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EP1100836A1 - Materiaux et preparations durcissables par un rayonnement haute energie et/ou par la chaleur - Google Patents

Materiaux et preparations durcissables par un rayonnement haute energie et/ou par la chaleur

Info

Publication number
EP1100836A1
EP1100836A1 EP99944332A EP99944332A EP1100836A1 EP 1100836 A1 EP1100836 A1 EP 1100836A1 EP 99944332 A EP99944332 A EP 99944332A EP 99944332 A EP99944332 A EP 99944332A EP 1100836 A1 EP1100836 A1 EP 1100836A1
Authority
EP
European Patent Office
Prior art keywords
groups
acrylate
substances
ether
meth
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP99944332A
Other languages
German (de)
English (en)
Inventor
Rainer Blum
Peter Keller
Horst Binder
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 SE
Original Assignee
BASF SE
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by BASF SE filed Critical BASF SE
Publication of EP1100836A1 publication Critical patent/EP1100836A1/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Withdrawn legal-status Critical Current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
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F299/00—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers
    • C08F299/02—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates
    • C08F299/06—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates from polyurethanes
    • C08F299/065—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates from polyurethanes from polyurethanes with side or terminal unsaturations
    • 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
    • C08F2/00—Processes of polymerisation
    • C08F2/46—Polymerisation initiated by wave energy or particle radiation
    • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
    • 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
    • C08F299/00—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
    • C08G18/3203—Polyhydroxy compounds
    • C08G18/3206—Polyhydroxy compounds aliphatic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/67—Unsaturated compounds having active hydrogen
    • C08G18/671—Unsaturated compounds having only one group containing active hydrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/67—Unsaturated compounds having active hydrogen
    • C08G18/671—Unsaturated compounds having only one group containing active hydrogen
    • C08G18/672—Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • C09D175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
    • C09D175/16—Polyurethanes having carbon-to-carbon unsaturated bonds having terminal carbon-to-carbon unsaturated bonds

