MXPA00010761A - Compositions suitable for electrochemical cells - Google Patents

Abstract

The invention relates to a composition which contains (a) between 1 and 99 weight%of a pigment (I) with a primary particle size of 5 nm to 100&mgr;m, which is a solid Ia or a compound Ib acting as cathode material in electrochemical cells or a compound Ic acting as anode material in electrochemical cells or a mixture of the solid Ia with the compound Ib or Ic;(b) between 1 and 99 weight%of a polymer material (II) which contains:(IIa) between 1 and 100 weight%of a polymer or copolymer (IIa) which has reactive groups (RG) in a terminal or lateral position or at the chain, which can give rise to thermal and/or UV radiation-induced cross-linking reactions, and (IIb) between 0 and 99 weight%of at least one polymer or copolymer (IIb) which has no reactive groups (RG).

Description

ADEQUATE COMPOSITIONS FOR ELECTROCHEMICAL CELLS The present invention relates to compositions which are suitable, inter alia, for electrochemical cells having electrolytes containing lithium ions, to their use, for example, in or as solid electrolytes, separators and electrodes, to solid electrolytes, separators, electrodes, detectors, electrochromic windows, screens, capacitors and ion conductive films in which this composition is present and the electrochemical cells containing these solid electrolytes, separators and / or electrodes. Electrochemical cells, in particular rechargeable cells, are generally known, for example, from Ullmann's Encyclopedia of Industrial Chemistry, 5th edition, vol A3, VCH Verlagsgesellschaft mbH, Weinheim 1985, pages 343-397. Among these cells, lithium batteries and lithium ion batteries occupy a special position, particularly as secondary cells, due to their high density of specific energy storage. The cathode of these cells contains, as described for example in the aforementioned reference of "Ullmann", mixed oxides of magnesium, cobalt, vanadium or nickel lithium, as can be described in the simplest case from the stoichiometric point of view as LiMn20, LiCo02, LiV205 or LiNi02. These mixed oxides react reversibly with the compounds that can incorporate lithium ions in their lattice, for example, graphite, to liberate the lithium ions from the crystalline lattice, with metal ions such as manganese, cobalt or nickel being oxidized in the reticle. This reaction can be used for the storage of electrical energy in an electrochemical cell by separating the compound that takes the lithium ions, that is, the anode material, and the mixed oxide containing lithium, that is, the cathode material through an electrolyte through from which the lithium ions migrate from the mixed oxide to the anode material (loading process). Compounds which are suitable for the reversible storage of lithium ions are customarily fixed to make contact with the electrodes by means of a binder. During the charging of the cell, the electrons flow through an external energy source and the lithium cations flow through the electrolyte to the anode material. When the cell is used, the lithium cations flow through the electrolyte and the electrons, on the other hand, flow through a working resistor from the anode material to the cathode material.

To avoid a short circuit inside the electrochemical cell, an electrically insulating layer through which, however, the lithium cations can pass is located between the two electrodes. This can be a solid electrolyte or an ordinary separator. The solid electrolytes and separators consist, as already known, of a support material in which a dissociable compound containing lithium cations is incorporated to increase the conductivity of the lithium ion and normally other additives such as solvents. As support material, US-A 5296318 and US-A 5429891 propose, for example, a copolymer of vinylidene fluoride and hexafluoropropene. However, the use of these (co) high strength polymers presents a number of disadvantages. These polymers are not only expensive but also difficult to bring to solution. In addition, due to their comparatively low conductivity of the lithium cation, these increase the cell's resistance so that the electrolyte, which normally consists of a compound containing lithium cations, for example, LiPF6, LiAsFß or LiSbFe and an organic solvent such as ethylene carbonate or propylene carbonate, was added during the production of the insulating layer (US-A 5296318, US-A 5429891). Furthermore, these polymers can be processed only in the presence of, for example, high proportions of plasticizers, for example, di-n-butylphthalate, and pyrogenic silicas which are added, first of all, to ensure that the electrolytic layer is sufficiently film-forming and cohesive and can be adhesively bonded to the electrode layers and, second, to ensure sufficient conductivity and permeability for lithium cations. The plasticizer then has to be removed quantitatively from the laminar assembly of the anode, the solid electrolyte or separating layer and the cathodic layer before the use of the batteries by means of an extraction belt which is very difficult and costly on an industrial scale. WO 97/37397 refers, inter alia, to a mixture consisting of a mixture containing: a) from 1 to 95% by weight of a solid III, preferably a basic solid III, having a primary particle size from 5 nm to 20 μ, and b) from 5 to 99% by weight of a polymer composition IV obtainable by polymerization of: bl) from 5 to 100% by weight, based on the composition IV, of a condensation product V of: a) at least one compound VI that can react with a carboxylic acid or sulfonic acid or a derivative thereof or a mixture of two or more of these, and b) at least one mole per mole of compound VI of a carboxylic acid or sulphonic acid VII having at least one functional group polymerizable by free radicals, or a derivative thereof or a mixture of two or more of these and b2) from 0 to 95% by weight, based on in composition IV, of another compound VIII having an average molecular weight (number average) of at least 5000 and with polyether segments in a main or side chain, where the weight ratio of the mixture in the mixture is from 1 to 100% by weight Although the systems described there have excellent properties, particularly when used in electrochemical cells, for example, excellent short circuit resistance, high mechanical stability and good processing capacity, when these systems are used it is usually necessary to produce the actual film or the step of photo crosslinking in the production of, for example, films emptied under inert gas conditions. An object of the present invention is to offer another improved system for use in electrochemical cells. In particular, an object of the present invention is to provide a composition that can be processed more easily, that is, by avoiding inert gas conditions. We have found that this objective is achieved by a composition containing: (a) from 1 to 99% by weight of a pigment (I) having a primary particle size from 5 nm to 100 μ, which is a solid or a compound Ib acting as cathode material in electrochemical cells or a compound which acts as an anode material electrochemical cells or a mixture of solid with compound Ib or compound le, (b) from 1 to 99% by weight of a material polymer (II) containing: (Ha) from 1 to 100% by weight of a polymer or copolymer (Ha) having, as part of the chain, at the end (s) of the chain and / or laterally in the chain, reactive groups (RG) which are capable of cross-linking reactions under the action of heat and / or UV radiation, and (Hb) from 0 to 99% by weight of at least one polymer or copolymer (Hb) which is free of reactive groups RG. In particular, this composition is notable for the novel crosslinker system (polymer Ha).

The pigment I can be a solid. Conveniently, the solids are very largely insoluble in the liquid used as an electrolyte and are electrochemically inert in the middle of the battery. The term "solid" when used within the present invention, represents all compounds that are present as solids under normal conditions, which, during the use of the battery, neither absorb nor emit electrons under the conditions that exist when they are charged batteries, particularly lithium-ion batteries. Preferably, it is a solid selected from the group consisting of: an inorganic solid, preferably a basic inorganic solid selected from the group consisting of: oxides, mixed oxides, carbonates, silicates, sulfates, phosphates, amides, imides, nitrides and carbides of the elements of major groups I, II, III and IV, and transition group IV of the Periodic Table; a polymer selected from the group consisting of: polyethylene, polpylene, polystyrene, polytetrafluoroethylene, polyvinylidene fluoride, polyamides, polyimides; a dispersion of solids that contains as a polymer: glass powder, glass particles in nano sizes such as Monosper® (Merck), glass microparticles such as Spheriglas® (Potters-Ballotini), filamentary crystallites in nano sizes and a mixture of two or more of these, to give a composition that can be used as solid electrolyte and / or separator. Specific examples are: oxides such as silicon dioxide, aluminum oxide, magnesium oxide or titanium dioxide, mixed oxides, for example from the elements silicon, calcium, aluminum, magnesium, titanium; silicates such as ladder, chain, sheet and structure silicates, for example, talc, pyrophyllite, muscovite, phlogopite, amphibole, nesosilicates, pyroxenes, sorosilicates, zeolites, feldspars, ollastonite, in particular hydrophobized wollastonite, mica, phyllosilicates; sulfates such as sulfates of alkali metals and alkaline earth metals; carbonates, for example, alkali metal and alkaline earth metal carbonates such as calcium, magnesium or barium carbonate or lithium, potassium or sodium carbonate; phosphates, for example, apatites; amides; imides; nitrides; carbides; polymers such as polyethylene, polypropylene, polystyrene, polytetrafluoroethylene, polyvinylidene fluoride, polyamides, polyimides or other thermoplastics, thermosets or microgels, crosslinked polymer particles such as Agfaperl®, solid dispersions, in particular those containing the aforementioned polymers and also mixtures of two or more than the solids mentioned above. In addition, the inorganic solids that conduct Li ions, preferably a basic inorganic solid that conducts Li ions, can be used according to the present invention as the inert solid. Examples that may be mentioned are: lithium borates such as Li4B60n * xH20, Li3 (B02) 3, Li2B407 * xH20, LiB02, where x can be from 0 to 20; Lithium aluminates such as Li20 * A1203 * H20, Li2Al204, LiA102; lithium aluminosilicates such as zeolites containing lithium, feldspars, feldspar-like compounds, phyllosilicates and inosilicates, and in particular, LiAlSi206 (spodumeno), LiAlSi4O? 0 (petulite), LiAlSi04 (eucriptite), mica, for example, K [Li, Al ] 3 [AlSi] O? O (F-OH) 2, K [Li, Al, Fe] 3 [AlSi] 4O? O (F-OH) 2; lithium zeolites, in particular those in the form of fiber, layer or cube, especially those having the formula Li2 / zO * Al203 * xSi03 * xSi02 * yH20 where z corresponds to the valence, x is from 1.8 to approximately 12 and y is from 0 to approximately 8; lithium carbides such as Li2C2, LiC; Li3N; lithium oxides and combined oxides such as LiA102, Li2Mn03, Li20, Li202, Li2Mn04, Li2Ti03; Li2NH; LiNH2; lithium phosphates such as Li3P04, LiP03, LiAlFP0, LiAl (OH) P04, LiFeP04, LiMnP04; LI2C03; lithium silicates in the form of ladder, chain foil and scaffold, for example, Li2Si03, Li2Si0 and LÍ6Si2; lithium sulfates such as Li2S04, LiHS04, LiKS04; and also the Li compounds mentioned as compound Ib, with the presence of conductive carbon black being excluded when used as the solid; and also mixtures of two or more of the aforementioned solids that conduct Li ions. As a solid, preference is given to the use of hydrophobic solids, most preferably hydrophobicized compounds of the aforementioned type. The solids that are particularly convenient are basic solids. For the purposes of the present invention, basic solids are those whose mixing with a liquid diluent, containing water, which itself has a pH of no greater than 7, has a higher pH than this diluent. The present invention also relates to a composition in which the pigment I is a compound Ib which acts as a cathodic material in the electrochemical cells and is selected from the group consisting of: LIC0O2, LiNiO2, LiNixCoyO2, LiNixCoyAlzO2, where 0 < x, y, z < l, LixMnO2 (0 <x = l), L_xMn2O. (0 <x = 2), LixMoO2 (0 < x < 2), LixMnO3 (0 < x < l), LixMnO2 (0 < x < 2), LixMn2O4 (0 < x = 2), UxV2O4 (0 <x <2.5), LxV2O3 (0 <x <3.5), LixVO2 (0 <x <l), LixWO2 (0 <x__l), LixWO3 (0 <x l), LixTiO2 (0 <x <l), LixTi2O4 (0 <x = 2), LixRuO2 (0 <x__l), LixFe2O3 (0 <x = 2), LixFe3O4 (0 <x <2), I__xCr2O3 (0 <x <3), LixCr3O4 (0 <x = 3.8), LixV3S5 (0 <x = 1.8), LixTa2S2 (0 <x = l), LixFeS (0 <x = l), LixFeS2 (0 <x = l), LixNbS2 (0 <x <2.4), LixMoS2 (0 <x <3), LixTiS2 (0 <x <2) 5 LixZrS2 (0 <x <2), LixNbSe2 (0 <x <3), LixVSe2 (0 <x < x < x <; l), LixNiPS2 (0 <x = 1.5), LixFePS2 (0 <x < 1.5), LiNixB? (0 <x <l), LiNixAl1.xO2 (0 <x <l), LiNixMg? .xO2 (0 <x <l), LiNixCo? .xVO4 (1 = x> 0), LiNixCoyMnzO2 (x + y + z = 1), LiFeO_, LiCrTiO4, LiaMbLcOd (1.15> a> 0; 1.3> b + c = 0.8; 2.5__d = 1.7; M = Ni, Co, Mn; L = Ti, Mn, Cu, Zn, alkaline earth metal), LiCu? PCu? PIMn (2. (? + Y »° 4 (2> x + y> 0), LiCrTiO, LiGaxMn2-xO4 (Ol = x = O), poly (carbon sulfides) of carbon polysulfides) of the structure: - [C (Sx)] n-, V205, one or mixture of two or more of these, and a mixture of compound Ib with the solid and the composition also contains from 0.1 to 20% by weight, based on the total weight of components I and II, of conductive carbon black, giving a composition that can be used, in particular, as a cathode. present invention provides a composition in which the pigment I is a compound that acts as an anode material in the electrochemical cells and is selected from the group consisting of: lithium, metal alloy containing lithium, micronized carbon black, natural and synthetic graphite , synthetic graphitized carbon powder, a carbon fiber, titanium oxide, zinc oxide, tin oxide, molybdenum oxide, tungsten oxide, carbonate d e titanium, molybdenum carbon, zinc carbonate, LixMySiOz (l > x > 0.1y > 0, z > 0), Sn2BP04, conjugated polymers such as polypyrroles, polyanilines, polyacetylenes, polyphenylenes, lithium metal compounds LixM, such as those in which M = Sn, Bi, Sb, Zn, Cd, Pb and 5 >; x > 0; Li-Sn-Cd, CdO, PbO, a mixture of two or more of these, or a mixture of the compound with the solid, and the composition also contains up to 20% by weight, based on the total weight of the components I and II, of conductive carbon black, giving a composition that can be used, in particular, as an anode. Particularly suitable pigments I are those having a primary particle size from 5 nm to 20 μ, preferably from 0.01 to 10 μ and, in particular, from 0.1 to 5 μ, where the indicated particle sizes are determined by electron microscopy . The melting point of the pigments is preferably above the operating temperature customary for electrochemical cells, with melting points above 120 ° C, in particular above 150 ° C, having been found particularly useful. The pigments can have a symmetrical external shape, that is, with a ratio of height: width: length (ratio between dimensions) of about 1 and be in the form of spheres, granules, roughly round structures, or in the form of any polyhedron , for example, cuboids, tetrahedra, hexahedra, octahedra or as bipyramids, or may have a distorted or asymmetric shape, that is, with a ratio of height: width: length (relationship between dimensions) that is different from 1 and be in shape of, for example, needles, asymmetric tetrahedrons, asymmetric bipyramids, asymmetric hexahedra or octahedrons, platelets, disks or fibrous structures. If the solids are in the form of asymmetric particles, the upper limit before indicating for the primary particle size is based on the smallest axis in each case. The composition of the present invention contains from 1 to 95% by weight, preferably from 25 to 90% by weight, more preferably from 50 to 85% by weight, in particular from 65 to 80% by weight of a pigment I and from 5 to 99% by weight, preferably from 10 to 75% by weight, more preferably from 15 to 50% by weight, in particular from 20 to 35% by weight of the polymeric binder II. This polymeric binder II contains from 1 to 100% by weight of at least one polymer Ha having, as part of the chain, at the end (s) of the chain and / or laterally in the chain, reactive groups ( RG) which are capable of cross-linking reactions under the action of heat and / or UV radiation, and from 0 to 99% by weight of at least one polymer or copolymer (Hb) which is free of reactive groups RG. As polymers Ha, it is possible, in principle, to use all polymers that are thermally crosslinkable and / or under high energy radiation, preferably under UV light, and have, as part of the chain, at the end (s) ) of the chain and / or laterally in the chain, reactive groups (RG), preferably reactive groups RGa or RGb or RGa and RGb, by means of which the polymers can crosslink under the action of heat and / or radiation.

