CH694562A5 - Radiation sensitive composition, useful for production of e.g. paint and inks, contains cationic or acid catalysed polymerizable compound and novel dirayliodonium salt - Google Patents

Abstract

A radiation sensitive composition contains a cationic or acid catalysed polymerizable or cross-linkable compound or a compound that increases its solubility in a developer in the presence of an acid and a dirayliodonium salt whereby both phenyl rings bonded to the I atom are not identically substituted. A radiation sensitive composition contains (A1) a cationic or acid catalysed polymerizable or cross-linkable compound or (A2) a compound that increases its solubility in a developer in the presence of an acid and (B) a dirayliodonium salt of formula (I) whereby both phenyl rings bonded to the I atom are not identically substituted. [Image] X : branched 3-20C alkyl or 3-8C cycloalkyl; X 1H, linear 1-20C alkyl, branched 3-20 C alkyl or 3-8C cycloalkyl whereby the sum of C atoms in X and X 1is at least 4; Y : linear or branched 1-10C alkyl or 3-8C cycloalkyl; A : non-nucleophilic anion, preferably (BF 4) ->, (SbF 6) ->, (B(C 6F 5) 4) ->, 1-20C alkylsulfonate, 2-20 C haloalkylsulfonate, unsubstituted 6-10C arylsulfonate, camphor sulfonate, 1-20C perfluoroalkylsulfonylmethide, 1-20C perfluoroalkylsulfonyl imide and 6-10C arylsulfonate, optionally substituted by halogen, NO 2, 1-12C alkyl, 1-12C haloalkyl, 1-12C alkoxy or COOR; R 11-20C alkyl, phenyl, benzyl or phenyl, optionally substituted by 1-12C alkyl, alkoxy or halogen Independent claims are included for; (1) Process for the photopolymerizaiton or cross-linking of compounds (A1) by means of electromagnetic radiation or electron beams by the addition of a photolatent acid source (B); (2) Substrate coated with the composition (I); (3) Process for the production of relief images using the composition (I); (4) Negative, positive or chemically reinforcing photoresist containing the composition (I); and (5) Compound of formula (I).

Description

       

  



   The invention relates to selected iodonium salt compounds and their use as photoinitiators.



   It is known to use iodonium salts as photoinitiators in cationically polymerizable compositions. Such disclosures are, for example, J. V. Crivello, "Photoinitiated Cationic Polymerization" in: UV Curing: Science and Technology, Editor S. P. Pappas, pp. 24-77, Technology Marketing Corporation, Norwalk, Conn. 1980, ISBN no. 0-686-23773-0; J.V. Crivello, J.H.W. Lam, Macromolecules, 10, 1307 (1977) and J.V. Crivello, Ann. Rev. Mater. Sci. 1983, 13, pages 173-190 and J.V. Crivello, Journal of Polymer Science, Part A: Polymer Chemistry, Vol. 37, 4241-4254 (1999). WO 98/46647 discloses 4,4'-dialkylphenyl-iodonium compounds containing at least one isopropyl group in photohardenable compositions. In J. Chem. Soc. Perkin trans.

   I, 1997, 17, pages 2463-2465, discloses a special preparation process for unsymmetrically substituted diaryliodonium triflates and trifluoroacetates, with which 4-tert-butylphenyl-2'-methylphenyliodonium triflate or trifluoroacetate can be prepared.



   The iodonium salt-containing radiation-reactive compositions known hitherto and available for industrial applications have a number of disadvantages which can be attributed to the iodonium salts used. Thus, for example, diphenyliodonium salts are poorly soluble in the formulations, which limits their usefulness in practice, since only a small concentration of the iodonium salt can be used or there is a risk of crystallization. In addition, phenyliodonium salts liberate benzene as a photoproduct which can migrate from the cured mass or coating (e.g., ink) into the substrate and is highly undesirable for toxicological reasons (e.g., in food packaging printing).

   Although the substitution of one of the phenyl rings by longer-chain alkyl or alkoxy substituents can improve the solubility, the disadvantage of benzene formation is still retained therewith. As a rule, large substituents not only reduce the reactivity, but also result in significantly poorer handling of the compounds, which then no longer arise as crystalline compounds and can only be produced poorly in the high purity required for applications in microelectronics. In addition, it has been found that phenyl-aryl-iodonium salts, from which benzene can form on exposure, are positive in the AMES test, which is used for the first detection of a mutagenic potential. with suspected mutagenic effects, react.



   It has now been found that radiation-sensitive compositions comprising (a1) a catalytically or acid catalytically polymerisable or crosslinkable compound or (a2) a compound which increases its solubility under the action of acid in a developer; and (b) at least one diaryliodonium salt of formula I



   
EMI2.1
 



   X is branched C 3 -C 20 -alkyl or C 3 -C 8 -cycloalkyl; X 1 is hydrogen, linear C 1 -C 20 alkyl, branched C 3 -C 20 alkyl or C 3 -C 8 cycloalkyl; with the proviso that the sum of the carbon atoms in X and X 1 is at least 4;



   Y is linear C 1 -C 10 alkyl, branched C 3 -C 10 alkyl or C 3 -C 8 cycloalkyl; A 'is a non-nucleophilic anion selected from the group (BF 4)', (SbF 6) ', (PF 6)', (B (C 6 F 5)) 4 ', C 1 -C 2 0 alkyl sulfonate, C C 2 -C 20 haloalkylsulfonate, unsubstituted C 6 -C 10 arylsulfonate, camphorsulfonate, C 1 -C 20 perfluoroalkylsulfonylmethide, C 1 -C 20 perfluoroalkylsulfonylimide, and, with halogen, NO 2, C 1 -C 12 -alkyl C 1 -C 12 haloalkyl, C 1 -C 12 alkoxy or COOR 1 substituted C 6 -C 10 arylsulfonate; and R 1 is C 1 -C 20 alkyl, phenyl, benzyl; or phenyl which is mono- or polysubstituted by C 1 -C 12 -alkyl, C 1 -C 12 -alkoxy or halogen; with the proviso that the two phenyl rings on the iodine atom are not the same;

   have an optimal balance between high sensitivity, good storage stability, good solubility and low crystallization tendency.



   Linear C 1 -C 20 -alkyl is, for example, C 1 -C 12 -, C 1 -C 8 -, C 1 -C 6 - or C 1 -C 4 -alkyl. Examples are methyl, ethyl, propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tetradecyl, n- Pentadecyl, n-hexadecyl, n-heptadecyl, n-octadecyl, n-nonadecyl or n-lcosyl. For example, Y is C 1 -C 8 alkyl, especially C 1 -C 6 alkyl, preferably C 1 -C 4 alkyl, e.g. Methyl or n-butyl. Particularly preferred is methyl.



     Branched C 3 -C 20 -alkyl is, for example, C 3 -C 12 -, C 3 -C 8 -, C 3 -C 6 - or C 3 -C 4 -alkyl. Examples are branched propyl, such as isopropyl, branched butyl, such as sec-butyl, isobutyl, tert-butyl, branched pentyl, such as 2-methylbutyl, 3-methylbutyl, 1-methylbutyl, branched hexyl, such as 1-methylpentyl, 2- Methylpentyl, 4-methylpentyl, branched heptyl, such as 1-methylhexyl, 1-ethylpentyl, 4-ethylpentyl, 1-methylhexyl, 5-methylhexyl, branched octyl, such as 2,4,4-trimethylpentyl, 2-ethylhexyl, 1-methylheptyl, branched nonyl, branched decyl, branched undecyl, branched dodecyl, branched tetradecyl, branched pentadecyl, branched hexadecyl, branched heptadecyl, branched octadecyl, branched nonadecyl or branched icosyl.

   For example, Y is branched C 3 -C 8 -alkyl, especially branched C 3 -C 6 -alkyl, preferably branched C 3 -C 4 -alkyl, e.g. Isopropyl, sec-butyl, iso-butyl or tert-butyl.



   Branched C 4 -C 20 -alkyl may have the abovementioned meanings, up to the corresponding number of carbon atoms. X is, for example, C 4 -C 12 - or C 4 -C 8 -alkyl, such as sec-butyl, isobutyl, tert-butyl, tert-amyl, in particular isobutyl and tert-amyl.



   C 1 -C 20 -alkyl is linear or branched and is, for example, C 1 -C 12 -, C 1 -C 8 -, C 1 -C 6 - or C 1 -C 4 -alkyl. Examples are methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, pentyl, hexyl, hep-tyl, 2,4,4-trimethyl-pentyl, 2-ethylhexyl, octyl, Nonyl, decyl, undecyl, dodecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl or icosyl. C 1 -C 12 -alkyl is likewise linear or branched and has meanings given above up to the corresponding number of carbon atoms.



   C 3 -C 8 cycloalkyl is e.g. Cyclopropyl, cyclopentyl, cyclohexyl, or cyclooctyl, especially cyclopentyl and cyclohexyl, preferably cyclohexyl.



   Halogen is fluorine, chlorine, bromine and iodine, in particular chlorine and fluorine, preferably fluorine.



   C 1 -C 20 -haloalkyl is C 1 -C 20 -alkyl which is mono- or polysubstituted by halogen. The alkyl radical may be substituted by a plurality of identical, but also with different halogen atoms.



   When C 1 -C 20 -alkyl is substituted one or more times with halogen, e.g. 1 to 3 or 1 or 2 halogen substituents on the alkyl radical.



     C 1 -C 20 -alkylsulfonate is RSO 3 'wherein R is linear or branched C 1 -C 20 -alkyl as described above. Examples are methylsulfonate, ethylsulfonate, propylsulfonate, pentylsulfonate, hexylsulfonate.



   C 2 -C 2 -haloalkylsulfonate is RSO 3 'wherein R is C 2 -C 20 -alkyl substituted with halogen, C 2 -C 10 -, C 2 -C 8 - or C 4 -C 8 -alkyl , Examples are C 2 F 5 SO 3 ', C 4 F 9 SO 3', C 8 F 17 SO 3 '.



   Unsubstituted C 6 -C 10 arylsulfonate is RSO 3 'wherein R is C 6 -C 10 aryl, e.g. Phenyl or naphthyl.



   Alkyl-substituted arylsulfonates are e.g. Toluenesulfonate, 2,4,6-trimethylbenzenesulfonate, 2,4,6-tris (isopropyl) benzenesulfonate, 4-t-butylbenzenesulfonate, 4-dodecylbenzenesulfonate.



   Halogen-substituted arylsulfonates are e.g. 4-chlorobenzenesulfonate, 4-fluorobenzenesulfonate, 2,4,6-trifluorobenzenesulfonate, pentafluorobenzenesulfonate.



   
EMI4.1
 



   C 1 -C 12 -alkoxy represents linear or branched radicals and is, for example, C 1 -C 8 -, C 1 -C 6 - or C 1 -C 4 -alkoxy. Examples are methoxy, ethoxy, propoxy, isopropoxy, n-butyloxy, sec-butyloxy, isobutyl-oxy, tert-butyloxy, pentyloxy, hexyloxy, heptyloxy, 2,4,4-trimethylpentyloxy, 2-ethylhexyloxy, octyloxy, nonyloxy, Decyloxy or dodecyloxy, especially methoxy, ethoxy, propoxy, isopropoxy, n-butyloxy, sec-butyloxy, iso-butyloxy, tert-butyloxy, preferably methoxy.



   Mono- or polysubstituted phenyl is one to five times, e.g. one, two or three times, in particular one or two times substituted.



   C1-20 perfluoroalkylsulfonylmethide
EMI4.2
 C 1 -C 20 perfluoroalkylsulfonylimide



   Ra - SO 2 -N'-SO 2 -R b, where R a, R b and R c independently of one another are unsubstituted or N (R d) (R e) -substituted C 1 -C 20 -perfluoroalkyl or R a, R b and R c represent phenyl substituted with CF 3, or R a and R b together represent C 1 -C 6 perfluoroalkylene, which is optionally interrupted by -O-; R d and R e are independently C 1 -C 12 alkyl or R d and R e together are C 1 -C 6 perfluoroalkylene, which is optionally interrupted by O or N (C 1 -C 12 alkyl).



   Perfluoroalkyl is alkyl which is completely substituted by fluorine, i. the hydrogen atoms are replaced by fluorine. The same applies to perfluoroalkylene. Examples of such anions are (C 2 F 5 SO 2) 2 N ', (C 4 F 9 SO 2) 2 N', (C 8 F 17 SO 2) 3 C ', (CF 3 SO 2) 3 C' , (CF 3 SO 2) 2 N ', (C 4 F 9 SO 2) 3 C', (CF 3 SO 2) 2 (C 4 F 9 SO 2) C ', (CF 3 SO 2) (C 4 F 9 SO 2) N ', [(3,5-bis-



   
EMI5.1
 



   
EMI5.2
 



   These anions are known to the person skilled in the art. The anions and their preparation are e.g. in US 5 554 664.



   The position of the radicals X and Y on the phenyl rings of the iodonium salt compound of the formula I is e.g. in the 4,4'-position, 4,2'- or 4,3'-position, especially in the 4,4'-position or 4,2'-position, preferably in the 4,4'-position.



   The position of the radicals X, X 1 and Y on the phenyl rings of the iodonium salt compound of the formula I is e.g. 2,4,4'-position, 2,4,2'- or 2,4,3'-position, especially in the 2,4,4'-position or 2,4,2'-position, preferably in the 2,4,4-position. X is branched C 3 -C 20 -alkyl or C 3 -C 8 -cycloalkyl, preferably branched C 3 -C 8 -alkyl, cyclohexyl or cyclopentyl, in particular branched C 3 -C 4 -alkyl or cyclohexyl, e.g. Isopropyl, isobutyl, sec-butyl or tert-butyl. X 1 is hydrogen, linear C 1 -C 20 -alkyl, branched C 3 -C 20 -alkyl or C 3 -C 8 -cycloalkyl, preferably hydrogen, linear C 1 -C 10 -alkyl, branched C 3 -C 8 - Alkyl, in particular hydrogen or branched C 3 -C 4 -alkyl. More preferably, X 1 is hydrogen.



   The sum of the carbon atoms in the substituents X and X 1 in the compounds according to the invention is always at least 4, i. the sum is 4 or greater than 4, e.g. 4-40, 4-20, 4-10, 4-8, 5-40, 6-40, etc. Y is linear C 1 -C 10 alkyl, branched C 3 -C 10 alkyl or C 3 -C 8 -Cycloalkyl, preferably linear C 1 -C 8 or linear C 1 -C 6 alkyl, branched C 3 -C 8 - or branched C 3 -C 6 alkyl, cyclohexyl or cyclopentyl, for example Isopropyl or linear C 1 -C 4 -alkyl.

   A is a non-nucleophilic anion selected from the group (BF 4) ', (SbF 6)', (PF 6) ', (B (C 6 F 5)) 4', C 1 -C 20 alkyl sulfonate, C 2 -C 2 0 haloalkylsulfonate, unsubstituted C 6 -C 10 arylsulfonate, camphorsulfonate, C 1 -C 20 perfluoroalkylsulfonylmethide, C 1 -C 20 perfluoroalkylsulfonylimide, and, with halogen, NO 2, C 1 -C 12 alkyl C 1 -C 12 -haloalkyl, C 1 -C 12 -alkoxy or COOR 1 -substituted C 6 -C 10 -arylsulfonate; e.g. selected from the group (SbF 6) ', (PF 6)', (B (C 6 F 5)) 4 ', C 2 -C 20 -haloalkylsulfonate, camphorsulfonate, C 1 -C 12 -alkylsulfonate, phenylsulfonate, p- methylphenylsulphonate; in particular selected from the group (SbF 6) ', (PF 6)', (B (C 6 F 5)) 4 ', C 2 -C 20 haloalkylsulfonate.



   Characteristic of the novel compounds of the formula I is that the two phenyl rings on the iodine atom are not the same substituted, i. they are "unsymmetrical" iodonium salts. X or X 1 and Y are each different. Furthermore, it should be noted that a phenyl ring is always substituted by at least one branched alkyl group or cycloalkyl. Wherein the branched alkyl X, if X 1 is hydrogen, is at least one C 4 alkyl. When X 1 is other than hydrogen, the branched alkyl X may also be a C 3 alkyl. The sum of the carbon atoms of the radicals X + X 1 is thus always at least 4. A further feature of the compounds according to the invention is that both phenyl rings necessarily carry substituents on the iodine atom, so that the formation of benzene is avoided during the cleavage.



   The compounds of the invention offer an optimal balance of required reactivity - for a wide variety of broad applications (as described below and in the Examples) - good solubility in the formulations, and they prevent the release of benzene. In addition, a lower toxicological burden is to be expected by the substitution.



   General preparation processes for aryliodonium salt compounds are familiar to the person skilled in the art and described in the literature. Analogously to these processes, the novel photoinitiator compounds of the formula I can also be obtained. For example, compounds of formula I can be prepared by methods described in US Pat. Nos. 4,399,071 and 4,329,300 and DE 2,754,853. It is possible, e.g. the preparation of the hexafluorophosphate salts by replacing the anions from the simple salts of the corresponding iodonium compounds (such as the bissulfates). These methods are e.g. by Beringer et al. in J. Am. Chem. Soc. 81, 342 (1959). Various methods for the preparation of the abovementioned simple salts can be found in this reference.

   For example, the reaction of two aromatic compounds with iodoyl sulfate in sulfuric acid, the reaction of two aromatic compounds with iodate in acetic acid, acetic anhydride, sulfuric acid, the reaction of two aromatic compounds with iodoacylate in the presence of an acid, or the condensation of an iodoso compound, an iodosodiacetate or an iodoxy compound with another aromatic compound in the presence of an acid.



   In some cases, an aryl iodide may also be oxidized in situ and then condense with the other aromatic compound. This variant of the condensation proceeds, for example, in dilute sulfuric acid (EP 119 068).



   Preferred are radiation-sensitive compositions, wherein in the compounds of the formula I X is branched C 4 -C 12 -alkyl or cyclohexyl.



   Other interesting compositions are those wherein in the compounds of formula I Y is linear C 1 -C 6 alkyl or cyclohexyl.



   Particular mention should be made of compositions according to the invention in which in the compounds of the formula IA 'a non-nucleophilic anion selected from the group (PF 6)' (B (C 6 F 5)) 4 ', C 1 -C 12 -alkyl sulfonate, C 2 -C 12 haloalkyl sulfonate, unsubstituted phenyl sulfonate, camphorsulfonate, C 1 -C 20 perfluoroalkylsulfonyl methide, C 1 -C 20 perfluoroalkylsulfonyl imide, and, with halogen, NO 2, C 1 -C 12 alkyl, C 1 -C 12 haloalkyl, C 1 -C 12 alkoxy or COOR 1 substituted phenylsulfonate represents. In particular, A 'is a non-nucleophilic anion selected from the group (PF 6)', (B (C 6 F 5)) 4 ', C 1 -C 12 alkyl sulfonate, C 2 -C 12 haloalkyl sulfonate, unsubstituted phenyl sulfonate, And sulfonate substituted with halogen, NO 2, C 1 -C 12 -alkyl, C 1 -C 12 -haloalkyl, C 1 -C 12 -alkoxy or COOR 1 substituted phenylsulfonate.



   In particular, radiation-sensitive compositions are preferred in which in the compounds of the formula I X is branched C 4 -C 6 -alkyl or cyclohexyl; X 1 is hydrogen or branched C 4 -C 6 alkyl; Y is linear C 1 -C 4 -alkyl, branched C 3 -C 4 -alkyl or cyclohexyl;



     A 'is a non-nucleophilic anion selected from the group consisting of (PF 6)', camphorsulfonate, and C 1 -C 4 alkyl-substituted phenylsulfonate.



   Also of interest are compositions in which in the compounds of the formula I X is branched C 4 -C 6 -alkyl or cyclohexyl; Y is linear C 1 -C 4 alkyl, branched C 3 -C 4 alkyl or cyclohexyl; A 'is a non-nucleophilic anion selected from the group (PF 6)', (B (C 6 F 5)) 4 ', C 1 -C 2 -alkyl sulfonate, C 1 -C 20 haloalkyl sulfonate, unsubstituted C 6 - C 10 -arylsulfonate, camphorsulfonate, and C 6 -C 10 -arylsulfonate substituted by halogen, NO 2, C 1 -C 12 -alkyl, C 1 -C 12 -haloalkyl, C 1 -C 12 -alkoxy or COOR 1, represents; and R 1 is C 1 -C 12 alkyl, phenyl, benzyl, or phenyl substituted one or more times with C 1 -C 4 alkyl.