Definitions

  • the invention relates to high-energy radiation and / or thermally hardenable substances and preparations and their uses according to the invention
  • UV-curable lacquers for use in liquid form and powder lacquers.
  • lacquer systems are gaining more and more fields of application for reasons of solvent savings.
  • a main problem with known UV lacquers is the inhibition of curing on the Paint surface due to atmospheric oxygen This inhibition must be covered by lamps with a very high energy density and acceleration of curing by airunoin initiators. These amines are often the
  • the glass transition temperature and melting point should be as high as possible, but for good flow and use on thermosensitive substrates As low as possible to avoid a hardening reaction before the formation of an optimal surface smoothness and damage to the substrate.
  • the melt should have a low viscosity and the reaction should only be used after a delay.
  • These ideas can be achieved with powder coatings, the hardening of which on a of the known thermally activated reactions between resin and hardener, for example polyepoxy resin and dicarboxylic acid hard, are difficult to realize because At the same time as the melting process, a viscosity-increasing reaction already begins.
  • radiation-hardenable powder coatings on the other hand, it should be possible to separate the melting process and crosslinking.
  • Various approaches have become known in the prior art to meet this requirement
  • the US-A-4, 129,488 and US-A-4, 163,810 disclose UV-hardenable powder coatings with special spatial arrangements of ethylenically unsaturated polymers.
  • the binder consists of an epoxy-polyester polymer, in which the epoxy adduct is spatially so is arranged so that it is spaced from the polyester adduct by means of a linear polymer chain.
  • the polymer additionally contains a chemically bound photoinitiator
  • EP-A 0 650 978, EP-A 0 650 979 and EP-A 0 650 985 disclose copolymers, the essential component of which is a relatively high proportion of the monomers with the structural element of methacrylic acid, and which are used as binders for UV Light-curable powder coatings can be used.
  • the copolymers are distinguished by a relatively narrow molecular weight distribution
  • EP-A 0 410 242 discloses binders for UV-curable powder coatings which consist of polyurethanes which have certain (meth) acryloyl groups without
  • Crosslinker component or peroxides can be crosslinked and are therefore stable in storage.
  • the crosslinking by means of UV radiation requires the addition of photoinitiators
  • EP-A 0 636 669 discloses a UV-curable binder for powder coatings, which consists of unsaturated polymers which may contain cyclopentadiene and a crosslinking agent which has vinyl ether, vinyl ester or (meth) acrylic groups
  • WO-A-93/25596 discloses polyacrylates as topcoats for automobiles, which are functionalized in a wide variety of ways with double bonds
  • DE-A-42 26 520 discloses liquid compositions which consist of unsaturated polymer in the form of unsaturated polyesters and compounds which contain (meth) acryloyl groups and / or vinyl ether groups. These compositions can be crosslinked and also by means of radical images and by radiation curing used as a binder for paints When crosslinking by UV radiation, it is necessary to add photoinitiators
  • EP-A-0 322 808 has disclosed a prior art which discloses a liquid binder which can be hardened by high-energy radiation and which consists of a mixture of an ethylenically unsaturated polyester component which also contain an ethylenically unsaturated polyester oligomer and a non-polymerized vinyl ether component.
  • the vinyl ether component is selected so that it averages at least two vinyl ether components.
  • the present invention had the object of providing substances and preparations which, when used in paint systems which can be hardened by high-energy radiation and / or thermally hardenable paint systems, do not inhibit the paint surface from oxygen, so that the use of odor-damaging amines and other coinitiators is dispensed with can be, and which can also be used for a wider application
  • Lacquer systems which have such substances surprisingly show a high UV reactivity and no oxygen inhibition of the surface during curing in air. This has the advantage that the use of amines and other coinitiators can be dispensed with
  • polymer molecules can also be formed which are functionalized only in one way, for example with the methyl ether groups a) or not at all, since such less or not functionalized polymeric base structures at all
  • the functional groups a) and b) can be linked at the same point and / or different points to the oligomeric or polymeric basic structure, and terminate them as desired.
  • the functional groups a) and b) can also be present more than once on the same group.
  • two glycidyl methacrylates can react on a terminal NH 2 group or one molecule of ethanol amine divinyl ether on a terminal epoxy group.
  • polymeric basic structures that are laterally or terminally in the same position can have several OH groups Have groups, are vinylated
  • n is between 0 and 6, preferably it is 1 or 2
  • the oligomeric or polymeric basic structure can be formed by CC linkages which have double and / or triple bonds and / or are selected from ester, ether, urethane, A id, imide, imidazole, ketone, sulfide -, sulfone, acetal, urea, carbonate and siloxane linkages
