EP1613708A1 - Melanges contenant des amorceurs activables par rayonnement actinique et systemes a deux ou plusieurs composants, procede de production et utilisation associes - Google Patents

Melanges contenant des amorceurs activables par rayonnement actinique et systemes a deux ou plusieurs composants, procede de production et utilisation associes

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Publication number
EP1613708A1
EP1613708A1 EP04719388A EP04719388A EP1613708A1 EP 1613708 A1 EP1613708 A1 EP 1613708A1 EP 04719388 A EP04719388 A EP 04719388A EP 04719388 A EP04719388 A EP 04719388A EP 1613708 A1 EP1613708 A1 EP 1613708A1
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EP
European Patent Office
Prior art keywords
groups
actinic radiation
activated
isocyanate
component
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.)
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Application number
EP04719388A
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German (de)
English (en)
Inventor
Hubert Baumgart
Uwe Meisenburg
Jan Weikard
Markus Mechtel
Wolfgang Fischer
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
Covestro Deutschland AG
Original Assignee
BASF Coatings GmbH
Bayer MaterialScience AG
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Filing date
Publication date
Application filed by BASF Coatings GmbH, Bayer MaterialScience AG filed Critical BASF Coatings GmbH
Publication of EP1613708A1 publication Critical patent/EP1613708A1/fr
Withdrawn legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
    • C08L75/04—Polyurethanes

Definitions

  • a dual-curable composition which, as isocyanate-reactive constituents, contains saturated polyols, such as hydroxy-functional (meth) acrylate (co) polymers, reactive diluents which can be activated with actinic radiation, such as 1,6-hexanediol diacrylate, by UV Radiation-activatable initiators, such as benzoin, benzoin ether, Michler's ketone or chlorinated polycyclic aromatic hydrocarbons, and polyisocyanates.
  • saturated polyols such as hydroxy-functional (meth) acrylate (co) polymers
  • reactive diluents which can be activated with actinic radiation, such as 1,6-hexanediol diacrylate
  • UV Radiation-activatable initiators such as benzoin, benzoin ether, Michler's ketone or chlorinated polycyclic aromatic hydrocarbons, and polyisocyanates.
  • Isocyanate groups and groups which can be activated with actinic radiation are Isocyanate groups and groups which can be activated with actinic radiation
  • the new two-component or multicomponent systems containing at least one initiator that can be activated by actinic radiation consisting of
  • Isocyanate groups and groups which can be activated with actinic radiation are Isocyanate groups and groups which can be activated with actinic radiation
  • systems in which the major or all amount of the initiator which can be activated by actinic radiation is present in the component (s) (II).
  • the new two- or multi-component systems containing at least one initiator that can be activated by actinic radiation are collectively referred to as “systems according to the invention”.
  • the new process for the production of at least one two-component or multicomponent system containing initiator that can be activated by actinic radiation is referred to as the “process according to the invention”.
  • the components (I) of the systems according to the invention could be stored for a long time even at higher temperatures, for example when they are shipped in containers during the summer, without losing their technological properties, and also withstood high and persistent shear forces How they occur, for example, when they are processed, in particular in paint shops, in ring lines, in delivery units, such as gear pumps, and / or during the grinding of pigmented components (I) in grinding units and lead locally or overall to an increase in the temperature of the components (I).
  • the technological properties of the components (I) did not change adversely under mechanical and / or thermal stress - and not under the influence of light either.
  • the mixtures and systems according to the invention or the components (I) and (II) are liquid.
  • the components (I) and the mixtures or components (II) according to the invention are aqueous, organic and / or aqueous-organic molecularly disperse solutions and / or dispersions.
  • Components (I) preferably contain and (II) their constituents in the form of molecularly disperse solutions and / or dispersions in organic solvents.
  • the solids content of the components (I) of the systems according to the invention ie their content of constituents which, after the preparation and curing of the dual-cure-curable compositions according to the invention, also build up the dual-cure-hardened compositions according to the invention, can vary very widely and are directed especially according to the reactivity and the solubility and / or dispersibility of the constituents, the number of reactive functional groups contained in them and the desired viscosity of the components (I).
  • the solids content of components (I) is preferably 5 to 90, preferably 10 to 80, particularly preferably 15 to 75, very particularly preferably 20 to 70 and in particular 25 to 65% by weight, in each case based on component (I).
  • Dual-cure hardened masses with build up vary very widely. It also depends primarily on reactivity and solubility and / or
  • the solids content is preferably
  • the multicomponent systems consist of at least one component (I) free of isocyanate groups and at least two components (II) free of isocyanate-reactive functional groups or of at least two components (I) free of isocyanate groups and at least one component (II) free of isocyanate groups.
  • the systems according to the invention are preferably two-component systems which consist of a component (I) and a component (II).
  • the systems according to the invention contain at least one initiator which can be activated by actinic radiation. At least two, in particular two or three, initiators are preferably used.
  • the initiator is emitted by high-energy electromagnetic radiation, such as near infrared (NIR), visible light, UV radiation, X-rays or gamma radiation, in particular UV radiation, and high-energy radiation, such as electron beams, beta radiation, proton radiation, neutron radiation or alpha radiation
  • Electron radiation thereby activating and initiating the curing via the groups which can be activated with actinic radiation and which are contained in the dual-curable compositions according to the invention.
  • the initiators are preferably photoinitiators.
  • the photoinitiator or the photoinitiators are preferably selected from the group consisting of unimolecular (type I) and bimolecular (type II) photoinitiators.
  • Type I photoinitiators from the group consisting of benzophenones in combination with tertiary amines, alkylbenzophenones, 4,4'-
  • Bis (dimethylamino) benzophenone (Michler's ketone), anthrone and halogenated benzophenones, and the photoinitiators of type II from the group consisting of benzoin, benzoin derivatives, in particular benzoin ethers, benzil ketals, acylphosphine oxides, especially in the case of 4,6-trimethylbenzoyl-diphenylphosphine oxide, bisacylphosphinoxide .