More preferably, the polymer Ha is a polymer having, in each case as part of the chain, at the end (s) of the chain and / or laterally in the chain, at least a first reactive group RGa and at least one RGb group that is different from RGa and is coreactive with RGa, with at least one RGa and at least one RGb being present on average in all polymeric molecules. The polymer Ha may also be formed by a mixture of a plurality of polymers of which some have only RGa and others have only RGb. The polymer Ha may also be formed of a mixture of a plurality of polymers of which some have only RGa and others have only RGb and other polymers having RGa and RGb. In general, the polymer Ha is constituted of a uniform polymeric class, preferably of the polyacrylate class. However, mixtures of different kinds of polymers are also possible. The polymer Ha includes polymeric and oligomeric materials and also mixtures of polymeric and oligomeric materials. The oligomeric and / or polymeric base structure of the polymers Ha includes the polymers known as, for example, those constituted by means of C / C bonds, which may also contain double and / or triple bonds, and also by means of bonds ether, ester, urethane, amide, imide, imidazole, ketone, sulfide, sulfone, acetal, urea, carbonate and siloxane. In addition, the oligomeric or polymeric base structure can be linear, branched, cyclic or dendrimetric. The polymers used in accordance with the invention can be obtained by polymerization, polyaddition or polycondensation of monomeric building blocks having RGa and / or RGb in addition to the groups by means of which polymer formation occurs, so that the polymers have are functionalized according to the present invention are formed directly in the preparation of the polymers. The polymers used in accordance with the present invention can also be obtained by analogous reaction of the polymers of the functional polymers with compounds having RGa and / or RGb and at least one other group that can react with the functional groups of the oligomeric base structure or polymeric It is also possible to incorporate one of the functional groups RGa and / or RGb in the preparation of the polymer and then introduce the other RG in the polymer terminated by functionalization analogous to the polymer. The RGa groups are groups having structures which, under high energy radiation, preferably UV light, are capable, in the triple excited state, of abstracting hydrogen (photo initiator groups of the Norrish II type known from the literature). These structures are known to those skilled in the art of chemical photo. In addition, acrylate compounds (derivatives having these structures are mentioned herein) Further details of these compounds can be found in US 5 558 911, the important content of which is incorporated by reference in the present application. with the present invention, use other monomers, oligomers or polymers containing these RGa structures. where ip -CHT, or C6Hs R is "-H or CH3 wherein "-. CnCln + l with n = lto3? R C6H5, K 15"10 R ís - O -,? C- O -, - I - or - © N (R 1! 1V R, 0is H or CnH2n-l with n = lto8, and R "is CnH2n-l with n = 1 to 4 (40) (41), wherein R is H or CH 3- The concomitant use of these RGa-acrylates makes it readily possible, for example, by copolymerization with other acrylates, to obtain acrylate copolymers that are functionalized by RGa according to the present invention. In addition, base polymers containing, for example, amino groups but not RGa groups can be easily functionalized by RGa through a Michael addition of these RGa-acrylates. Preferred RGa groups are the benzophenone groups. A particularly high UV light reactivity is achieved in the case of polyacrylates containing benzophenone derivatives in which the benzophenone group is attached to the main polymer chain via a spacer group. Particularly preferred polyacrylates can be obtained by copolymerization with acrylates of formulas 24 to 26 and formula 34. Another inexpensive and preferred way of introducing RGa into polymers is the reaction of hydroxybenzophenones, preferably 4-hydroxybenzophenone, with the epoxide groups of a polymer, preferably the addition of 4-hydroxybenzophenone in polyacrylates containing a proportion of glycidyl (meth) acrylate. Another elegant method is the reaction of an addition product of 1 mole of diisocyanate and 1 mole of 4-hydroxybenzophenone with a polymer having free hydroxyl groups. A preferred method for introducing RGa into the polyesters comprises the concomitant use of benzophenone carboxylic acids or benzofenocarboxylic anhydrides in the polycondensation or the reaction or esterification of polymers containing hydroxyl groups, epoxide groups, isocyanate groups and / or amino groups with benzophencarboxylic acids or benzophenonecarboxylic anhydrides. The RGb groups are groups that can interact with the excited Norrish II photo initiator groups. A particular interaction of this type known to those skilled in the art is the transfer of hydrogen to the structure of Norrish II, giving rise to the formation of free radicals, in the case of the hydrogen donor and in the case of the Norrish II structure of abstraction. The combination of free radicals makes direct cross-linking of polymers possible. In addition, the initiation of polymerization initiated by free radicals is also possible. A polymerization initiated by free radicals of, for example, polymerizable functional groups RGb, for example, maleate, fumarate (meth) acrylate, allyl, epoxide, alkenyl, cycloalkenyl, vinyl ether, vinyl ester, vinylaryl and cinnamate can also be initiated by radicals free photo generator chemically.

Preference is given to RGb that interact as donors of H with RGa, that is, systems that are free of double bonds. An inherent advantage in these systems is the low sensitivity to the interference of the systems because they have, compared to the unsaturated UV systems, a reduced reactivity towards the other constituents of the total formulation. Of course, this does not regulate the (concomitant) use of unsaturated materials and an optimization procedure for the individual case. The donor groups of H are known to those skilled in the art of chemical photo. These are, in principle, groups having hydrogen atoms having a low binding energy, particularly groups containing hydrogen atoms having a binding energy of less than 397 kJ / mol. The values of the binding energies are known from the literature and can be found, for example, in Morrison, Robert Thorton Organic Chemistry, Table: Hemolytic Union Dissociation Energies on the deck side, in the Library of Congress Cataloging- in-Publication Data ISBNO-205-08453-2, 1987, by Allyn and Bacon, Inc. A Division of Simon & Schuster, Newton, Massachusetts, USA. Examples are the amine, furfuryl, tetrahydrofurfuryl, isobornyl and isoalkyl compounds and compounds having groups of the following structures: -r "(CH2) n (n = 2 oder 3) wherein R3 = an aliphatic, cycloaliphatic, heterocyclic or aromatic divalent residue, this residue being optionally substituted, or a single bond; R 4 = H, or linear or branched alkyl, for example, having 1 to 8 carbon atoms, aryl or isoamyl phenyl substituted with halogen; R5 = alkyl, halogen substituted alkyl, aryl or isoamyl substituted with halogen. These formulas are examples only and do not constitute a limitation. Preference is given to groups of this type which have, as easily removable H atoms, H atoms at position a for a double bond (allylic H atoms). As RGb, particular preference is given to the groups: RGbl n = 0-10 Methods of incorporating such structures are, for example, the concomitant use of the ester of (oligo) -dihydrodicyclopentadienol.

RGb2 n = l-10 The monoesters of maleate / fumarate (oligo) -dihydrodicyclopentadienol are easily obtained in the industry from maleic acid and DCPD. These monoesters can be obtained in a mild reaction from maleic anhydride (MA), water and dicyclopentadiene.

(DCPD) or by direct addition of DCPD over MA. It is also possible to add DCPD directly to other acids and / or acid polyesters. However, these reactions usually do not proceed as easily and require catalysis, for example, by BF3 etherate.

Furthermore, it is known, for example, from US-A 252,682 that secondary reactions according to the following reaction scheme can take place to a subordinate degree in the DCPD and MA reaction. These by-products likewise serve to introduce structures of the formula RGbl.

In addition, dihydrodicyclopentadienol and dihydrodicyclopentadienyl acrylate are commercially available and are convenient for introducing particularly preferred RGb structures.

RGb4 RGb5 The hydroxy functional compounds for introducing groups of the formula RGbl are the dihydrodicyclopentadienyl alcohol and preferably the addition products of DCPD and glycols which can be obtained in an inexpensive manner in the presence of acid catalysts according to the following reaction scheme: RGb6 Other RGb groups of interest are the endomethylenetetrahydrophthalic acid structures obtainable, for example, by the addition of CPD in maleate groups.

The introduction of the structures of endomethylenetetrahydrophthalic acid by the addition of CPD into the double bonds of unsaturated polyesters is of particular interest.