  • the oligomeric or polymeric basic structure can be linear, branched, ring-shaped or dentrimeric
  • the substances according to the invention are preferably obtained by polymer-analogous reaction of functional polymers with compounds which have functional groups a) or b) and at least one further group which can react with the functional groups of the oligomeric or polymeric basic structure.
  • maleate, fumarate, itaconate, (meth) acrylate, allyl, epoxy, alkenyl, cycloalkenyl, vmylaryl and cinnamate groups and / or preferably structural units of the general formula come as coreactive, preferably copolymerizable functional group b) I considered.
  • the coating systems in the production are distinguished by a low sensitivity to heat and nevertheless good baking curability under atmospheric oxygen, short curing times when heat, UV light are used in combination Powder coatings are characterized by a good blocking resistance of the powders during storage and a very good surface smoothness of the coatings obtained from them.
  • the structural units of the general formula I can be incorporated in the coreactive groups b) in the form of esters of (oligo) dihydrodicyclopentadienol with mono- or polyfunctional carboxylic acids of the general formula II.
  • the basic structures are multiply functional epoxy-functional polymeric, oligomeric or monomeric compounds, for example of the bisphenol A epoxy compound type or of the bisphenol A epoxy resin type, by reaction with compounds which are reactive with epoxy groups
  • the epoxy groups can be functionalized with compounds which have methyl ether groups a) and thus coreactive groups b) and at least one further group which can react with epoxides. Examples of compounds of this type according to the invention are the products from partial
  • Polyurethane resins represent another important class of polymers according to the invention, which are obtained by reacting polyfunctional isocyanate compounds with acrylates and vinyl compounds, hydroxy- or aminoacrylates and hydroxy- or amino-vinylates, optionally with the use of further compounds reactive with isocyanate groups, such as hydroxy compounds
  • isocyanate compounds commercially available compounds known per se can be used, such as, for example, tolylene diisocyanate (TDI), 4,4-methylene di (phenyl isocyanate) (MDI), isophorone diisocyanate (LPDI), hexamethylene diisocyanate (HMDI), further C 2 -C 2 -Alkylene diisocyanates, further C 2 -G 2 cycloalkylene diisocyanates, naphthalene diisocyanates, further alkaryl diisocyanates such as phenylene diisocyanates, diphenyl diisocyanates and the various positional isomers of these compounds
  • isocyanate-derived, high-isocyanate-functional biuretization and isocyanurate ethoxylation products such as urocyanuration ethers trimerized or oligomerized isocyanates, and those from the simple isocyanates mentioned above by dimerization or oligomerization with
  • polyisocyanates which have diisocyanurate groups.
  • trimerization products of the diisocyanates mentioned above should be mentioned here in particular
  • the isocyanates mentioned or mixtures of these isocyanates are reacted with those compounds which are reactive with the isocyanates and, in addition to the groups reactive with isocyanates, furthermore contain groups a) and b).
  • those with isocyanate-reactive compounds can also be used that do not have groups a) or b).
  • the reacted with the isocyanate-reactive compounds can be mono- or polysubstituted any isocyanate-reactive linear, branched, aromatic, cycloaliphatic, araliphatic, heterocyclic and / or Examples C ⁇ -C 2 are o-hydroxyalkyl, such as Hydroxyethylmonovinylether, Hydroxybutylmono- vinyl ether, cyclohexanedimethanol monovinyl , Hexanediol monovinyl ether,
  • DCPD dicyclopentadienol
  • glycols according to the general formula scheme V given further below, ethylene glycol, polyethylene glycols, propylene glycol, polypropylene glycols, butanediol isomers, hexanediol, neopentyl glycol, trimethylolpropane, glycerol, pentaerythritol, unsaturated hydroxyl compounds, such as allyl alcohol, partially etherified polyfunctional hydroxyl trimethyl etherol etherol monol ether, mono ether
  • the selection and combination of the desired starting compounds depends on the desired properties of the substances to be produced therefrom.
  • the desired molecular weight and, if appropriate, the viscosity can be set by using monofunctional compounds.
  • polyurethanes is also intended to include those compounds whose main chain is not only linked via urethane compounds, but also those compounds which have ester or ether chain links, ie the polyester urethanes and polyether urethanes
  • Saturated and unsaturated polyester resins which are functionalized according to the invention with groups a) and b), represent a further important class of polymer for the binders according to the invention.
  • Monofunctional compounds can also be used, for example to To regulate the molecular weight of the polycondensates
  • suitable carboxylic acid components are ⁇ , ⁇ -ethylenically unsaturated carboxylic acids, such as maleic acid, maleic anhydride, fumaric acid, itaconic acid, citraconic acid, saturated aliphatic carboxylic acids or their anhydrides, such as succinic acid, adipic acid, cork acid, natural acid, natural fatty acid, sebacic acid Leinolfettsaure, dimer and Polymerleinolfettsaure, castor oil, Rizinusolfettsaure, saturated cycloaliphafische carboxylic acids or their anhydrides, such Tetrahydrophthalsaure, Hexahydrophthalsaure, Endomethylentetrahydrophthalsaure, Norbonendicarbonsaure, aromatic carboxylic acids or their anhydrides, such as phthalic acid in its isomeric forms, also tri- and tetra-carboxylic acids or their Andydride as trimellitic , Pyromellitic acid, polycarbox