  • the predominant amount, ie more than 50% by weight, of the initiator present, which can be activated with actinic radiation, or its entire amount, in particular its total amount, is contained in the component (s) (II).
  • the content of initiator in component (s) (II) can vary widely and depends primarily on the amount of initiator required for curing with actinic radiation of the dual-cure curable compositions according to the invention, which consists of or the relevant component (s) (II) are produced, is necessary or advantageous.
  • This content is preferably 0.1 to 15, preferably 0.2 to 12, particularly preferably 0.3 to 10, very particularly preferably 0.4 to 8, in particular 0.5 to 7% by weight, in each case based on the solid the dual-cure curable composition according to the invention.
  • Component (I) is free of isocyanate groups. It contains groups that can be activated with actinic radiation and isocyanate-reactive functional groups.
  • the groups that can be activated with actinic radiation contain at least one, in particular one, bond that can be activated 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.
  • bonds which can be activated with actinic radiation are preferably selected from the group consisting of carbon-hydrogen and carbon-halogen single bonds, carbon-carbon,
  • bonds that can be activated with actinic radiation are carbon-carbon double bonds (“double bonds”).
  • the double bonds in groups which can be activated with actinic radiation are preferably selected from the group consisting of (meth) acrylate, ethacrylate, crotonate, cinnamate, vinyl ether, vinyl ester, dicyclopentadienyl, Norbornenyl, isoprenyl, isopropenyl, allyl and butenyl groups; Dicyclopentadienyl, norbornenyl, isoprenyl, isopropenyl, allyl and butenyl ether groups and dicyclopentadienyl, norbornenyl, isoprenyl, isopropenyl, allyl and butenyl ester groups are present.
  • the double bonds are acrylate groups.
  • the content of components (I) in groups which can be activated with actinic radiation can vary widely and depends primarily on the reactivity of the groups and the crosslinking density, which, in the dual-cure-hardened compositions according to the invention, consist of those with the aid of the components in question (I) produced dual-cure curable compositions according to the invention are formed.
  • This content is preferably 1 to 5, preferably 1.5 to 4 and in particular 2 to 3 mEqu / g.
  • the isocyanate-reactive functional groups are preferably selected from the group consisting of hydroxyl groups, thiol groups, primary and secondary amino groups and imino groups. In particular, hydroxyl groups are used.
  • the content of components (I) in isocyanate-reactive functional groups can vary widely and depends primarily on the reactivity of the groups and the crosslinking density, which in the dual-cure-hardened compositions according to the invention, which consist of the components (I ) produced dual-cure curable compositions according to the invention should be present.
  • This content is preferably 1 to 5, preferably 1.5 to 4 and in particular 2 to 3 mEqu / g.
  • the above-described groups curable with actinic radiation and the isocyanate-reactive functional groups are those in US Pat predominant number of available or the only reactive functional groups in component (I). "Predominant number” means that the reactive functional groups in question make up more than 50, preferably more than 60 and in particular more than 70 equivalent%, in each case based on all reactive functional groups present in component (I).
  • the additional reactive functional groups which may be present and which differ from the reactive functional groups described above are thermally activatable reactive functional groups, such as carboxyl groups, methylol ether groups, epoxy groups and / or blocked isocyanate groups, as are customarily used in one-component systems become.
  • the two types of groups can be present in one and the same low molecular weight, oligomeric and / or polymeric constituents.
  • the groups which can be activated with actinic radiation, on the one hand, and the isocyanate-reactive functional groups, on the other hand, can also be present in various low-molecular, oligomeric and / or polymeric constituents which are free from the respective other groups.
  • the selection of the constituents depends primarily on the performance profile that the dual-cure-hardened compositions according to the invention, which are formed from the relevant dual-cure-curable compositions according to the invention produced with the aid of components (I), should have.
  • an oligomer is understood to mean a compound which generally has on average 2 to 15 basic structures or monomer units.
  • a polymer is understood to mean a compound which generally has on average at least 10 basic structures or monomer units.
  • Compounds of this type are also referred to by experts as binders or resins.
  • a low-molecular compound is to be understood as a compound which essentially derives only from a basic structure or a monomer unit.
  • Compounds of this type are generally referred to by the experts as reactive thinners.
  • Suitable reactive diluents which contain at least one, in particular at least two, bond (s) which can be activated with actinic radiation are olefinically unsaturated monomers, preferably vinylaromatic monomers and acrylates, in particular acrylates, with at least one free-radically polymerizable double bond and preferably at least two, preferably at least three , particularly preferably at least four and in particular at least five free-radically polymerizable double bonds.
  • Suitable reactive thinners are described in detail in Römpp Lexikon Lacke und Druckmaschine, Georg Thieme Verlag, Stuttgart, New York, 1998, "Reeducationver Printerner", pages 491 and 492, in German patent application DE 199 08 013 A1, column 6, line 63, to Column 8, line 65, in German patent application DE 199 08 018 A1, page 11, lines 31 to 33, in German patent application DE 198 18 735 A1, column 7, lines 1 to 35, or German patent DE 197 09 467 C 1, page 4, line 36, to page 5, line 56. Pentaerythritol tetraacrylate and / or dipentaerythritol pentaacrylate are preferably used.
  • Suitable polymers or oligomers used as binders which contain at least one, in particular at least two, bond (s) which can be activated with actinic radiation, usually have a number average molecular weight of 500 to 50,000, preferably 1,000 to 5,000. They preferably have a double bond equivalent weight of 400 to 2,000, particularly preferably 500 to 900. In addition, they preferably have a viscosity of 250 to 11,000 mPas at 23 ° C.
