masser à mouler durcissables, obtenues à partir de polyesters insaturés
JPH0748422A (ja) * 1993-08-06 1995-02-21 Denki Kagaku Kogyo Kk 活性エネルギー線硬化性樹脂組成物

Non-Patent Citations (4)

* Cited by examiner, † Cited by third party
Title
CHEMICAL ABSTRACTS, vol. 123, no. 14, 2 October 1995, Columbus, Ohio, US; abstract no. 172886, KASAI TAKANORI ET AL.: "Radiation-curable compositions containing urethane (meth)acrylates for coating metal surfaces" *
DATABASE WPI Week 9517, Derwent World Patents Index; AN 95-126184 *
PATENT ABSTRACTS OF JAPAN vol. 013, no. 290 (C - 614) 5 July 1989 (1989-07-05) *
PATENT ABSTRACTS OF JAPAN vol. 095, no. 005 30 June 1995 (1995-06-30) *

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DE19600136A1 (de) 1997-07-10
AR005348A1 (es) 1999-04-28

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