  • hydroxyl components which may be alkoxylated, at least dihydric aliphatic and / or cycloaliphatic alcohols such as ethylene glycol, propylene glycol, polyethylene glycols, polypropylene glycols, butanediol isomers,
  • DCPD can also be attached to the double bonds of the unsaturated polyesters used, which makes it possible to incorporate endomethylene tetrahydrophthalic acid structures according to the general formula IV
  • These endomethylene tetrahydrophthalic acid structures can be present on the chain double bonds of the polyesters and / or on terminal double bonds, as are introduced, for example, via substances according to the general formula in
  • Groups a) and b) according to the invention can be introduced by cocondensation and or by polymer-analogous reactions on polyesters with functional groups.
  • cocondensation are the use of trimethylol propane di and monoallyl ether, pentaerythritol di and monoallyl ether, butene-2-diol -l, 4, alkoxylated butene-2-diol-l, 4 and allyl alcohol
  • polymer-analogous reactions on polyesters with functional groups are, for example, additions to incompletely condensed linear and / or branched prepolymer polyester resins which have both free hydroxyl groups and free OH groups.
  • Suitable unsaturated glycidyl compounds are, for example, glycidyl (meth) acrylate, undecenoic acid glycidyl ester, (meth) acrylation products of polyfunctional epoxy resins and / or allyl glycidyl ether (preferably glycidyl glycidyl) -) Acrylate is added After these reactions, the hydroxyl groups are then reacted with diisocyanates and hydroxyvinyl ethers
  • Reactivity for example isophorone diisocyanate
  • hydroxyl-functional acrylates can be used in addition to the hydroxyvinylethers.
  • Pure hydroxyl-functional prepolymeric polyesters can also be used in the last described manner Hydroxyvinyl ether and hydroxyl functional compounds which have groups b), for example hydroxyalkyl (meth) acrylates or allyl alcohol are reacted.
  • groups according to the general formula I is likewise possible in this way by using commercially available dihydrodicyclopentadienol.
  • Groups according to the general formula I are introduced via the cocondensation of the half esters of maleic acid with dihydrodicyclopentadienol according to the general formula LH in polyester. These half esters are in a smooth reaction from maleic anhydride (MSA), water and dicyclopentadiene (DCPD) or by a direct addition of DCPD MSA available It is also possible to add DCPD directly to other acids and / or acidic polyesters. However, these reactions proceed usually worse and require catalysis, for example with BF 3 etherate
  • Hydroxy-functional compounds for introducing groups according to the general formula I are dihydrodicyclopentadienyl alcohol and preferably the adducts of DCPD with glycols which are inexpensive to obtain under acid catalysis and glycols according to the formula VI
  • Polyacrylate resins which are functionalized according to the invention with groups a) and b) represent another important class of polymers according to the invention and are obtained by copolymerization of acrylic esters, if appropriate with further copolymerizable compounds
  • a preferred method for the production of polyacrylates is the solvent-free, radical bulk polymerization in the stirred reactor, optionally under pressure or particularly preferably in continuous flow reactors at temperatures above the melting temperature of the polymers formed, preferably above 140 ° C.
  • Suitable components for the construction of polyacrylate resins are, for example, the known esters of acrylic acid and methacrylic acid with aliphatic, cycloaliphatic, araliphatic and aromatic alcohols with 1 to 40 carbon atoms, such as methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, tert-butyl (meth) acrylate, amyl (meth) acrylate, isoamyl (meth) acrylate, hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, decyl (meth) acrylate, undecyl (meth) acrylate, dodecyl (meth) acrylate, tridecyl (meth) acryl
  • Methylol methacrylamide acrylic acid, methacrylic acid, 3-phenylacrylic acid, hydroxyalkyl (meth) acrylates, such as ethyl glycol mono (meth) acrylate, butyl glycol mono (meth) acrylates, hexanediol mono (meth) acrylate, glycol ether (meth) acrylates, such as Methoxyethylglycol mono (meth) acrylate, ethyloxyethylglycol mono (meth) acrylate, butyloxyethylglycol mono (meth) acrylate, phenyloxyethylglycol mono (meth) acrylate,
  • Glycidyl acrylate glycidyl methacrylate, amino (meth) acrylates such as 2-aminoethyl (meth) acrylate
  • Other components include free-radically copolymerizable monomers, such as styrene, 1-methylstyrene, 4-tert-butylstyrene, 2-chlorostyrene, vinyl esters of fatty acids
  • 2 to 20 carbon atoms such as vinyl acetate, vinyl propionate, vinyl ethers of alkanols with 2 to 20 carbon atoms, such as vinyl isobutyl ether, vinyl chloride, vinylidene chloride, vinyl alkyl ketones, dienes, such as butadiene and isoprene and esters of maleic and crotonic acid in question.
  • Suitable monomers are also cyclic vinyl compounds, such as vinyl pyridine, 2-methyl-1-vinylimidazole, 1- Vinyl imidazole, 5-vinyl pyrrolidone and N-vinyl pyrrolidone Allylic unsaturated monomers can also be used, such as, for example, allyl alcohol, allyl alkyl esters, monoallyl phthalate and allyl phthalate. Acrolein and methacrolein and polymerizable isocyanates are also suitable