Also of interest is the introduction of the structures of endomethylenetetrahydrophthalic acid and tetrahydrophthalic acid by the imides of these acids with hydroxyalkylamines., as is known, for example, from DE-A-15700273 or DE-A-17200323. The oligomeric and / or polymeric base structure of the Ha polymers includes the polymers known as, for example, constituted by CC bonds which may also have double and / or triple bonds, and by ether, ester, urethane, amide, imide, imidazole, ketone, sulfur, sulfone, acetal, urea, carbonate and siloxane, cream of the functionalizations that have been precisely defined in the foregoing. Preference is given to the use of polyesters, polyethers, polyurethanes and, particularly preferably, polyacrylates. For the purposes of the present invention, the polyesters are saturated and unsaturated polyester resins. To prepare the polyester resins, it is possible to use the customary and known carboxylic acids which have >; 2 carboxyl groups and / or their anhydrides and / or their esters and hydroxyl compounds having > 2 OH groups. The concomitant use can also be made of the monofunctional compounds, for example, to regulate the molecular weight of the polycondensates.

Suitable carboxylic acid components are, for example, α, β-ethylenically unsaturated carboxylic acids such as maleic acid, maleic anhydride, fumaric acid, itaconic acid, citraconic acid, saturated or aliphatic carboxylic acids or their anhydrides, for example, succinic acid , adipic acid, suberic acid, sebacic acid, azelaic acid, natural fatty acids and polymerized natural fatty acids, for example, leinoleic acid [sic] and dimeric and polymeric leinoleic acid, castor oil, ricinoleic acid, saturated cycloaliphatic carboxylic acids or their anhydrides, for example, tetrahydrophthalic, hexahydrophthalic acid, endomethylenetetrahydrophthalic acid, norbornenedicarboxylic acid, aromatic carboxylic acids or their anhydrides, for example, phthalic acid and its isomeric forms, also tricarboxylic and tetracarboxylic acids or their anhydrides, for example, he trimellitic acid, pyromellitic acid, polycarboxylic acids that have been partially esterified by allyl alcohol, for example, monoalyl trimellitate or diallyl pyromellitate, with benzophenonecarboxylic acids being of particular importance because these copolymers allow the incorporation of structures excitable by UV light. The possible hydroxyl components are, for example, aliphatic and / or cycloaliphatic alcohols alkoxylated or non-alkoxylated, at least dihydric such as ethylene glycol, propylene glycol, polyethylene glycols, polypropylene glycols, isomers of butanediol, hexanediol, trimethylolpropane, pentaerythritol, neopentyl glycol, cyclohexanedimethanol. , bisphenol A, hydrogenated bisphenol A, polyfunctional OH polymers such as hydroxyl-modified polybutadienes or polyurethane prepolymers carrying hydroxyls, glycerol, monoglycerides and diglycerides of saturated and unsaturated fatty acids, in particular monoglycerides of linseed oil or sunflower oil.

In addition, it is also possible to use unsaturated alcohols such as the polyfunctional hydroxyl compounds that have been (partially) etherified by alkyl alcohol, for example, trimethylol ethanoalkylether, trimethylol ethanedialyl ether, trimethylene propanemonoallyl ether, trimethylol propanediallyl ether, pentaerythritol monoallyl ether or pentaerythritol diallyl ether, 2-butan-1-diol and 2-butan-1, 4- alkoxylated diol. If monofunctional substances are used to regulate the molecular weight, these are preferably monofunctional alcohols such as ethanol, propanol, butanol, hexanol, decanol, isodecanol, cyclohexanol, benzyl alcohol or allyl alcohol. For the purposes of the present invention, the term "polyesters" includes polycondensates having amide and / or imide groups in addition to the ester groups, as obtained by the concomitant use of the amino compounds. Polyesters which have been modified in this way are known, for example, from DE-A-15700273 and DE-A-17200323. If the structures of endomethylene tetrahydrophthalic acid and tetrahydrophthalic acid are introduced by the imides of these acids with hydroxyalkyl amines as already ioned herein, these are RGb groups for the purposes of the present invention. Additional DCPD is also possible in the unsaturated polyester double bonds used, which makes it possible to incorporate the structures of the endomethylene tetrahydrophthalic acid representing the RGb groups for the purposes of the present invention. These structures of endomethylenetetrahydrophthalic acid may be present in the internal double bonds of the polyesters and / or in the terminal double bonds as introduced, for example, by substances of the formula 3. The double bonds from unsaturated dicarboxylic acids and / or unsaturated diols are chain RGb groups for the purposes of the present invention. The introduction of GRs can be achieved by co-condensation and / or analogous reactions to polymers on polyesters having functional groups. Examples of co-condensation are concomitant use of trimethylolpropanediallyl and monoallyl ethers, pentaerythritol dialyl and monoallylethers, 2-butan-1,4-diol, 2-butan-1, -diol alkoxylated, allyl alcohol and compounds of the formulas 3, 4, 7, 8. A preferred way to introduce the RGa is the -condensation of benzophenonecarboxylic acids or their anhydrides. In addition, preference is given to the addition of the reaction products of hydroxybenzophenones with an excess of diisocyanates in the hydroxy-functional polyesters. The RGb groups can also be introduced into hydroxy-functional polyesters in this mode. For this purpose, diisocyanates having isocyanate groups of different reactivity, for example, isophorone diisocyanate or 1,4-toluene diisocyanate, preferably first react with half the stoichiometric amount of, for example, hydroxy acrylates, hydroxyvinyl ethers, hydroxyallyl esters, hydroxyallyl ethers or hydroxy-DCPD compounds of the formulas AGb4 and AGb6 and these reaction products are then reacted with the hydroxy-functional polyesters. In the reactions mentioned, it is possible to use hydroxy-functional substances of different types at the same time. The poly (meth) acrylate resins which are functionalized according to the present invention by RG represent another important class of polymers to be used in accordance with the present invention and are obtained by copolymerization of acrylic esters with or without other copolymerizable compounds. The poly (meth) acrylate resins used according to the present invention may also be prepared in solvents. Another advantageous method for preparing poly (meth) acrylates is mass polymerization without solvents, free radicals in a reactor with stirring, at atmospheric or superatmospheric pressure, or in continuous reactors at temperatures above the melting point of the formed polymers. . Suitable components for preparing poly (meth) acrylate resins are, for example, the known esters of acrylic acid and methacrylic acid with aliphatic, cycloaliphatic, araliphatic and aromatic alcohols having from 1 to 40 carbon atoms, for example, (meth ) methyl acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, likewise isobutyl (meth) acrylate, -butyl amyl (meth) acrylate, isoamyl (meth) acrylate, hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, decyl (meth) acrylate, undecyl (metha) acrylate, (meth) acrylate of dodecyl, tridecyl (meth) acrylate, cyclohexyl (meth) acrylate, methylcyclohexyl (meth) acrylate, benzyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, furfuryl (meth) acrylate and the esters of phenylacrylics and their different isomeric forms, for example, methyl cinnamate, ethyl namate, butyl cinnamate, benzyl cinnamate, cyclohexyl cinnamate, isoamyl cinnamate, tetrahydrofurfuryl cinnamate and furfuryl cinnamate, acrylamide, methacrylamide, methylol acrylamide, methylol methacrylamide, acrylic acid, methacrylic acid 3-phenylacrylic acid, (met hydroxylalkyl acrylate such as ethylene glycol mono (meth) acrylate, butylene glycol mono (meth) acrylate and hexanediol mono (meth) acrylate, glycol ether (meth) acrylates such as methoxyethylene glycol mono (meth) acrylate, ethoxyethylene glycol (meth) acrylate, butoxyethylene glycol mono (meth) acrylate, mono (meth) acrylate phenoxyethylene glycol, glycidyl acrylate and glycidyl methacrylate, and amino (meth) acrylates such as 2-aminoethyl (meth) acrylate. Other possible components are free radical copolymerizable monomers such as styrene, 1-methylstyrene, 4-tert-butylstyrene, 2-chlorostyrene, vinyl esters of fatty acids having 2 to 20 carbon atoms, for example, vinyl acetate and vinyl propionate. , vinyl ethers of alkanols having from 2 to 20 carbon atoms, for example, vinyl isobutyl ether, vinyl chloride, vinylidene chloride, vinyl alkyl ketones, dienes such as butadiene and isoprene and also the esters of maleic and crotonic acid. Other suitable monomers are cyclic vinyl compounds such as vinylpyridine, 2-methyl-1-vinylimidazole, 1-vinylimidazole, 5-vinylpyrrolidone and N-vinylpyrrolidone. It is also possible to use aulically unsaturated monomers such as allyl alcohol, allylalkyl esters, monoalyl phthalate and allyl phthalate. Acrolein and methacrolein and the polymerizable isocyanates are also suitable. The RG can be incorporated by copolymerization in the preparation of poly (meth) acrylates or by subsequent reactions analogous to the polymer. Easily polymerizable compounds having RGb groups are, for example, dihydrodicyclopentadienyl (meth) acrylate, dihydrocyclopentadienyl ethacrylate and dihydrodicyclopentadienyl cinnamate. Easily polymerizable compounds having other groups in which analogous functionalization of the polymer is possible are, for example, copolymerizable epoxide compounds such as glycidyl (meth) acrylate or hydroxyalkyl (meth) acrylates. The hydroxyl and / or epoxide groups incorporated in this way are anchor groups for analogous functionalization reactions of the polymer of the polymers. Epoxide groups are suitable, for example, for introducing acrylic double bonds by reaction with (meth) acrylic acid (RGb) and / or for introducing vinyl ether groups (RGb) by reaction with amino vinyl ether compounds such as diethanolamine divinyl ether or to introduce benzophenone groups (RGa) by reaction with hydroxybenzophenones and / or aminobenzophenones. The polyurethanes which are functionalized according to the present invention by RG represent another important class of polymers to be used according to the present invention, and are obtained in a manner known to those skilled in the art from polyfunctional, usually bifunctional isocyanates. and polyhydroxy and / or polyamino compounds. In this case, it is also possible to introduce RGa and / or RGb directly during the formation of the polyurethanes or later in the functional polyurethanes. In this case, the chemical reactants are practically the same as in the polymers described above. The RGa groups are preferably introduced by the concomitant use of benzophenone functional compounds, and the RGb groups are preferably introduced by the hydroxy-DCPD compounds of the formulas RGb4 and RGbd.