  • components (I) that in the dual-cure curable compositions according to the invention produced therefrom, a binder content of 5 to 50% by weight, preferably 6 to 45% by weight, particularly preferably 7 to 40% by weight, very particularly preferably 8 to 35% by weight and in particular 9 to 30% by weight, based in each case on the solid of the dual-cure-curable composition according to the invention.
  • Suitable binders or resins come from the oligomer and / or polymer classes of the (meth) acrylic functional groups
  • (Meth) acrylic copolymers polyether acrylates, polyester acrylates, polyester, epoxy acrylates, urethane acrylates, amino acrylates, melamine acrylates, silicone acrylates and phosphazene acrylates and the corresponding methacrylates. It is preferred to use binders which are free from aromatic structural units. Urethane (meth) acrylates, phosphazene (meth) acrylates and / or are therefore preferred
  • Polyester (meth) acrylates particularly preferably urethane (meth) acrylates, in particular aliphatic urethane (meth) acrylates, are used.
  • the urethane (meth) acrylates are obtained by reacting a di- or polyisocyanate with a chain extender from the Group of the diols / polyols and / or diamines / polyamines and / or dithiols / polythiols and / or alkanolamines and subsequent reaction of the remaining free isocyanate groups with at least one hydroxyalkyl (meth) acrylate or hydroxyalkyl ester of other ethylenically unsaturated carboxylic acids.
  • chain extenders di- or polyisocyanates and hydroxyalkyl esters are preferably chosen so that
  • the equivalent ratio of the NCO groups to the reactive groups of the chain extender is between 3: 1 and 1: 2, preferably 2: 1, and
  • the OH groups of the hydroxyalkyl esters of the ethylenically unsaturated carboxylic acids are present in a stoichiometric amount in relation to the free isocyanate groups of the prepolymer of isocyanate and chain extender.
  • part of the isocyanate groups of a diisocyanate are first reacted with a diol, then another part of the isocyanate groups can be reacted with the hydroxyalkyl ester and then the remaining isocyanate groups can be reacted with a diamine.
  • the urethane (meth) acrylates can be made more flexible, for example, by reacting corresponding isocyanate-functional prepolymers or oligomers with longer-chain, aliphatic diols and / or diamines, in particular aliphatic diols and / or diamines with at least 6 C atoms.
  • This flexibilization reaction can be carried out before or after the addition of acrylic or methacrylic acid to the oligomers or prepolymers.
  • Suitable urethane (meth) acrylates include the following, commercially available polyfunctional aliphatic urethane acrylates:
  • Urethane (meth) acrylates containing hydroxyl groups are known, for example, from the patents US 4,634,602 A or US 4,424,252 A.
  • oligomeric or polymeric binders which contain at least one, in particular at least two, isocyanate-reactive functional group (s) are linear and / or branched and / or block-like, comb-like and / or randomly constructed oligomers or polymers, such as (meth) acrylate ( co) polymers, polyesters, alkyds, aminoplast resins, polyurethanes, polylactones, polycarbonates, polyethers, epoxy resin-amine adducts, (meth) acrylate diols, partially saponified polyvinyl esters or polyureas, of which the (meth) acrylate copolymers, the polyesters, the polyurethanes, the Polyethers and the epoxy-amine adducts, but especially (meth) acrylate (co) polymers and polyesters, are advantageous.
  • the (meth) acrylate copolymers contain an amount corresponding to their 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-butylene 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, in particular acrylic acid and methacrylic acid. They are derived from an alkylene glycol esterified with the acid, or they are from the reaction of the acid with an alkylene oxide such as ethylene oxide or propylene oxide available.
  • 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-1 H-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.
  • 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 branched in the alpha position with 5 to 18 carbon atoms per molecule, in particular one Versatic® acid, or an equivalent instead of the reaction products Amount of the olefinic and saturated acids listed above, in particular Acrylic and / or methacrylic acid, which during or after the polymerization reaction with the glycidyl ester of a monocarboxylic acid with 5 to 18 C atoms per molecule branched in the alpha position, in particular one Versatic® acid (cf.Römpp Lexikon Lacke und Druckmaschinetician, Georg Thieme Verlag, Stuttgart, New York, 1998, »Versatic® acids«, pages 605 and 606).
  • 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 (meth) acrylate copolymers can also contain other isocyanate-reactive functional groups, such as primary and secondary amino groups.
  • the (meth) acrylate copolymers can also contain additional, thermally activatable, reactive functional groups, such as carboxyl groups, methylol ether groups, epoxy groups and / or blocked isocyanate groups, in minor amounts.
  • (a31) monomers which carry at least one amino group per molecule, such as - aminoethyl acrylate, aminoethyl methacrylate, allylamine or N-methylaminoethyl acrylate; and or
  • Acrylic acid beta-carboxyethyl acrylate, methacrylic acid, ethacrylic acid, crotonic acid, maleic acid, fumaric acid or itaconic acid;
  • Vinylbenzoic acid (all isomers), alpha-methyl vinylbenzoic acid (all isomers) or
  • the (meth) acrylate copolymers can also contain, in copolymerized form, at least one olefinically unsaturated monomer (a4) which is essentially or completely free of reactive functional groups, such as: Monomers (a41):
  • Essentially acid-group-free (meth) acrylic acid esters such as (meth) acrylic or alkyl cycloalkyl esters with up to 20 carbon atoms in the alkyl radical, in particular methyl, ethyl, n-propyl, n-butyl, sec.-butyl, tert.- Butyl, hexyl, ethylhexyl, stearyl and lauryl acrylate or methacrylate; cycloaliphatic (meth) acrylic acid esters, in particular cyclohexyl, isobomyl, dicyclopentadienyl, octahydro-4,7-methano-1 H-indene methanol or tert-butylcyclohexyl (meth) acrylate; (Meth) acrylic acid oxaalkyl esters or oxacycloalkyl esters such as ethoxytriglycol (meth) acrylate
  • (Meth) acrylic acid derivatives (further examples of suitable monomers (31) 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. Subordinate amounts of higher-functional monomers (a41) are
  • the branched monocarboxylic acids can be obtained by reacting formic acid or
  • paraffinic hydrocarbons such as mineral oil fractions
  • a mixture of carboxylic acids is formed in which the carboxyl groups are predominantly located on a quaternary carbon atom.