  • the vinyl ether groups a) and the co-reactive groups b) can be incorporated by copolymerization in the preparation of the polyacrylates or preferably by subsequent polymer-analogous reaction.
  • Compounds which can be polymerized well and which are additionally reactive with vinyl ethers are, for example, copolymerizable epoxy compounds, such as glycidyl (meth -) acrylate or dihydrodicyclopentadienol (meth) acrylate, dihydrodicyclopentadienyl ethacrylate and dihydrodicyclopentadienyl cinnamate.
  • the epoxy groups of copolymerized glycidyl (meth) acrylate can polymerize with vinyl ethers directly according to a cationic mechanism, but are also anchor groups for introducing polymer reactions to polymer reactions for the purpose of introducing polymer analogs of acrylic double bonds by reaction with (meth) acrylic acid and / or for the introduction of vinyl ether groups by reaction with aminovinyl ether compounds, such as, for example, diethanolamine divinyl ether
  • Dihydrodicyclopentadienyl groups of copolymerized dihydrodicyclopentadienyl compounds can be copolymerized or crosslinked directly with methyl ether groups by starting under UV radiation and / or thermally with compounds which are free from radicals
  • the invention is not restricted to the polymer classes mentioned. It can be advantageous to use mixtures of different polymer classes. Mixtures of relatively soft and elastic polyurethane resins or polyacrylate resins with hard, non-blocking powders are particularly preferred. good non-blocking polyester resins.
  • the various functionalization methods mentioned can be carried out in any combination in uniform polymeric precursors or mixtures of different polymeric precursors. A type of modular system is available which allows the properties of the powder coatings to be varied
  • the substances according to the invention can also be mixed with other compounds which are reactive and preferably solid with the methyl ether groups a) and / or the groups b) which are reactive therewith, such as, for example, unsaturated, preferably partially crystalline polyesters, monomeric and / or polymeric acrylates, vinyl esters, vinyl ethers, Allyl esters and allyl ethers, for example polyester acrylates, polyether acrylates, polyurethane acrylates and polyurethane vinyl ethers, Even in such mixtures, the disruptive oxygen inhibition of the surface is advantageously suppressed
  • the substances according to the invention can have copolymer built-in photoinitiators, as are explained in more detail below
  • the invention also relates to preparations which contain the substance according to the invention.
  • the preparation according to the invention can contain at least one compound which provides radicals and / or cations thermally or under high-energy radiation
  • the invention also relates to uses of the preparation according to the invention.
  • the use as or in a binder for liquid lacquer systems, with or without the use of solvents, lacquer dispersions or powder lacquers, also pays
  • such coating systems can be crosslinked with a surprisingly high reactivity and, even without coinitiators, do not show any oxygen inhibition of the surface. They are also thermally radical-providing
  • Connections can be hardened by baking
  • curing takes place with conventional photoinitiators of the Norrish I or II type or with catalysts which provide thermal radicals, such as peroxides, azo starters or CC-labile compounds, such as those of the Pinacol type Painting and / or
  • Copolymer-bound photoinitiators are particularly preferred as photoinitiators.
  • A-40 07 318 are known and in particular include those compounds which are derived from aromatic or partially aromatic ketones and have thioxanthone structures, can also be used by addition of, for example, hydroxybenzophenone to copolymerized epoxy compounds, for example
  • polymers which have, for example, copolymer-bound benzophenone groups can be UV-crosslinked with high sensitivity. This reactivity is further increased if structural units of the general formula I are simultaneously present as functional group b)
  • coating systems containing the preparations according to the invention also have compounds which provide radicals and / or cations thermally or under high-energy radiation
  • curing can be purely thermal, for example by baking in air and / or by high-energy radiation with starters such as peroxides, Azostartem or CC-labile compounds are made
  • Such coating systems can be used for coating and / or painting a wide variety
  • the surfaces can generally be flat or shaped as well as fibrous or particle-like substrates made of any materials, such as
  • the polymeric basic structure to be combined and the coreactive groups b) for the binder of the respective powder coating are carried out in accordance with the requirements of the intended use in such a way that the finished lacquer coatings meet the requirements.
  • the highest degree of elasticity and adhesion are important.
  • the price of the monomers can also be a selection criterion if, for certain applications, the quality is not high the paintwork, but a low price is required