Other details related to the basic polyurethane structures that can be used can be found in the corresponding description of the polyurethanes that can be used as the Hb polymer. The preparation of the polymers Ha to be used according to the invention is carried out in accordance with generally known rules and are known to those skilled in the art of polymers, for example, with respect to the arrangement of a desired molecular weight by the concomitant use of regulating or monofunctional starting materials or the arrangement of a desired glass transition temperature by balancing the hard / soft components. Compounds which are particularly suitable for introducing RGa into the polymers used in accordance with the present invention, particularly in, as already described, epoxy and / or hydroxy-functionalized polyesters, polyurethanes or polyacrylates are: 2-, 3- and 4-hydroxybenzophenone , 2-hydroxy-5-methylhydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octyloxybenzophenone, 2-hydroxy-4-dodecyloxybenzophenone, 2-hydroxy-5-chlorohydroxybenzophenone, 2-hydroxy-4-methoxy-4 '-methylbenzophenone, 2-hydroxy-4-methoxy-4'-chlorobenzophenone, 4-hydroxy-3-methylbenzophenone, 4-hydroxy-4'-methoxybenzophenone, 4-hydroxy-4'-chlorobenzophenone, 4-hydroxy-4' - fluorobenzophenone, 4-hydroxy-4'-cyanobenzophenone, 4-hydroxy-2 ',' dimethoxybenzophenone, 2, 2 ', 4, 4'- and 2,4-dihydroxybenzophenone, 4-tert-butyl-2, -dihydroxybenzophenone, 2 , 2'-dihydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4-octoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2,4,4'-, 2,3,4- and 2 4,6-trihydroxybenzophenone 2 , 2'-, 4,4'-, 2,3,4,4'- and 2, 3 ', 4, 4'-tetrahydroxybenzophenone, 2-, 3- and 4-amino-benzophenone, 2-amino-4 -methylbenzophenone, 2-amino-6-methylbenzophenone, 2-amino-4'-methyl-benzophenone, 2-amino-4'-chloro-5-fluorobenzophenone, 2-amino-5-chlorobenzophenone, 2-amino-5-bromobenzophenone , 2-amino-5-methylbenzophenone, 2-amino-N-ethylbenzophenone, 2-amino-2 ', 5' dimethylbenzophenone, 4-amino-2-chlorobenzophenone, 4-amino-4'-methoxybenzophenone, 3,4-, 4,4'-and 3,3'-diaminobenzophenone, 4,4'-bis (methylamino) benzophenone, 3,3 ', 4,4'-tetrahydrobenzophenone, 2-, 3- and 4-benzoylbenzoic acid, 2- benzoyl-3'-methylbenzoic acid, 2-benzoyl-4'-ethylbenzoic acid, 2-benzoyl-3,6-dimethylbenzoic acid, 2-benzoyl-2 ', 6'-dimethylbenzoic acid, 2-benzoyl-3'-acid '-dimethylbenzoic acid, 2-benzoyl-2', 4 ', 6-dimethylbenzoic acid, 2-benzoyl-p-hydroxybenzoic acid, 2-benzoyl-4'-methyl-3'-chlorobenzoic acid, 2-benzoyl-6-acid Chlorobenzoic acid, 4-benzoyl-4'-isopropylbenzoic acid, 4-benzoyl acid -4'-chlorobenzoic acid, 4-benzoyl-4 '- (2-carboxypropyl) benzoic acid, 2,4-, 3,4- and 4,4'-benzophenodicarboxylic acid, 2', 3, 4-, 3, 3 ', 4- and 3,4,4'-benzophenonetricarboxylic acid, 3, 3', 4,4'-benzophenone tetracarboxylic acid and dianhydride, 2-hydroxy-4-methoxy-5-sulfobenzophenone, 4- (4-carboxyphenyloxy) benzophenone , 4- (3,4-bis (carboxy) phenyloxy) benzophenone and the corresponding anhydride, 4 '- (4-carboxyphenyloxy) benzophenone-4-carboxylic acid, 4' - (4-carboxyphenyloxy) benzophenone-3, 4- dicarboxylic acid and the corresponding anhydride, 4 '- (3,4-bis (carboxy) phenyloxy) benzophenone-2,4- and 3,4-dicarboxylic acid and the corresponding anhydrides, 4- (4-cyanobenzoyl) thiophenol, 4- ( 2-hydroxyethoxy) phenyl 2-hydroxy-2-propyl ketone, 4- (2-aminoethoxy) phenyl 2-hydroxy-2-propyl ketone, 4- (2-hydroxycarbonylmethoxy) phenyl 2-hydroxy-2-propyl ketone, 4- (2-isocyanatoethoxy) phenyl 2-hydroxy-2-propyl ketone, 4- (2-isocyanatomethoxy) phenyl 2-hydroxy-2-propyl ketone, 2 - ([2-] 6-isocyanate to hexylaminocarbonyloxy) ethoxythioxanthone and phenylglyoxylic acid. In addition, the polymers and copolymers described below under "Hb polymers" can also be used as Ha polymers provided that they are provided with reactive groups RG, in particular RGa and / or RGb. In this case, particular mention can be made of the polymers and copolymers of olefinic compounds containing halogen (group 4f) which have been provided with reactive groups RG. The crosslinking of the polymers used in accordance with the present invention is preferably carried out by means of high energy radiation, in particular by UV light. In most cases, no further addition of the initiator photo is necessary, ie the materials are self-crosslinking, and a particular advantage is their low inhibition by air. However, the addition of other commercial photo initiators is not ruled out. In addition, many Ha polymers are also thermally crosslinkable. The particularly high thermal crosslinking capacity is obtained in the presence of peroxides and / or labile substances C-C of the benzopinacol type in the case of unsaturated systems which also have DCPD groups. Some of these systems can also be thermally cured in the absence of peroxides. Particularly rapid crosslinking is achieved, for example, by the combined use of heat and UV light, for example, a combination of IR and UV sources. As Hb polymers, use is made of thermoplastic polymers and ion conductors. Particular mention may be made of: 1) homopolymers, copolymers or block copolymers (Ubi polymers) obtainable by polymerization of: b) from 5 to 100% by weight, based on the Hbl polymer, of a condensation product of a) at least one compound (a) that can react with a carboxylic acid or a sulfonic acid or a derivative thereof or a mixture of two or more of these, and, b) at least one mol per mol of this compound (a) ) of a carboxylic acid or sulfonic acid (b) having at least one functional group polymerizable by free radicals, or a derivative thereof or a mixture of two or more of these and b2) from 0 to 95% by weight, based on in the Hbl polymer, of another compound (c) having an average molecular weight (number average) of at least 5000 and having polyether segments in a main or side chain. The polymer Hbl can preferably be obtained by polymerization of: b) from 5 to 100% by weight, based on the polymer Hbl, of a condensation product of: a) a polyhydric alcohol containing carbon and oxygen atoms in the chain main, and b) at least one mole per mole of polyhydric alcohol of a carboxylic acid, a, β-unsaturated, and b2) from 0 to 95% by weight, based on the polymer Hbl, of another compound (c) having an average molecular weight (numerical average) of at least 5000 and having polyether segments in a main or side chain. As a compound (a) which can react with a carboxylic acid or a sulfonic acid (b) or a derivative thereof or a mixture of two or more of these, in principle it is possible to use all the compounds that meet this criterion and are free of reactive groups RG. The compound (a) is preferably selected from the group consisting of a monohydric or polyhydric alcohol having only carbon atoms in the main chain; a monohydric or polyhydric alcohol which in the main chain has at least two carbon atoms plus at least one atom selected from the group consisting of: oxygen, phosphorus and nitrogen; a cond containing silicon; an amine having at least one primary amino group, an amine having at least one secondary amino group; an amino alcohol; a monohydric or polyhydric thiol, a cond containing at least one thiol group and at least one hydroxyl group; and a mixture of two or more of these. Among these, preference is given to conds (a) having two or more functional groups capable of reacting with carboxylic acid or sulfonic acid. When cond (a) containing amino groups are used as functional groups, preference is given to the use of those having secondary amino groups so that, after condensation, no free NH groups or only a small number of these are present in the coition of the present invention. Specific examples of the preferred conds (a) are: Monohydric or polyhydric alcohols having only carbon atoms in the main chain and having from 1 to 20, preferably from 2 to 20, and in particular from 2 to 10 alcoholic OH groups, in particular dihydric, trihydric and tetrahydric alcohols, preferably having from 2 to 20 carbon atoms, for example, ethylene glycol, 1,2- or 1,3-propanediol, 1,2- or 1,3-butanediol, 1,4-butenediol or 1,4-butynediol, 1, 6-hexanediol, neopentyl glycol, 1,2-dodecanediol, glycerol, trimethylolpropane, pentaerythritol or sugar alcohols, hydroquinone, novolak, bisphenol A, although it is also possible, as indicated by the above definition, monohydric alcohols such as methanol, ethanol, propanol, n-, sec- or tert-butanol, etcetera; it is also possible to use polyhydroxyolefins, preferably those having two terminal hydroxyl groups, for example, α, β-dihydroxybutadiene; polyester polyols as are known, for example, from Ullmanns Encyclopaedia der technischen Chemie, 4th edition, volume 19, pages 62-65, and are obtained, for example, by the reaction of dihydric alcohols with polybasic polycarboxylic acids, preferably dibasic; monohydric or polyhydric alcohols containing at least two carbon atoms plus at least one oxygen atom in the main chain, preferably polyether alcohols such as the products of the polymerization of alkylene epoxides, for example, isobutylene oxide, propylene oxide , ethylene oxide, 1,2-epoxybutane, 1,2-epoxypentane, 1,2-epoxyhexane, tetrahydrofuran, styrene oxide, it being also possible to use polyether alcohols which have been modified in the terminal groups, for example, alcohols of polyether modified by terminal NH2 groups; these alcohols preferably have a molecular weight (number average) from 100 to 5,000, more preferably from 200 to 1000, and in particular, from 300 to 800; these compounds are known per se and are available commercially, for example, under the Pluriol® or Pluronic® brands (from BASF Aktiengesellschaft); the alcohols, as already defined, in which some or all of the carbon atoms are replaced by silicon, as it is possible to use, in particular, polysiloxanes, or alkylene oxide / siloxane copolymers or mixtures of polyether alcohols and polysiloxanes as described, for example, in EP-B 581 296 and EP-A 525 728; with respect to the molecular weight of these alcohols, what was said in the above is applied in the same way; alcohols, as already defined, in particular polyether alcohols, in which some or all of the oxygen atoms are replaced by sulfur atoms; with respect to the molecular weight of these alcohols, what was said in the above is applied in the same way; monohydric or polyhydric alcohols which in the main chain contain at least two carbon atoms plus at least one phosphorus atom or at least one nitrogen atom, for example, diethanolamine, triethanolamine; the zones coming from compounds of the formula H0- (CH3) z-COOH, where z is from 1 to 20, for example, e-caprolactone, β-propiolactone, β-butyrolactone or methyl-e-caprolactone; a silicon-containing compound such as dichlorosilane or trichlorosilane, phenyltrichlorosilane, diphenyldichlorosilane, dimethylvinylchlorosilane; silanols such as trimethylsilanol; an amine having at least one primary and / or secondary amino group, for example, butylamine, 2-ethylexylamine, ethylenediamine, hexamethyldiamine, diethylenetriamine, tetraethylenepentamine, pentaethylenehexamine, aniline, phenylenediamine; polyether diamine such as 4,7-dioxidecan-1, 10-diamine, 4,11-dioxytetradecan-1, 14-diamine; monohydric or polyhydric thiols, for example, aliphatic thiols such as metantiol, ethantiol, cyclohexanthiol, dodecantiol, aromatic diols such as thiophenol, 4-chlorothiophenol, 2-mercaptoaniline; a compound containing at least one thiol group and at least one hydroxyl group, for example, 4-hydroxythiophenol and also monothiol derivatives of the polyhydric alcohols defined above; amino alcohols such as ethanolamine, N-methylethanolamine, N-ethylethanolamine, N-butylethanolamine, 2-amino-1-propanol, 2-amino-1-phenylethanol; monoamino or polyamino polyols having more than 2 aliphatically bound hydroxyl groups, for example, tris (hydroxymethyl) methylamine, glucamine, N, N'-bis (2-hydroxyethyl) ethylenediamine and mixtures thereof.

It is also possible to use mixtures of two or more of the compounds (a) described above. The aforementioned compounds (a) are, according to the present invention, condensed with carboxylic acid or sulfonic acid (b) having at least one functional group polymerizable by free radicals, or a derivative thereof or a mixture of two or more of these, with at least one, preferably all free groups capable of condensation in the compounds (a) being condensed with the compound (b). As the carboxylic acid or sulfonic acid (b) used for the purposes of the present invention, in principle it is possible to use any of the carboxylic or sulphonic acids having at least one functional group polymerizable by free radicals, and also derivatives thereof. The term "derivatives" used herein includes those compounds that are derived from a carboxylic or sulfonic acid that have been modified in the acid function, for example, esters, acid halides or acid anhydrides, and also compounds that come from a carboxylic acid or sulphonic which is modified in the carbon skeleton of the carboxylic or sulphonic acid, for example, halocarboxylic or halo-sulphonic acids.