  • Other olefinic starting materials are, for example, propylene trimer, propylene tetramer and diisobutylene.
  • the vinyl esters can also be prepared from the acids in a manner known per se, for example by letting the acid react with acetylene. Because of the good availability, vinyl esters of saturated aliphatic monocarboxylic acids having 9 to 11 carbon atoms which are branched on the alpha carbon atom are particularly preferably used. Vinyl esters of this type are sold under the VeoVa® brand (see also Römpp Lexikon Lacke und Druckmaschine, Georg Thieme Verlag, Stuttgart, New York, 1998, page 598).
  • Diarylethylenes in particular those of the general formula I:
  • radicals R 1 , R 2 , R 3 and R 4 are each independently of one another hydrogen atoms or substituted or unsubstituted alkyl, cycloalkyl ,.
  • 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, cycloalkylaryl, arylalkyl and arylcycloalkyl radicals; Aryloxy, alkyloxy and cycloalkyloxy radicals; and / or arylthio, alkylthio and cycloalkylthio radicals.
  • Diphenylethylene, dinaphthaleneethylene, eis or trans-stilbene or vinylidene-bis (4-nitrobenzene), in particular diphenylethylene (DPE), are particularly advantageous, which is why they are preferably used.
  • the monomers (a33) are used in order to regulate the copolymerization advantageously in such a way that a radical copolymerization in a batch mode is also possible.
  • Vinylaromatic hydrocarbons such as styrene, vinyltoluene, diphenylethylene or alpha-alkylstyrenes, especially alpha-methylstyrene.
  • Nitriles such as acrylonitrile and / or methacrylonitrile.
  • vinyl compounds in particular vinyl and / or vinylidene dihalides such as vinyl chloride, vinyl fluoride, vinylidene dichloride or
  • Polysiloxane macromonomers which have a number average molecular weight Mn of 1,000 to 40,000 and an average of 0.5 to 2.5 ethylenically unsaturated double bonds per molecule; in particular polysiloxane macromonomers which have a number average molecular weight Mn of 2,000 to 20,000, particularly preferably 2,500 to 10,000 and in particular 3,000 to 7,000 and on average 0.5 to 2.5, preferably 0.5 to 1.5, ethylenically unsaturated double bonds per molecule, as in DE 38 07 571 A 1 on pages 5 to 7, DE 37 06 095 A 1 in columns 3 to 7, EP 0 358 153 B 1 on pages 3 to 6, in US 4,754,014 A 1 in columns 5 to 9, in DE 44 21 823 A1 or in international patent application WO 92/22615 on page 12, line 18 to page 18, line 10.
  • the monomers (a1) and (a2) and (a3) and / or (a4) are selected so that the OH numbers and glass transition temperatures given above result.
  • Tg glass transition temperature of the poly (meth) acrylate
  • W n weight fraction of the nth monomer
  • Tg n glass transition temperature of the homopolymer from the nth monomer
  • x number of different monomers.
  • the production of the (meth) acrylate copolymers to be used according to the invention 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 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 19628 142 A1, EP 0 554 783 A1, WO 95/27742, WO 82/02387 or WO 98/02466.
  • the copolymerization can, however, also be carried out in polyols as the reaction medium, as is described, for example, in German patent application DE 198 50243 A1.
  • Suitable free-radical initiators are dialkyl peroxides, such as di-tert-butyl peroxide or dicumyl peroxide; Hydroperoxides, such as cumene hydroperoxide or tert-butyl hydroperoxide; Peresters such as tert-butyl perbenzoate, tert-butyl perpivalate, tert-butyl per-3,5,5-trimethyl hexanoate or tert-butyl per-2-ethyl hexanoate; peroxodicarbonates; Potassium, sodium or ammonium peroxodisulfate; Azo initiators, for example azo dinitriles such as azobisisobutyronitrile; C-C-cleaving initiators such as 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.
  • oligomers and polymers which are well suited as binders are, for example, under the trade names Desmophen® 650, 2089, 1100, 670, 1200 or 2017 from Bayer, under the trade names Priplas or Pripol® from Uniqema, under the trade names Chempol® Polyester or Polyacrylate-polyol from CCP, under the trade names Crodapol® 0-25, 0-85 or 0-86 from Croda or under the trade name Formrez® ER417 from Witco.
  • the reactive diluents and the binders are preferably selected according to their type and quantity so that the dual-curable compositions according to the invention, after they have hardened, have a storage modulus E 'in the rubber-elastic range of at least 10 ⁇ .5 Pa and a loss factor tan ⁇ at 20 ° C. of at most 0. 10, wherein the memory module E ' and the loss factor have 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 components (I) to the above-described reactive diluents and binders may vary very widely and depends in particular on the reactivity of these components and the number of the herein 'reactive functional groups present and the profile of performance properties, the cured dual-cure according to the invention Masses that are to be formed from the dual-cure curable compositions produced with the aid of the relevant components (I).
  • the content of components (I) is preferably on the reactive diluents and binders, in particular the binders, adjusted such that in the dual-curable compositions according to the invention a content of reactive diluents and binders, in particular binders, of 10 to 80, preferably 15 to 75, particularly preferably 20 to 70, very particularly preferably 25 to 65 and in particular 25 to 65% by weight, based in each case on the solids of the dual-cure-curable compositions according to the invention.