   Examples of compounds of the formula I which are suitable as component (b) in the compositions according to the invention are 4-isobutylphenyl-4'-methylphenyliodonium hexafluorophosphate; 4-iso-butylphenyl-4'-methylphenyliodonium-pentafluoroethylsulfonat; 4-isobutylphenyl-4'-methylphenyliodoniumtresylat; 4-isobutylphenyl-4'-methylphenyliodonium nonaflate; 4-isobutylphenyl-4'-methylphenyliodonium tosylate; 4-isobutylphenyl-4'-methylphenyliodonium 4-methoxyphenylsulfonat; 4-isobutylphenyl-4'-methylphenyliodonium-4-chlorophenyl-sulfonate; 4-lsobutyIphenyl-4'-methylphenyliodonium 4-fluorophenylsulfonat; 4-isobutylphenyl-4'-methylphenyliodonium-2,4,6-trimethylphenylsulfonate; 4-isobutylphenyl-4'-methylphenyliodonium-2,4,6- (tri-isopropyl) -phenylsulfonat; 4-isobutylphenyl-4'-methylphenyliodonium 4-dodecylphenylsulfonat;

    4-isobutylphenyl-4'-methylphenyliodonium-camphor-10-sulfonate; 4-isobutyl-phenyl-4'-methylphenyl-iodonium-tetrakis (pentafluorophosphyl) borate; 4- (2-methylbut-2-yl) phenyl-4'-methylphenyliodonium-hexafluoro-ophosphat; 4- (2-methylbut-2-yl) phenyl-4'-methylphenyliodonium-pentafluorethylsulfonat; 4- (2-methylbut-2-yl) phenyl-4'-methylphenyliodonium tetrakis (pentafluorophenyl) borate; 4- (2-methylbut-2-yl) phenyl-4'-methylphenyliodonium hexafluorophosphate; 4- (2-methylbut-2-yl) phenyl-4'-methylphenyliodonium-pentafluorethylsulfonat; 4- (2-methylbut-2-yl) phenyl-4'-methylphenyliodonium nonaflate; 4- (2-methylbut-2-yl) phenyl-4'-methylphenyliodonium 4-trifluoromethyl phenylsulfonate; 4- (2-methylbut-2-yl) phenyl-4'-methylphenyliodonium tosylate; 4- (2-methylbut-2-yl) phenyl-4'-methylphenyliodonium-camphor-10-sulfonate;

    4-cyclohexyl-4'-methylphenyliodonium hexafluorophosphate; 4-cyclohexyl-4'-methylphenyliodonium-pentafluorethylsulfonat; 4-cyclohexyl-4'-methylphenyliodoniumkampher-10-sulfonate; 4-cyclohexyl-4'-methylphenyliodonium tetrakis (pentafluorophenyl) boron; 4-cyclohexyl-4'-methylphenyliodonium tosylate; 4-tert-butylphenyl-4'-methylphenyliodonium hexafluorophosphate; 4-tert-butylphenyl-4'-methylphenyliodonium pentafluoroethylsulfonate; 4-tert-butylphenyl-4'-methylphenyliodonium-camphor-10-sulfonate; 4-tert-butylphenyl-4'-methylphenyliodonium tetrakis (pentafluorophenyl) borate; 4-tert-butylphenyl-4'-methylphenyliodonium 4-chlorophenylsulfonat; 4-tert-butylphenyl-4'-methylphenyliodonium 4-fluorophenylsulfonat; 4-tert-butylphenyl-4'-methylphenyliodonium 4-methoxyphenylsulfonate;

    4-tert-butylphenyl-4'-methylphenyliodonium hexafluorophosphate; 4-isobutylphenyl-4'-methylphenyliodonium nonafluorobutylsulfone at; 4-cyclohexyl-4'-methylphenyliodonium hexafluoroantimonate; 4- (2-methylbut-2-yl) phenyl-4 <'> - methylphenyliodonium nonafluorobutylsulfonate; 4-lsobutylphen-yl-2'-methylphenyliodonium hexafluorophosphate; 4-isobutylphenyl-4'-ethylphenyliodonium hexafluorophosphate; 4- (branched dodecyl) -4-methylphenyliodonium hexafluorophosphate.



   The compounds of formula I as described above are novel and therefore also form an object of this invention. The preferences are also as indicated above.



   The compositions according to the invention contain as component (a1) e.g. Resins and compounds that can be cationically polymerized by alkyl- or aryl-containing cations or by protons. Examples include cyclic ethers, in particular epoxides and oxetanes, and vinyl ethers, hydroxyl-containing compounds. Lactone compounds and cyclic thioethers as well as vinyl thioethers can also be used. Further examples are aminoplasts or phenolic resole resins. These are above all melamine, urea, epoxy, phenolic, acrylic, polyester and alkyd resins, but especially mixtures of acrylic, polyester or alkyd resins with a melamine resin. These include modified lacquer resins such as e.g. acrylic modified polyester and alkyd resins.

   Examples of individual types of resins, including acrylic, polyester and alkyd resins, are e.g. in Wagner, Sarx / Lackkunstharze (Munich, 1971), pages 86 to 123 and 229 to 238, or in Ullmann / Encyclopaedia der techn. Chemie, 4th Edition, Volume 15 (1978), pages 613 to 628, or Ullmann's Encyclopedia of Industrial Chemistry, Verlag Chemie, 1991, Vol. 18, 360 ff., Vol. A19, 371 ff., Described. Preferably, the paint contains an amino resin. Examples of these are etherified or unetherified melamine, urea, guanidine or biuret resins. Of particular importance is acid catalysis for the curing of paints containing etherified amino resins, e.g. methylated or butylated melamine resins (N-methoxymethyl or N-butoxymethylmelamine) or methylated / butylated glycolurils.



     For example, all conventional epoxides can be used, such as aromatic, aliphatic or cycloaliphatic epoxy resins. These are compounds having at least one, preferably at least two epoxide groups in the molecule. Examples of these are the glycidyl ethers and beta-methylglycidyl ethers of aliphatic or cycloaliphatic diols or polyols, e.g. those of ethylene glycol, propane-1,2-diol, propane-1,3-diol, butane-1,4-diol, diethylene glycol, polyethylene glycol, polypropylene glycol, glycerol, trimethylolpropane or 1,4-dimethylolcyclohexane or 2,2-bis - (4-hydroxycyclohexyl) -propane and N, N-bis (2-hydroxyethyl) aniline; the glycidyl ethers of di- and polyphenols, for example of resorcinol, of 4,4'-dihydroxyphenyl-2,2-propane, of novolaks or of 1,1,2,2-tetrakis- (4-hydroxyphenyl) -ethane.

    Examples are phenyl glycidyl ethers, p-tert-butyl glycidyl ethers, o-lesyl glycidyl ethers, polytetrahydrofuran glycidyl ethers, n-butyl glycidyl ethers, 2-ethylhexyl glycidyl ethers, C 12/15 alkyl glycidyl ethers, cyclohexane dimethanol diglycidyl ethers. Further examples are N-glycidyl compounds, e.g. the glycidyl compounds of ethyleneurea, 1,3-propyleneurea or 5-dimethylhydantoin or 4,4'-methylene-5,5'-tetramethyldihydantoin, or such as triglycidyl isocyanurate.



   Further examples of glycidyl ether components (a1) which are used in the formulations according to the invention are, for example, glycidyl ethers of polyhydric phenols obtained by reaction of polyhydric phenols with an excess of chlorohydrin, for example epichlorohydrin (eg glycidyl ethers of 2,2-bis (2 Other examples of glycidyl ether epoxides that can be used in the context of the present invention are described, for example, in US 3,018,262 and in the "Handbook of Epoxy Resins" by Lee and Neville, McGraw-Hill Book Co. , New York (1967).



   There are also a variety of commercially available as component (a1) suitable glycidyl etherepoxides such as glycidyl methacrylate, diglycidyl ethers of bisphenol A, e.g. those available under the trade names EPON 828, EPON 825, EPON 1004 and EPON 1010 from Shell; DER-331, DER-332 and DER-334 from Dow Chemical; 1,4-butanediol diglycidyl ether of phenol formaldehyde novolak, e.g. DEN-431, DEN-438 from Dow Chemical; and resorcinol diglycidyl ether; Alkyl glycidyl ethers such as C 8 -C 10 glycidyl ethers, e.g. HELOXY modifier 7, C 12 -C 14 glycidyl ether, e.g. HELOXY modifier 8, butylglycidyl ether, e.g. HELOXY modifier 61, cresyl glycidyl ether, e.g. HELOXY modifier 62, p-tert-butylphenyl glycidyl ether, e.g. HELOXY modifier 65, polyfunctional glycidyl ethers such as diglycidyl ether of 1,4-butanediol, e.g.

   HELOXY modifier 67, diglycidyl ether of neopentyl glycol, e.g. HELOXY modifier 68, diglycidyl ether of cyclohexanedimethanol, e.g. HELOXY modifier 107, trimethylolethane triglycidyl ether, e.g. HELOXY modifier 44, trimethylolpropane triglycidyl ether, e.g. HELOXY Modifer 48, polyglycidyl ethers of aliphatic polyols, e.g. HELOXY Modifier 84 (all HELOXY glycidyl ethers are available from Shell).



   Also suitable are glycidyl ethers containing copolymers of acrylic esters, e.g. Styrene-glycidyl methacrylate or methyl methacrylate-glycidyl acrylate. Examples are 1: 1 styrene / glycidyl methacrylate, 1: 1 methyl methacrylate / glycidyl acrylate, 62.5: 24: 13.5 methyl methacrylate / ethyl acrylate / glycidyl methacrylate.



   For example, the polymers of the glycidyl ether compounds may also contain other functionalities, provided they do not interfere with the cationic cure. Other glycidyl ether compounds which are commercially available as component (a1) and commercially available from Ciba Spezialitätenchemie are polyfunctional liquid and solid novolak glycidyl ether resins, e.g. PY 307, EPN 1179, EPN 1180, EPN 1182 and ECN 9699. Of course, mixtures of different glycidyl ether compounds can also be used as component (a1).



   The glycidyl ethers (a1) are, for example, compounds of the formula II



   
EMI11.1
  x is a number from 1 to 6; and R 5 represents a monovalent to hexahydric alkyl or aryl radical.



   Preferred are e.g. Glycidyl ether compounds of the formula II



   
EMI11.2
  x is a number 1, 2 or 3; and R 5 when x = 1, unsubstituted or C 1 -C 12 alkyl-substituted phenyl, naphthyl, anthracyl, biphenylyl, C 1 -C 2 0 alkyl, or C 2 -C 20 interrupted by one or more oxygen atoms, Represents alkyl, or



     R 5 when x = 2, 1,3-phenylene, 1,4-phenylene, C 6 -C 10 -cycloalkylene, unsubstituted or halogen-substituted C 1 -C 10 -alkylene, C 2 -C interrupted by one or more oxygen atoms 40



   kylene, or a group
EMI12.1
 means, or

 R 5 if x = 3, for a remainder
EMI12.2
 or



   
EMI12.3
 



   y is a number from 1 to 10; and



   R 6 is C 1 -C 20 -alkylene, oxygen or
EMI12.4
  The glycidyl ethers (a1) are e.g. Compounds of formula IIa



   
EMI12.5
 



   R 7 is phenyl which is unsubstituted or substituted by C 1 -C 12 -alkyl; naphthyl; anthracyl; biphenylyl; C 1 -C 20 alkyl, interrupted by one or more oxygen atoms C 2 -C 20 alkyl or a group



   the formula
EMI12.6
 represents;



   R 5 is phenylene, C 1 -C 20 -alkylene, C 2 -C 20 -alkylene interrupted by one or more oxygen atoms,



   or a group
EMI12.7
 means; and



   R 6 is C 1 -C 20 alkylene or oxygen.



   Preference is given to the glycidyl ether compounds of the formula IIb



   
EMI13.1
 



   R 5 is phenylene, C 1 -C 20 -alkylene, interrupted by one or more oxygen atoms C 2 -C 20 alkylene



   or a group
EMI13.2
 means; and



   R 6 is C 1 -C 2 0 alkylene or oxygen.



   Further examples of component (a1) are polyglycidyl ethers and poly (beta-methylglycidyl) ethers which are obtained by reacting a compound containing at least two free alcoholic and / or phenolic hydroxyl groups per molecule with the corresponding epichlorohydrin under alkaline conditions or in the presence of a acidic catalyst with subsequent alkali treatment, are available. It is also possible to use mixtures of different polyols.



   These ethers can be reacted with poly (epichlorohydrin) from acyclic alcohols, such as ethylene glycol, di-ethylene glycol and higher poly (oxyethylene) glycols, propane-1,2-diol and poly (oxy-propylene) glycols, propane 1,3-diol, butane-1,4-diol, poly (oxytetramethylene) -glycols, pentane-1,5-diol, hexane-1,6-diol, hexane-2,4,6-triol, glycerol, 1,1,1-trimethylolpropane, pentaerythritol and sorbitol, from cycloaliphatic alcohols such as resorcite, quinitol, bis (4-hydroxycyclohexyl) methane, 2,2-bis (4-hydroxycyclohexyl) -propane and 1,1-bis - (hydroxymethyl) cyclohexene-3, and from alcohols with aromatic nuclei, such as N, N-bis (2-hydroxyethyl) aniline and p, p'-bis (2-hydroxyethylamino) -diphenyImethan produce.

   They can also be obtained from mononuclear phenols, such as resorcinol and hydroquinone, and polynuclear phenols, such as bis (4-hydroxyphenyl) methane, 4,4-dihydroxydiphenyl, bis (4-hydroxyphenyl) sulfone, 1,1,2, 2-tetrakis- (4-hydroxyphenyl) -ethane, 2,2-bis (4-hydroxyphenyl) -propane (bisphenol A) and 2,2-bis (3,5-dibromo-4-hydroxyphenyl) -propane ,



   Further suitable hydroxy compounds for preparing polyglycidyl ethers and poly (beta-methylglycidyl) ethers are those obtained by condensation of aldehydes, such as formaldehyde, acetaldehyde, chloral and furfural, and phenols, such as, for example, phenol, o-cresol, m-cresol, p-aldehyde. Cresol, 3,5-dimethylphenol, 4-chlorophenol and 4-tert-butylphenol, available novolaks.



   Poly (N-glycidyl) compounds can be prepared, for example, by dehydrochlorinating the reaction products of epichlorohydrin with amines having at least two amino hydrogen atoms, such as aniline, n-butylamine, bis (4-aminophenyl) methane, bis (4-aminophenyl) propane, Bis (4-methylaminophenyl) methane and bis (4-aminophenyl) ether, sulfone and sulfoxide. Further suitable poly (N-glycidyl) compounds are triglycidyl isocyanurate and N, N'-diglycidyl derivatives of cyclic alkylene ureas, such as ethyleneurea and 1,3-propyleneurea, and hydantoins, such as, for example, 5,5-dimethylhydantoin.



   Poly (S-glycidyl) compounds are also suitable. Examples are the di-S-glycidyl derivatives of dithiols such as ethane-1,2-dithiol and bis (4-mercaptomethylphenyl) ether.



   Also suitable as component (a1) are epoxy resins in which the glycidyl groups or β-methylglycidyl groups are bonded to heteroatoms of various types, e.g. the N, N, O-triglycidyl derivative of 4-aminophenol, the glycidyl ether / glycidyl ester of salicylic acid or p-hydroxybenzoic acid, N-glycidyl-N '- (2-glycidyloxypropyl) -5,5-dimethylhydantoin and 2-glycidyloxy-1 , 3-bis- (5,5-dimethyl-1-glycidylhydantoinyl-3) propane.



   Preference is given to diglycidyl ethers of bisphenols. Examples are bisphenol A diglycidyl ethers, e.g. ARALDIT GY 250 from Ciba Specialty Chemicals, bisphenol F diglycidyl ether and bisphenol S-diglycidyl ether. Particularly preferred is bisphenol A diglycidyl ether.



   Other glycidyl compounds of industrial importance are the glycidyl esters of carboxylic acids, especially di- and polycarboxylic acids. Examples of these are the glycidyl esters of succinic acid, adipic acid, azelaic acid, sebacic acid, phthalic acid, terephthalic acid, tetra- and hexahydrophthalic acid, isophthalic acid or trimellitic acid, or of dimerized fatty acids.



   Examples of polyepoxides which are not glycidyl compounds are the epoxides of vinylcyclohexane and dicyclopentadiene, 3- (3 ', 4'-epoxycyclohexyl) -8,9-epoxy-2,4-dioxaspiro [5.5] undecane, the 3', 4'-Epoxicyclohexylmethylester of 3,4-Epoxicyclohexancarbonsäure, (3,4-EpoxycycIohexylmethyl-3,4-epoxycyclohexanecarboxylate), butadiene diepoxide or isoprene diepoxide, epoxidized linoleic acid derivatives or epoxidized polybutadiene.



   Other suitable epoxide compounds are e.g. Lime monoxide, epoxidized soybean oil, bisphenol A and bisphenol F epoxy resins, e.g. Araldite < <TM>> GY 250 (A), Araldite < <TM>> GY 282 (F), Araldite < <TM>> GY 285 (F) (from Ciba Spezialitätenchemie), as well as photocrosslinkable siloxanes containing epoxide groups.



     Other suitable cationically polymerizable or crosslinkable components (a1) are e.g. US Pat. Nos. 3,117,099, 4,299,938 and 4,339,567.



   The monofunctional alpha-olefin epoxides having an unbranched chain consisting of 10, 12, 14 and 16 carbon atoms are particularly suitable from the group of aliphatic epoxides.



   The fact that today a large number of different epoxy compounds is commercially available, the properties of the binder can vary widely. One variation, e.g. Depending on the intended use of the composition, there is the use of mixtures of different epoxy compounds and in the addition of flexibilizers and reactive diluents.



   The epoxy resins may be diluted with a solvent to facilitate the application, for example, when the application is done by spraying. Preferably, however, the epoxy compound is used in a solvent-free state. At room temperature, viscous to solid resins can be applied in hot condition.



   Also suitable as component (a1) are all customary vinyl ethers, such as aromatic, aliphatic or cycloaliphatic vinyl ethers, and also silicon-containing vinyl ethers. These are compounds having at least one, preferably at least two, vinyl ether groups in the molecule. Examples of vinyl ethers which are suitable for use in the compositions according to the invention are triethylene glycol divinyl ether, 1,4-cyclohexanedimethanol divinyl ether, 4-hydroxybutyl vinyl ether, the propenyl carbonate propenyl carbonate, dodecyl vinyl ether, tert-butyl vinyl ether, tert-amyl vinyl ether, cyclohexyl vinyl ether, 2 Ethylhexyl vinyl ether, ethylene glycol monovinyl ether, butanediol monovinyl ether, hexanediol monovinyl ether, 1,4-cyclohexanedimethanol monovinyl ether, diethylene glycol monovinyl ether, ethylene glycol divinyl ether, ethylene glycol butylvinyl ether, butanediol-1,4-divinyl ether,

   Hexanediol divinyl ether, diethylene glycol divinyl ether, triethylene glycol divinyl ether, triethylene glycol methyl vinyl ether, tetraethylene glycol divinyl ether, pluriol E-200 divinyl ether, polytetrahydrofuran divinyl ether-290, trimethylolpropane trivinyl ether, dipropylene glycol divinyl ether, octadecyl vinyl ether, (4-cyclohexylmethylenoxyethene) glutaric acid methyl ester and (4-butyloxyethene) isophthalic acid ester.



     Examples of hydroxyl-containing compounds are polyester polyols, e.g. Polycaprolactones or polyester adipate polyols, glycols and polyether polyols, castor oil, hydroxy-functional vinyl and acrylic resins, cellulose esters, e.g. Cellulose acetate butyrate, and phenoxy resins.



   Other cationically curable formulations are e.g. to see EP-A-119 425.



   Cycloaliphatic epoxides or epoxides based on bisphenol A are preferably used as component (a1).



   The invention therefore also provides a radiation-sensitive composition in which component (a1) is at least one compound selected from the group of cycloaliphatic epoxy compounds, glycidyl ethers, oxetane compounds, vinyl ethers, acid-crosslinkable melamine resins, acid-crosslinkable hydroxymethylene compounds and acid-crosslinkable alkoxymethylene compounds.



   If desired, the composition of the invention may also contain radically polymerizable components, e.g. ethylenically unsaturated monomers, oligomers or polymers. Suitable materials contain at least one ethylenically unsaturated double bond and are capable of undergoing addition polymerization.



   Examples of suitable monomers containing one ethylenic double bond are alkyl and hydroxyalkyl acrylates and methacrylates such as methyl, ethyl, propyl, isopropyl, butyl, hexyl, 2-ethylhexyl and 2-hydroxyethyl (meth) acrylate , Stearyl acrylate, isobornyl acrylates. Other suitable examples are acrylonitrile, acrylamide, methacrylamide, N-substituted (meth) acrylamides, vinyl esters, e.g. Vinyl acetate, vinyl ethers such as isobutyl vinyl ether, styrene, alkyl- and halogen-substituted styrene, N-vinylpyrrolidone, vinyl chloride and vinylidene chlorides.



   Examples of suitable monomers containing at least two double bonds are glycerol diacrylates, glycerol triacrylates, ethylene glycol diacrylates, diethylene glycol diacrylates, diethylene glycol dimethacrylate, triethylene glycol dimethacrylates, 1,3-propanediol diacrylate, 1,3-propanediol dimethacrylate, neopentyl glycol diacrylates, hexamethylene glycol diacrylate, bisphenol A diacrylates, 4,4'- bis (2-acryloyloxyethoxy) diphenylpropane, pentaerythritol triacrylate or tetraacrylate, pentaerythritol tetramethacrylate, trimethylolpropane triacrylate, 1,2,4-butanetrioltrimethacrylate, 1,4-cyclohexanediol diacrylate, sorbitol hexacrylate, bis [1- (2-acryloxy)] - p -ethoxyphenyldimethylmethane, bis [1- (3-acryloxy-2-hydroxy)] - p-propoxyphenyldimethylmethane and trishydroxyethyl isocyanurate trimethacrylate;

    the bis-acrylates and bis-methacrylates of molecular weight 200-500 poly (ethylene glycol), diallyl phthalate, divinylsuccinate, divinyl adipate and divinyl phthalate, vinyl acrylate, divinylbenzene, triallyl phosphate, triallyl isocyanurate and tris (2-acryloylethyl) isocyanurate.



   Examples of relatively high molecular weight (oligomeric) polyunsaturated compounds are acrylated epoxy resins, acrylated or vinyl ether or epoxy groups-containing polyesters, polyurethanes and polyethers. Further examples of unsaturated oligomers are unsaturated polyester resins which are usually prepared from maleic acid, phthalic acid and one or more diols and have molecular weights of about 500 to 3,000. In addition, it is also possible to use vinyl ether monomers and oligomers, and maleate-terminated oligomers with polyester, polyurethane, polyether, polyvinyl ether and epoxide main chains. In particular, combinations of vinyl ether group-bearing oligomers and polymers as described in WO 90/01512 are well suited. But copolymers of vinyl ether and maleic acid functionalized monomers are also suitable.