Particular examples of the compound (b) are: α, β-unsaturated carboxylic acids or β, β-unsaturated carboxylic acids or derivatives thereof. Particularly convenient α, β-unsaturated carboxylic acids are those of the formula: where R1, R2 and R3 are hydrogen or C? -C4 alkyl radicals, and among these in turn acrylic acid and methacrylic acid are preferred; also useful are cinnamic acid, maleic acid, fumaric acid, itaconic acid or p-vinylbenzoic acid, and also derivatives thereof, for example, anhydrides such as maleic anhydride or itaconic anhydride; The halides, in particular, in particular chlorides such as acryloyl or methacryloyl chloride; the esters as (cyclo) alkyl (meth) acrylates having up to 20 carbon atoms in the alkyl radical, for example, methyl, ethyl, propyl, butyl, hexyl, 2-ethylhexyl, stearyl, lauryl, cyclohexyl, benzyl (meth) acrylate , trifluoromethyl, hexafluoropropyl or tetrafluoropropyl, polypropylene glycol mono (meth) acrylates, polyethylene glycol mono (meth) acrylates, poly (meth) acrylates of polyhydric alcohols, for example, glycerol di (meth) acrylate, di (meth) acrylate of trimethylolpropane, di or tri (meth) acrylates pentaerythritol acrylate, bis (mono) -2-acryloxy) ethyl) carbonate of diethylene glycol, poly (meth) acrylates of alcohols which in turn have a free radical polymerizable group, example, esters of (meth) acrylic acid and vinyl and / or allyl alcohol; vinyl esters of other aliphatic or aromatic carboxylic acids, for example, vinyl acetate, vinyl propionate, vinyl butanoate, vinyl hexanoate, vinyl octanoate, vinyl decanoate, vinyl stearate, vinyl palmitate, vinyl crotonate, adipate of divinyl, divinyl sebacate, 2-vinyl 2-ethylhexanoate, vinyl trifluoroacetate; the allyl esters of other aliphatic or aromatic carboxylic acids, for example, allyl acetate, allyl propionate, allyl butanoate, allyl hexanoate, allyl octanoate, allyl decanoate, allyl stearate, allyl palmitate, allyl crotonate, allyl salicylate, allyl lactate, diallyl oxalate, allyl stearate, [sic], allyl succinate, diallyl glutarate, diallyl adipate, diallyl pimelate, thialyl cinnamate, diallyl maleate, diallyl phthalate, isophthalate diallyl, triallyl-1, 3, 5-triallyl tricarboxylate, tialyl fluoracetate, allyl perfluorobutyrate, allyl perfluoro octanoate; β, α-unsaturated carboxylic acids and derivatives thereof, for example, vinylacetic acid, 2-methnylacetic acid, isobutyl 3-butenoate, allyl 3-butenoate, allyl 2-hydroxy-3-butenoate, diketene; Particularly suitable sulphonic acids are, for example, vinylsulfonic acid, allylsulfonic acid and methallylsulfonic acid, and also their esters and halides, vinylbenzenesulfonate, 4-vinylbenzenesulfonamide. It is also possible to use mixtures of two or more of the above-described carboxylic and / or sulfonic acids. The Hbl polymer can be obtained by reaction from 5 to 100% by weight, preferably from 30 to 70% by weight, based on the polymer Hbl, of the condensation product defined above and from 0 to 95% by weight, in particular from 30 to 70% by weight, based on the Ubi polymer, of a compound (c). 2) Homopolymers, copolymers or block copolymers IIb2 (Hb2 polymers), obtainable by polymerization of: bl) from 5 to 75% by weight, based on the polymer IIb2, of a polymerizable compound (d), preferably an unsaturated compound (d) capable of free radical polymerization, which is different from the carboxylic acid or sulfonic acid ( b) mentioned above or a derivative thereof, or a mixture of two or more of these, and b2) from 25 to 95% by weight, based on polymer IIb2, of the other compound (c) having an average molecular weight (numerical average) of at least 5000 and polyether segments in a main or side chain.

Specific examples of the compounds (d) which are capable of free radical polymerization and which can be used to prepare the Hb2 polymer are: Olefinic hydrocarbons such as ethylene, propylene, butylene, isobutene, hexene or higher homologs and vinylcyclohexane; (meth) acrylonitrile; olefinic compounds containing halogen such as vinylidene fluoride, vinylidene chloride, vinyl fluoride, vinyl chloride, hexafluoropropene, trifluoropropene, 1,2-dichloroethylene, 1,2-difluoroethylene and tetrafluoroethylene; vinyl alcohol, vinyl acetate, N-vinylpyrrolidone, N-vinylimidazole, vinylformamide; phosphonitrile chlorides such as phosphonitrilic dichloride, hexachloro (triphosphazene) and also their derivatives that are partially or completely substituted by alkoxy, phenoxy, amino and fluoroalkoxy groups, that is, compounds that can be polymerized to form polyphosphazenes; aromatic olefinic compounds such as styrene, α-methylstyrene; vinyl ethers such as methyl vinyl ether, ethyl vinyl ether, propyl vinyl ether, isopropyl vinyl ether, butyl vinyl ether, isobutyl vinyl ether, hexyl vinyl ether, octyl vinyl ether, decyl vinyl ether, dodecyl vinyl ether, 2-ethylhexyl vinyl ether, cyclohexyl vinyl ether, benzyl vinyl ether, trifluoromethyl vinyl ether, hexafluoropropyl vinyl ether or tetrafluoropropyl vinyl ether. Of course, it is also possible to use mixtures of the aforementioned compounds (d), which then produce copolymers which, depending on the method of preparation, have the monomers distributed randomly or arranged in blocks (block copolymers). These compounds (d) are, like the condensation products described above, polymerized in conventional forms well known to those skilled in the art, preferably polymerized by a free radical mechanism; with respect to the molecular weights obtained, what is said below with respect to the compound (c) is applied. Possible compounds (c) are the first major compounds having an average molecular weight (number average) of at least 5000, preferably from 5,000 to 20,000,000, in particular from 100,000 to 6,000,000, which can solvate lithium cations and function as binders . Suitable compounds (c) are, for example, polyethers and copolymers containing at least 30% by weight of the following structural unit, based on the total weight of compound (c): where R1, R2, R3 and R4 are aryl groups, alkyl groups, preferably methyl or hydrogen groups, are identical or different and may contain heteroatoms such as oxygen, nitrogen, sulfur or silicon. These compounds are described, for example, in: M. B. Armand et al., Fast Ion Transport in Solids, Elsevier, New York, 1979, p. 131-136, or in FR-A 7832976. The compound (c) can also be a mixture of these compounds. The Hb2 polymer can be obtained by the reaction of: from 5 to 75% by weight, preferably from 30 to 70% by weight, based on the polymer Hb2, of a compound (d) and from 25 to 95% by weight, in particular from 30 to 70% by weight, based on the polymer Hb2, of a compound (c). 3) Polycarbonates such as polyethylene carbonate, polypropylene carbonate, polybutadiene carbonate, polyvinylidene carbonate. 4) Homopolymers, copolymers and block copolymers prepared from: a) olefinic hydrocarbons such as ethylene, propylene, butylene, isobutene, propene, hexene or higher homologs, butadiene, cyclopentene, cyclohexene, norbornene, vinylcyclohexane, 1,3-pentadiene, 1,3-, 1,4- and 1,5- hexadiene, isoprene, vinylnorbornene. b) aromatic hydrocarbons such as styrene and methyl styrene; c) acrylic or methacrylic esters such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, hexyl, octyl, decyl, dodecyl, 2-ethylhexyl, cyclohexyl, benzyl, trifluoromethyl, hexafluoropropyl or tetrafluoropropyl acrylate or methacrylate; d) acrylonitrile, methacrylonitrile, N-methylpyrrolidone, N-vinylimidazole, vinyl acetate; e) vinyl ethers such as methyl vinyl ether, ethyl vinyl ether, propyl vinyl ether, isopropyl vinyl ether, butyl vinyl ether, isobutyl vinyl ether, hexyl vinyl ether, octyl vinyl ether, decyl vinyl ether, dodecyl vinyl ether, 2-ethylhexyl vinyl ether , cyclohexyl vinyl ether, benzyl vinyl ether, trifluoromethyl vinyl ether, hexafluoro propyl vinyl ether, tetrafluoro propyl vinyl ether; f) polymers and copolymers of olefinic compounds containing halogen such as vinylidene fluoride, vinylidene chloride, vinyl fluoride, vinyl chloride, hexafluoropropene, trifluoropropene, 1,2-dichloroethylene, 1,2-difluoroethylene and tetrafluoroethylene; preferably polymers or copolymers of vinyl chloride, acrylonitrile, vinylidene fluoride; copolymers of vinyl chloride and vinylidene chloride, vinyl chloride and acrylonitrile, vinylidene fluoride and hexafluoro propylene, vinylidene fluoride and hexafluoropropylene; terpolymers of vinylidene fluoride and hexafluoro propylene together with a member of the group consisting of vinyl fluoride, tetrafluoroethylene and a trifluoroethylene; in particular a copolymer of vinylidene fluoride and propylene hexafluoride; and more preferably a copolymer containing from 75 to 92% by weight of vinylidene fluoride and from 8 to 25% by weight of hexafluoropropylene; g) 2-vinylpyridine, 4-vinylpyridine, vylene carbonate [sic] In the preparation of the aforementioned polymers, it is possible to use, if necessary and / or desired, regulators such as mercaptans. 5) polyurethanes, for example, those obtainable by the reaction of: a) organic diisocyanates having from 6 to 30 carbon atoms, for example, non-cyclic aliphatic diisocyanates such as 1,5-hexamethylene diisocyanate, 1,6- hexamethylene diisocyanate, cyclic aliphatic diisocyanates such as cyclohexylene 1,4-diisocyanate, dicyclohexylmethane diisocyanate and isophorone diisocyanate or aromatic diisocyanates such as 2,4-tolylene diisocyanate, 2,6-toluene diisocyanate, m-tetramethylxylene diisocyanate, diisocyanate of p-tetramethylxylene, 1,5-tetrahydronaphthalene diisocyanate and 4, '-diphenylmethane diisocyanate or mixtures of these compounds, with b) polyhydric alcohols such as polyesterols, polyetherols and diols. Polyesterols are for convenience primarily linear polymers having terminal OH groups, preferably those having 2 or 3, in particular 2 terminal OH groups. The acid number of the polyesterols is less than 10 and preferably less than 3. The polyesterols can be prepared in a simple manner by esterification of aliphatic or aromatic dicarboxylic acids having from 4 to 15 carbon atoms, preferably from 4 to 6. carbon atoms, with glycols, preferably glycols having from 2 to 25 carbon atoms, or by polymerization of lactones having from 3 to 20 carbon atoms. The dicarboxylic acids which can be used are, for example, glutaric acid, pimelic acid, suberic acid, sebacic acid, dodecanoic acid and preferably adipic acid and succinic acid. Suitable aromatic dicarboxylic acids are terephthalic acid, isophthalic acid, phthalic acid or mixtures of these dicarboxylic acids with other dicarboxylic acids, for example, diphenic acid, sebacic acid, succinic acid and adipic acid. The dicarboxylic acids can be used individually or as mixtures. To prepare the polyesterols, it may be convenient to use the corresponding acid derivatives as carboxylic anhydrides or carboxylic acid chlorides instead of the carboxylic acids. Examples of suitable glycols are diethylene glycol, 1,5-pentanediol, 1,10-decanediol and 2,2-trimethylpentan-1,5-diol. Preference is given to the use of 1,2-ethanediol, 1,3-propanediol, 2-methyl-1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, 2,2-dimethylpropan-1,3-diol. , 1,4-dimethylolcyclohexane, 1,4-diethanolcyclohexane and the ethoxylated or propoxylated products of 2,2-bis (4-hydroxyphenyl) -propane (bisphenol A). Depending on the desired properties of the polyurethanes, the polyols can be used only as mixtures in different mixing proportions. Suitable lactones for preparing polyesterols are, for example, a, α-dimethyl-β-propiolactone, β-butyrolactone and preferably e-caprolactone. Polyetherols are substantially linear substances that have terminal hydroxyl groups and contain ether linkages. Suitable polyetherols can be easily prepared by the polymerization of cyclic ethers such as tetrahydrofuran or by reaction of one or more alkylene oxides having from 2 to 4 carbon atoms in the alkylene radical, with a starter molecule containing 2 active hydrogen atoms in the form bound to the alkylene radical, examples of the suitable alkylene oxides are ethylene oxide, 1,2-propylene oxide, epichlorohydrin, 1,2-butylene oxide and 2,3-butylene oxide. The alkylene oxides may be used individually, otherwise in succession or as a mixture. Examples of suitable initiator molecules are water, glycols such as ethylene glycol, polypropylene glycol, 1,4-butanediol and 1,6-hexanediol, amines such as ethylenediamine, hexamethylenediamine, and 4,4'-diaminodiphenylmethane and amino alcohols such as ethanolamine. Suitable polyesterols and polyetherols and also their preparation are described, for example, in EP-B 416 386, while suitable polycarbonate diols, preferably those based on 1,6-hexanediol and their preparation are described, for example, in US-A 4 131 731.