  • components (I) can also comprise at least one customary and known constituent selected from the group consisting of purely physically hardening binders which differ from the binders described above; crosslinking agents other than the isocyanatoacrylates and polyisocyanates described below; thermally curable reactive thinners; molecularly dispersible dyes; Light stabilizers, such as UV absorbers and reversible radical scavengers (HALS); antioxidants; Venting means; Wetting agents; emulsifiers; slip additives;
  • HALS reversible radical scavengers
  • polymerization inhibitors include Thermal crosslinking catalysts; thermolabile free radical initiators; Adhesion promoters; Leveling agents; film-forming aids; Rheology aids such as thickeners and pseudoplastic Sag control agents, SCA; Flame retardants; Corrosion inhibitors; anti-caking agents; To grow; driers; Biocides and matting agents.
  • Components (I), which contain the constituents described above, are used primarily for the production of dual-cure curable compositions according to the invention, in particular broom sealants (especially clear lacquers), adhesives and sealants, and also preliminary products for moldings and films which are used Production of clear, transparent, dual-cure compositions, in particular coatings (especially clear coats), adhesive layers, seals, molded parts and foils.
  • broom sealants especially clear lacquers
  • adhesives and sealants and also preliminary products for moldings and films which are used Production of clear, transparent, dual-cure compositions, in particular coatings (especially clear coats), adhesive layers, seals, molded parts and foils.
  • the components (I) can, however, also be pigmented. They then preferably also contain at least one pigment selected from the group consisting of organic and inorganic, transparent and opaque, coloring and / or effect-giving, electrically conductive, magnetically shielding and fluorescent pigments, fillers and nanoparticles.
  • the pigmented components (I) are used primarily for the production of dual-cure-curable compositions, in particular coating materials (especially fillers, basecoats and solid-color top coats), adhesives and sealants, and preliminary products for moldings and films, which are used to produce pigmented dual Cure-hardened masses, especially coatings (especially filler coatings or stone chip protection primers, basecoats and solid-color coatings), adhesive layers, seals, molded parts and foils are used.
  • the pigmented components (I) can also be used to produce clear, transparent dual
  • Cure-curable compositions especially coating materials (especially Clear lacquers), adhesives and sealants as well as intermediate products of molded parts and foils.
  • components (I) in the process 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 processes and devices such as stirred kettles, stirred mills, extruders, kneaders, Ultraturrax, In- Iine dissolvers, static mixers, micromixers, ring gear dispersers, pressure relief nozzles and / or microfluidizers.
  • the systems according to the invention contain at least one mixture according to the invention as component (II).
  • Component (II) of the systems according to the invention is free from isocyanate-reactive functional groups. It contains isocyanate groups and none of the groups described above which can be activated with actinic radiation. Alternatively, it contains isocyanate groups and the groups described above which can be activated with actinic radiation. The isocyanate groups or isocyanate groups and the groups which can be activated with actinic radiation are the predominant number or the only, preferably the only, reactive functional groups in the components (II).
  • Predominant number means that the reactive functional groups in question make up more than 50, preferably more than 60 and in particular more than 70 equivalent%, in each case based on all reactive functional groups present in component (II).
  • the additional reactive functional groups which may be present and which differ from the reactive functional groups described above are thermally activatable, non-isocyanate-reactive, reactive functional groups, such as carboxyl groups, methylol ether groups, epoxy groups and / or blocked isocyanate groups, as are customarily described in Single component systems are used.
  • Additional reactive functional groups which are complementary to the additional reactive functional groups present in components (I) are preferably used.
  • the isocyanate groups can be present in a wide variety of components. They are preferably present in polyisocyanates.
  • components (II) which are optionally present and described above and which can be activated with actinic radiation can be present in constituents which are different from the polyisocyanates. However, they are preferably present in the polyisocyanates.
  • the relevant, very particularly preferred constituents are also referred to by experts as isocyanatoacrylates.
  • the polyisocyanates are preferably selected from the group consisting of polyisocyanates which contain on average at least 2.0 to 10, preferably 2.1 to 6 blocked isocyanate groups in the molecule.
  • the polyisocyanates are preferably selected from the group consisting of polyisocyanates which, on statistical average, contain at least one isocyanurate, biuret, allophanate, iminooxadiazinedione, urethane, urea, carbodiimide and / or uretdione group in the molecule.
  • Examples of suitable polyisocyanates are from German patent application DE 199 24 170 A1, column 3, line 61, to column 6, line 14, and column 10, line 60, to column 11, line 38, or the documents CA 2,163,591 A, US 4,419,513 A, US 4,454,317 A, EP 0 646 608 A 1, US 4,801,675 A, EP 0 183 976 A 1, DE 40 15 155 A 1, EP 0 303 150 A 1, EP 0 496 208 A 1, EP 0 524 500 A 1, EP 0 566 037 A 1, US 5,258,482 A 1, US 5,290,902 A 1, EP 0 649 806 A 1, DE 42 29 183 A 1, EP 0 531 820 A 1 or DE 100 05 228 A 1 are known.
  • polyisocyanates can still be partially blocked.
  • suitable blocking agents for blocking some of the free isocyanate groups in the polyisocyanates and isocyanatoacrylates are known from German patent application DE 199 24 170 A1, column 6, lines 19 to 53.
  • the type and amount of the polyisocyanates and isocyanatoacrylates are preferably selected so that the dual-curable compositions according to the invention, after they have hardened, have a storage module E 'in elastic range of at least 10 ⁇ , 5 p a unc
  • components (II) in the polyisocyanates and isocyanatoacrylates described above can vary very widely and depends in particular on the reactivity of these constituents and the number of reactive functional groups present therein and the application properties profile which the dual-cure-cured compositions according to the invention which are to be formed from the dual-cure-curable compositions prepared with the aid of the relevant components (II).