   Such unsaturated oligomers may also be referred to as prepolymers.



   Functionalized acrylates are also suitable. Examples of suitable monomers commonly used to form the backbone of the functionalized acrylate or methacrylate polymer include acrylate, methacrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-butyl acrylate, n-butyl methacrylate, isobutyl acrylate, isobutyl methacrylate, Ethylhexyl acrylate, 2-ethylhexyl methacrylate, etc. In addition, suitable proportions of functional monomers are copolymerized during the polymerization to obtain the functional polymers. Acid-functionalized acrylate or methacrylate polymers are obtained by reacting acid functional monomers, e.g. Acrylic acid or methacrylic acid can be used.

   Hydroxy-functional acrylate or methacrylate polymers are prepared from hydroxy-functional monomers, e.g. 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate and 3,4-dihydroxybutyl methacrylate obtained. Epoxy-functionalized acrylate or methacrylate polymers are obtained by reacting epoxy-functional monomers, e.g. Glycidyl methacrylate, 2,3-epoxybutyl methacrylate, 3,4-epoxybutyl methacrylate, 2,3-epoxycyclohexyl methacrylate, 10, 11-epoxyundecyl methacrylate, etc. are used. It is also possible to use isocyanate-functional polymers from isocyanate-functionalized monomers, such as e.g. to obtain meta-isopropenyl-alpha, alpha-dimethylbenzyl isocyanate.



   Particularly suitable are e.g. Esters of ethylenically unsaturated mono- or polyfunctional carboxylic acids and polyols or polyepoxides, and polymers having ethylenically unsaturated groups in the chain or in side groups, such as e.g. unsaturated polyesters, polyamides and polyurethanes and copolymers thereof, alkyd resins, polybutadiene and butadiene copolymers, polyisoprene and isoprene copolymers, polymers and copolymers having (meth) acrylic groups in side chains, and mixtures of one or more such polymers.



   Examples of suitable mono- or polyfunctional unsaturated carboxylic acids are acrylic acid, methacrylic acid, crotonic acid, itaconic acid, cinnamic acid, maleic acid and fumaric acid and unsaturated fatty acids such as linolenic acid or oleic acid. Preferred are acrylic and methacrylic acid.



   However, mixtures of saturated di- or polycarboxylic acids with unsaturated carboxylic acids may also be used. Examples of suitable saturated di- or polycarboxylic acids include e.g. Tetrachlorophthalic acid, tetrabromophthalic acid, phthalic anhydride, adipic acid, tetrahydrophthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, heptanedicarboxylic acid, sebacic acid, dodecanedicarboxylic acid, hexahydrophthalic acid, etc.



   Suitable polyols are aromatic and especially aliphatic and cycloaliphatic polyols. Examples of aromatic polyols are hydroquinone, 4,4'-dihydroxydiphenyl, 2,2-di (4-hydroxyphenyl) -propane, as well as novolacs and resoles. Examples of polyepoxides are those based on said polyols, especially the aromatic polyols and epichlorohydrin. Further, polymers and copolymers containing hydroxyl groups in the polymer chain or in side groups, e.g. Polyvinyl alcohol and copolymers thereof or hydroxyalkyl polymethacrylates or copolymers thereof, suitable as polyols. Other suitable polyols are oligoesters with hydroxyl end groups.



   Examples of aliphatic and cycloaliphatic polyols are alkylenediols having preferably 2 to 12 C atoms, such as ethylene glycol, 1,2- or 1,3-propanediol, 1,2-, 1,3- or 1,4-butanediol, pentanediol, hexanediol , Octanediol, dodecanediol, diethylene glycol, triethylene glycol, Polyethyl englykole having molecular weights of preferably 200 to 1500, 1,3-cyclopentanediol, 1,2-, 1,3- or 1,4-cyclohexanediol, 1,4-dihydroxymethylcyclohexane, glycerol, tris - (beta-hydroxyethyl) amine, trimethylolethane, trimethylolpropane, pentaerythritol, dipentaerythritol and sorbitol.



   The polyols may be partially or fully esterified with one or more unsaturated carboxylic acids, wherein in partial esters the free hydroxyl groups are modified, e.g. etherified or esterified with other carboxylic acids.



   Examples of esters are: trimethylolpropane triacrylate, trimethylolethane triacrylate, trimethylolpropane trimethacrylate, trimethylolethane trimethacrylate, tetramethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol diacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol diacrylate, dipentaerythritol triacrylate, dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, Tripentaerythritoctaacrylat, pentaerythritol dimethacrylate, pentaerythritol trimethacrylate, dipentaerythritol methacrylate, Dipentaerythrittetramethacrylat, Tripentaerythritoctamethacrylat, pentaerythritol , Di-pentaerythritol trisitaconate, dipentaerythritol pentaitaconate, dipentaerythritol hexaitaconate, ethylene glycol diacrylate, 1,3-butanediol diacrylate, 1,3-butanediol dimethacrylate, 1,4-butanediol diitaconate, sorbitol triacrylate,

    Sorbitol tetraacrylate, pentaerythritol modified triacrylate, sorbitol tetra methacrylate, sorbitol pentaacrylate, sorbitol hexaacrylate, oligoester acrylates and methacrylates, glycerol di- and triacrylate, 1,4-cyclohexanediacrylate, bisacrylates and bismethacrylates of polyethylene glycol of 200 to 1500 molecular weight, or mixtures thereof.



   Suitable unsaturated radically polymerizable compounds are also the amides of the same or different unsaturated carboxylic acids and aromatic, cycloaliphatic and aliphatic polyamines having preferably 2 to 6, especially 2 to 4 amino groups suitable. Examples of such polyamines are ethylenediamine, 1,2- or 1,3-propylenediamine, 1,2-, 1,3- or 1,4-butylenediamine, 1,5-pentylenediamine, 1,6-hexylenediamine, octylenediamine, dodecylenediamine, 1,4-diaminocyclohexane, isophoronediamine, phenylenediamine, bisphenylenediamine, di-beta-aminoethyl ether, diethylenetriamine, triethylenetetramine, di (beta-aminoethoxy) - or di (beta-aminopropoxy) ethane. Other suitable polyamines are polymers and copolymers with optionally additional amino groups in the side chain and oligoamides with amino end groups.

    Examples of such unsaturated amides are: methylene-bis-acrylamide, 1,6-hexamethylene-bis-acrylamide, bis (methacrylamidopropoxy) -ethane, beta-methacrylamidoethyl methacrylate, N [(beta-hydroxyethoxy) ethyl] acrylamide.



   Suitable unsaturated polyesters and polyamides are derived e.g. of maleic acid and diols or diamines. The maleic acid may be partially replaced by other dicarboxylic acids. They may be used together with ethylenically unsaturated comonomers, e.g. Styrene, are used. The polyesters and polyamides may also be derived from dicarboxylic acids and ethylenically unsaturated diols or diamines, especially from longer chain with e.g. 6 to 20 carbon atoms. Examples of polyurethanes are those which are composed of saturated or unsaturated diisocyanates and unsaturated or saturated diols.



   Polybutadiene and polyisoprene and copolymers thereof are known. Suitable comonomers are e.g. Olefins such as ethylene, propene, butene, hexene, (meth) acrylates, acrylonitrile, styrene or vinyl chloride. Polymers with (meth) acrylate groups in the side chain are also known. It can be e.g. reaction products of novolac-based epoxy resins with (meth) acrylic acid to form homopolymers or copolymers of vinyl alcohol or their hydroxyalkyl derivatives esterified with (meth) acrylic acid, or homo- and copolymers of (meth) acrylates hydroxyalkyl (meth ) acrylates are esterified.



   Furthermore, both radically and cationically crosslinkable compounds can be used. For example, they contain both a vinyl group and a cycloaliphatic epoxy group. Examples thereof are JP-A-2-289611 and US Pat. No. 6,048,953.



   Also, mixtures of two or more of these radically polymerizable materials may be used.



   Binders can also be added to the compositions according to the invention, which is particularly expedient if the photopolymerizable compounds are liquid or viscous substances. The amount of the binder may e.g. 5-95, preferably 10-90 and especially 40-90 wt .-%, based on the total solids. The choice of binder is made depending on the field of application and properties required for this, such as developability in aqueous and organic solvent systems, adhesion to substrates and oxygen sensitivity.



     Suitable binders are e.g. Polymers having a molecular weight of about 2,000-2,000,000, preferably 5,000-1,000,000. Examples are: homo- and copolymers acrylates and methacrylates, e.g. Copolymers of methyl methacrylate / ethyl acrylate / methacrylic acid, poly (methacrylic acid alkyl ester), poly (acrylic acid alkyl ester); Phenolic resins, cellulose derivatives, e.g. Cellulose esters and ethers, e.g.

   Cellulose acetate, cellulose acetate butyrate, methyl cellulose, ethyl cellulose; Polyvinyl butyral, polyvinyl formal, polyolefins, cyclized rubber, polyethers such as polyethylene oxide, polypropylene oxide, polytetrahydrofuran; Polystyrene, polycarbonate, polyurethane, chlorinated polyolefins, polyvinyl chloride, copolymers of vinyl chloride / vinylidene chloride, copolymers of vinylidene chloride with acrylonitrile, methyl methacrylate and vinyl acetate, polyvinyl acetate, copoly (ethylene / vinyl acetate), polymers such as polycaprolactam and poly (hexamethylene adipamide), polyesters such as poly (ethylene glycol terephthalate ) and poly (hexamethylene glycol succinate); and polyamides.



   The resins listed below under (C1) can also be used as a radically curable component. Of particular interest are e.g. unsaturated acrylates with reactive functional groups. The reactive functional group may be selected, for example, from a hydroxyl, thiol, isocyanate, epoxy, anhydride, carboxyl, amino or blocked amino group. Examples of unsaturated acrylates containing OH groups are hydroxyethyl and hydroxybutyl acrylates and also glycidyl acrylates.



   The unsaturated compounds may also be used in admixture with non-photopolymerizable film-forming components. These may e.g. physically drying polymers or their solutions in organic solvents, e.g. Nitrocellulose or cellulose acetobutyrate. However, these may also be chemically or thermally curable resins, such as e.g. Polyisocyanates, poly-epoxides or melamine resins. Also, dry oils, e.g. Linseed oil, linseed oil modified alkyd resins, wood oil and soybean oil may be included. The concomitant use of thermosetting resins is important for use in so-called hybrid systems, which are photopolymerized in a first stage and are crosslinked in a second stage by thermal aftertreatment.



   Thus, the radiation-curable compositions of the present invention may also contain:



     (A1) compounds having one or more free radically polymerizable double bonds which additionally contain at least one further functional group which is reactive in addition and / or condensation reactions (examples are given above);



   (A2) compounds having one or more free radically polymerizable double bonds which additionally contain at least one further functional group which is reactive in addition and / or condensation reactions, this additional functional group being complementary or reactive to the additional functional group of component (A1) is;



   (A3) at least one monomeric, oligomeric and / or polymeric compound having at least one functional group which is reactive in addition and / or condensation reactions with respect to the functional groups of component (A1) or (A2), in addition to the free radically polymerizable double bonds are present.



   The component (A2) in each case carries the groups which are complementary or reactive with respect to the component (A1). In one component, various types of functional groups may also be present.



   Component (A3) represents a component containing other functional groups which are reactive in addition and / or condensation reactions and which are capable of reacting with the functional groups of (A1) or (A2), in addition to the free radically polymerizable double bonds are present. The components (A3) contain no free radically polymerizable double bonds. Examples of such combinations (A1), (A2), (A3) can be found in WO 99 755 785.



   Examples of suitable functional groups are hydroxyl, isocyanate, epoxy, anhydride, carboxyl and blocked amino groups. Examples are described above.



   Components of the thermally curable component (C) are, for example, thermally curable coating or coating system components, as are customary in the art. The component (C) may therefore consist of a plurality of constituents. Examples of component (C) are oligomers and / or polymers derived from alpha, beta-unsaturated acids and derivatives thereof, e.g. Polyacrylates and polymethacrylates, polymethyl methacrylates impact-modified with butyl acrylate, polyacrylamides and polyacrylonitriles. Further examples of component (C) are urethanes, polyurethanes derived on one side of polyethers, polyesters and polyacrylates having free hydroxyl groups and on the other side of aliphatic or aromatic polyisocyanates, and educts thereof.

   The component (C) therefore comprises e.g. also crosslinkable acrylic resins derived from substituted acrylic acid esters, e.g. Epoxy acrylates, urethane acrylates and polyester acrylates. Alkyd resins, polyester resins and acrylate resins and modifications thereof which are crosslinked with melamine resins, urea resins, isocyanates, isocyanurates, polyisocyanates, polyisocyanurates and epoxy resins may also be part of component (C).



   For example, the component (C) is generally a film-forming binder based on a thermoplastic or thermosetting resin, especially on a thermosetting resin. Examples include alkyd, acrylic, polyester, phenolic, melamine, epoxy and polyurethane resins and mixtures thereof. Examples of this can be found, for example, in Ullmann's Encyclopedia of Industrial Chemistry, 5th Ed., Vol. A18, pp. 368-426, VCH, Weinheim 1991.



   The component (C) may also be a cold-curable or heat-curable binder, wherein optionally the addition of a curing catalyst is advantageous. Suitable catalysts which accelerate the curing of the binder, for example, Ullmann's Encyclopedia of Industrial Chemistry, Vol. A18, p 469, VCH Verlagsgesellschaft, Weinheim 1991, refer to.



   Specific examples of binders suitable as component (C) are:



   1. Surface coatings based on cold- or hot-crosslinkable alkyd, acrylate, polyester, epoxy or melamine resins or mixtures of such resins, optionally with the addition of a curing catalyst;



   2. two-component polyurethane surface coatings based on hydroxyl-containing acrylate, polyester or polyether resins and aliphatic or aromatic isocyanates, isocyanurates or polyisocyanates;



   3. one-component polyurethane surface coatings based on blocked isocyanates, isocyanurates or polyisocyanates which are deblocked during heating; it is also possible to optionally add melamine resins;



   4. one-component polyurethane surface coatings based on aliphatic or aromatic urethanes or polyurethanes and hydroxyl-containing acrylate, polyester or polyether resins;



     5. one-component polyurethane surface coatings based on aliphatic or aromatic urethane acrylates or polyurethane acrylates with free amine groups in the urethane structure and melamine resins or polyether resins, optionally with the addition of a curing catalyst;



   6. two-component surface coatings based on (poly) ketimines and aliphatic or aromatic isocyanates, isocyanurates or polyisocyanates;



   7. two-component surface coatings based on (poly) ketimines and an unsaturated acrylate resin or a polyacetoacetate resin or a methacrylamidoglycolate methyl ester;



   8. two-component surface coatings based on carboxyl or amino group-containing polyacrylates and polyepoxides;



   9. two-component surface coatings based on anhydride group-containing acrylate resins and a polyhydroxy or polyamino component;



   10. two-component surface coatings based on acrylate-containing anhydrides and polyepoxides;



   11. Two-component surface coatings based on (poly) oxazolines and anhydride group-containing acrylate resins or unsaturated acrylate resins or aliphatic or aromatic isocyanates, isocyanurates or polyisocyanates;



   12. two-component surface coatings based on unsaturated polyacrylates and polymalonates;



   13. Thermoplastic polyacrylate surface coatings based on thermoplastic acrylate resins or extrinsically crosslinking acrylate resins in combination with etherified melamine resins;



   14. Surface coating systems based on urethane (meth) acrylate having (meth) acryloyl groups and free isocyanate groups and on one or more compounds which react with isocyanates, e.g. free or esterified polyols. Such systems are e.g. published in EP 928 800.



   Blocked isocyanates, which can also be used as component (C), are e.g. in Organic Metal Protection: Development and Application of Coating Materials, pages 159-160, Vin-centz Verlag, Hannover (1993). These are compounds in which the highly reactive NCO group is "blocked" by reaction with specific radicals, e.g., primary alcohol, phenol, ethyl acetate, epsilon-caprolactam, phthalimide, imidazole, oxime or amine. The blocked isocyanate is stable in liquid systems and also in the presence of hydroxy groups. On heating, the blocking group (protecting group) is removed again and the NCO group is released.



   1-component (1K) and 2-component (2K) systems can be used as component (C). Examples of such systems are described in Ullmann's Encyclopedia of Industrial Chemistry, Vol. A18, Paints and Coatings, pages 404-407, VCH Verlagsgesellschaft mbH, Weinheim (1991).



   It is possible to optimize the composition by specific adaptation, e.g. by varying the binder / crosslinker ratio. Such measures are known to the person skilled in the art and are customary in coating technology.



   In the curing process according to the invention, component (C) is preferably a mixture based on acrylate / melamine (and melamine derivatives), 2-component polyurethane, 1-component polyurethane, 2-component epoxy / carboxy or 1-component epoxy / carboxy. Mixtures of such systems are also possible, for example the addition of melamine (or derivatives thereof) to 1-component polyurethanes.



   Component (C) is preferably a binder based on a polyacrylate with melamine or on a melamine derivative or a system based on a polyacrylate and / or polyester polyol with an unblocked polyisocyanate or polyisocyanurate.



   Component (C) may also contain monomeric and / or oligomeric compounds having ethylenically unsaturated bonds (prepolymers) which additionally contain at least one or more OH, NH 2, COOH, epoxy or NCO groups (= C1) which react with the binder and / or the crosslinker component of component (C). After application and thermal curing, the ethylenically unsaturated bonds are converted by irradiation with UV light into a crosslinked, high molecular weight form. Examples of such components (C) are e.g. in the above-mentioned publication, Ullmann's Encyclopedia of Industrial Chemistry, 5th Ed., Vol. A18, pages 451-453, or by S. Urano, K. Aoki, N. Tsuboniva, and R. Mizuguchi in Progress in Organic Coatings, 20 (1992), 471-486, or by H. Terashima and O. Isozaki in JOCCA 1992 (6), 222.



     (C1) may also be, for example, an OH-containing unsaturated acrylate, e.g. Hydroxyethyl or hydroxybutyl acrylate or a glycidyl acrylate. Component (C1) may be of any structure (eg, it may contain polyester, polyacrylate, polyether units, etc.) provided that it has one ethylenically unsaturated double bond plus, in addition, free OH, COOH, NH 2, epoxy, or NCO groups contains. For example, (C1) can also be obtained by reacting an epoxy-functional oligomer with acrylic acid or methacrylic acid. A typical example of an OH-functional oligomer having vinylic double bonds is



   
EMI26.1
 



   



   obtained by reaction of CH 2 = CHCOOH with



   
EMI26.2
 



   Another way to obtain component (C1) is, for example, the reaction of an oligomer containing only one epoxy group and having a free OH group at another position of the molecule.



   The amount ratio of the free-radically-radiation-polymerizable components to the thermally-polymerizable component (C) in the UV and thermally crosslinkable formulations is not critical. "Dual-cure" systems are known in the art, which is therefore familiar with the optimum mixing ratios of the free-radically and thermally crosslinkable component - depending on the intended use. For example, the ratio may range from 5:95 to 95: 5, from 20:80 to 80:20, or from 30:70 to 70:30, e.g. from 40:60 to 60:40.



   Examples of "dual-cure" systems, i. Systems containing both radiation curable and thermally curable components can be used i.a. US 5,922,473, columns 6 to 10 are taken.



   The formulations of the invention may further comprise, as component (a1), nonaqueous coating compositions based on an oxidatively drying alkyd resin having at least one, preferably two or more, functional groups capable of undergoing polymerization or polycondensation reactions in the presence to enter an acid. Examples of such resins are vinyl ether-functionalized alkyd resins, acetal-functionalized alkyd resins, and / or alkoxysilane-functionalized alkyd resins, e.g. in WO 99/47617 proposed These modified alkyd resins can be used alone or in combination with other alkyd resins.

   At least a portion of the alkyd resin composition in the non-aqueous coating is oxidatively dry by the incorporation of a large number of unsaturated aliphatic compounds wherein at least a portion is polyunsaturated.



   Formulations containing these modified alkyd resins as component (a1) may optionally contain an oxidative dryer in addition to the photoinitiator (b). Suitable oxidative dryers are e.g. Metal siccatives. Examples of suitable siccatives are the metal salts of (cyclo) aliphatic acids, such as octanoic acid and naphthenic acid; the metals to be used are, for example, cobalt, manganese, lead, zirconium, calcium, zinc and rare earth metals. Mixtures of siccatives can be used. Preference is given to metal salts of cobalt, zirconium and calcium, or mixtures thereof. The siccatives (calculated as metal) are usually used in an amount of 0.001 to 3 wt .-%.



   In addition, under certain conditions, it may be advantageous to use one or more mono- or bisacylacylphosphine oxide photoinitiators in addition to the diaryliodonium salt of formula (I) when the modified alkyd resins are used as component (a1). Suitable monoacyl or bisacylphosphine oxide photoinitiators include, for example, monoacylphosphine oxides such as (2,4,6-trimethylbenzoyl) -diphenyl-phosphine oxide (Lucirin < <TM>> TPO) or (2,4,6-trimethylbenzoyl-phenyl-ethoxy-phosphine oxide or bisacylphosphine oxide photoinitiators such as bis (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentyl-phosphine oxide, bis- (2,6- dimethoxybenzoyl) -2,2,4-trimethylpentyl-phosphine oxide, bis (2,4,6-trimethylbenzoyl) - (2,4-dipentoxyphenyl) phosphine oxide and bis (2,4,6-trimethylbenzoyl) -phenyl-phosphine oxide. 