It may be advantageous to use amounts of up to 30% by weight, based on the total mass of the alcohols, of the aliphatic diols having from 2 to 20, preferably from 2 to 10 carbon atoms, for example 1, 2- ethanediol, 1,3-propanediol, 1-butanediol, 1,6-hexanediol, 1,5-pentanediol, 1, 10-decanediol, 2-methyl-1,3-propanediol, 2, 2-dimethyl-1,3. -propanediol, 2-methyl-2-butyl-1,3-propanediol, 2,2-dimethyl-1,4-butanediol, 1,4-dimethylolcyclohexane, neopentyl glycol hydroxypivalate, diethylene glycol, triethylene glycol and methyldiethanolamine, aliphatic aromatic diols or cycloaliphatic aromatics having from 8 to 30 carbon atoms, where the possible aromatic structures are heterocyclic ring systems or preferably isocitic ring systems such as naphthalene or, in particular, benzene derivatives such as bisphenol A, symmetrically diethoxylated bisphenol A, bisphenol A symmetrically dipropoxylated, bisphenol A derivatives more highly ethoxylates, or propoxylates or bisphenol F derivatives, and also mixtures of these compounds. It may be advantageous to use amounts of up to 5% by weight, based on the total mass of the alcohols, of aliphatic triols having from 3 to 15, preferably from 3 to 10 carbon atoms, for example, trimethylolpropane or glycerol, reaction product of these compounds with ethylene oxide and / or propylene oxide and also mixtures of these compounds. The polyhydric alcohols can carry functional groups, for example, neutral groups such as siloxane groups, basic groups such as, in particular, tertiary amino groups or acid groups or their salts or groups which are easily transformed into acid groups, which are introduced through a polyhydric alcohol. Preference is given to the use of diol compounds carrying such groups, for example, N-methyldiethanolamine, diethyl N, N-bis (hydroxyethyl) aminomethylphosphonate or N, N-bis (hydroxyethyl) -2-amino-3-sulfopropyl acetate, or dicarboxylic acids that carry such groups and can be used for the preparation of polyesterols, for example, the acid -sulfoisophthalic. The acid groups are, in particular, phosphoric acid, phosphonic acid, sulfuric acid, sulfonic acid, carboxyl or ammonium groups. Groups which are easily converted into acidic groups are, for example, the ester group, the salts, preferably alkali metals such as lithium, sodium, or potassium. 6) The polyesterols described above, where attention must be paid to obtaining the molecular weights in the range from 10,000 to 2,000,000, preferably from 50,000 to 1,000,000. 7) polyamines, polysiloxanes and polyphosphazenes, in particular those which have already been described in the description of the polymer Hb2. 8) polyetherols which have been described, for example, in the above description of the polymer Hbl as compound (c) or in the description of the polyurethanes.

Of course, it is also possible to use mixtures of the aforementioned Hb polymers. The Hb copolymers used according to the present invention can, depending on the method of preparation, have the monomers randomly distributed or arranged in blocks (block copolymers). Ha and Hb polymers are polymerized by traditional methods well known to those skilled in the art, preferably polymerized by a free radical mechanism. The polymers Ha and Hb can be used in the form of high molecular weight or oligomeric or as a mixture of these. The proportion of the polymer Ha in the polymeric binder II is, in general, from 1 to 100% by weight, preferably from 20 to 80% by weight, more preferably from 30 to 60% by weight. Correspondingly, the proportion of the polymer Hb in the polymeric binder II is, in general, from 0 to 99% by weight, preferably from 20 to 80% by weight and, most preferably from 40 to 70% by weight. The present invention preferably offers the following compositions: The compositions as defined above in which the Ha polymer has, as part of the chain, at the end (s) of the chain and / or laterally in the chain, at least one reactive group RGa which in the excited state in the triplet under the action of heat and / or UV radiation is capable of extracting hydrogen and has, as part of the chain, at the end (s) of the chain and / or laterally in the chain, at least one RGb group that is different from RGa and is coreactive with RGa, with at least one RGa group and at least one RGb group being present on average on all polymeric molecules. Compositions as defined above in which the polymer Ha is a polymer or copolymer of an acrylate or methacrylate and has reactive groups RGa comprising benzophenone units and reactive groups RGb comprising dihydrodicyclopentadiene units. Compositions as defined above in which the polymer Hb is selected from the group consisting of a polymer or copolymer of vinyl chloride, acrylonitrile, vinylidene fluoride; a copolymer of vinyl chloride and vinylidene chloride, vinyl chloride and acrylonitrile, vinylidene fluoride and hexafluoropropylene, vinylidene chloride and hexafluoropropylene; a terpolymer of vinylidene fluoride and hexafluoropropylene together with a member of the group consisting of vinyl fluoride, tetrafluoroethylene and a trifluoroethylene. Compositions as already defined in which the polymer Ha is a polymer or copolymer of an acrylate or methacrylate and has reactive groups RGa comprising benzophenone units and reactive groups RGb comprising dihydrodicyclopentadiene units and the polymer Hb is a copolymer of vinylidene fluoride and hexafluoro propylene.

The compositions of the present invention may also contain a plasticizer III. However, it is not necessary that a plasticizer be present. If present, the proportion of the plasticizer III, based on the composition, is from 0.1 to 100% by weight, preferably from 0.5 to 50% by weight and, in particular from 1 to 20% by weight. The plasticizers III that can be used are aprotic solvents, preferably those solvating Li ions, for example, dimethyl carbonate, ethylmethyl carbonate, diethyl carbonate, dipropyl carbonate, diisopropyl carbonate, dibutyl carbonate, propylene carbonate; cyclic carbonates of the empirical formula CnHn + iOy, n = 2-30, m = 3-7, for example, ethylene carbonate, 1,2-propylene carbonate, 1,3-propylene carbonate, 1,2-butylene carbonate, carbonate of 1, 3-butylene, 1,4-butylene carbonate, 2,3-butylene carbonate; Oligoalkylene oxides, such as dibutyl ether, di-tert-butyl ether, dipentyl ether, dihexyl ether, diheptyl ether, dioctyl ether, dinonyl ether, didecyl ether, didodecyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, l-ter- butoxy-2-methoxyethane, l-tert-butoxy-2-ethoxyethane, 1,2-dimethoxypropane, 2-methoxyethyl ether, 2-ethoxyethyl ether, diethylene glycol dibutyl ether, dimethylene glycol tert-butyl methyl ether, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether,? -butyrolactone, dimethylformamide; dimethyl-β-butyrolactone, diethyl-β-butyrolactone, β-valerolactone, 4,5-dimethyl-1,3-dioxolan-2-one, 4, 4-dimethyl-1,3-dioxolan-2-one, 4- ethyl-l, 3-dioxolan-2-one, 4-methyl-5-ethyl-l, 3-dioxolan-2-one, 4,5-diethyl-1,3-dioxolan-2-one, 4, 4- diethyl-l, 3-dioxolan-2-one, 1,3-dioxan-2-one, 4-methyl-l, 3-dioxan-2-one, 5-methyl-l, 3-dioxan-2-one, 4, 4-dimethyl-1,3-dioxan-2-one, 5,5-dimethyl-1,3-dioxan-2-one, 4,6-dimethyl-1,3-dioxan-2-one, 4, 4,6-trimethyl-1,3-dioxan-2-one, 5,5-diethyl-l, 3-dioxan-2-one, spiro- (1,3-oxan-2-cyclohexanone) 5 ', 5' , 1 ', 3' -oxacyclohexane; 4-dimethyl-ethoxysilyl-l, 2-butylene carbonate; dicarboxylic esters of the formula R1OCOOR2OCOOR3 (R1, R2, R3 = Ci-C20 hydrocarbons), organic esters of the formula R1-COOR2 (R1 and R2 = hydrocarbons of C? -C20); hydrocarbons of the formula CnH2n + 2 where 7 < n < fifty; organic phosphorus compounds, in particular phosphates and phosphonates, for example trimethyl phosphate, triethyl phosphate, tripropyl phosphate, tributyl phosphate, triisobutyl phosphate, tripentyl phosphate, trihexyl phosphate, trioctyl phosphate, trisphosphate (2) -ethylhexyl), tridecyl phosphate, diethyl n-butyl phosphate, tris (butoxyethyl) phosphate, tris (2-methoxyethyl) phosphate, tris (tetrahydrofuryl) phosphate, tris (1H, 1H, 5H-octafluoropentyl) phosphate ), tris (1H, lH-trifluoroethyl) phosphate, tris (2- (diethylamino) ethyl phosphate), tris (methoxyethoxyethyl) phosphate, tris (methoxyethoxy) trifluorophosphazene, tris (ethoxycarbonyloxyethyl) phosphate, diethyl ethylphosphonate, propylphosphonate dipropyl, dibutyl butylphosphonate, dihexyl hexylphosphonate, dioctyl octylphosphonate, ethyl dimethylphosphonoacetate, methyl diethylphosphonoacetate, triethyl phosphonoacetate, dimethyl (2-oxopropyl) phosphonate, (2-oxopropyl) phosphonate of diethyl, dipropyl (2-oxopropyl) phosphonate, ethyl diethoxyphosphinylformate, trimethylphosphonoacetate, triethylphosphonoacetate, tripropyl phosphonoacetate, tributyl phosphonoacetate; organic sulfur compounds such as sulfates, sulfonates, sulfoxides, sulfones and sulphites, for example, dimethyl sulfite, diethyl sulphite, glycol sulfite, dimethyl sulfone, diethyl sulfone, diethylpropyl sulfone, dibutyl sulfone, tetramethylene sulfone, methylsulfolane, dimethyl sulfoxide, diethyl sulfoxide, dipropyl sulfoxide, dibutyl sulfoxide, tetramethylene sulfoxide, ethyl methanesulfonate, bis (methanesulfonate) 1,4-butanediol, diethyl sulfate, dipropyl sulfate, dibutyl sulfate, dihexyl sulfate, dioctyl sulfate, S02C1F; nitriles such as acrylonitrile; The dispersants, in particular those having a surfactant structure; and also mixtures of these. In addition, it is possible to use, very generally, convenient organic compounds such as CnHxFy alkanes where n = 5-30, x + and 2n + 2; ethers CnHxFyOz where n = 5-30, x + y = 2n + 2, z = 1-14; ketones CnHxFy or where n = 5-30, x + y = 2n; esters CnHxFy02 where n = 5-30, x + y = 2n; carbonates CnHxFy03 where n = 5-30, x + y = 2n; lactones CnHxFy02 where n = 5-30, x + y = 2n-2; cyclic carbonates CnHxFy03 where n = 5-20, x + y = 2n + 2; and esters of boric acid, where: R1-R4 = hydrocarbons of C1-C10, and X = hydrocarbons of C1-C10, Si (CH3) 2 m = 1 or 2.

In particular, trimethyl borate, triethyl borate, tripropyl borate, tributylborate, trimethyleneborate, 2-methyl-1, 3, 2-dioxanborinan, 2-ethyl-1, 3, 2-dioxaborin, 2-propyl-1 , 3, 2-dioxaborin, 2-butyl-l, 3, 2-dioxaborin, 2-phenyl-1, 3, 2-dioxaborin, as plasticizers V.