  • the content of components (II) in the polyisocyanates and isocyanatoacrylates is preferably adjusted so that in the dual-cure curable compositions according to the invention, a content of polyisocyanates and isocyanatoacrylates of 5 to 50% by weight, preferably 6 to 45% by weight , particularly preferably 7 to 40% by weight, very particularly preferably 8 to 35% by weight and in particular 9 to 30% by weight, in each case based on the solid of the dual-cure-curable composition according to the invention.
  • the components (II) can also comprise at least one customary and known constituent selected from the group consisting of free from isocyanate-reactive functional groups, crosslinking agents different from the isocyanatoacrylates and polyisocyanates described above and isocyanate-reactive functional groups Groups of free light stabilizers, such as UV absorbers and reversible radical scavengers (HALS), contain.
  • at least one customary and known constituent selected from the group consisting of free from isocyanate-reactive functional groups, crosslinking agents different from the isocyanatoacrylates and polyisocyanates described above and isocyanate-reactive functional groups
  • Groups of free light stabilizers, such as UV absorbers and reversible radical scavengers (HALS) contain.
  • the preparation of the mixtures or components (II) according to the invention in the context of the process according to the invention likewise has no peculiarities, but rather takes place by mixing and homogenizing the above-described constituents with the aid of the conventional and known mixing methods and devices described above, preferably with exclusion of actinic radiation.
  • the systems according to the invention are produced by mixing at least one, in particular one, component (I) and at least one, in particular one, component (II) and homogenizing the resulting mixtures.
  • component (I) in particular one
  • component (II) in particular one, component (II)
  • homogenizing the resulting mixtures.
  • the usual and known mixing methods and devices described above can be used.
  • the process is preferably carried out with the exclusion of actinic radiation.
  • the quantitative ratio of component (s) (I) to component (s) (II) can vary very widely and depends on the ratio of the reactive functional groups present in components (I) and (II).
  • the quantitative ratio (l) :( ll) is preferably selected such that the equivalent ratio of isocyanate-reactive functional groups in component (s) (I) to the isocyanate groups in component (s) (II) 0.5: 1 to 1: 0.5, preferably 0.6: 1 to 1: 0.6, particularly preferably 0.7: 1 to 1: 0.7, very particularly preferably 0.8: 1 to 1: 0.8 in particular 0.9: 1 to 1: 0.9.
  • the components (I) described above of the systems according to the invention can also be used for a long time at higher temperatures, for example when they are shipped to Containers occur during the summer and / or when stored outdoors for a long time, can be transported and / or stored without losing their technological properties. They also resist high and permanent shear forces, such as those that occur during their manufacture and processing, particularly in paint shops in ring lines, in delivery units such as gear pumps, and / or during the grinding of pigmented components (I) in grinding units and locally or to increase the temperature of the components ( I) lead overall. Overall, the technological properties of the components (I) do not change disadvantageously under mechanical and / or thermal loading - and not under the influence of light either.
  • the dual-cure curable compositions according to the invention produced from the systems according to the invention have a very good pot life or processing time of several hours up to one working day with a high reactivity, which particularly simplifies their further processing.
  • the dual-cure curable compositions according to the invention can be used with particular advantage in a variety of ways pigmented and unpigmented coating materials, adhesives, sealing compounds and preliminary products for molded parts and films, preferably coating materials, in particular clearcoats, fillers, basecoats and solid-color topcoats, are used.
  • the dual-cure-curable compositions according to the invention are used to produce dual-cure-cured compositions according to the invention, preferably coatings, adhesive layers, seals, moldings and foils, preferably coatings, particularly preferably clearcoats, filler coatings or
  • Solid-color topcoats very particularly preferably clearcoats and in particular clearcoats of color and / or effect multi-layer coatings which are produced by the customary and known wet-on-wet processes.
  • the dual-cure-hardenable compositions according to the invention are applied to customary and known temporary or permanent substrates.
  • Customary and known temporary substrates are preferably used for the production of films and molded parts according to the invention, such as metal and plastic strips or hollow bodies made of metal, glass, plastic, wood or ceramic, which can be easily removed without damaging the films and molded parts according to the invention ,
  • dual-cure curable compositions according to the invention are used for the production of coatings, adhesives and seals
  • permanent substrates such as means of transportation, including aircraft, ships, rail vehicles, muscle-powered vehicles and motor vehicles, and parts thereof, structures indoors and outdoors and parts thereof, doors, windows, furniture, hollow glass bodies, coils, containers, packaging, small parts, electrotechnical components and components for white goods.
  • the films and moldings according to the invention can also serve as substrates.
  • the application of the dual-curable compositions according to the invention has no peculiarities, but can be carried out by all customary and known application methods suitable for the particular mixture of substances, such as e.g. Electro dipping, spraying, spraying, knife coating, brushing, pouring, dipping, trickling or rolling. Spray application methods are preferably used.
  • the applied dual-cure compositions according to the invention are generally cured after a certain rest period or flash-off time. It can have a duration of 30 seconds to 2 hours, preferably 1 minute to 1 hour and in particular 1 to 45 minutes.
  • the rest period is used, for example, for the course and degassing of the applied dual-cure curable compositions and for the evaporation of volatile constituents such as solvents and / or water.
  • the ventilation can be accelerated by an elevated temperature, which is not yet sufficient for hardening, and / or by a reduced air humidity.
  • the thermal curing of the applied dual-curable compositions according to the invention can, for example, with the aid of a gaseous, liquid and / or solid, hot medium, such as hot air, heated oil or heated rollers, or of microwave radiation, infrared light and / or near infrared light (NIR).