   These monoacyl or bisacylphosphine oxides are suitably used in an amount of 0.5-5%.  



   When component (a1) contains modified alkyd resins, it is possible to use, in addition to the photoinitiator (b), an oxidative drier and suitable monoacyl or bisacylphosphine oxide photoinitiators.                                                      



   The alkyd resins used as component (a1) contain a large number of unsaturated aliphatic compounds, of which at least some are polyunsaturated.  The unsaturated aliphatic compounds which are preferably used for the preparation of these alkyd resins are unsaturated aliphatic monocarboxylic acids, in particular polyunsaturated aliphatic monocarboxylic acids.   Examples of mono-unsaturated fatty acids are myristoleic acid, palmitic acid, oleic acid, gadoleic acid, erucic acid, and ricinoleic acid.   Preference is given to using fatty acids containing conjugated double bonds, such as dehydrated castor oil fatty acid and / or wood oil fatty acid.   Other suitable monocarboxylic acids include tetrahydrobenzoic acid and hydrogenated or non-hydrogenated abietic acid or its isomers. 

    If desired, the particular monocarboxylic acid may be used, in whole or in part, as triglyceride, e.g. B.  as a vegetable oil, used in the preparation of the alkyd resin.  If desired, mixtures of two or more of such monocarboxylic acids or triglycerides may be employed, optionally in the presence of one or more saturated (cyclo) aliphatic or aromatic monocarboxylic acids, e.g. B. , Pivalic acid, 2-ethylhexanoic acid, lauric acid, palmitic acid, stearic acid, 4-tert. Butylbenzoic acid, cyclopentanecarboxylic acid, naphthenic acid, cyclohexanecarboxylic acid, 2,4-dimethylbenzoic acid, 2-methylbenzoic acid, and benzoic acid.  



   If desired, polycarboxylic acids may also be incorporated into the alkyd resin, such as phthalic acid, isophthalic acid, terephthalic acid, 5-tert-butylisophthalic acid, trimellitic acid, pyromellitic acid, succinic acid, adipic acid, 2,2,4-trimethyladipic acid, azelaic acid, sebacic acid, dimerized fatty acids, cyclopentane. 1,2-dicarboxylic acid, cyclohexane-1,2-dicarboxylic acid, 4-methylcyclohexane-1,2-dicarboxylic acid, tetrahydrophthalic acid, endomethylene-cyclohexane-1,2-dicarboxylic acid, butane-1,2,3,4-tetracarboxylic acid, endoisopropylidene cyclohexane-1,2-dicarboxylic acid, cyclohexane-1,2,4,5-tetracarboxylic acid and butane-1,2,3,4-tetracarboxylic acid.   If desired, the particular carboxylic acid may be used as the anhydride or in the form of an ester, e.g. B. , an ester of an alcohol of 1-4 carbon atoms.  



   In addition, the alkyd resin may be composed of di- or polyvalent hydroxyl compounds.  Examples of suitable divalent hydroxyl compounds are ethylene glycol, 1,3-propanediol, 1,6-hexanediol, 1,12-dodecanediol, 3-methyl-1,5-pentanediol, 2,2,4-trimethyl-1,6-hexanediol, 2 , 2-dimethyl-1,3-propanediol, and 2-methyl-2-cyclohexyl-1,3-propanediol.  Examples of suitable triols are glycerol, trimethylolethane and trimethylolpropane.  Suitable polyols having more than 3 hydroxyl groups are pentaerythritol, sorbitol and etherified products of the respective compounds, such as ditrimethylolpropane and di-, tri- and tetrapentaerythritol.  Preference is given to compounds having 3-12 carbon atoms, for. B.  Glycerol, pentaerythritol and / or dipentaerythritol used.  



   The alkyd resins can be obtained by direct esterification of the ingredients, with the option that some of these components have already been converted to ester diols or polyester diols.  In addition, the unsaturated fatty acids may be used in the form of a drying oil such as linseed oil, tuna oil, dehydrated castor oil, coconut oil and dehydrated coconut oil.  By transesterification with the other added acids and diols then the finished alkyd resin is obtained.  This transesterification is conveniently carried out at a temperature in the range from 115 to 250 ° C., if appropriate in the presence of solvents such as toluene and / or xylene.  The reaction is conveniently carried out in the presence of a catalytic portion of a transesterification catalyst. 

   Examples of such suitable transesterification catalysts include acids such as p-toluenesulfonic acid, basic compounds such as an amine or compounds such as calcium oxide, zinc oxide, tetraisopropyl orthotitanate, dibutyltin oxide, and triphenylbenzylphosphonium chloride.                                 



   The vinyl ether, acetal and / or alkoxysilane compounds used as part of component (a1) preferably contain at least two vinyl ether, acetal and / or alkoxysilane groups and have a molecular weight of 150 or more.  These vinyl ether, acetal and / or alkoxysilane compounds may, for. B.  are obtained by reaction of commercially available vinyl ether, acetal and / or alkoxysilane compounds containing a vinyl ether, acetal and / or alkoxysilane group and additionally at most one functional amino, epoxy, thiol, isocyanate, acrylic, hydride or hydroxyl group with a compound having at least two groups capable of reacting with an amino, epoxy, thiol, isocyanate, acrylic, hydride or hydroxyl group. 

   As examples, compounds having at least two epoxy, isocyanate, hydroxyl and / or ester groups or compounds having at least two ethylenically or ethynylenically unsaturated groups can be listed.  



   Preferred as component (a1) is a composition in which the vinyl ether, acetal and / or alkoxysilane compounds are covalently bonded to the alkyd resin by addition via a reactive group such as an amino, hydroxyl, thiol, hydride, epoxy and / or isocyanate group.  For this purpose, these compounds must contain at least one group capable of forming an adduct with the reactive groups present in the alkyd resin.  



   To introduce vinyl ether groups into the alkyd resin is a vinyloxyalkyl compound whose alkyl group has a reactive group, such as a hydroxyl, amino, epoxy or isocyanate group, capable of forming an adduct with one or more of the reactive groups present in the alkyd resin , substituted is used.  



     Preferred as component (a1) are compositions in which the ratio of the number of oxidatively drying groups present in the alkyd resin to the number of reactive groups in the presence of an acid ranges from 1/10 to 15/1, in particular from 1 / 3 to 5/1, is.  Instead of a single modified alkyd resin, various alkyd resins can be used with one alkyd resin highly modified and the others less or not modified at all.  



   Examples of vinyl ether compounds capable of being covalently bonded to the alkyd resin include ethylene glycol monovinyl ether, butanediol monovinyl ether, triethylene glycol monovinyl ether, cyclohexanedimethanol monovinyl ether, 2-ethylhexanediol monovinyl ether, polytetrahydrofuran monovinyl ether, tetraethylene glycol monovinyl ether, trimethylolpropane divinyl ether and aminopropyl vinyl ether.  



   Adducts may, for. B.  are formed by reaction of the vinyl ether compounds containing a hydroxyl or amino group with an excess of a diisocyanate, followed by reaction of this free isocyanate group-containing adduct with the free hydroxyl groups of the alkyd resin.   Preferably, a process is used in which first the free hydroxyl groups of the alkyd resin react with an excess of a polyisocyanate, and then the free isocyanate groups react with an amino group- or hydroxyl-containing vinyl ether compound.  Instead of a diisocyanate, a diester may also be used. 

   Transesterification of the hydroxyl groups present in the alkyd resin with an excess of the diester, followed by transesterification or transamidation of the remaining ester groups with hydroxy-functional vinyl ether compounds or  amino-functional vinyl ether compounds gives vinyl ether-functional alkyd resins.  Moreover, during the preparation of the alkyd resin, it is possible to introduce (meth) acrylate groups into the alkyd resin by carrying out the preparation in the presence of a hydroxy-functional (meth) acrylate ester, such as hydroxyethyl methacrylate (HEMA), followed by reaction of the thus-functionalized alkyd resin with a Michael Reaction with a vinyl ether group-containing and a primary amino-containing compound and subsequent reaction with z. B.  an isocyanate compound to obtain a non-basic nitrogen atom.  



   An example of such an implementation is z. B.  described in WO 99/47617.  Esterification of ricinic fatty acid with dipentaerythritol, followed by transesterification of free hydroxyl groups with diethyl malonate and 4-hydroxybutyl vinyl ether in a suitable ratio, results in a vinyl ether functional alkyd resin suitable for use as component (a1).  



   For the preparation of acetal-functional alkyd resins, use is normally made of dialkyl acetal functionalized with an amino group.  Examples of suitable acetal compounds are 4-aminobutyraldehyde dimethyl acetal and 4-aminobutyraldehyde diethyl acetal.  The alkyd resin is modified by adding the aminoacetal monomer to an alkyd resin functionalized with isocyanate groups, ester groups of a low-boiling alcohol or (meth) acrylate groups.  The thus-obtained dialkyl acetal-modified alkyd resin may be incorporated into the coating composition having a high solid content and a low viscosity. 

    Furthermore, the preparation of acetal-functional alkyd resins can be carried out by reaction of hydroxyacetal with the carboxyl groups of the alkyd resin, or by reaction of a diisocyanate or diester compound with the hydroxyl groups of the alkyd resin.  



   An example of this method of preparation is described in WO 99/47617, e.g. B the esterification of a hydroxyl-functional alkyd resin with diethyl malonate, followed by a transamidation of the free ester group with 4-Aminobutyraldehyddimethylacetal in a suitable ratio.  The acetal-modified alkyd resin thus obtained is suitable as component (a1).  



   To introduce alkoxysilane groups into the alkyd resin, use is made of a siloxane compound having one or more reactive group (s), which are subsequently reacted with one or more constituents which form the alkyd resin.  TDAS are z. B.  Alkoxysilanes of the formula:



    X a -Si (R 1) b (R 2) c wherein R 1 is alkoxy or oxyalkylene alkoxy, or when X is hydrogen, halo; R 2 is an aliphatic, cycloaliphatic or aromatic group, and X is hydrogen or an alkyl group substituted with an amino, isocyanato, mercapto or epoxy group; a = 1 to 3; b = 1 to 3; c = 0 to 2, and a + b + c = 4.   R 1 is preferably an alkoxy group having 1 to 4 carbon atoms in the alkoxy group, and R 2 is preferably a group having not more than 18 carbon atoms. 

    Examples of suitable siloxane compounds are 3-aminopropyltriethoxysilane, polyglycol ether-modified aminosilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltrismethoxyethoxyethoxysilane, 3-aminopropylmethyldiethoxysilane, N-2-aminoethyl-3-aminopropyltrimeth oxy-silane, N-2-aminoethyl-3-aminopropyl-methyldimethoxy-silane, N-methyl-3-aminopropyl-trimethoxysilane, 3-ureidopropyl-triethoxysilane, 3,4,5-dihydroimidazol-1-yl-propyltriethoxysilane, 3 Methacryloxypropyltrimethoxysilane, 3-glycidyloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane and 3-mercaptopropylmethyldimethoxysilane, triethoxysilane, diethoxymethylsilane, dimethoxymethylsilane, trimethoxysilane, trichlorosilane, triiodosilane, tribromosilane, dichloromethylsilane and dibromomethylsilane.  



   The alkyd resin may, for. B.  be modified by incorporating an amino group-modified alkoxysilane to an alkyd resin which is modified with a polyisocyanate or a polyester of a low-boiling alcohol.   Hydride-functional alkoxysilanes may be bonded directly to the alkyd, i. H. without modification with a compound molecule such as a diisocyanate or diester, by adding a compound containing a silyl hydride group to an ethylenically unsaturated group in the alkyd resin.  This addition is catalyzed by a transition metal.   In this method, use is preferably made of a halogenated silyl hydride and, for the completion of the addition reaction, conversion into an alkoxysilane compound with a low-boiling alcohol. 

    The addition reaction proceeds advantageously in the absence of sterically hindering groups and proceeds optimally when the ethylenically unsaturated groups are end groups, such as. B.  for esters of 10-undecenecarboxylic acid.                                           



   Examples of the preparation of alkoxysiloxane-modified alkyd resins are described in WO 99/47617.  Esterification of a hydroxyl-functional alkyd resin with diethyl malonate, followed by transamidation of the free ester group with 3-aminopropyltriethoxysilane in an appropriate ratio, results in an alkoysilane-modified alkyd resin.  In addition, hydroxyl-modified alkyd resin can be reacted with an excess of isophorone diisocyanate followed by reaction of the free isocyanate groups with 3-aminopropyltriethoxysilane.  Both alkoxysiloxane-modified alkyd resins obtained by these described processes are suitable for use in component (a1).  



   If free-radically polymerizable components are added to the formulation according to the invention, it may be  advantageous to also add one or a mixture of corresponding radical photoinitiator (s).  Z. B.  Benzophenone and derivatives, acetophenone and derivatives, e.g. B.   alpha -hydroxycyclohexyl phenyl ketone or 2-hydroxy-2-methyl-1-phenyl-propanone, 2-hydroxy-1- [3- [4- (2-hydroxy-2-methyl-propionyl) -phenyl] -1,1,3 -trimethyl-indan-5-yl] -2-methyl-propan-1-one, alpha-hydroxy or alpha-aminoacetophenone, such as. B.  (4-methylthiobenzoyl) -1-methyl-1-morpholino-ethane, (4-morpholinobenzoyl) -1-benzyl-1-dimethylamine-o-propane, 4-aroyl-1,3-dioxolanes, benzoin alkyl ethers and benzil ketal. such as B.  Benzildi methylketal, phenylglyoxalate and derivatives, mono- or Bisacylphosphinoxid, such as. B. 

   (2,4,6-trimethylbenzoyl) -phenyl-phosphine oxide, bis (2,6-dimethoxybenzoyl) - (2,4,4-trimethyl-pent-1-yl) -phosphine oxide, bis (2,4,6-trimethylbenzoyl) -phenyl-phosphine oxide or bis (2,4,6-trimethyl-benzoyl) - (2,4-dipentoxyphenyl) phosphine oxide.            



   Other additional components may include, for example, hydroxy-functional components such as. B.  Alcohols, polyester polyols, polyether polyols, hydroxyl-containing polyurethanes, castor oil, etc.  be.  Examples are aliphatic and cycloaliphatic polyols such as alkylenediols having preferably 2 to 12 C atoms, for. B.  Ethylene glycol, 1,2- or 1,3-propanediol, 1,2-, 1,3- or 1,4-butanediol, pentanediol, hexanediol, octanediol, dodecanediol, diethylene glycol, triethylene glycol, polyethylene glycols having molecular weights of preferably 200 to 1500, 1,3-cyclopentanediol, 1,2-, 1,3- or 1,4-cyclohexanediol, 1,4-dihydroxymethylcyclohexane, glycerol, tris- (beta-hydroxyethyl) amine, trimethylolethane, trimethylolpropane, pentaerythritol, dipentaerythritol and sorbitol , 

   The polyols may be partially or completely esterified with one or more unsaturated carboxylic acids, wherein modified in partial esters, the free hydroxyl groups, for. B.  etherified or esterified with other carboxylic acids.   Examples of esters are: trimethylolpropane triacrylate, trimethylolethane triacrylate, trimethylolpropane trimethacrylate, trimethylolethane trimethacrylate, tetramethylene glycol dimethacrylate, Triethylenglykoldimeth acrylate, tetraethylene glycol diacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol diacrylate, dipenta-erythrittriacrylat, dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, Tripentaerythritoctaacrylat, pentaerythritol dimethacrylate, pentaerythritol trimethacrylate, dipentaerythritol dimethacrylate, Dipentaerythrittetramethacrylat .

   Tripentaerythritoctamethacrylat, pentaerythritol, Dipentaerythrittrisitaconat, dipentaerythritol, dipentaerythritol hexaitaconate, ethylene glycol diacrylate, 1,3-butanediol diacrylate, 1,3-butanediol dimethacrylate, 1,4-butanediol diitaconate, Sorbittriacrylat, sorbitol tetraacrylate, pentaerythritol-modified triacrylate, sorbitol tetramethacrylate, sorbitol pentaacrylate, sorbitol hexaacrylate, oligoester acrylates and methacrylates, Glycerol di- and tri-acrylate, 1,4-cyclohexanediacrylate, bisacrylates and bismethacrylates of polyethylene glycol having a molecular weight of 200 to 1500, or mixtures thereof.  



   Furthermore, the iodonium salt of the formula I z. B.  also serve as light activatable hardener for siloxane-containing resins.  These resins may, for. B.  either self-condensation via an acid-catalyzed hydrolysis or with a second resin component, such as. B.  a polyfunctional alcohol, a hydroxyl group-containing acrylic or polyester resin, a partially saponified polyvinyl acetal or a polyvinyl alcohol.  This type of polycondensation of polysiloxanes is described, for example, in J. J.  Lebrun, H.  Pode, Comprehensive Polymer Science Volume 5, page 593, Pergamon Press, Oxford, 1989.  



   Examples of compounds which increase their solubility under the influence of acid in a developer (component (a2)) are oligomers, polymers and copolymers obtained by co-polymerization of e.g. B.  the following monomers can be obtained: noncyclic or cyclic secondary and tertiary alkyl (meth) acrylates such as tert. Butyl acrylate, tert. Butyl methacrylate, 3-oxocyclohexyl (meth) acrylate, tetrahydropyranyl (meth) acrylate, 2-methyl-2-adamantyl (meth) acrylate, cyclohexyl (meth) acrylate, norbornyl (meth) acrylate, isobornyl methacrylate, 5-norbornene-2-tert , butyl ester, 8-ethyl-8-tricyclodecanyl- (meth) acrylate, (2-tetrahydropyranyl) oxynorbonyl alcohol acrylate, (2-tetrahydropyranyl) oxymethyltricyclododecanemethanol methacrylate, trimethylsilylmethyl (meth) acrylate, (2-tetrahydropyranyl) oxynorbonyl alcohol-acrylate, (2- tetrahydropyranyl)

  oxymethyltricyclododecanemethanolmethacrylate, trimethylsilylmethyl (meth) acrylate, o- / m- / p- (3-oxocyclohexyloxy) styrene, o- / m- / p- (1-methyl-1-phenylethoxy) styrene, o- / m- / p-tetrahydropyranyloxystyrene, o- / m- / p-adamantyloxystyrene, o- / m- / p-cyclohexyloxystyrene, o- / m- / p-norbornyloxystyrene, non-cyclic or cyclic alkoxycarbonylstyrenes, such as o- / m- / p- tert. Butoxycarbonylstyrene, o- / m- / p- (3-oxocyclohexyloxycarbonyl) -styrene, o- / m- / p- (1-methyl-1-phenylethoxycarbonyl) styrene, o- / m- / p-tetrahydropyranyloxycarbonylstyrene, o- / m- / p-adamantyloxycarbonylstyrene, o- / m- / p-cyclohexyloxycarbonylstyrene, o- / m- / p-norbornyloxycarbonylstyrene, non-cyclic or cyclic alkoxycarbonyloxystyrenes such as o- / m- / p-tert. Butoxycarbonyloxystyrene, o- / m- / p- (3-oxocyclohexyloxycarbonyloxy) styrene, o- / m- / p- (1-methyl-1-phenylethoxycarbonyloxy) styrene, o- / m- / p-tetrahydropyranyloxycarbonyloxystyrene,

    o- / m- / p-adamantyloxycarbonyloxystyrene, o- / m- / p-cyclohexyloxycarbonyloxystyrene, o- / m- / p-norbornyloxycarbonyloxystyrene, non-cyclic or cyclic alkoxycarbonylalkoxystyrenes, such as o / m / p-butoxycarbonylmethoxystyrene, p-tert- Butoxycarbonylmethoxystyrene, o- / m- / p- (3-oxocyclohexyloxycarbonylmethoxy) styrene, o- / m- / p- (1-methyl-1-phenylethoxycarbonylmethoxy) -styrene, o- / m- / p-tetrahydropyranyloxycarbonylmethoxystyrene, o- / m- / p-adamantyloxycarbonylmethoxystyrene, o- / m- / p-cyclohexyloxycarbonylmethoxystyrene, o- / m- / p-norbornyloxycarbonylmethoxystyrene, trimethylsiloxystyrene, dimethyl (butyl) siloxystyrene, unsaturated alkylacetates, such as isopropenylacetate and its derivatives, norbornenyl-2-tert. butyl;

   also monomers which carry acid-labile groups with low activation energy, such as. B.  p- or m- (1-methoxy-1-methyl-ethoxy) -styrene, p- or m- (1-methoxy-1-methylethoxy) -methylstyrene, p- or m- (1-methoxy-1-methylpropoxy) styrene, p- or m- (1-methoxy-1-methylpropoxy) -methylstyrene, p- or m- (1-methoxyethoxy) -styrene, p- or m- (1-methoxyethoxy) -methylstyrene, p- or m- (1-ethoxy-1-methylethoxy) styrenes, p- or m- (1-ethoxy-1-methylethoxy) -methylstyrene, p- or m- (1-ethoxy-1-methylpropoxy) styrene, p- or m- ( 1-ethoxy-1-methylpropoxy) -methylstyrene, p- or m- (1-ethoxyethoxy) styrene, p- or m- (1-ethoxyethoxy) -methylstyrene, p- (1-ethoxyphenylethoxy) styrene, p- or m- (1-n-propoxy-1-metylethoxy) styrene, p- or m- (1-n-propoxy-1-metylethoxy) -methylstyrene, p- or m- (1-n-propoxyethoxy) styrene, p- or m - (1-n-propoxyethoxy) methylstyrene,

    p- or m- (1-isopropoxy-1-methylethoxy) styrene, p- or m- (1-isopropoxy-1-methylethoxy) -methylstyrene, p- or m- (1-isopropoxyethoxy) styrene, p- or m- (1-isopropoxyethoxy) -methylstyrene, p- or m- (1-isopropoxy-1-methylpropoxy) styrene, p- or m- (1-isopropoxy-1-methylpropoxy) -methylstyrene, p- or m- (1-isopropoxypropoxy ) styrene, p- or m- (1-isopropoxypropoxy) -methylstyrene, p- or m- (1-n-butoxy-1-methylethoxy) styrene, p- or m- (1-n-butoxyethoxy) styrene, p- or m- (1-isobutoxy-1-methylethoxy) styrene, p- or m- (1-tert-butoxy-1-methylethoxy) styrene, p- or m- (1-n-pentoxy-1-methylethoxy) styrene, p- or m- (1-isoamyloxy-1-methylethoxy) styrene, p- or m- (1-n-hexyloxy-1-methylethoxy) styrene, p- or m- (1-cyclohexyloxy-1-methylethoxy) styrene, p- or m- (1-trimethylsilyloxy-1-methylethoxy) styrene, p- or m- (1-trimethylsilyloxy-1-methylethoxy) -methylstyrene,

    p- or m- (1-Benzyloxy-1-methylethoxy) styrene, p- or m- (1-benzyloxy-1-methylethoxy) -methylstyrene, p- or m- (1-methoxy-1-methylethoxy) styrene, p - or m- (1-methoxy-1-methylethoxy) -methylstyrene, p- or m- (1-trimethylsilyloxy-1-methylethoxy) styrene, p- or m- (1-trimethylsilyloxy-1-methylethoxy) -methylstyrene.   Further examples of polymers with alkoxyalkyl ester-labile groups can be found in US Pat. No. 5,225,316 and EP 829,766.  Examples of polymers with acetal protecting groups are e.g. B.  in US 5,670,299, EP 780,732, US 5,627,006, US 5,558,976, US 5,558,971, US 5,468,589, EP 704,762, EP 762,206, EP 342,498, EP 553,737 and ACS Symp.  Ser.   614, Microelectronics Technology, S.  35-55 (1995), J.  Photopolymer Sci.  Technol.  Vol.  10, no.  4 (1997), p.  571-578, J.  Photopolymer Sci.  Technol. 