  • the hardness, the glass transition temperature and the softening temperature of the polymers can be increased by higher proportions of "hard” monomers, such as, for example, styrene or the (meth) acrylates of C1 to C3 alcohols, while, for example, butyl acrylate, ethylhexyl acrylate or tridecyl acrylate as "soft" monomers lower these properties but improve the elasticity.
  • "hard” monomers such as, for example, styrene or the (meth) acrylates of C1 to C3 alcohols
  • butyl acrylate, ethylhexyl acrylate or tridecyl acrylate as "soft” monomers lower these properties but improve the elasticity.
  • Minor proportions of (meth) acrylic acid or (meth) acrylamide improve them
  • Phenyl acrylic acids further improve the weather resistance of the paints than built-in stabilizers
  • the paint preparations can also contain pigments and / or customary paint auxiliaries, such as flow control agents, ventilation aids, other wetting agents and dispersants,
  • aqueous dispersions so-called powder slurries, are also possible in order to make the powder lacquers accessible to a liquid application
  • Aqueous dispersions can also be prepared, for example by (partially) neutralizing polymer-bound amino groups or dispersing with the aid of protective colloids. It is advantageous to set a pH of> 7 in order to avoid acid-catalyzed saponification of the vinyl ethers
  • the invention also relates to the use of the preparation according to the invention as or in adhesives.
  • adhesives can be applied from the melt, as a liquid system, as a solution or dispersion in suitable solvents or water.
  • the curing can also be carried out thermally and / or with high-energy radiation, preferably UV radiation. Light done
  • the preparation according to the invention can also be used as a casting and drinking agent for electronics and / or electrical engineering.
  • the preparations from the melt can be applied as systems which are liquid at room temperature or as a solution or dispersions in suitable solvents or water / or with high-energy radiation, preferably UV light
  • Another use according to the invention relates to the production of preparations for the production of molded articles which can contain flat-shaped and / or disorderly fibrous reinforcing agents.
  • Such reinforcing agents can be, for example, glass fibers and / or other fillers and reinforcing materials
  • Example 1 Polyurethane with vinyl ether and acrylate groups
  • the mixture is heated to 80 ° C. under a gentle stream of nitrogen and a dissolved mixture of
  • Example 2 Polyurethane with vinyl ether and acrylate groups
  • Basonat HI 100 trimerized hexamethylene diisocyanate with 21.8% NCO
  • the mixture is heated to 80 ° C. under a gentle stream of nitrogen and a dissolved mixture of 11.4 g of butanediol-1,4 (0, 125 mol) and 87 g of hydroxyethyl acrylate (0.75 mol) is dissolved in one hour.
  • Example 3 Polyacrylate with aminovinyl ether and acrylate groups
  • Example 4 Polyacrylate with aminovinyl ether and dihydrodicyclopentadienyl groups Weighed in a Ruhr flask with an inlet vessel and a reflux condenser
  • Example 5 Polyacrylate with aminovinyl ether, acrylate and dihydrodicyclopentadienyl groups
  • Comparative Example 1 Comparative Example Polyacrylate with only acrylate groups
  • VL1 162 g VB1 (approx. 100 g resin content) + 3 g BDMK
  • VL2 162 g VB 1 (approx. 100 g resin content) +50 g TEGDVE + 3 g BDMK
  • VL3 162 g VB 1 (approx. 100 g resin content) +50 g HDA + 3 g BDMK
  • BDMK benzil dimethyl ketal (photo initiator)
  • TEGDVE triethylene glycol divinyl ether
  • HDA hexanediol diacrylate
  • test lacquers The preparation of the test lacquers and the production of the test panels were carried out in a laboratory protected against UV light.
  • the components of the test lacquers were premixed in glass bottles with a spatula, these mixtures were stored in a drying cabinet at 50 ° C for one hour and then stirred again after cooling to room temperature Clear viscous solutions in all cases.
  • the solutions were then applied to a degreased, bare steel sheet using a doctor blade with a gap height of 60 .mu.m.
  • the sheets with the solutions L6 to L 14 and VL1 to VL3 were then removed in a vacuum drying cabinet at 40 ° C. to remove the solvent butyl acetate Stored overnight On all test panels there are then liquid viscous resin films.
  • test panels Under a UV light mercury vapor lamp with an emission maximum at approx. 365 nm and an energy output of 19 mJ / cm in the level of the exposure, the test panels were then irradiated until the films underneath an acetone-damp cotton ball after 10 minutes no ch remained without attack if a surface inhibition of the films was observed, a non-cross-linked, acetone-free layer then present was first wiped off and the swellability of the cross-linked layer below was assessed
  • VL2 240 s acetone-resistant, no surface inhibition
  • VL3 240 s acetone-resistant, with non-sticky surface inhibition * Surface inhibition: under a thin, sticky or tack-free surface layer that remains acetone-insoluble, the layers are insoluble in acetone.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Polymers & Plastics (AREA)
  • Medicinal Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Wood Science & Technology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Materials Engineering (AREA)
  • Engineering & Computer Science (AREA)
  • Macromonomer-Based Addition Polymer (AREA)
  • Paints Or Removers (AREA)
  • Polyurethanes Or Polyureas (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)
  • Polymerisation Methods In General (AREA)
  • Epoxy Resins (AREA)
  • Adhesives Or Adhesive Processes (AREA)