  • the heating is preferably carried out in a forced air oven or by irradiation with IR and / or NIR lamps.
  • thermal curing can also be carried out in stages. The thermal curing advantageously takes place at temperatures from room temperature to 200.degree.
  • the applied dual-curable compositions according to the invention are preferably cured with UV radiation.
  • a radiation dose of 80 to 6,000, preferably 200 to 3,000, preferably 300 to 1,500 and particularly preferably 500 to 1,200 mJcm "2 is preferably used for the irradiation, the range ⁇ 1,200 mJcm " 2 being very particularly preferred.
  • the radiation intensity can vary widely. It depends in particular on the radiation dose on the one hand and the radiation duration on the other. For a given radiation dose, the radiation duration depends on the belt or feed speed of the substrates in the radiation system and vice versa.
  • the radiation intensity is preferably from 1x10 ° to 3x10 5 , preferably 2x10 ° to 2x10 5 , particularly preferably 3x10 ° to 1, 5x10 5 and in particular 5x10 ° to 1, 2x10 5 Wm "2 .
  • High or medium pressure mercury vapor lamps are used as radiation sources, for example, the mercury vapor being modified by modification with other elements such as gallium or iron.
  • Laser-pulsed lamps which are known under the name UV flash lamps, halogen lamps or excimer lamps can also be used.
  • the lamps and emitters can be equipped with filters which prevent a part of the emitted emitter spectrum from escaping. For example, for reasons of occupational hygiene, the radiation assigned to the UV-C or UV-C and UV-B range can be filtered out. Lamps and Emitters that only emit UV-A radiation and possibly longer-wave radiation can be used particularly advantageously where the risk to people from high-energy UV radiation cannot be prevented by other measures such as shielding.
  • the UV lamps or lamps in particular the UV-A lamps or lamps, can be installed immobile or movable so that the goods to be irradiated can move past the radiation source by means of mechanical devices or the UV lamps or lamps can move past them irradiating, stationary goods are passed.
  • Suitable UV-A lamps or lamps are, for example, from Panacol-Elosol GmbH, Oberursel, Federal Republic of Germany, under the designation UV-H 254, Quick-Start UV 1200, UV-F 450, UV-P 250C, UV- P 280/6 or UV-F 900 sold.
  • Other suitable UV lamps or lamps are from R. Stephen Davidson, »Exploring the Science, Technology and Applications of U.V. and E.B. Curing «, Sita Technology Ltd., London, 1999, Chapter I,» An Overview «, page 16, Figure 10, or Dipl.-Ing. Peter Klamann, “eltosch system competence, UV technology, guidelines for users”, page 2, October 1998.
  • Suitable flash lamps are flash lamps from VISIT.
  • the distance from the applied dual-cure curable compositions to be irradiated can vary surprisingly widely and can therefore be adjusted very well to the requirements of the individual case.
  • the distance is preferably 2 to 200, preferably 5 to 100, particularly preferably 10 to 50 and in particular 15 to 30 cm.
  • Their arrangement can also be adapted to the conditions of the substrate and the process parameters. In the case of complicated shaped substrates, such as those intended for automobile bodies, the Areas not accessible to direct radiation (shadow areas), such as cavities, folds and other design-related areas
  • the irradiation is carried out under an oxygen-depleted atmosphere or with the complete exclusion of oxygen, i.e. H. carried out under an inert gas atmosphere.
  • 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 vol%.
  • Inert gas is understood to be a gas which, under the curing conditions used, is not decomposed by the actinic radiation, does not inhibit curing and does not react with the dual-cure curable compositions of the invention applied.
  • the applied dual-cure curable compositions according to the invention can also be covered during irradiation with media which are transparent to the actinic radiation, are not decomposed by the actinic radiation under the curing conditions used, do not inhibit curing and cannot be inhibited with the applied dual according to the invention -Cure-curable masses react.
  • suitable media are plastic films, glass or liquids such as water.
  • Both thermal curing and curing with actinic radiation can be carried out in stages. They can take place one after the other (sequentially) or simultaneously. Sequential curing is advantageous according to the invention and is therefore used with preference. It is advantageous to carry out the thermal hardening after the hardening with actinic radiation.
  • the resulting films, moldings, coatings, adhesive layers and seals according to the invention are outstandingly suitable for coating, gluing, sealing, wrapping and packaging of means of transportation, including aircraft, ships, rail vehicles, muscle-powered vehicles and motor vehicles, and parts thereof, structures inside - and outdoor areas and parts thereof, doors, windows, furniture, hollow glass bodies, coils, containers, packaging, small parts such as nuts, screws, rims or hubcaps, electrotechnical components such as winding goods (coils, stators, rotors) and components for white goods, such as radiators, household appliances, refrigerator panels or washing machine panels.
  • means of transportation including aircraft, ships, rail vehicles, muscle-powered vehicles and motor vehicles, and parts thereof, structures inside - and outdoor areas and parts thereof, doors, windows, furniture, hollow glass bodies, coils, containers, packaging, small parts such as nuts, screws, rims or hubcaps, electrotechnical components such as winding goods (coils, stators, rotors) and components for white goods, such as radiators, household appliances, refrigerator
  • the substrates according to the invention which are coated with coatings according to the invention, bonded with adhesive layers according to the invention, sealed with a seal according to the invention and / or enveloped or packaged with films and / or moldings according to the invention, have excellent long-term use properties and a particularly long service life.
  • Production Example 1 The production of a methacrylate copolymer
  • a monomer mixture of 652 parts by weight of ethyl hexyl acrylate, 383 parts by weight of 2-hydroxyethyl methacrylate, 143 parts by weight of styrene, 212 parts by weight of 4-hydroxybutyl acrylate and 21 parts by weight of acrylic acid were added within four hours and an initiator solution of 113 parts by weight of the aromatic solvent and 113 parts by weight of tert-butyl perethylhexano Metered evenly into the template for 4.5 hours.