   Vol.  12, no.  4 (1999) p.  591-599 as well as in "Proceedings of SPIE", Advances in Resist Technology and Processing XVII, Vol.   3999, Part One, S.  579-590, 28.  Feb. -1.  March 2000 described.  However, the polymers useful in the composition of this invention are not limited thereto.  



   The monomers with an acid-labile group may optionally  also with other free-radically polymerizable monomers which do not bear acid-labile groups, such as. B.  Styrene, acrylonitrile, methyl (meth) acrylate, (meth) acrylic acid, 4-hydroxystyrene, 4-acetoxystyrene, 4-methoxystyrene, 4-vinylcyclohexanol, norbornene, ethylnorbornene, maleic anhydride, to adjust certain solubility and adhesive properties.  Alternatively, the acid labile groups can also be introduced later in a polymer-analogous reaction.  It is also known to the person skilled in the art that the prepolymer can be modified in a targeted manner before such a polymer-analogous reaction, eg. B.  by partial hydrogenation, partial alkylation, partial acetylation. 

   This means that the polymer with acid-labile groups does not always have to be built up by copolymerization of monomers.  



   It is also possible to introduce acid labile crosslinks such. B.   in H. -T.  Shaft, P.  Falcigno, N.  Muenzel, R.  Schulz, and A.  Medina, ACS Symp.  Ser.  706 (Micro and Nano-patterning Polymers), S.  78-94.1997; H. -T.  Shaft, N.  Muenzel, P.  Falcigno, H.  Holzwarth, and J.  Schneider, J.  Photopolymer Science and Technology, Vol. 9, (1996), 573-586.   Such acid-crosslinked systems are preferred in resist applications, from the standpoint of heat stability.  Such acid-labile crosslinks can also by reaction of phenol-containing polymers such. B.  of 4-hydroxystyrene-co-polymers, with di- and polyfunctional vinyl ethers.  



   Other examples of component (a2), which upon reaction with acid increase their solubility in an alkaline developer, are monomeric compounds, such as e.g. B.  Carboxylic acids and phenol-containing compounds in which the carboxylic acid group or  phenolic OH group was blocked by acid labile protecting groups.  Such acid labile blocks may, for. B.  by conversion of the carboxyl group into a tert-butyl ester group, a 2-methyl-2-adamantyl ester group, an 8-ethyl-8-tricyclodecanyl ester group, a tetrahydropyranyl ester group or other acid-cleavable ester groups.  Phenolic OH groups can by known methods by conversion z. B.  in acid-cleavable tert. Butyl carbonate groups, silyl ethers, acetal groups and ketal groups are blocked.  



   The invention also relates to a radiation-sensitive composition, wherein component (a2) is at least one compound selected from the group of cycloaliphatic copolymers, 4-hydroxyphenyl group-containing copolymers, maleic anhydride-containing copolymers and acrylic acid, acrylic ester and methacrylic acid ester-containing copolymers with the proviso that these copolymers bear functional groups that increase the solubility of the polymer upon reaction with an acid in an alkaline developer.  



   In the compositions according to the invention, the photoinitiator (b) is expediently used in an amount of 0. 05% to 15%, z. B.  0th 5% to 10%, preferably 0. 1% to 5%, based on the composition used.                                                           



   The novel compositions can be used in numerous applications, for. B.  in cationic radiation-curable inks, in possibly  pigmented, cationically radiation-curable coating compositions, in cationic radiation-curable adhesives, coatings and moldings, including fiberglass and carbon fiber reinforced composites, and inner and outer layers of printed circuit boards.  



   The novel compositions also include adhesives such as those used for bonding (DVD bonding) in the production of Digital Versatile Disks (DVD) and are described, for example, in: WO 99/66506, WO 99/63017, JP 11 241 055 A2 Heisei, JP 11 181 391 A2 Heisei, WO 98/31 765, as well as radiation-curable laminating adhesives for flexible packaging (s.  z. B.  U.S. Patent 5,328,940), optical adhesives (e.g. B.  German Patent Application DD 225 985) and Pressure Sensitive Adhesives (z. B.  U.S. Patent 4,988,741 and European Patent EP 115,870).  



   The novel compositions are advantageously used where hard, on paper, glass, metal, silicon, polycarbonate, acrylate polymers and other polymer substrates well adhering, only slightly shrinking during curing coatings, bonds or photopolymerized dimensionally stable three-dimensional molded parts (eg. B.   for rapid prototyping).  



   Preference is also given to a composition as described above comprising in addition to components (a1) or (a2) and (b) additional additives (c) and / or sensitizer compounds (d) and optionally  further photoinitiators (e).  



   The photopolymerizable mixtures may contain various additives (c) in addition to the photoinitiator.  Examples of these are thermal inhibitors, light stabilizers, optical brighteners, fillers, pigments, both white and colored pigments, dyes, antistatic agents, adhesion improvers, wetting agents, leveling agents, lubricants, waxes, non-stick agents,



     Dispersing aids, emulsifiers, antioxidants, fillers, eg. B.  Talc, gypsum, silica, rutile, carbon black, zinc oxide, iron oxides, reaction accelerators, thickeners, matting agents, defoamers, and other such. B.  Contain in the paint and coating technology customary auxiliaries.  



   The formulations may also contain dyes and / or white or colored pigments as additional additives (c).  Depending on the application, both inorganic and organic pigments can be used.  Such additives are known in the art, some examples are titanium dioxide pigments, for. B.  rutile or anatase type, carbon black, zinc oxide such as zinc white, iron oxides such as iron oxide yellow, iron oxide red, chrome yellow, chrome green, nickel titanium yellow, ultramarine blue, cobalt blue, bismuth vanadate, cadmium yellow or cadmium red.  Examples of organic pigments are mono- or Bisazopigmente, and metal complexes thereof, phthalocyanine pigments, polycyclic pigments, such as. B.  Perylene, anthraquinone, thioindigo, quinacridone or Triphenylmethanpigmente, and diketo-pyrrolo-pyrol, isoindolinone, z. B. 

   Tetrachloroisoindolinone, isoindoline, dioxazine, benzimidazolone and quinophthalone pigments.                                                              



   The pigments can be used individually, but also as a mixture in the formulations.  Depending on the intended use, the pigments are added to the formulations in amounts customary in the art, for example in an amount of from 1 to 60% by weight. -%, or 10 to 30 wt. -%, relative to the total mass.  



   The formulations may also contain, for example, organic dyes of various classes.  Examples are azo dyes, methine dyes, anthraquinone dyes or metal complex dyes.   Usual concentrations are for example 0. 1 to 20%, in particular 1 to 5%, based on the total mass.  



   Optionally, the added pigments, latent pigments or dyes or  added differently colored precursors of such pigments and dyes, are selected so that they undergo a color change in the presence of the acid formed by irradiation from the iodonium salt.  Such compositions then indicate by color change that they have been irradiated and may, for. B.  as well as dose indicators for radiation, e.g. B.  for UV radiation, electron radiation, X-rays, etc.  be used.  



     The choice of additives depends on the particular field of application and the properties desired for this area.  The additives (c) described above are conventional in the art and are therefore used in amounts customary in the art.  



   An acceleration of the photopolymerization can also be done by adding photosensitizers as further additives (d), which shift the spectral sensitivity or  broaden.   These are in particular aromatic carbonyl compounds such as. B.   Benzophenon-, thioxanthone, in particular isopropylthioxanthone, phenothiazine derivatives, anthraquinone and 3-acylcumarin derivatives, terphenyls, styryl ketones, and 3- (aroylmethylene) thiazolines, camphorquinone, but also eosine, rhodamine and erythrosine dyes, and anthracene derivatives, such as z. B.  9-methylanthracene, 9,10-dimethylanthracene, 9-methoxyanthracene, 9,10-diethoxyanthracene, 9-anthracenemethanol, especially 9,10-dimethoxy-2-ethyl-anthracene and 9,10-diethoxyanthracene.  Other suitable photosensitizers are z. B.  mentioned in WO 9 847 046.  



   The invention therefore also relates to radiation-sensitive compositions as described above, containing in addition to components (a1) or (a2) and (b) at least one sensitizer compound (d), in particular benzophenone, thioxanthone, anthracene or derivatives thereof.  



   It can also electron donor compounds such. B.  Alkyl and aryl-amine donor compounds are used in the composition.  Such compounds are for. B.  4-dimethylaminobenzoic acid, ethyl 4-dimethylaminobenzoate, 3-dimethylaminobenzoic acid, 4-dimethylaminobenzoin, 4-dimethyl-aminobenzaldehyde, 4-dimethylaminobenzonitrile and 1,2,4-trimethoxybenzene.  Such donor compounds are preferably used in a concentration of zero. 01-5%, more preferably in a concentration of 0. 05-0. 50%, based on the formulation used.                                                          



   Further examples of suitable photosensitizers (d) are 1.  thioxanthones



   Thioxanthone, 2-isopropylthioxanthone, 2-chlorothioxanthone, 2-dodecylthioxanthone, 2,4-diethylthioxanthone, 2,4-dimethylthioxanthone, 1-methoxycarbonylthioxanthone, 2-ethoxycarbonylthioxanthone, 3- (2-methoxyethoxycarbonyl) thioxanthone, 4-butoxycarbonylthioxanthone, 3 Butoxycarbonyl-7-methylthioxanthone, 1-chloro-4-propoxythioxanthone, 1-cyano-3-chlorothioxanthone, 1-ethoxycarbonyl-3-chlorothioxanthone, 1-ethoxycarbonyl-3-ethoxythioxanthone, 1-ethoxycarbonyl-3-aminothioxanthone, 1-ethoxycarbonyl 3-phenylsulfurylthioxanthone, 3,4-di- [2- (2-methoxyethoxy) ethoxycarbonyl] thioxanthone, 1-ethoxycarbonyl-3- (1-methyl-1-morpholinoethyl) -thioxanthone, 2-methyl-6-dimethoxymethyl thioxanthone, 2-methyl-6- (1,1-dimethoxybenzyl) -thioxanthone, 2-morpholinomethylthioxanthone, 2-methyl-6-morpholinomethylthioxanthone, N-allylthioxanthhone-3,4-dicarboximide, N-octylthioxanthone-3,4-dicarboximide, N- (1,1,3,

  3-tetramethylbutyl) thioxanthone-3,4-dicarboximide, 1-phenoxythioxanthone, 6-ethoxycarbonyl-2-methoxythioxanthone, 6-ethoxycarbonyl-2-methylthioxanthone, 1,3-dimethyl-2-hydroxy-9H-thioxanthene-9 2-ethylhexyl ether, 2-hydroxy-3- (3,4-dimethyl-9-oxo-9H-thioxanthone-2-yloxy) -N, N-trimethyl-1-propanamine mchlorid; Second  benzophenones



   Benzophenone, 4-phenylbenzophenone, 4-methoxybenzophenone, 4,4'-dimethoxybenzophenone, 4,4'-dimethylbenzophenone, 4,4'-dichlorobenzophenone 4,4'-dimethylaminobenzophenone, 4,4'-diethylaminobenzophenone, 4-methylbenzophenone, 2 , 4,6-trimethylbenzophenone, 4 (4-methylthiophenyl) benzophenone, 3,3'-dimethyl-4-methoxybenzophenone, methyl 2-benzoylbenzoate, 4- (2-hydroxyethylthio) benzophenone, 4- (4-tolylthio) benzophenone, 4-benzoyl-N, N, N-trimethylbenzenemethanaminium chloride, 2-hydroxy-3- (4-benzoylphenoxy) -N, N, N-trimethyl-1-propanaminium chloride monohydrate, 4- (13-acrylol-1,4, 7,10,13-penta-oxatridecyl) -benzophenone, 4-benzoyl-N, N-dimethyl-N- [2- (1-oxo-2-propenyl) oxy] ethyl-benzenemethanaminium chloride; Third  3-Acylkumarine



   3-benzoylcoumarin, 3-benzoyl-7-methoxycoumarin, 3-benzoyl-5,7-di (propoxy) -coumarin, 3-benzoyl-6,8-dichlorocoumarin, 3-benzoyl-6-chloro-coumarin, 3,3 'Carbonylbis [5,7-di (propoxy) coumarin], 3,3'-carbonylbis (7-methoxycoumarin), 3,3'-carbonylbis (7-diethylaminocoumarin), 3 Isobutyroylcoumarin, 3-benzoyl-5,7-dimethoxycoumarin, 3-benzoyl-5,7-diethoxycoumarin, 3-benzoyl-5,7-dibutoxycoumarin, 3-benzoyl-5,7-di (methoxyethoxy) -coumarin, 3-benzoyl-5,7-di (allyloxy) -coumarin, 3-benzoyl-7-dimethylaminocoumarin, 3-benzoyl-7-diethylaminocoumarin, 3-isobutyroyl-7-dimethylaminocoumarin, 5,7-dimethoxy-3 - (1-naphthoyl) -coumarin, 5,7-dimethoxy-3- (1-naphthoyl) -coumarin, 3-benzoylbenzo [f] coumarin, 7-diethylamino-3-thienoylcoumarin, 3- (4-cyanobenzoyl) -5 , 7-dimethoxykumarin; 4th  3- (aroylmethylene) -thiazolines



   3-methyl-2-benzoylmethylene-beta-naphthothiazoline, 3-methyl-2-benzoylmethylene-benzothiazoline, 3-ethyl-2-propionylmethylene-beta-naphthothiazoline; 5th  Other carbonyl compounds



     Acetophenone, 3-methoxyacetophenone, 4-phenylacetophenone, benzil, 2-acetylnaphthalene, 2-naphthaldehyde, 9,10-anthraquinone, 9-fluorenone, dibenzosuberone, xanthone, 2,5-bis (4-diethylaminobenzylidene) cyclopentanone, alpha - (para -dimethylaminobenzylidene) ketones, such as 2- (4-dimethylaminobenzylidene) -indan-1-one or 3- (4-dimethylamino-phenyl) -1-indan-5-yl-propenone, 2-benzoyl-3- (4 -dimethylaminophenyl) -2-propene-nitrile, 3-phenylthiophthalimide, N-methyl-3,5-di (ethylthio) phthalimide, N-methyl-3,5-di (ethylthio) phthalimide.                           



   The sensitizers (d) described above are conventional in the art and accordingly are used in amounts customary in the art, preferably in a concentration of 0. 05-5%, more preferably in a concentration of 0. 1-2%, based on the composition used.                                                           



   The novel compositions may additionally contain other photoinitiators (e), such as. B.  cationic photoinitiators, photoacid generators and radical photoinitiators as co-initiators in amounts of 0. 01 to 15%, preferably from 0. 1 to 5%.  



   Examples of cationic photoinitiators and acid formers are phosphonium salts, diazonium salts, pyridinium salts, sulfonium salts, ferrocenium salts, such as. B.  (eta <6> -isopropylbenzene) (eta <5> -CyclopentadienyI) iron-ll hexafluorophosphate <RTM> Irgacure 261, nitrobenzylsulfonates, alkyl- and aryl-N-sulphonyloxyimides and also other known alkylsulfonic acid esters, haloalkylsulfonic acid esters, 1,2-disulfones, oxime sulfonates, benzoin tosylate, tolylsulfonyloxy-2-hydroxy-2-methyl-1-phenyl-1-propanone and other known beta-ketosulfones, beta-sulfonylsulfones, bis (alkylsulfonyl) diazomethane, bis (4-tert-butyl-phenyl-sulfonyl) diazomethane, benzoyl-tosyl-diazomethane, iminosulfonates and imidosulfonates and trichloromethyl-s-triazines and other haloalkyl-containing compounds and other compounds mentioned below under (b1).



   Examples of free-radical photoinitiators as co-initiators are carbonyl compounds as described in US Pat. No. 4,560,709, 1-benzoylcyclohexanol, 2-benzoyl-2-propanol, oligo [2-hydroxy-2-methyl-1 - [4- (1 -methylvinyl) phenyl] propanone] and 2-hydroxy-1- [3- [4- (2-hydroxy-2-methylpropionyl) phenyl] -1,1,3-trimethyl-indan-5-yl] -2 methyl-propan-1-one.



  The compositions according to the invention can be used for various purposes, for example as printing ink, such as screen printing ink, flexographic printing ink or offset printing ink, as clearcoat material, as colorless ink, as white lacquer, e.g. for wood or metal, as powder coatings, as a paint, u.a. for paper, wood, metal or plastic, as a light-curable architectural and road marking paint, for photographic reproduction, for holographic recording materials, for image recording or for the production of printing plates, which are developable with organic solvents or aqueous-alkaline, for the production of masks for the screen printing, as Zahnfüllmassen, as radiation-curable adhesives, as pressure-sensitive adhesives, as non-stick coatings, as laminating resins, as photoresists, eg

   Galvanoresists, etch or permanent resist, both liquid and dry films, as photostructurable dielectrics, and as solder masks for electronic circuits, as resists for the production of color filters (color filters) for each screen type or for creating structures in the production process of plasma displays and electroluminescence Displays, for the manufacture of optical switches, optical grids (interference gratings), for coating or sealing of electronic parts, eg as electrical insulating compositions or as coatings for optical fibers, for coil coatings, as indicator systems for UV radiation, X-radiation and electron radiation and for the production of three-dimensional objects, e.g. for stereolithography as well as for composites, e.g. for glass or carbon, or

   Graphite fiber reinforced composites. The compositions are further suitable for the preparation of optical lenses, e.g. Contact lenses or Fresnel lenses, as well as for the production of medical devices, aids or implants.



   The photocurable compositions of this invention are useful e.g. as coating materials for substrates of all kinds, e.g. Wood, textiles, paper, ceramics, glass, marble, plastics such as polyester, polyethylene terephthalate, polyolefins or cellulose acetate, especially in the form of films, and metals such as Al, Cu, Ni, Fe, Zn, Mg or Co and GaAs, Si or SiO 2, on which a coating or by imagewise exposure an image or a patterned resist layer is to be applied.



   The coating of the substrates can be carried out by applying a liquid composition, a solution or suspension to the substrate. The choice of solvent and the concentration depend mainly on the type of composition and the coating process. The solvent should be inert, i. it should not undergo a chemical reaction with the components and it should be able to be removed during drying after coating again. Suitable solvents are e.g.

   Ketones, ethers and esters such as methyl ethyl ketone, isobutyl methyl ketone, cyclopentanone, cyclohexanone, 2-heptanone, methyl amyl ketone, N-methyl pyrrolidone, gamma-butyrolactone, dioxane, tetrahydrofuran, 2-methoxyethanol, 2-ethoxyethanol, 1-methoxy-2-propanol, 1 , 2-dimethoxyethane, ethyl acetate, butyl acetate, propylene glycol monomethyl ether acetate, ethyl lactate, propylene carbonate and ethyl 3-ethoxy-propionate.



   After coating the substrates, the solvent is usually removed by drying.



   The formulation is uniformly applied to a substrate by known coating techniques, e.g. by spin coating, dipping, knife coating, curtain coating, brushing, spraying, especially by electrostatic spraying and reverse roll coating, as well as by electrophoretic deposition. It is also possible to place the photosensitive layer on a temporary, flexible support and then transfer the layer by lamination to the final substrate, e.g. a copper-clad circuit board, to coat.



   The quantity applied (layer thickness) and the type of substrate (substrate) depend on the desired application area. The layer thickness range generally comprises values of about 0.1 μm to more than 100 μm, preferably 0.5 μm to 50 μm. In the manufacture of three-dimensional objects, e.g. With stereolithography, the realizable dimensions of the objects are limited only by the size of the exposure device.