In addition, at least one ester of the formulas (El) to (E5), as shown below, can be used as a plasticizer (V): OR1 B OR2 OR3 < E1) OR1 OR2 (E2) OR1 OR2 ^ OR3 (E3) OR1 < ? OR2 (E4) R40 OR1 If RO OR2 ÍE5) where R1, R2, R3, R4 are identical or different and are each, independent of each other, a linear or branched C1-C4 alkyl group, (-CH2-CH2-0) n-CH3 where n = 1-3, a cycloalkyl group of C3-Cd, an aromatic hydrocarbon group which may in turn be substituted, provided that at least one, of the groups R1, R2, R3, R4 is (-CH2- CH2-0) n.CH3 where n = 1-3. Among the esters mentioned above, of the formulas (El) a (E5), preference is given to the use of phosphoric esters of the formula (E3). The examples of the groups R1, R2 and if they are present, R3 and / or R4 are the methyl, ethyl, n- and isopropyl, n- and tertbutyl, cyclopentyl and cyclohexyl groups and the benzyl group and also (-CH2-CH20) n-CH3 where n = 1-3, but, as As already mentioned, at least one of the groups R1, R2, R3 and R4 must be (-CH2-CH20) n-CH3 in which n = 1-3, preferably 1 or 2. In addition preference is given to the use of the esters of the formulas (El) to (E5) in which R1, R2 and if R3 and / or R4 are present are identical and are each -CH2-CH20-CH3 or (-CH2-CH20) 2-CH3 , the corresponding phosphoric esters being again preferred. Examples of the compounds that are particularly preferably used are the compounds of the formulas (Ela) a (E5a): B (- OCH2 CH2OCH3) O • C (OCH2CH2OCH3) 2 (E2a; or P (- or CH2 CH. O CH3) (E2a) (E4a) Yes (-0-CH2-CH2-OCH3) 4 (E5a) The esters described herein have the properties that make them particularly useful as plasticizers in the films and, in general, have a viscosity at room temperature of < 10 mPas, preferably < 5 mPas and in particular < 3 mPas. These have boiling points of, in general, above 200 ° C or more, preferably above 250 ° C or more and in particular above 300 ° C or more, in each case measured at atmospheric pressure, and temperatures from about -50 ° C to about 150 ° C which occur during use have a sufficiently low vapor pressure from about 10 ~ 5 to about 10 °. Due to their boiling points, these can be distilled and can thus be prepared in high purity. In addition, these esters are liquids in a wide temperature range at atmospheric pressure. These in general, are still liquid at about -30 ° C, preferably below about -40 ° C. The esters described herein can be used as solvents in electrolyte systems for Li ion accumulators at at least about 80 ° C, preferably at least about 120 ° C, more preferably at least about 150 ° C. Of course, the esters used according to the present invention can also be used as mixtures with the aforementioned plasticizers. Preference is given to solvent combinations that have a sufficiently low viscosity and can solvate the ions of the electrolyte salts strongly, are liquid over a wide temperature range and are electrochemically and chemically stable and resistant to hydrolysis. The esters used in accordance with the present invention are prepared by the traditional methods as described, for example, in K. Mura Kami in Chem. High Polymers (Japan), 7, pp. 188-193 (1950) and in H. Steiberg Organoboron Chemistry, chapter 5, J. Wiley & Sons, N. Y. 1964. These methods, in general, start from the predecessor acids, acid anhydrides or chlorides of the esters, for example, boric acid, C (0) C12, P0C13, S02C12 and SiCl4, which are reacted in a known manner with monohydric or polyhydric alcohols suitable or sterols. The compositions of the present invention can be dissolved or dispersed in an inorganic or organic liquid diluent, preferably in an organic liquid diluent, where the mixture according to the present invention should have a viscosity preferably from 100 to 50,000 mPas, and subsequently be applied to a support material in a manner known per se, for example, by spray coating, pouring, dipping, spin coating, roll coating, lithographic printing, gravure or flat bed processes or screen printing. Other processing may be performed in a customary manner, for example, by removing the diluent and curing the mixture. Convenient organic diluents are aliphatic ethers, in particular tetrahydrofuran and thioxane, hydrocarbons, in particular mixtures of hydrocarbons such as petroleum spirits, toluene and xylene, aliphatic esters, in particular ethyl acetate and butyl acetate and ketones, in particular acetone, ethylmethyl ketone. and cyclohexanone, and also DMF and NMP. It is also possible to use combinations of these diluents. Suitable support materials are commonly used materials for electrodes, preferably metals such as aluminum and copper. In the same way it is possible to use temporary intermediate supports such as films, in particular polyester films such as polyethylene terephthalate films. These films can conveniently be provided with a release layer, preferably polysiloxanes. The production of these solid electrolytes and separators can likewise be carried out by thermoplastic processing, for example, by injection molding, casting the melt, compressing, kneading or extruding the mixture according to the present invention, if desired, followed by one pressing step. After the formation of the film of the mixture according to the invention, volatile components such as solvents or plasticizers can be removed from crosslinking. The crosslinking of the composition of the present invention can be carried out in a manner known per se, for example, irradiation with ionic or ionizing radiation, by electron beam, preferably at an accelerator voltage of from 20 to 2,000 kV and a dose of the radiation from 5 to 50 Mrad, UV or visible light, where an initiator such as benzyldimethyl ketal or 1,3,5-trimethylbenzoyltriphenylphosphine oxide may be added in amounts of, in particular, not greater than 1% by weight, based on the polymer Ha and the crosslinking can be carried out for a period of, generally, from 0.5 to 15 minutes; the addition of an initiator is not necessary since the systems used herein are generally self-crosslinked by thermal crosslinking through free radical polymerization, preferably above 60 ° C, where an initiator such as azobisisobutyronitrile can be conveniently added in amounts of, in general, no greater than 5% by weight, preferably from 0.05 to 1% by weight, based on the Ha polymer; by electrochemically induced polymerization; or by ionic polymerization, for example, by acid-catalyzed cationic polymerization, where the possible catalysts are the first and major acids, preferably Lewis acids BF3 or, in particular, LiBF4 or LiPF6 [sic]. Catalysts containing lithium ions, for example, LiBF4 or LiPF6 can conveniently remain as the electrolyte salt in the solid electrolyte or separator. The crosslinking described above may be, but does not necessarily have to be, carried out under inert gas.

If the composition of the present invention is to be used as a solid electrolyte or separator in an electrochemical cell, a dissociable compound containing lithium cations, ie, an electrolytic salt and, if desired, other additives such as, in particular, is incorporated. , organic solvents, that is, an electrolyte. Some or all of these materials can be mixed during the production of the layer of the composition can be introduced into the layer after it has been produced there. The electrolyte salts that can be used are those generally known and described, for example, in EP-A 0 096 629. According to the present invention, the preferred electrolyte salts are LiPF6, LiBF4, LiC10, LiAsF6, LICF3S03, LiC (CF3S02 ) 3, LiN (CF3S02) 2, LiN (S02CnF2n.?) 2. LiC [CnF2n +?) S02] 3, Li (CnF2n +?) S02, where n is in each case from 2 to 20, LiN (S02CnF) 2, LIA1C134, LiSiF6, LiSbF6, (RS02) nXli (nX =? O, ls, 2N, 2P, 3Si; R = Cmf2m +? Where m = 0-10 or hydrocarbons of C_-C2o), Li-imide salts or a mixture of two or more of these; Particular preference is given to the use of LiPF6 as an electrolyte salt. Suitable organic electrolytes are the compounds described above under "plasticizers", giving preference to the use of customary organic electrolytes, preferably esters such as ethylene carbonate, propylene carbonate, dimethyl carbonate and diethyl carbonate or mixtures of these compounds. The solid electrolytes, separators and / or electrodes according to the present invention which are suitable for electrochemical cells, conveniently have a thickness from 5 to 500 μ, preferably from 10 to 500 μ, most preferably from 10 to 200 μ and , in particular from 20 to 100 μ. The compositions of the present invention can be used in electrochemical cells as solid electrolyte and / or separator and / or single electrode or in mixtures with other solid separating electrodes and / or electrodes. These are preferably used as a solid electrolyte. The present invention also provides a compound that can be used, in particular, in electrochemical cells, preferably in the form of a film, most preferably in the form of a film having a total thickness from 15 to 1500 μ, in particular having a total thickness from 50 to 500 μ, consisting of at least one first layer containing a composition defined above containing a compound Ib or a compound le and at least a second layer containing a composition defined above comprising a solid and free of compounds le and Ib. This compound can also be combined with traditional electrodes, for example, a graphite anode. The first layer defined above then comprises a compound Ib so as to form the following element: anode (traditional) / second layer / first layer (separator) (cathode) In addition, the present invention offers a process for producing such a compound, which consists of the following steps: (I) the production of at least one first layer, as already defined; (II) the production of at least one second layer, as already defined; and (III) contacting the first layer or layers and the second layer or layers by a traditional coating process. The second layer or layers preferably occurs (n) in a temporary support. In accordance with the present invention, it is possible to use the temporary supports that are normally used, for example, a release film of a polymer or a preferably coated paper, for example a siliconized polyester film. However, this second layer can also be produced in a permanent support, such as a contact electrode or without support. The assembly or production of the above defined layers is carried out by non-pressurized methods for coating or for the production of films, for example, casting or scalpel coating, or by processing methods that employ pressure, for example, extrusion, lamination, pressing. Due to the self-crosslinking ability of the Ha polymers as used in accordance with the invention, a step is not necessary in which the system is cross-linked after assembly, for example, by thermal lamination of the layers. In case it is desired to crosslink the system after thermal lamination, the compound produced in this way can be crosslinked or cured thermally, electrochemically or by radiation. As can be seen from the above, in this way it is possible to produce a compound containing a releasing / separating film (second layer) / electrode (first layer). In addition, the double-sided coating makes it possible to provide a compound containing anode / separator / cathode. This can be obtained, for example, by the following procedure: First, a first compound, for example graphite or conductive carbon black, a polymeric binder II, an electrolyte salt and a plasticizer, for example propylene carbonate, they are mixed together and the resulting mixture is poured over a contact electrode and subsequently irradiated with UV light (component 1). Then, a cathode material, for example LiMn204, is applied to a contact electrode coated with conductive carbon black, and a mixture of the composition of the present invention containing a solid and free of compounds Ib and le, a salt of electrolytes and a plasticizer is then poured over this cathodic material. This compound is also subsequently irradiated with UV light (component 2). The assembly of the two components described above gives a compound which, in combination with any solid and / or liquid electrolyte, can be used as an electrochemical cell. A solid electrolyte / anode or solid electrolyte / cathode compound or a solid cathode / electrolyte / anode compound can be produced without other additives by laminating together the separating film and the anodic film and / or the cathodic film a >80 ° C. Thus, it is easily possible to laminate, for example, a composition according to the present invention containing a solid on a traditional anode or cathode to obtain an anode or cathode / solid electrolyte compound (separated) which can in turn be combined with a traditional cathode or anode. An anode / separator / cathode compound, as already described, can also be produced without the use of a support or contact electrodes, since the compound consisting of a first layer and a second layer, as already defined, has sufficient Intrinsic mechanical stability for use in electrochemical cells. The composition of the present invention in this way makes the following configurations possible.

The charging of these compounds with an electrolyte and an electrolyte salt can be carried out before or, preferably, after contacting the layers, if applicable, after combination with suitable contact electrodes, for example a metal foil, and even after the introduction of the compound into a stack housing. The specific microporous structure of the layers, when using the mixture of the present invention, in particular due to the presence of the solid defined above in the separator and possibly in the electrodes, makes it possible for the electrolyte and the electrolyte salt to be entrained the pores and the air moves. The charge with the electrolyte and the electrolyte salt can be carried out at temperatures in the range from 0 ° C to approximately 100 ° C, depending on the electrolyte used. The electrochemical cells of the present invention can be used, in particular, as a battery or stack for dashboard, automobiles, instruments or flat, as well as a battery for static applications and an electrotraction of batteries. As can be seen from the foregoing, the present invention also offers the use of the composition of the present invention or the above described compound to produce a solid electrolyte, a separator or an electrode or in a detector, an electrochromic window, a screen, a capacitor or an ion conducting film, and also provides a solid electrolyte, a separator, an electrode, a detector, an electrochromic window, a screen, a capacitor or an ion conducting film each containing the mixture of the present invention or the compound described above. In addition, there is provided an electrochemical cell containing a solid electrolyte, separator or an electrode as defined above or a combination of two or more of these, and provides for the use of the electrochemical cell defined above as a car battery, instrument battery or a flat battery. The composition of the present invention has the following advantages over the systems hitherto offered with use in electrochemical cells: • The step of photo-crosslinking, in the production of the cast film, if carried out does not require inert gas conditions; • The mechanical properties of the films resulting from the composition can be controlled through the composition of the polymer Ha to obtain films in a range from hard / brittle to flexible / elastic; • As a result of the presence of the Hb polymer, the resulting film is thermoplastic and can be thermally laminated on the active electrodes without addition of other auxiliaries. The present invention also deals with the use of a Ha polymer, as already defined, as a crosslinking system in a solid electrolyte, a separator or an electrode. The present invention is illustrated by the following examples: Figures 1 to 3 show the cycling results (voltage: 4.15V) of the electrochemical cells obtained as described in Examples 1 to 3, respectively.