  • the metering of the monomer mixture and the initiator solution was started simultaneously. After the initiator feed had ended, the resulting reaction mixture was heated to 140 ° C. with stirring for a further two hours and then cooled.
  • the resulting solution of the methacrylate copolymer (A) was diluted with a mixture of 1-methoxypropylacetate-2, butylglycol acetate and butyl acetate.
  • the resulting solution had a solids content of 65% by weight, determined in a forced air oven (one hour / 130 ° C.), an acid number of 15 mg KOH / g solids, an OH number of 175 mg KOH / g solids and a glass transition temperature from -21 ° C to.
  • Methacrylate copolymer of preparation example 1 35.9 35.9
  • UV absorber substituted hydroxyphenyltriazine
  • HALS N-methyl-2,2,6,6-tetramethylpiperidinyl ester
  • Irgacure ⁇ 184 (commercially available photoinitiator from
  • Genocure ® MBF commercially available photoinitiator from
  • Lucirin ® TPO commercially available photoinitiator from
  • V 1-1 series V 1-1 (8 ° C / bright), V 1-1 (RT / bright), V 1-1 (40 ° C / bright) and V 1-2: V 1-2 (8 ° C / dark), V 1-2 (RT / dark), V 1-2 (40 ° C / dark).
  • component V 1 required a considerably greater effort in storage and transport than component I in order to remain usable.
  • Isocyanatoacrylat Roskydal ® UA VPLS 2337 from Bayer AG (basis: trimeres hexamethylene diisocyanate; content of isocyanate groups: 12% by weight) 27.84 27.84
  • Isocyanatoacrylate based on the trimers of isophorone diisocyanate (70.5% in butyl acetate; viscosity: 1,500 mPas; content of
  • Irgacure ⁇ 184 (commercially available photoinitiator from
  • Genocure ® MBF (commercially available photoinitiator from Rahn) 1, 0 -
  • Lucirin ® TPO commercially available photoinitiator from
  • Component II (storage time 28 days at 60 ° C) used according to Example 2.
  • the resulting clearcoats were homogenized.
  • steel panels were coated in succession with cathodically deposited and immersed in a drying layer thickness of 18 to 22 ⁇ m at 170 ° C. for 20 minutes.
  • the steel sheets were then coated with a commercially available two-component water filler from BASF Coatings AG, as is usually used for plastic substrates.
  • the resulting filler layers were baked at 90 ° C. for 30 minutes, so that a dry layer thickness of 35 to 40 ⁇ m resulted.
  • a commercial black waterborne basecoat from BASF Coatings AG was then applied with a layer thickness of 12 to 15 ⁇ m, after which the resulting waterborne basecoat films were flashed off at 80 ° C.
  • the clear coats (I + II) and (V 1 + V 2) were applied pneumatically in a cloister with a gravity cup gun with a layer thickness of 40 to 45 ⁇ m.
  • the water-based lacquer layers and the clear lacquer layers were cured for 5 minutes at room temperature, for 10 minutes at 80 ° C., followed by exposure to UV radiation at a dose of 1,500 mJ / cm 2 , and finally for 20 minutes at 140 ° C.
  • an oxygen-depleted atmosphere of air / nitrogen with 5 vol.% Oxygen was used.
  • Example 1 Surprisingly, the multi-layer coatings of Example 1 and Comparative Experiment V 3 essentially had the same excellent profile of properties.
  • Both multi-layer paints had an excellent flow and were free from surface defects such as specks, stoves and pinholes.

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  • Chemical Kinetics & Catalysis (AREA)
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  • Organic Chemistry (AREA)
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Abstract

L'invention concerne des mélanges exempts de groupes fonctionnels réactifs à l'isocyanate et contenant, en majorité ou comme seuls groupes fonctionnels réactifs, des groupes isocyanate, mais pas de groupe activable par rayonnement actinique, ou bien des groupes isocyanate et des groupes activables par rayonnement actinique. Ces mélanges comportent aussi au moins un amorceur activable par rayonnement actinique, des amorceurs activables par rayonnement actinique contenant des systèmes à deux ou plusieurs composants constitués par (I) des composants exempts de groupes isocyanate, contenant des groupes activables par rayonnement actinique et des groupes fonctionnels réactifs à l'isocyanate en tant que groupes fonctionnels réactifs seuls ou majoritaires, ainsi que par (II) des composants exempts de groupes fonctionnels réactifs à l'isocyanate contenant, en majorité ou comme seuls groupes fonctionnels réactifs, des groupes isocyanate, mais pas de groupe activable par rayonnement actinique, ou bien des groupes isocyanate et des groupes activables par rayonnement actinique, la majorité ou la totalité de l'amorceur se trouvant dans les composants (II). La présente invention porte également sur un procédé pour produire ces mélanges et sur leur utilisation.
EP04719388A 2003-04-12 2004-03-11 Melanges contenant des amorceurs activables par rayonnement actinique et systemes a deux ou plusieurs composants, procede de production et utilisation associes Withdrawn EP1613708A1 (fr)

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DE10316890A DE10316890A1 (de) 2003-04-12 2003-04-12 Mit aktinischer Strahlung aktivierbare Initiatoren enthaltende Mischungen sowie Zwei- und Mehrkomponentensysteme, Verfahren zu ihrer Herstellung und ihre Verwendung
PCT/EP2004/002475 WO2004090057A1 (fr) 2003-04-12 2004-03-11 Melanges contenant des amorceurs activables par rayonnement actinique et systemes a deux ou plusieurs composants, procede de production et utilisation associes

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