   The radiation-sensitive compositions according to the invention find e.g. Use as negative resists, which have a very high photosensitivity and can be developed without swelling in an aqueous-alkaline medium. They are useful as photoresists for electronics, such as galvano resist, etch resist, in both liquid and dry films, solder resist, as resists for making color filters for any type of screen, or for forming structures in the manufacturing process of Plasma displays and electroluminescent displays, for the production of printing plates, such as

   Offset printing plates, for the production of printing plates for high-pressure, planographic, gravure, flexographic or screen printing, the production of relief prints, for example for the production of texts in braille, for the production of stamps, for use in die-cutting or for use as a microresist in the manufacture of integrated circuits. The compositions may also be used as photopatternable dielectrics, for encapsulating materials, or as an insulator coating for the manufacture of computer chips, printed circuits, and other electrical or electronic parts. Accordingly different are the possible layer carriers and the processing conditions of the coated substrates.



   The compounds according to the invention are also used for producing monolayer or multilayer materials for image recording or image multiplication (copying, reprography), which can be monochrome or multicolor. Included are holographic information storage materials, e.g. for holographic images or 3-dimensional holographic data storage. Furthermore, these materials can also be used in color proofing systems. In this technology, formulations containing microcapsules may also be used and, for image formation, a thermal step may follow the exposure step. Such systems and technologies and their application are e.g. in US Pat. No. 5,376,459.



   For photographic information records, e.g. Polyester films, cellulose acetate or plastic coated papers; specially treated aluminum for offset printing plates, copper-clad laminates for the production of printed circuits and silicon wafers for the production of integrated circuits. The layer thicknesses for photographic materials and offset printing forms are generally about 0.5 μm to 10 μm, for printed circuits 1.0 μm to about 100 μm.



   The invention also provides the use of compounds of the formula I as radiation-sensitive acid donors in the production of paints, printing inks, printing plates, dental compositions, stereolithography resins, adhesives, non-stick coatings, color filters, resist materials or image recording materials.



   The invention also relates to a coated substrate which is coated on at least one surface with a composition according to the invention, and to a process for the production of relief images, characterized in that a composition according to the invention is applied to a substrate and subsequently imagewise exposed.



     The term "imagewise" exposure includes both exposure through a mask containing a predetermined pattern, such as a transparency, a metal mask, a chrome mask on a transparent support, exposure by a laser beam, for example, moving computer-controlled over the surface of the coated substrate and thus creates an image, as well as the irradiation with computer-controlled electron beams. Images can also be generated by interference of two beams or images, for example for holographic applications. It is also possible to use masks of liquid crystals which can be driven pixel by pixel to produce digital images, e.g. by A. Bertsch, J.Y. Jezequel, J.C.

   Andre in the Journal of Photochemistry and Photobiology A: Chemistry 1997, 107, p. 275-281 and from K.-P. Nicolay in Offset Printing 1997, 6, p. 34-37.



   As already mentioned, the compounds of the formula I can also be used in particular as acid donors in photoresists. Resist systems can be obtained by imagewise exposure of formulations comprising compounds of the formula I and subsequent development step. The term "photoresists" is not limited to the chemically amplified resists described in more detail below, but encompasses all resist materials in which reactions are initiated by radiation-chemical generation of acid, which leads to a solubility differentiation between exposed and unexposed areas in a development step.

   For example, aqueous processable resists are also included, e.g. in US Pat. No. 5,998,092 and in SPIE, Vol. 3999, pp. 569-578 (2000), as well as resists based on the Pinacol rearrangement, e.g. in SPIE, Vol. 3999, pp. 62-73 (2000).



   According to the invention, therefore, a photoresist containing as radiation-sensitive acid donor a compound of the formula I.



   By chemically amplified photoresist is meant a resist formulation wherein the radiation-sensitive component provides a catalytic amount of acid which, in turn, catalyzes a chemical reaction of at least one acid-sensitive component of the resist. This results in a difference in the solubility of the irradiated and unirradiated parts of the resist. Because of the catalytic nature of this process, an acid molecule can initiate reactions at many sites because it diffuses through the reactive polymer matrix from one reaction site to the next, as long as it is not captured or destroyed by secondary reactions. Therefore, a low acid concentration is already sufficient to achieve large differences in solubility between irradiated and unirradiated parts of the resist.

    Therefore, it is usually sufficient to add only a small amount of latent acid compound. However, it is necessary that the latent acid donors are chemically and thermally stable as long as they are not irradiated. In addition, it is necessary that the latent catalysts be well soluble in the liquid resist formulation as well as the solid resist film to avoid the formation of particles that would adversely affect the use of the resists in microelectronic fabrication processes.



   It will be apparent from the foregoing discussion that chemical and thermal stability of the latent acid donor is indispensable for its use in chemically amplified photoresists.



   The difference in solubility in the resist between exposed and unexposed areas, which is due to the action of the acid catalyzed reaction, depends on the other components in the resist. If the compositions according to the invention contain components which reduce the solubility of the composition in the developer after irradiation u. if necessary, increase thermal aftertreatment, it is a positive-working photoresist.



   The invention therefore also relates to a positive-working photoresist. However, if the components of the composition lower the solubility in the developer after irradiation and optionally thermal aftertreatment, it is a negative working photoresist.



   The invention therefore also relates to a negative-working photoresist. An overview of chemically amplified photoresists can be found, for example, in: H. Ito, IBM Journal of Research and Development, Vol. <1> / 2, page 69 (1997); H. Ito, SPIE Vol. 3678, page 2 (1999); for negative-working resists in: J.M. Shaw et al. IBM Journal of Research and Development, Vol. <1> / 2, page 81 (1997).  



   A monomeric, oligomeric or polymeric compound which, in unexposed portions, lowers the solubility rate of an alkali-soluble binder polymer also present in the resist formulation and which itself is alkali-insoluble in the unexposed portions such that the resist film is in the unexposed portion After developing in alkaline solution, however, which is cleaved in the presence of an acid or capable of being rearranged so that the reaction product becomes soluble in alkaline developer, hereinafter referred to as the solubility inhibitor.  



   The invention also includes a chemically amplified positive alkaline developable photoresist composition comprising (a3) at least one polymer having acid labile groups which decompose in the presence of an acid and increase the solubility of the resist film in an alkaline developing solution in the irradiated areas; and (b) at least one compound of the formula I.  



   Another object of the invention is a chemically amplified positive alkaline developable photoresist composition comprising (a4) at least one monomeric or oligomeric solubility inhibitor having at least one acid labile group which decomposes in the presence of an acid and increases solubility in aqueous alkaline developer solutions, and at least one alkali-soluble polymer, and (b) at least one compound of formula I.  



   Another object of the invention is a chemically amplified positive alkaline developable photoresist composition comprising (a3) at least one polymer having acid labile groups which decompose in the presence of an acid and increase the solubility in aqueous alkaline developing solution in the exposed area; (a4) a monomeric or oligomeric solubility inhibitor having at least one acid labile group which decomposes in the presence of an acid and increases the solubility in aqueous alkaline developing solution in the exposed area; (a5) an alkali-soluble monomeric, oligomeric or polymeric compound in a concentration which keeps the resist film completely insoluble in alkaline developer in unexposed areas, and (b) at least one compound of formula I.  



   The invention also relates to a chemically amplified photoresist composition comprising (a3) at least one polymer having an acid labile group which decomposes in the presence of an acid and increases the solubility in aqueous alkaline developing solution, and / or (a4) at least one monomeric or oligomeric solubility inhibitor an acid labile group which decomposes in the presence of an acid and increases the solubility in aqueous alkaline developing solution, and / or (a5) at least one alkali-soluble monomeric, oligomeric or polymeric compound; and (b) as the photosensitive acid donor, at least one compound of the formula I.  



   The compositions may contain, in addition to component (b), other photosensitive acid donors and / or other additives (c) and / or photosensitizers (d).  Corresponding suitable additives (c) and photosensitizers (d) are described above.  



   Such chemically amplified positive photoresist systems are e.g. B.   in E.  Reichmanis, F.  M.  Houlihan, O.  Nalamasu, T.  X.  Neenan, Chem.   Mater.  1991, 3, 394; or in C.  G.  Willson, "Introduction to Microlithography," 2nd.  Ed. ; L.  S.  Thompson, C.  G.  Willson, M.  J.  Bowden, Eds. , Amer.   Chem.  Soc, Washington DC, 1994, p. p.  139, described.  



   Suitable examples of acid labile groups which decompose in the presence of an acid and form aromatic hydroxyl groups, carboxyl groups, keto groups and aldehyde groups and increase solubility in aqueous alkaline developing solutions are alkoxyalkyl ether groups, benzyl ether groups, tetrahydrofuranyl ether groups, tetrahydropyranyl ether groups, tert. Alkyl ester groups, 2-methyl-2-adamantyl ester groups, 8-ethyl-8-tricyclodecanyl ester groups, trityl ether groups, silyl ether groups, alkyl carbonate groups, such as. B.  tert. Butyloxycarbonyloxy, trityl ester groups, silylester groups, alkoxymethylester groups, cumylester groups, acetal groups, ketal groups, tetrahydropyranylester groups, tetrafuranylester groups, tertiary alkylether groups, tertiary alkylester groups and so on.  



   The polymers having functional groups which decompose under the action of an acid to increase the solubility of the resist film containing this polymer in an alkaline developing solution and which can be added to the compositions of the present invention may include the acid labile groups in the polymer backbone and / or carry the side chains.  The acid-labile groups are preferably located in the side chain of the polymer.  



     Suitable polymers with acid-labile groups can be obtained by polymer-analogous reactions in which alkali-soluble groups are partially or completely converted into the respective acid-labile group.  Also possible is the direct preparation by (co) polymerization of monomers which already contain the acid-labile groups.  Examples of the preparation are published in EP 254 853, EP 878 738, EP 877 293, JP-A-2-25 850, JP-A-3-223 860, and JP-A-4-251 259.  



   Polymers z. B.  Silyl ethers, acetals, ketals, and alkoxyalkyl ester groups (so-called "Iow-activation energy blocking groups") cleave these protecting groups in the presence of acid even at relatively low temperatures upon post-exposure heating (usually between room temperature and 110 ° C) DEG C).  Polymers t the tert-butyl ester groups, adamantyl ester groups or tert. Butyloxycarbonyl groups (TBOC groups) or other ester groups bearing a secondary or tertiary carbon atom adjacent to the oxygen atom of the ester linkage (so-called "high-activation energy blocking groups") typically require heating for complete cleavage of the protecting groups in the presence of acid after exposure. 

   Hybrid systems wherein both high activation energy protecting groups and low activation energy protecting groups are present in the same polymer can also be used.  Furthermore, so-called.  "dual-mode" protecting groups are known which contain an easily cleavable bond, e.g. B.  in an acetal group, and a heavier cleavable bond, e.g. B.  in a tert-butyl ester group, combine such. B.  in "Proceedings of SPIE", Advances in Resist Technology and Processing XVII, Vol.   3999, Part One, pages 579-590, 28.  Feb. -1.  March 2000 described.   In addition, it is also possible to use mixtures of polymers having different protective group chemistry in the photosensitive compositions according to the invention.  



   Preferred polymers having acid labile protecting groups are polymers and copolymers containing the following different monomer types:



   1) monomers containing acid labile groups which decompose in the presence of an acid and increase the solubility in aqueous alkaline developing solution and



   2) monomers free of acid labile groups and free of groups contributing to the solubility in alkaline solution and / or



     3) monomers that contribute to the aqueous-alkaline solubility of the polymer.  



   Examples of monomers of type 1) are those already described above as suitable component (a2).  



   Examples of type 2 comonomers are:



   Aromatic vinyl monomers such as styrene, alpha-methylstyrene, acetoxystyrene, alpha-methylnaphthalene, acenaphthalene, vinyl ethers such as ethyl vinyl ether and 3,4-dihydro-2H-pyran, cyclohexyl vinyl ethers, cycloolefins such as norbornene, 2-hydroxy-5-norbornene, 2- Norbornen-5-yl (2-hydroxyethyl) -carboxylate, vinyl-alicyclic compounds such as vinylnorbornane, vinyladamantane, vinylcyclohexane, alkyl (meth) acrylates such as methyl methacrylate, acrylonitrile, vinylcyclohexane, vinylcyclohexanol and maleic anhydride.  



   Examples of comonomers of type 3) are:



   Vinyl aromatic compounds such as hydroxystyrene, acrylic acid compounds such as methacrylic acid, ethylcarbonyloxystyrene and derivatives thereof, and cycloolefinic acids such as 5-norbornene-2-carboxylic acid.  Such polymers are for. B.  in US 5,827,634, US 5,625,020, US 5,492,793, US 5,372,912, EP 660,187, US 5,679,495, EP 813 113 and EP 831,369.   Further examples are crotonic acid, isocrotonic acid, 3-butenoic acid, acrylic acid, 4-pentenoic acid, propionic acid, 2-butyric acid, maleic acid, fumaric acid, and acetylenecarboxylic acid.  However, the polymers useful in the composition of the present invention are not limited to the above examples.  



   The content of acid-labile monomers in the polymer can vary widely and depends on the content of the other comonomers and the alkali solubility of the protected polymer.  In general, the content of monomer having acid-labile groups in the polymer is between 5 and 60 mol%.  



   Preferably, the copolymers having acid labile groups have an M w of from about 3,000 to about 200,000, more preferably from about 5,000 to about 50,000, having a molecular weight distribution of about 3 or less, more preferably about 2 or less.  Non-phenolic monomers, e.g. B.  a copolymer of alkyl acrylate such as. B.  t-butyl acrylate or t-butyl methacrylate and an alicyclic vinyl compound such as a vinylnorbonanyl or vinylcyclohexanol compound may be obtained by free-radical polymerization or other known processes and may conveniently have an M w of from about 8,000 to about 50,000. and a molecular weight distribution of about 3 or less.  Other comonomers may conveniently be added in a suitable amount, for example, the glass transition temperature o. Ä.  to control.  



   In the present invention, mixtures of two or more polymers having acid labile groups may also be used.  For example, a mixture of polymers having acid labile groups which are very readily cleavable, such as acetal groups or tetrahydropyranyloxy groups, and a polymer having acid labile groups which are less likely to cleave, such as e.g. B.  tertiary alkyl ester groups are used.  In addition, acid labile groups of different sizes can be prepared by mixing two or more polymers with different acid labile groups, such as e.g. B.  a tert-butyl ester group and 2-methyl-adamantyl group or a 1-ethoxy-ethoxy group and a tetrahydropyranyloxy group can be used.  A mixture of non-crosslinked resin and crosslinked resin can also be used. 

   The proportion of these polymers is according to the invention preferably from about 30 to 99% by weight, in particular from 50 to 98% by weight, based on the solids content.  An alkali-soluble resin or an alkali-soluble monomeric or oligomeric compound without acid-labile groups may also be incorporated in the composition, e.g. B.  to control the alkali solubility.   Examples of polymer blends with different acid-labile groups are, for. B.  EP 780 732, EP 679 951 and US Pat. No. 5,817,444.                                                         



   Preferably, monomeric and oligomeric solubility inhibitors (a4) are used in the composition according to the invention.  



   Suitable monomeric or oligomeric solubility inhibitors (a4) in the composition according to the invention are compounds having at least one acid-labile group which cleaves in the presence of acid and increases the solubility in aqueous alkaline developer solution.  Examples are alkoxymethyl ether groups, tetrahydrofuranyl ether groups, tetrahydropyranyl ether groups, alkoxyethyl ether groups, trityl ether groups, silyl ether groups, alkyl carbonate groups, trityl ester groups, silyl ester groups, alkoxymethyl ester groups, vinyl carbamate groups, tertiary alkyl carbamate groups, tritylamino groups, cumylester groups, acetal groups, ketal groups, tetrahydropyranylester groups, tetrafuranylester groups, tertiary alkyl ether groups, tertiary alkylester groups, and so on. 

   The molecular weight of the acid-cleavable solubility inhibitors useful in the present invention is about 3,000 or lower, more preferably from about 100 to 3,000, preferably from about 200 to 2,500.  



   Examples of monomeric and oligomeric solubility inhibitors with acid-labile groups are described, for example, as compounds of the formulas (I) to (XVI) in EP 0 831 369.  Other suitable examples of such compounds are described in US 5,356,752, US 5,037,721, US 5,015,554, JP-A-1-289,946, JP-A-1-289,947, JP-A-2-2,560, JP-A-3-128959, JP-A-3-158855, JP-A-3-179353, JP-A-3-191351, JP-A-3--200251, JP-A-3 -200,252, JP-A-3-200,253, JP-A-3-200,254, JP-A-3-200,255, JP-A-3-259149, JA-3-279958, JP-A -3-279,959, JP-A-4-1,650, JP-A-4-1,651, JP-A-11,260, JP-A-4-12356, JP-A-4-123,567, JP -A-1-289 946, JP-A-3-128959, JP-A-3-158855, JP-A-3-179353, JP-A-3-191351, JP-A-3- 200,251, JP-A-3-200,252, JP-A-3-200,253, JP-A-3-200,254, JP-A-3-200,255, JP-A-3-259149, JA- 3-279 958, JP-A-3-279959, JP-A-4-1 650, JP-A-4-1 651, JP-A-11 260, JP-A-4-12356,

   JP-A-4-12357 and Japanese Patent Application Nos.  3-33 229, 3-230 790, 3-320 438, 4-254 157, 4-52 732, 4-103 215, 4-104 542, 4-107 885, 4-107 889, 4-152 195, 4-254 157, 4-103 215, 4-104 542, 4-107 885, 4-107 889, and 4-152 195.  For resists in the short-wave UV range z. B.   in particular compounds such as tert. Butylcholate, t-butyl-deoxycheolate and tert. Butylcholate glutarate dimer suitable (see, for. B.  SPIE Vol.   3999, p.  127 (2000).  



   The composition of the invention may also contain polymeric solubility inhibitors, e.g. B.  Polyacetals as described in US Pat. No. 5,354,643, or poly-N, O-acetals such as those described in US Pat. No. 5,498,506, both in combination with an alkali-soluble polymer and in combination with a polymer having acid-labile groups which have the solubility of the resist film in the developer after exposure, or in a combination of both types of polymers described.                                                              



   In the compositions according to the invention, the content of the solubility inhibitor is from about 3 to 55% by weight, in particular from about 5 to 45% by weight, preferably from 10 to 35% by weight, based on the solids content, if solubility inhibitors having acid-labile groups are used in combination with alkali-soluble polymers and / or polymers with acid-labile groups are used.  



   Preference is given to using polymers (a5) which are soluble in aqueous alkaline solution in the compositions according to the invention.  Examples include novolak resins, hydro genated novolak resins, acetone pyrogallol resins, poly (o-hydroxystyrene), poly (m-hydroxystyrene), poly (p-hydroxystyrene), hydrogenated poly (hydroxystyrene) s, halo or alkyl substituted poly ( hydroxystyrene), hydroxystyrene / N-substituted maleimide copolymers, o / p and m / p-hydroxystyrene copolymers, partially o-alkylated poly (hydroxystyrene) s, [e.g. B. , o-methylated, o- (1-methoxy) ethylated, o- (1-thoxy) -ethylated, o-2-tetrahydropyranylated, and o- (t-butoxycarbonyl) methylated poly (hydroxystyrene) s having a substitution content of about 5 to 30 mol% of hydroxyl groups], o-acylated poly (hydroxystyrene) e [e.g. B. 

   o-acetylated and o- (t-butoxy) carbonylated poly (hydroxystyrene) s with a substitution content of about 5 to 30 mol% of hydroxyl groups], styrene / maleic anhydride copolymers, styrene / hydroxystyrene copolymers, alpha-methylstyrene / hydroxystyrene copolymers, carboxylated methacrylic resins , and derivatives thereof.  Also suitable are poly (meth) acrylic acid [e.g. B.  Poly (acrylic acid)], (meth) acrylic acid / (meth) acrylate copolymers [e.g. B.  Acrylic acid / methyl acrylate copolymers, methacrylic acid / methyl methacrylate copolymers or methacrylic acid / methyl methacrylate / t-butyl methacrylate copolymers], (meth) acrylic acid / alkene copolymers [e.g. B.  Acrylic acid / ethylene copolymers], (meth) acrylic acid / (meth) acrylamide copolymers [e.g. B.  Acrylic acid / acrylamide copolymers], (meth) acrylic acid / vinyl chloride copolymers [e.g. B.  Acrylic acid / vinyl chloride copolymers], (meth) acrylic acid / vinyl acetate copolymers [e.g. B. 

   Acrylic acid / vinyl acetate copolymers], maleic acid / vinyl ether copolymers [e.g. B.  Maleic acid / methyl vinyl ether copolymers], maleic acid monoester / methyl vinyl ester copolymers [e.g. B.   Maleic acid monomethyl ester / methyl vinyl ether copolymers], maleic acid / (meth) acrylic acid copolymers [e.g. B.  Maleic acid / acrylic acid copolymers or maleic acid / methacrylic acid copolymers], maleic acid / (meth) acrylate copolymers [e.g. B.  Maleic acid / methyl acrylate copolymers], maleic acid / vinyl chloride copolymers, maleic acid / vinyl acetate copolymers and maleic / alkene copolymers [e.g. B.  Maleic acid / ethylene copolymers and maleic acid / 1-chloropropene copolymers].  However, the polymers suitable for the compositions according to the invention are by no means limited to the examples given above.  