Preparative Example 1 (PA1) First, 800 g of xylene were placed in a reaction vessel and heated to 85 ° C. Then, the addition of a feed stream I consisting of a mixture of: 100 g of lauryl acrylate, 300 g of dihydrodicyclopentadienyl acrylate, 120 g of glycidyl methacrylate, 480 g of ethylhexyl acrylate and 2 g was started simultaneously. of mercaptoethanol, and the addition of a feed stream II consisting of: 30 g of Wako V 59 (azo initiator V 59) and 200 g of xylene feed stream I was fed to the initial charge for a period of 1.5 hours and the feed stream II was fed for a period of 2 hours. During the addition, the temperature was maintained in the range from 80 to 90 ° C. The reaction mixture was subsequently allowed to react for a further 3 hours at 90 ° C. Then a mixture was added consisting of: 166 g of 4-hydroxybenzophenone and 0.83 g of dimethylaminopyridine the reaction mixture was further allowed to react for 2 to 3 hours until an epoxide value of < 0.01.

Preparative Example 2 (PA2) First, 660 g of xylene were placed in a reaction vessel and heated to 85 ° C. Subsequently, a feed stream I was fed simultaneously consisting of: 200 g of dihydrodicyclopentadienyl acrylate, 80 g of glycidyl methacrylate, and 580 g of ethylhexyl acrylate and a feed stream II consisting of: 30 g of Wako V 59 ( initiator azo V 59) and 200 g of xylene at the initial charge for a period of 1.5 hours (feed stream I) and for a period of 2 hours (feed stream II). During the addition, the temperature was maintained in the range of 80 to 90 ° C. The reaction mixture was subsequently allowed to react for a further 3 hours at 90 ° C. Then a mixture consisting of: 110.67 g of 4-hydroxybenzophenone, and 0.83 g of dimethylaminopyridine was added. The reaction mixture was then allowed to react further for 2 to 3 hours until an epoxide value of < 0.01.

Example 1 20 g of a wollastonite hydrophobized with methacrylsilane (Tremin® 283-600 MST) were dispersed in g of acetone. Then, 54 g of a solution of 6 g of a copolymer of vinylidene fluoride-hexafluoropropylene (Kynarflex® 2801, ELF-Atochem) and a solution of 4.6 g of PAl, prepared as described in Preparative Example 1, in 34 g of xylene were added. Finally, 2.8 g of tris- (2-ethylhexyl) phosphate were added. The composition thus obtained was subsequently applied at 60 ° C to a support material by means of a scalpel having a slotted hole of 500 μ, the solvents were removed for a period of 5 minutes and, after removing the dried coating, a film with a thickness of approximately 30 μ was obtained. This was photoreticulated by illumination for 10 minutes at a distance of 5 cm under a field of superactinic fluorescent tubes (TL 09, Philips). The film obtained in this way was used as a solid electrolyte and was combined with LiCo02 as cathode and graphite as the anode to produce a round sandwich cell. An electrochemical cell was obtained using LiPF6 as an electrolyte salt and a 1: 1 mixture of ethylene carbonate and diethylene carbonate as a liquid electrolyte and this cell was cycled by application of a voltage of 4.15V. The specific data of the battery obtained by means of this cell were as follows: Battery test Cathode area: 1 cm2 Anode area: 1 cm2 Weight per unit area of the cathode: 263.6 g / m2 Electrolyte: LiPF6 lM / ethylene carbonate (EC): diethylene carbonate (DEC) = 1: 1 The results of this cycling are shown in Figure 1. As can be seen, this cell presented, for example, a specific charge capacity at the cathode of 106.4 mAh / g in the fifth cycle.

EXAMPLE 2 A film was produced by a method similar to Example 1 used as a crosslinking system, but a film with a thickness of 40 μ was produced in Example 2. The film obtained in this way was used as a solid electrolyte and was combined with LiCo02 as a cathode and graphite as an anode to produce a flat, round sandwich pressure cell (operating pressure 600 N / 10 cm2). Using LiPF6 as an electrolyte salt and a 1: 1 mixture of ethylene carbonate and diethylene carbonate as the liquid electrolyte, the cycling was performed at a voltage of approximately 4.15 V. The results of this cycling are shown in Figure 2. In In the fifth cycle, a specific charge capacity at the cathode of approximately 93 mAh / g was obtained for this cell.

Example 2 A composition according to the present invention was prepared in the same manner as in Example 1, but this time using a solution of 5 g of PA2 in 32 g of xylene. In addition, 2.1 g of tris (2-ethylhexyl) phosphate was used. From this composition a film was produced in the same manner as in Example 1 and this was in turn used to produce an electrochemical sandwich cell by the same method as described in Example 1. This cell was tested in the same way. way as the cell obtained in Example 1. The specific data of the battery obtained by means of this cell were as follows: Battery test Cathode area: 1 cm2 Anode area: 1 cm2 Weight per unit area of the cathode: 263.6 g / m2 Electrolyte LiPF6 1 M / ethylene carbonate (EC): diethylene carbonate (DEC) = 1: 1 Discharge capacity (fifth cycle): 75 mAh / g Discharge capacity (eleventh cycle): 66 mAh / g Discharge rate (3.0 mA / cm2): 87%

Claims (13)

1. A composition containing: (a) from 1 to 99% by weight of a pigment (I) having a primary particle size from 5 nm to 100 μ, which is a solid or a compound Ib which acts as a cathode material in the electrochemical cells or a compound that acts as anode material electrochemical cells or a mixture of the solid with the compound Ib or the compound le, (b) from 1 to 99% by weight of a polymeric material (II) containing: ( Ha) from 1 to 100% by weight of a polymer or copolymer (Ha) having, as part of the chain, at the end (s) of the chain and / or laterally in the chain, reactive groups (RG) ) which are capable of crosslinking reactions under the action of heat and / or UV radiation, and (Hb) from 0 to 99% by weight of at least one polymer or copolymer (Hb) which is free of reactive groups RG.

2. The composition as claimed in claim 1, wherein the pigment I is a solid which is selected from the group consisting of an inorganic solid selected from the group consisting of: oxides, mixed oxides, silicates, sulphates, carbonates, phosphates, nitrides, amides, imides and carbides of the elements of the main groups I, II, III and IV, and the transition group IV of the Periodic Table; a polymer selected from the group consisting of polyethylene, polypropylene, polystyrene, polytetrafluoroethylene, polyvinylidene fluoride, polyamides and polyimides; and a dispersion of solids containing this polymer; and a mixture of two or more of these.

3. The composition as claimed in claim 1 or 2, wherein the pigment I is a compound Ib which acts as a cathodic material in the electrochemical cells and is selected from the group consisting of: LiCoO2, LiNiO2, LiNixCoyO2, LiNixCoyAlzO2, where 0 < x, y, z < l, LixMnO2 (0 <x <1), LixMn2O (0 <x <2), LixMoO2 (0 <x <2), LixMnO3 (0 <x <l), LixMnO2 (0 <l; x <2), LixMn2O4 (0 <x < 2), LixV2O4 (0 <x 2.5), LixV2O3 (0 <x <3.5), LixVO2 (0 <x <l), LixWO2 (0 <x = l), LixWO3 (0 <x <l) , LixTiO2 (0 <x__l), LixTi2O (0 <x = 2), LixRuO (0 <x <l), LixFe2O3 (0 <x = 2), LixFe3O4 (0 <x <2) , LixCr2O3 (0 <x = 3), LixCr3O4 (0 <x = 3.8), LixV3S5 (0 <x <-1.8), LixTa2S2 (0 <x = l), LixFeS (0 <x = l), LixFeS2 (0 <x <l), LixNbS2 (0 <x < 2.4), L × x MoS2 (0 <x <3), LixTiS2 (0 <x <2), LixZrS2 (0 <x <2), LixNbSe2 (0 <x = 3), LixVSe2 (0 <x = l ), LixNiPS2 (0 <x <1.5), LixFePS2 (0 <x <1.5), LiNixB1-xO2 (0 <x <l), LiNixAl ?. xO2 (0 <x <l), LiNixMg, .xO2 (0 <x <l), LiNixC? XVO4 (1 = x> 0), (x + y + z = 1), LiFeO2, LiCrTiO, LiaMbLcOd (1.15 > a > 0; 1.3 > b + c = 0.8; 2.5 = d = 1.7; M = Ni, Co, Mn; L = Ti, Mn, Cu, Zn, alkaline earth metal), LiCux "Cu? IIIMr_ (2. (x + y) A (2> x + y> 0), LiCrTiO4 > LiGaxMn2-xO4 (Ol = x = O), poly (carbon sulfides) of carbon polysulfides) of the structure: - [C (Sx)] n-, V205, one or a mixture of two or more of these, and a mixture of compound Ib with solid la; and the composition further contains from 0.1 to 20% by weight, based on the total weight of components I to III [sic], of conductive carbon black.

4. The composition as claimed in claim 1 or 2, wherein the pigment I is a compound which acts as an anodic material in the electrochemical cells and is selected from the group consisting of lithium, metallic alloy containing lithium, micronized carbon black, natural and synthetic graphite, synthetic graphitized carbon powder, a carbon fiber, titanium oxide, zinc oxide, tin oxide, molybdenum oxide, tungsten oxide, titanium carbonate, molybdenum carbonate, carbonate of zinc, LixMySiOz (l> x = 0.1y> 0, z> 0), Sn2BP04, conjugated polymers, lithium metal compounds LixM, and a mixture of two or more of these, and a mixture of the compound with the solid the; and the composition further contains up to 20% by weight, based on the total weight of components I to III, of conductive carbon black.

The composition as claimed in any of claims 1 to 4, wherein the polymer Ha has, as part of the chain at the end (s) of the chain and / or laterally in the chain, at least a reactive group RGa which in the excited state in the triplet under the action of heat and / or UV radiation is capable of extracting hydrogen and has, as part of the chain, at the end (s) of the chain and / or laterally in the chain, at least one RGb group that is different from RGa and is coreactive with RGa, with at least one RGa group and at least one RGb group being present on average for all the polymer molecules.

6. The composition as claimed in any of claims 1 to 5, wherein the polymer Ha is a polymer or copolymer of an acrylate or methacrylate and has reactive groups RGa comprising benzophenone units and reactive groups RGb comprising dihydrodicyclopentadiene units.

The composition as claimed in any of claims 1 to 6, wherein the polymer Hb is selected from the group consisting of a polymer or copolymer of vinyl chloride, acrylonitrile, vinylidene fluoride.; a copolymer of vinyl chloride and vinylidene chloride, vinyl chloride and acrylonitrile, vinylidene fluoride and hexafluoropropylene, vinylidene fluoride and hexafluoropropylene; a terpolymer of vinylidene fluoride and hexafluoropropylene together with a member of the group consisting of vinyl fluoride, tetrafluoroethylene and trifluoroethylene.

8. The composition as claimed in any of claims 1 to 7, wherein the polymer Ha is a polymer as defined in claim 6, and the polymer Hb is a copolymer of vinylidene fluoride and hexafluoropropylene.

A compound comprising at least one first layer containing a composition as claimed in any of claims 1 to 8 consisting of a compound Ib or a compound le, and at least a second layer comprising a composition as claimed in any of claims 1 to 8 which contains a solid and is free of compounds le and Ib.

10. A method of using a composition is claimed in any one of claims 1 to 8 or a compound as claimed in claim 9 for produ a solid electrolyte, a separator or an electrode or in a detector, an electrochromic window, a screen, a capacitor or an ion conducting film.

11. A solid electrolyte, separator, electrode, detector, electrochromic window, screen, ion-conducting capacitor or film in each case containing a composition as claimed in any one of claims 1 to 8 or a compound as claimed in claim 9.

12. An electrochemical cell consisting of a solid electrolyte, a separator or an electrode as claimed in claim 11 or a combination of two or more of these.

13. The method of using a polymer Ha as defined in any of claims 1, 5 and 6 as a cross-linking system in a solid electrolyte, a separator or an electrode.