Abstract

L'invention concerne des matériaux qui peuvent être durcis par un rayonnement haute énergie et/ou par la chaleur, et dont la structure de base, constituée d'oligomères ou de polymères, comprend au moins un groupe vinyléther (a) terminal ou latéral, et au moins un groupe (b), différent des groupes vinyléther (a) et réagissant avec eux. En moyenne, au moins un groupe vinyléther (a) et un groupe coréactif (b) sont présents par molécule d'oligomère ou de polymère. L'invention concerne également des préparations contenant le matériau ci-dessus, ainsi que l'utilisation de ladite préparation dans ou comme un liant destiné à des systèmes de laques fluides, à des laques en poudre, ou bien comme ou dans des adhésifs, des agents de coulée et d'imprégnation destinés à l'électronique et/ou l'électrotechnique, et pour la fabrication de corps moulés.
EP99944332A 1998-08-07 1999-08-04 Materiaux et preparations durcissables par un rayonnement haute energie et/ou par la chaleur Withdrawn EP1100836A1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE19835913A DE19835913A1 (de) 1998-08-07 1998-08-07 Durch energiereiche Strahlung und/oder thermisch härtbare Stoffe und Zubereitungen
DE19835913 1998-08-07
PCT/EP1999/005646 WO2000008081A1 (fr) 1998-08-07 1999-08-04 Materiaux et preparations durcissables par un rayonnement haute energie et/ou par la chaleur

Publications (1)

Publication Number Publication Date
EP1100836A1 true EP1100836A1 (fr) 2001-05-23

Family

ID=7876885

Family Applications (1)

Application Number Title Priority Date Filing Date
EP99944332A Withdrawn EP1100836A1 (fr) 1998-08-07 1999-08-04 Materiaux et preparations durcissables par un rayonnement haute energie et/ou par la chaleur

Country Status (7)

Country Link
EP (1) EP1100836A1 (fr)
JP (1) JP2002522580A (fr)
KR (1) KR20010072314A (fr)
CN (1) CN1317023A (fr)
CA (1) CA2339735A1 (fr)
DE (1) DE19835913A1 (fr)
WO (1) WO2000008081A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108707217A (zh) * 2018-05-30 2018-10-26 苏州中来光伏新材股份有限公司 交联剂、交联剂的制造方法及太阳能电池背板

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1221449A1 (fr) 2000-12-22 2002-07-10 Dsm N.V. Compositions de peroxides contenant des diluants reactifs
EP1225189A1 (fr) 2000-12-22 2002-07-24 Dsm N.V. Composition à deux composants pour la technique de fixation chimique
CN113462345A (zh) * 2021-07-13 2021-10-01 天能电池集团股份有限公司 一种紫外光固化色胶及其制备方法

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
MX169697B (es) * 1987-12-28 1993-07-19 Ppg Industries Inc Mejoras a composiciones fraguables por radiacion basadas sobre poliesteres insaturados y compuestos teniendo por lo menos dos grupos de vinil eter
US5334456A (en) * 1988-08-12 1994-08-02 Stamicarbon B.V. Free-radical curable compositions
US5252682A (en) * 1992-12-17 1993-10-12 Zircon Corporation Cationically initiated curable resin system
US5922473A (en) * 1996-12-26 1999-07-13 Morton International, Inc. Dual thermal and ultraviolet curable powder coatings

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO0008081A1 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108707217A (zh) * 2018-05-30 2018-10-26 苏州中来光伏新材股份有限公司 交联剂、交联剂的制造方法及太阳能电池背板

Also Published As

Publication number Publication date
KR20010072314A (ko) 2001-07-31
JP2002522580A (ja) 2002-07-23
CA2339735A1 (fr) 2000-02-17
WO2000008081A1 (fr) 2000-02-17
CN1317023A (zh) 2001-10-10
DE19835913A1 (de) 2000-02-10

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