   Particularly preferred as alkali-soluble polymers (a5) are novolak resins, poly (m-hydroxystyrene), poly (p-hydroxystyrene), copolymers of the corresponding hydroxystyrene monomers, for example with p-vinylcyclohexanol, alkyl-substituted poly (hydroxystyrene) s, partially o- or m-alkylated and o- or m-acylated poly (hydroxystyrene) s, styrene / hydroxystyrene copolymer, and alpha-methylstyrene / hydroxystyrene copolymers.  The novolak compounds are obtainable, for example, by addition-condensation reactions of one or more monomers as main constituents with one or more aldehydes in the presence of an acid catalyst.  



     Examples of suitable monomers for the preparation of alkali-soluble resins are hydroxylated aromatic compounds such as phenol, cresols, that is m-cresol, p-cresol, and o-cresol, dimethylphenols (xylenols), e.g. B.  2,5-dimethylphenol, 3,5-dimethylphenol, 3,4-dimethylphenol, and 2,3-dimethylphenol, alkoxyphenols, e.g. B.  p-methoxyphenol, m-methoxyphenol, 3,5-dimethoxyphenol, 2-methoxy-4-methylphenol, m-ethoxyphenol, p-ethoxyphenol, m-propoxyphenol, p-propoxyphenol, m-butoxyphenol, and p-butoxyphenol, dialkylphenols, e.g. , B.  2-methyl-4-isopropylphenol, and other hydroxylated aromatics including m-chlorophenol, p-chlorophenol, o-chlorophenol, dihydroxybiphenyl, bisphenol-A, phenylphenol, resorcinol, and naphthol.   These compounds can be used both alone and in mixtures of two or more. 

   The novolak resin monomers are not limited to the above examples.  



   Suitable examples of aldehydes for polycondensation with phenolic compounds in the preparation of novolaks are formaldehyde, p-formaldehyde, acetaldehyde, propionaldehyde, benzaldehyde, phenylacetaldehyde, alpha-phenylpropionaldehyde, beta-phenylpropionaldehyde, o-hydroxybenzaldehyde, m-hydroxybenzaldehyde, p-hydroxybenzaldehyde, o Chlorobenzaldehyde, m-chlorobenzaldehyde, p-chlorobenzaldehyde, o-nitrobenzaldehyde, m-nitrobenzaldehyde, o-methylbenzaldehyde, m-methylbenzaldehyde, p-methylbenzaldehyde, p-ethylbenzaldehyde, pn-butylbenzaldehyde, furfural, chloroacetaldehyde, and acetals derived therefrom, such as chloroacetaldehyde diethyl acetal.  Preferred is formaldehyde.                                                          



   These aldehydes may be used alone or in combination of two or more.  Examples of suitable acid catalysts are hydrochloric acid, sulfuric acid, formic acid, acetic acid and oxalic acid.                                                               



   The average molecular weight of the novolaks thus obtained is suitably in the range of about 1,000 to 30,000, preferably about 2,000 to 20,000.  The poly (hydroxystyrene) s, as well as derivatives and copolymers thereof, as described above as alkali-soluble polymers - except novolak resins - have expediently average molecular weights of about 2000 or higher, in particular from 4000 to 200,000, preferably from 5000 to 50,000.  When a polymer film having improved heat resistance is to be produced, the average molecular weight is preferably at least 5,000 or more.  



   In the context of the present invention, the average molecular weight is to be understood as meaning the molecular weight determined by gel permeation chromatography (calibrated with polystyrene standard).                                                           



     In the compositions according to the invention, the alkali-soluble polymers can be used in mixtures of two or more.  



   Suitably, the proportion of the alkali-soluble polymer is up to 80% by weight, in particular up to 60% by weight, preferably up to 40% by weight, based on the solids content of the formulation (i.e. H.  Solvent excluded) when a mixture of alkali-soluble polymer and a polymer containing groups which decompose under the action of an acid to increase the solubility in an alkaline developing solution is used.  



   When an alkali-soluble polymer is used together with a solubility inhibitor, without a polymer having acid-decomposing groups under the action of an acid, the proportion of the alklilöslichem polymer is suitably from 40 to 90% by weight, especially from 50 to 85% by weight, preferably from 60 to 80% by weight.  



   The proportion of compounds of the formula I (component (b)) in the positive resist formulation is advantageously between about 0. 01 to 20% by weight, based on the content of solids in the photoresist.  



   The use of the iodonium salts of formula I in chemically amplified systems based on the principle of releasing protective groups from a polymer normally forms a positive resist.   Positive resists are preferred over negative resists in many applications, especially for their better resolution.  However, there is also an interest in producing negative images using the positive resist mechanism to combine the advantages of good resolution of the positive resist with the properties of a negative resist.  This happens z. B.  by introducing a so-called image reversal step (image-reversal step) such. B.  in EP 361 906.  For this purpose, the imagewise exposed resist material before developing z. B.  treated with a gaseous base, wherein the acid formed is imagewise neutralized. 

   Thereafter, the entire resist is exposed and thermally treated, and the negative image is developed in a conventional manner.  Acid-sensitive components which form negative resists are typically compounds capable of undergoing a crosslinking reaction with themselves and / or one or more other components in the composition when catalyzed by acid (e.g. B.  the acid which is formed by exposure of the compounds of the formula I according to the invention).  Compounds of this type are, for example, the known acid-curable resins such. B.  Acrylate, polyester, alkyd, melamine, urea, epoxy and phenolic resins or mixtures thereof.  Amino resins, phenolic resins and epoxy resins are particularly suitable. 

   Acid-curable resins of this type are well known and are described, for example, in "Ullmann's Encyclopadie der technischen Chemie", Edition 4, Vol. 15 (1978), p.  613-628.  The crosslinker components should expediently be present in a concentration of about 2 to 40, preferably from 5 to 30,% by weight, based on the solids content of the negative-resist formulation.  



   The invention therefore also includes a chemically amplified negative alkaline developable photoresist comprising (a6) an alkali-soluble resin as the crosslinker component (a7) a component that undergoes a crosslinking reaction with itself and / or the crosslinker component under the action of acid, and (b) as photosensitive acid donor a compound of formula I, a.  



   The composition may contain, in addition to component (b), further photosensitive acid donors and / or further additives (c) and photosensitizers (d).  Suitable components (c) and (d) are described above.  



   Suitable components (a7) are the compounds given above in the description of component (a1).  



   Particularly preferred acid-curable resins (a7) Amino resins, such as unetherified or etherified melamine, urea, guanidine or biuret resins, in particular methylated melamine resins or butylated melamine resins, corresponding glycolurils (tetrahydroimidazo [4,5-d] -imidazole-2, 5- (1H, 3H) -diones) and urons.  By "resin" in this context is meant both conventional technical mixtures, which as a rule also contain oligomers, as well as pure and high-purity compounds.  N-hexa (methoxymethyl) melamine and tetramethoxymethylglucoril and N, N'-dimethoxymethyluron are the preferred acid-curable resins.  



   The concentration of the compound of the formula I in the negative resist is expediently about 0. 1 to 30, in particular up to 20, preferably from 1 to 15% by weight, based on the total solids content of the compositions.  



     The negative-resist compositions may optionally contain a film-forming polymeric crosslinker (binder) (a6).  This is preferably an alkali-soluble phenolic resin.  For example, aldehyde-derived novolaks, e.g. B.  Acetaldehyde or furfuraldehyde, in particular of formaldehyde, and a phenol, z. B.  unsubstituted phenol, mono- or di-chloro-substituted phenol, such as p-chlorophenol, with C 1 -C 9 alkyl mono- or di-substituted phenol, such as o-, m- or p-cresol, the various xylenols, p-tert Butylphenol, p-nonylphenol, p-phenylphenol, resorcinol, bis (4-hydroxyphenyl) methane or 2,2-bis (4-hydroxyphenyl) propane.   Also suitable are homo- and co-polymers based on ethylenically unsaturated phenols, eg. B. 

   Homopolymers of vinyl- and 1-propenyl-substituted phenols, such as p-vinylphenol or p- (1-propenyl) phenol, or copolymers of these phenols with one or more ethylenically unsaturated compounds, e.g. B.  Styrenes.  The proportion of crosslinking agents generally ranges from about 30 to 95, especially from 40 to 80% by weight.  



   A particularly preferred negative resist formulation contains from 0. From 5 to 15% by weight of a compound of the formula I (component (b)), from 40 to 99% by weight of a phenolic resin as crosslinker (component (a6)), and from 0. 5 to 30% by weight of a melamine resin (component (a7)), the percentages being based on the total solids content of the formulation.  



   Compounds of formula I can also be used as acid donors, which can be activated photochemically, for the crosslinking of z. B.  Poly (glycidyl) methacrylates are used in negative resist systems.  Such crosslinking reactions are described, for example, by Chae et al.  in Pollimo 1993, 17 (3), 292.                                                       



   The positive and negative photoresist formulations may contain, in addition to component (b), other photosensitive acid donors (b1), other additives (c), sensitizers (d) and / or other photoinitiators (e).  



   The invention therefore also provides chemically amplified resist compositions as described above, which in addition to the components (a1) or (a2) and (b), or the components (a3), (a4), (a5) and (b), or the components (a6), (a7) and (b), further additives (c), further photosensitive acid donors (b1), other photoinitiators (e), and / or sensitizers (d).  



     The compounds of the formula I can be used in the novel compositions in combination with other known photolatent acid donors (b1), such as. B.  other onium salts, 6-nitrobenzylsulfonates, bis-sulfonyldiazomethane compounds, oxime sulfonates, etc.  be used.  Examples of known photolatent acids for chemically amplified photoresists are, for. B.  US 5,731,364, US 5,800,964, EP 704,762, US 5,468,589, US 5 558 971, US 5 558 976 and more particularly EP 794 457 and EP 795 786.  When mixtures of compounds of formula I (b) with other photolatent acids (b1) are used, the ratio of (b) to (b1) is e.g. B.  from 1:99 to 99: 1.  



   Examples of suitable photolatent acids (b1) are



   (1) onium salt compounds, e.g. B further iodonium salts, sulfonium salts, phosphonium salts, diazonium salts, pyridinium salts.  Preference is given to diphenyliodonium triflate, diphenyliodonium pyrenesulfonate, diphenyliodonium dodecylphenylsulfonate, triphenylsulfonium triflate, triphenylsulfonium hexafluoroantimonate, diphenyliodonium hexafluoroantimonate, triphenylsulfonium naphthalene sulfonate, (hydroxyphenyl) benzylmethylsulfonium toluenesulfonate, etc.  



   (2) halogen-containing compounds haloalkyl group-containing heterocyclic compounds, haloalkyl group-containing hydrocarbon compounds, etc.  Preferred are (trichloromethyl) -s-triazine derivatives such as phenyl-bis (trichloromethyl) -s-triazine, methoxyphenyl-bis (trichloromethyl) -s-triazine, naphthyl-bis (trichloromethyl) -s-triazine, etc. ; 1. 1-bis (4-chlorophenyl) -2,2,2-trichloroethane, etc. ;



   (3) sulfone compounds, e.g. B.  beta-ketosulfones, b-sulfonylsulfones and their a-diazo derivatives, etc.  Phenacylphenylsulfone, mesitylphenacylsulfone, bis (phenylsulfonyl) methane, bis (phenylsulfonyl) diazomethane are preferred.                                               



   (4) sulfonate compounds, e.g. B.  Alkylsulfonic acid esters, haloalkylsulfonic acid esters, aarylsulfonic acid esters, iminosulfonates, imidosulfonates, etc.  Preferred are imidosulfonates, z. B.  N- (trifluoromethylsulfonyloxy) succinimide, N- (trifluoromethylsulfonyloxy) phthalimide, N- (trifluoromethylsulfonyloxy) naphthylimide, N- (trifluoromethylsulfonyloxy) diphenylmaleimide, N- (trifluoromethylsulfonyloxy) -bicyclo [2,2, -1] -hept-5-ene 2,3-dicarboximide, N- (trifluoromethyl-sulfonyloxy) -7-oxabicyclo [2,2,1] -hept-5-ene-2,3-dicarboximide, N- (trifluoromethylsulfonyloxy) -7-oxabicyclo [2 , 2,1] -hept-5-ene-2,3-dicarboximide, N- (trifluoromethylsulfonyloxy) -bicyclo [2,2,1] -heptane-5,6-oxy-2,3-dicarboximide, N- (Camphanylsulfonyloxy) succinimide, N- (camphanylsulfonyloxy) phthalimide, N- (camphanylsulfonyloxy) naphthylimide, N- (camphanylsulfonyloxy) diphenylmaleimide, N- (camphanylsulfonyloxy) bicyclo [2.2.1] hept-5-ene-2 .

  3-dicarboximide, N- (camphanylsulfonyloxy) -7-oxabicyclo [2,2,1] -hept-5-ene-2,3-dicarboximide, N- (camphanylsulfonyloxy) -7-oxabicyclo [2.2.1 ] hept-5-ene-2,3-dicarboximide, N- (camphanylsulfonyloxy) -bicyclo [2.2.1] heptane-5,6-oxy-2,3-dicarboximide, N- (4-methylphenylsulfonyloxy) succinimide, N- (4-methylphenylsulfonyloxy) phthalimide, N- (4-methylphenylsulfonyloxy) naphthylimide, N- (4-methylphenylsulfonyloxy) naphthylimide, N- (4-methylphenylsulfonyloxy) diphenylmaleimide, N- (4-methylphenylsulfonyloxy) -bicyclo [2 , 2,1] -hept-5-ene-2,3-dicarboximide, N- (4-methylphenylsulfonyloxy) -7-oxabicyclo [2,2,1] -hept-5-ene-2,3-dicarboximide, N- (4-methylphenylsulfonyloxy) -bicyclo [2.2.1] heptane-5,6-oxy-2,3-dicarboximide, N- (2-trifluoro-omethylphenylsulfonyloxy) succinimide, N- (2-trifluoromethylphenylsulfonyloxy) naphthylimide, N- (2-trifluoro-omethylphenylsulfonyloxy) diphenylmaleimide, N- (2-trifluoromethylphenyl-sulfonyloxy)

  -bicyclo [2,2,1] -hept-5-ene-2,3-dicarboximide, N- (2-trifluoromethylphenylsulfonyl-oxy) -7-oxabicyclo [2,2,1] -hept-5-ene 2,3-dicarboximide, N- (2-trifluoromethylphenylsulfonyl-oxy) -bicyclo [2,2,1] -heptane-5,6-oxy-2,3-dicarboximide, etc.  



   Other suitable sulfonate compounds are, for. B. , Benzoin tosylate, pyrogallol tristriflate, pyrogallolmethanesulfonic acid triester, nitorobenzyl 9,10-diethyoxyanthracyl-2-sulfonate, alpha - (4-toluenesulfonyloxyimino) benzyl cyanide, alpha - (4-toluenesulfonyloxyimino) -4-methoxybenzyl cyanide, alpha - (4- Toluene-sulfonyioxyimino) -2-thienylmethylcyanide, alpha - (methylsulfonyloxyimino) -1-cyclohexenylacetonitrile, alpha - (butylsulfonyloxyimino) -1-cyclopentenylacetonitrile, (4-methylsulfonyloxyimino-cyclohexa-2,5-dienylidene) -phenyl-acetonitrile, ( 5-methylsulfonyloxyimino-5H-thiophen-2-ylidene) -phenyl-acetonitrile, (5-methylsulfonyloxyimino-5H-thiophen-2-ylidene) - (2-methylphenyl) -acetonitrile, (5-methylsulfonyloxyimino-5H-thiophene-2 ylidene) - (2-chlorophenyl) -acetonitrile, etc. 

   Sulfonate compounds such as pyrogallolmethanesulfonic acid triester, N- (trifluoromethylsulfonyloxy) bicyclo- [2,2,1] -hept-5-ene-2,3-di-carboximide, N- (camphanylsulfonyloxy) naphthylimide, N- (2- Trifluoromethylphenylsulfonyloxy) phthalimide, N- (trifluoromethylsulfonyloxy) -bicyclo [2,2,1] -hept-5-ene-2,3-dicarboximide, N- (camphanylsulfonyloxy) naphthylimide, N- (2-trifluoromethylphenylsulfonyloxy) phthalimide, etc.  especially preferred.  



   (5) Quinone diazide compounds, e.g. B.  1,2-quinone diazide sulfonic acid ester compounds of polyhydroxy compounds.  Preferred are compounds having a 1,2-quinone diazide sulfonyl group, e.g. B.  a 1,2-benzoquinonediazide-4-sulfonyl group, a 1,2-naphthoquinonediazide-4-sulfonyl group, a 1,2-naphthoquinonediazide-5-sulfonyl group, a 1,2-naphthoquinonediazide-6-sulfonyl group, etc.  Particularly preferred are compounds having a 1,2-naphthoquinonediazide-4-sulfonyl group or a 1,2-naphthoquinonediazide-5-sulfonyl group. 

   Particularly suitable are 1,2-quinone diazide sulfonic acid esters of (poly) hydroxyphenylaryl ketones such as 2,3,4-trihydroxybenzophenone, 2,4,6-trihydroxybenzophenone, 2,3,4,4'-tetrahydroxybenzophenone, 2,2 ', 3,4- Tetrahydroxybenzophenone, 2,3,4,4'-tetrahydroxybenzophenone, 2,2 ', 4,4'-tetrahydroxybenzophenone, 2,2', 3,4,4'-pentahydroxybenzophenone, 2,2'3,2,6'- Pentahydroxybenzophenone, 2,3,3 ', 4,4'5'-hexahydroxybenzophenone, 2,3', 4,4 ', 5'6-hexahydroxybenzophenone, etc. ; 1,2-Quinone diazide sulfonic acid esters of bis [(poly) hydroxyphenyl] alkanes such as bis (4-hydroxyphenyl) ethane, bis (2,4-dihydroxyphenyl) ethane, 2,2-bis (4-hydroxyphenyl) propane, 2 , 2-bis (2,4-dihydroxyphenyl) -propane, 2,2-bis (2,3,4-trihydroxyphenyl) propane, etc. ;

   1,2-quinone diazide sulfonic acid esters of (poly) hydroxyphenylalkanes such as 4,4'-dihydroxytriphenylmethane, 4,4'4 "-trihydroxytriphenylmethane, 4,4'5,5'-tetramethyl-2,2'2" -trihydroxytriphenylmethane, 2 , 2,5,5'-tetramethyl-4,4 ', 4 "-trihydroxytriphenylmethane, 1,1,1-tris (4-hydroxyphenyl) ethane, 1,1-bis (4-hydroxyphenyl) -1-phenylethane, 1,1-bis (4-hydroxyphenyl) -1- (4- [1- (hydroxyphenyl) -1-methylethyl] phenyl) ethane, etc. ; 1,2-quinone diazide sulfonic acid esters of (poly) hydroxyphenylflavans such as 2,4,4-trimethyl-2 ', 4', 7-trihydroxy-2-phenylflavan, 2,4,4-trimethyl-2 ', 4', 5 ', 6,7-pentahydroxy-2-phenylflavan, etc.   Suitable further additives (c) are as described above.   



   Further examples of basic organic compounds which can be used in the resist compositions of the present invention are compounds which are stronger bases than phenol, especially nitrogenous bases.  These compounds may be ionic, such as tetraalkylammonium salts, or nonionic.  Preference is given to nitrogen-containing bases which have two or more nitrogen atoms in different chemical environments per molecule.  Particularly preferred are compounds containing both at least one substituted or unsubstituted amino group and at least one nitrogen-containing ring structure, as well as compounds having at least one alkylamino group. 

    Examples are guanidine, aminopyridine, aminoalkylpyridines, aminopyrrolidine, indazole, imidazole, pyrazole, pyrazine, pyrimidine, purine, imidazoline, pyrazoline, piperazine, aminomorpholine and aminoalkylmorpholines.  Suitable are both the unsubstituted and the substituted derivatives thereof.  Preferred substituents are amino, aminoalkyl, alkylamino, aminoaryl, arylamino, alkyl, alkoxy, acyl, acyloxy, aryl, aryloxy, nitro, hydroxy and cyano. 

   Specific examples of particularly preferred basic compounds are guanidine, 1,1-dimethylguanidine, 1,1,3,3-tetramethylguanidine, 2-aminopyridine, 3-aminopyridine, 4-aminopyridine, 2-dimethylaminopyridine, 4-dimethylaminopyridine, 2-diethylaminopyridine, 2- (Aminomethyl) pyridine, 2-amino-3-methylpyridine, 2-amino-4-methylpyridine, 2-amino-5-methylpyridine, 2-amino-6-methylpyridine, 3-aminoethylpyridine, 4-aminoethylpyridine, 3-aminopyrrolidine , Piperazine, N- (2-aminoethyl) piperazine, N- (2-aminoethyl) piperidine, 4-amino-2,2,6,6-tetramethylpiperidine, 4-piperidinopiperidine, 2-iminopiperidine, 1- (2-aminoethyl) pyrrolidine, pyrazole, 3-amino-5-methylpyrazole, 5-amino-3-methyl-1-p-tolylpyrazole, pyrazine, 2- (aminomethyl) -5-methylpyrazine, pyrimidine, 2,4-diaminopyrimidine, 4,6- Dihydroxypyrimidine, 2-pyrazoline, 3-pyrazoline, N-aminomorpholine and N- (2-aminoethyl) morpholine.  



   Other examples are DE 4 408 318, US 5 609 989, US 5 556 734, EP 762 207, DE 4 306 069, EP 611 998, EP 813 113, EP 611 998 and US Pat. No. 5,498,506.  However, the basic compounds suitable for the compositions of this invention are not limited to those described above.  



   The nitrogen-containing basic compounds may be used alone or in combination of two or more.  The proportion of these compounds is usually about 0. 001 to 10, in particular from 0. 01 to 5 parts by weight, per 100 parts by weight of the photosensitive composition according to the invention (without the solvent).  The composition may also contain an organic basic compound which decomposes under the action of actinic radiation ("suicide base") as described for example in EP 710 885, US 5 663 035, US 5 595 855, US 5 525 453, and EP 611 998 described.  



   Suitable examples of dyes (c) are the above-mentioned as well as oil-soluble dyes and basic dyes, for. B.  Oil Yellow # 101, Oil Yellow # 103, Oil Pink # 312, Oil Green BG, Oil Blue BOS, Oil Blue # 603, Oil Black BY, Oil Black BS, Oil Black T-505 (all from Orient Chemical Industries Ltd.). , Japan), Crystal Violet (CI42555), Methyl Violet (Cl 42535), Rhodamine B (Cl 45170B), Malachite Green (Cl 42000), and Methylene Blue (CI52015).  



   Examples of sensitizers (d) are as described above and e.g. B.  p, p'-tetramethyldiaminobenzophenone, p, p'-tetraethylethylaminobenzophenone, anthrone, pyrene, perylene, phenothiazine, benzil, acridine orange, benzoflavin, cetoflavin T, 9,10-diphenylanthracene, 9-fluorenone, phenanthrene, acetophenone, 2-nitrofluorene, 5 Nitroacenaphthene, benzoquinone, 2-chloro-4-nitroaniline, N-acetyl-p-nitroaniline, p-nitroaniline, N-acetyl-4-nitro-1-naphthylamine, picramide, anthraquinones, 2-ethylanthraquinone, 2-tert-butylanthraquinone , 1,2-benzanthraquinone, 3-methyl-1,3-diaza-1,9-benzanthrone, dibenzalacetone, 1,2-naphthoquinone, 3-acylcoumarin derivatives, 3,3'-carbonyl-bis (5, 7-dimethoxycarbonylcoumarin), 3- (aroylmethylene) thiazolines, eosin, rhodamine, erythrosine and coronene.   However, suitable sensitizers are not limited to these examples.  



   These sensitizers can also be used as light absorbers to absorb certain UV rays emitted by light sources.  In this case, the light absorber reduces the light reflection from the substrate and lowers the influence of multiple reflection within the resist film.  This lowers the effect of standing waves.  



   Further suitable additives (c) are acid amplifiers, compounds which accelerate acid formation or increase the acid concentration.  These compounds can be used both in the resist compositions according to the invention, but also in other applications for the novel compositions, such as in coatings of advantage.  Examples of such compounds are from Arimitsu, K.  et al.  in J.  Photopolym.  Sci.  Technol.  1995, 8, p.  43 ff. ; by Kudo, K.  et al.  in J.  Photopolym.  Sci.  Technol.  1995, 8, p.  45 ff. ; from W.  Huang et al.  in SPIE Vol.  3999, p.  591-597 (2000) and by Ichimura, K.  et al.  in Chem: Letters 1995, p.  551 ff. , described.                                                             



   Normally, the compositions according to the invention are dissolved in a suitable solvent before application to the substrate.   Examples of such solvents are ethylene dichloride, cyclohexanone, cyclopentanone, 2-heptanone, gamma-butyrolactone, methyl ethyl ketone, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, 2-methoxyethyl acetate, 2-ethoxyethyl acetate, 2-ethoxyethanol, diethyl glycol dimethyl ether, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, toluene, ethyl acetate, methyl lactate Ethyl lactate, methyl methoxypropionate, ethylethoxypropionate, methyl pyruvate, ethyl pyruvate, propylpyruvate, N, N-dimethylformamide, dimethylsulfoxide, N-methylpyrrolidone and tetrahydrofuran.  These solvents can be used singly or in combinations. 

   Preferred examples are esters such as 2-methoxyethyl acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, methyl methoxypropionate, ethylethoxypropionate and ethyl lactate.  



   A surfactant may be added to the solvent.  Examples of suitable agents are nonionic surfactants such as polyoxyethylene alkyl ethers, e.g. B.  Polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene acetyl ether and polyoxyethylene oleyl ether; Polyoxyethylene alkylaryl ethers, e.g. B.  Polyoxyethylene octylphenol ethers and polyoxyethylene nonylphenol ethers; Polyoxyethylene / polyoxypropylene block copolymers, sorbitol / fatty acid esters, e.g. B.  Sorbitol monolaurate, sorbitol monopalmitate, sorbitol monostearate, sorbitol monooleate, sorbitol trioleate; Fluorochemical surfactants such as F-top EF301, EF303, and EF352 (ex. New Akita Chemical Company, Japan). 

   Megafac F171 and F17. 3 (from Dainippon Ink & Chemicals, Inc.) , Japan), Fluorad FC 430 and FC 431 (from Sumitomo #M Ltd.). , Japan), Asahi Guard AG710 and Surflon S-382, SC101, SC102, SC103, SC104, SC105, and SC106 (from Asahi Grass Col, Ltd.). , Japan); Organosiloxane Polymer KP341 (ex Shin-Etsu Chemical Co. , Ltd. , Japan); and acrylic or methacrylic (co) polymeric poly-flow now. 75 and NO. 95 (by Kyoeisha Chemical Co. , Ltd. , Japan).   Typically, the level of surfactant in the composition is about 2 parts by weight or less, e.g. B.  0th 1 part by weight or less, per 100 parts by weight of solid content of the composition.   The surfactants may be used singly or in combinations.  



   The solution of the composition according to the invention is uniformly applied to a substrate by means of generally known methods already described above.  Also suitable layer thicknesses are already indicated above.  



   After coating, usually the solvent is removed by heating and a layer of photoresist remains on the substrate.  The drying temperatures must of course be lower than the temperatures at which components of the resist formulation can decompose or react.  Normally, the drying temperatures range from about 60 to 160 ° C.  



   The exposure of the coated substrates has already been described above.  After exposure and, if necessary, after the thermal treatment, the exposed areas of the composition (in the case of the positive resist) or the unexposed areas of the composition (in the case of the negative resist) are removed in a manner well known to those skilled in the art using a developer.  



   In order to accelerate the catalytic reaction and thus to ensure the formation of a sufficient solubility difference between exposed and unexposed areas of the resist coating, the coating is preferably heated prior to development.  



     It can also be heated during the exposure.  In general, temperatures between 60 and 160 ° C are used.  The optimum heating time depends on the heating method used and can be determined by simple experiments by a person skilled in the art.  It usually moves between a few seconds to several minutes, z. B.  from 10 to 300 seconds, when a hot plate is used, and z. B.  from 1 to 30 minutes when a convection oven is used.  



   Thereafter, development takes place, with the parts of the coating that are soluble in the developer being removed.  If necessary, the development step can be accelerated by gently moving the sample, gently brushing the coating in the developer bath, or developing in a spray developer apparatus.  Conventional aqueous-alkaline developer liquids can be used for this purpose.   Examples are sodium or potassium hydroxide, the corresponding carbonates, bicarbonates, silicates or metasilicates, metal-free bases such as ammonium compounds or amines such as ethylamine, n-propylamine, diethylamine, di-n-propylamine, triethylamine, methyldiethylamine, alkanolamines, eg. B.  Dimethylethanolamine, triethanolamine, quaternary ammonium hydroxides, e.g. B.  Tetramethylammonium hydroxide or tetraethylammonium hydroxide. 

    The developer solutions are usually up to 0. 5 N, but are usually diluted appropriately before use.   Z. B.  are solutions with a normality of approx.  0th 1-0. 3 well suited.   The choice of developer depends on the nature of the photohardenable coating, especially the nature of the crosslinker or the resulting photolysis products.  If necessary, the aqueous developer solutions may also contain small amounts of wetting agents and / or organic solvents.  Examples of typical organic solvents which may be added to the developer solutions are cyclohexanone, 2-ethoxyethanol, toluene, acetone, isopropanol, and mixtures of two or more such solvents.  A typical aqueous / organic developer system is one based on butyl cellosolve <RTM> / water.

                                        



   The invention also provides a process for producing a photoresist by (1) applying a composition as described above to a substrate; (2) heating the composition to a temperature between 60 ° C and 160 ° C; (3) imagewise exposure to light of wavelengths between 150 nm and 1500 nm; (4) optionally, heating the composition to temperatures between 60 ° C and 160 ° C; and



     (5) subsequent development with a solvent or an aqueous alkaline developer.



   The photoresist compositions can be used on all types of substrates and with any irradiation techniques known to those skilled in the art. For example, semiconductor substrates may be used, e.g. Silicon, gallium arsenide, germanium, indium antimonide; also substrates covered by oxide or nitride layers, such as silicon dioxide, silicon nitride, titanium nitride, siloxanes, as well as metal substrates and metal coated substrates, with metals such as e.g. Aluminum, copper, tungsten, etc. The substrate may also be coated with polymeric materials, e.g. with organic antireflective coatings, insulating layers and dielectric coatings of polymeric materials.



   The photoresist layer can be exposed by any conventional technique, such as direct lettering, i. with a laser beam or projection lithography in "step and repeat mode" or "scanning mode", or by contact printing through a mask.



   In the case of projection lithography, a variety of optical conditions may be selected, such as coherent, partially coherent or incoherent radiation. This also includes non-axial radiation techniques, e.g. annolar illumination and quadrupolar irradiation, where the radiation is allowed to pass only certain regions of the lens, excluding the lens center.



   The mask used to image the pattern may be a hard or flexible mask. The mask may include transparent, semi-transparent and opaque patterns. The pattern size may also include patterns that are at or below the resolution limit of the projection optics and attached to the mask in a particular manner to modify the atmospheric imaging, intensity and phase modulation of the radiation after passing through the mask. This also includes phase shifting masks and half tone phase shifting masks.



   The imaging process of the photoresist composition can be used to prepare patterns of any desired geometry and shape, e.g. dense and isolated lines, vias, trenches, cuts, points, etc.



     Preference is given to a process in which the imagewise exposure is carried out with monochromatic or polychromatic radiation in the wavelength range from 190 to 450 nm, in particular from 190 to 260 nm.



   The invention also provides the use of compounds of the formula I as described above as photolatent acid donors for the polymerization or crosslinking of cationic or acid-catalytically polymerizable or crosslinkable compounds or for increasing the solubility of compounds which increase their solubility in a developer under the action of acid , And a method for photopolymerization or crosslinking under the action of electromagnetic radiation of cationic or acid-catalytically polymerizable or crosslinkable compounds, characterized in that a compound of formula I is used as a photolatent acid donor.



   The UV irradiation to release the acid is usually carried out with light of wavelengths 157-600 nm. Suitable radiation contains e.g. Sunlight or light from artificial light sources. As light sources, a large number of different types are used. Both point sources and planar radiators (lamp carpets) are suitable. Examples are: carbon arc lamps, xenon arc lamps, medium pressure, high pressure and low pressure mercury lamps, optionally doped with metal halides (metal halide lamps), microwave excited metal halide lamps, excimer lamps, superactinic fluorescent tubes, fluorescent lamps, argon incandescent lamps, flash lamps, photographic flood lamps, electron beams and x-rays.

   The distance between the lamp and the substrate to be exposed may vary depending on the application and lamp type, e.g. between 2 cm to 150 cm. Also suitable are laser light sources, e.g. Excimer laser. Even lasers in the visible range can be used.



   The following examples further illustrate the invention. Parts and percentages, as in the rest of the description and claims, are by weight unless otherwise specified. If in the examples alkyl or alkoxy radicals with more than three carbon atoms are indicated without reference to their isomeric form, the statements relate to the respective n-isomers. Example 1:



   Preparation of (4-isobutylphenyl) -p-tolyl-iodonium hexafluorophosphate



   In a 750 ml flask with reflux condenser, thermometer, stirrer and nitrogen inlet 45.22 g (0.21 mol) of 4-iodotoluene are placed in 326 g of 75% sulfuric acid. Then 29.2 g (0.22 mol) of isobutylbenzene are added and the heterogeneous mixture is cooled to 10 ° C. 94.7 g (0.41 mol) of ammonium peroxodisulfate are added in portions so that the temperature does not exceed 15 ° C. The reaction mixture is stirred for 5 hours at room temperature. Thereafter, the reaction mixture is added over 40 min at 5-10 ° C. to a well-stirred suspension of 38.18 g (0.21 mol) of potassium hexafluorophosphate in 600 ml of water and 500 ml of ethyl acetate. The mixture is kept at room temperature for 1.5 h and the phases are separated.

   The organic phase is washed with water and 5% sodium bicarbonate and the solvent removed in vacuo. There are obtained 89 g (0.18 mol, 86%) of p-isobutylphenyl p-tolyl-iodonium hexafluorophosphate as a brownish resin. The product is further purified by chromatography (dichloromethane: ethanol 95: 5 on SiO 2) or recrystallization from chloroform / hexane.



   An analytically pure pattern has the following physical properties: white powder, melting point (m.p.) 90-92 ° C <1> H-NMR spectrum (CDCI 3) shows displacement signals at the following values [ppm]: 7.9 (4H, m, ArH), 7.23 (4H, m, ArH), 2.45 (2H, d, J = 6.2 Hz, CH 2), 1.81 (1H, m, CH (CH 3) 2), 0.85 (6H, d, J = 6.2Hz, 2 CH 3).



   Elemental Analysis: Calculated for C 17 H 20 F 6 I P (496.21)



     <Tb> <TABLE> Columns = 5 <ROW> <SEP> C [%] <SEP> H [%] <SEP> F [%] <SEP> P [%; <Tb> <SEP> <SEP> 41.15 <SEP> 4.06 <SEP> 22.97 <SEP> 6.24 <Tb> <SEP> gef .: <SEP> 41.15 <SEP> 4.19 <SEP> 22.82 <SEP> 5.95 <Tb> </ TABLE> Examples 2-13:



   The compounds of Examples 2-13 are prepared in a manner analogous to that described in Example 1 from the corresponding substituted aromatics. The structures and the physical data are shown in Table 1 Table 1



   
EMI67.1
 



   



     <Tb> <TABLE> Columns = 6 <tb> Head Col 1: Ex. <tb> Head Col 2: X / X 1 <tb> Head Col 3: Y <tb> Head Col 4: A <tb> Head Col 5: Physical Properties <tb> Head Col 6: Elemental Analysis Ber. [%] Gef. [%] C H F <Tb> <SEP> 2 <SEP> 4-C (CH 3) 3 / H <SEP> 4-CH 3 <SEP> PF 6 <SEP> white powder, mp 105-108 ° C <SEP> 41.15 4.06 22.97 41.27 4.23 22.81 <Tb> <SEP> 3 <SEP> 4-C (CH 3) 2 C 2 H 5 / H <SEP> 4-CH 3 <SEP> PF 6 <SEP> whitish powder, m.p.

    94-98 DEG C <SEP> 42.37 4.35 22.34 42.73 4.59 20.44 <Tb> <SEP> 4 <SEP> 4-cyclohexyl / H <SEP> 4-CH 3 <SEP> PF 6 <SEP> glassy, brown resin <SEP> 43.70 4.25 21.83 46.41 4.66 19.84 <Tb> <SEP> 5 <SEP> 4-CH 2 -CH (CH 3) 2 / H <SEP> 2-CH 3 <SEP> PF 6 <SEP> whitish powder, mp 120 ° C <SEP> 41.15 4.06 22.97 40.99 4.00 22.80 <Tb> <SEP> 6 <SEP> 4-CH 2 -CH (CH 3) 2 / H <SEP> 3-CH 3 <SEP> PF 6 <SEP> glassy, brown resin <SEP> 41.15 4.06 22.97 41.66 3.87 22.64 <Tb> <SEP> 7 <SEP> 4-C (CH 3) 3 / H <SEP> 3-CH 3 <SEP> PF 6 <SEP> yellow crystals smp.

   104-106 DEG C <SEP> 41.15 4.06 22.97 41.53 4.27 22.07 <Tb> <SEP> 8 <SEP> 4-CH 2 -CH (CH 3) 2 / H <SEP> 4-C 2 H 5 <SEP> PF 6 <SEP> glassy, brown resin <SEP> 42.37 4.35 22.34 43.02 4.32 21.70 <Tb> <SEP> 9 <SEP> 4-CH 2 -CH (CH 3) 2 / H <SEP> 4-CH 3 <SEP> SbF 6 <SEP> viscous oil <SEP> 34.79 3.43 19.42 34.75 3.47 19.29 <Tb> <SEP> 10 <SEP> 4-CH 2 -CH (CH 3) 2 / H <SEP> 4-CH- (CH 3) 2 <SEP> PF 6 <SEP> yellow resin <SEP> 43.53 4.61 21.74 43.55 4.77 20.63 <Tb> <SEP> 11 <SEP> 4-CH 2 -CH (CH 3) 2 / H <SEP> 4-CH 3 <SEP> 4-CH 3 -Ph-SO 3 <SEP> glassy, brown resin <SEP> 55.18 5.21 - 54.75 5.43 - <Tb> <SEP> 12 <SEP> 4-CH 2 -CH (CH 3) 2 / H <SEP> 4-CH 3 <SEP> (+/-) camphorsulfonate <SEP> glassy, brown resin <SEP> 55.67 6.06 - 55.71 6.21 - <Tb> <SEP> 13 <SEP> 4-CH (CH 3) 2/2-CH (CH 3) 2 <SEP> 4-CH 3 <SEP> PF 6 <SEP> beige powder, m.p.

   137-141 DEG C <SEP> 43.53 4.61 21.74 43.68 4.71 21.24 <Tb> </ TABLE> Example 14



   (4-Methylphenyl) (4'-isobutylphenyl) iodonium nonaflate 4.5 g of potassium nonaflate are suspended in 15 ml of water. To the suspension are added 4.93 g of crude, i. Unpurified (4-methylphenyl) (4'-isobutylphenyl) iodonium hydrogensulfate dissolved in 10 ml of methanol. The mixture is stirred for one hour at room temperature. 15 ml of methylene chloride are added to the mixture and stirred overnight at room temperature. The product is extracted with methylene chloride and the organic phase washed with water, dried over MgSO 4 and concentrated. The residue is purified by flash chromatography on silica gel with methylene chloride and ethanol (95: 5) as eluant to give 2.46 g (3.8 mmol, 34%) of (4-methylphenyl) (4'-isobutylphenyl) iodonium nonaflate as a brown resin.

   The structure is through the <1> H-NMR spectrum confirmed. <1> H-NMR (CDCl 3), delta [ppm]: 0.88 (d, 6H), 1.84 (m, 1H), 2.41 (s, 3H), 2.50 (d, 2H), 7.21-7.26 (m, 4H), 7.84 (d, 4H).



   Elemental analysis: calculated for C 21 H 2 O 3 F 9 SI



     <Tb> <TABLE> Columns = 4 <ROW> <SEP> C [%] <SEP> H [%] <SEP> F [%] <Tb> <SEP> <SEP> 38.78 <SEP> 3.10 <SEP> 26.29 <Tb> <SEP> gef .: <SEP> 38.80 <SEP> 3.09 <SEP> 26.17 <Tb> EXAMPLE 15 Photohardening of a White Pigmented Epoxy Resin Composition



   A photohardenable formulation is prepared by mixing the following components: 36.0 parts bisphenol A epoxy resin ( <RTM> Araldit GY 250, from Vantico), 14.4 parts of trimethylolpropane triglycidyl ether ( <RTM> Grinolit V51-31, from Emschemie), 9.6 parts of C 12/14 alkyl glycidyl ether ( <RTM> Grinolite Epoxy 8, from Emschemie), and 40.0 parts rutile titanium dioxide ( <RTM> R-TC2, from Tioxide).



   The formulation is heated to 50 ° C. and uniformly mixed in the presence of glass beads as an aid for 20 minutes by stirring. 1.5% of the compound of Example 1 and 0.5% of a mixture of 2-isopropylthioxanthone and 4-isopropylthioxanthone ( <RTM> Quantacure ITX) and dissolved in the formulation by stirring. The formulation is applied in a layer thickness of 12 micrometers on a brushed aluminum sheet and irradiated in a lighting system of Fa. Fördertechnik with a Fusion M lamp (120 W / cm). For this purpose, the sample is passed under the lamp on a conveyor belt which is moved at a speed of 10 m / min. A completely cured, tack-free surface is obtained. The gloss of the surface is measured at an angle of incidence of 60 ° and is 97.

    Example 16



   The procedure is analogous to Example 15, but instead of the compound from Example 1, the compound of Example 7 is used. A completely cured, tack-free surface is obtained. The gloss of the surface is measured at an angle of incidence of 60 ° and is 96. Example 17



   Determination of photocrosslinking reactivity in a cationically curable epoxy composition.



     A composition is prepared by dissolving 30.0 parts epoxy cresol novolac ( <RTM> Araldit ECN 9699, Vantico), 10.0 parts of 3,4-epoxycyclohexyl-methyl-3,4-epoxycyclohexane-carboxylate ( <RTM> Araldite CY 179, Vantico) in 60 parts of propylene glycol methyl ether acetate (PGMEA).



   1.6 parts of an iodonium salt and 0.4 part of a mixture of 2-isopropylthioxanthone and 4-isopropylthioxanthone ( <RTM> Quantacure ITX) and dissolved in the formulation by stirring.



   This composition is spun on a 0.5 mm thick, anodized aluminum sheet at 500 rpm for 30 seconds with a Convac spin coater and then dried at 110 ° C. on a hot plate for 60 seconds to form a solid, 5 μm thick film. Thereafter, the film on the aluminum substrate in a MJB 55 Sweet Contact Imager is exposed to a 15-step photoresist multi-density step tablet in the contact method for 100 seconds with a high pressure mercury emitter, followed by heating on a hot plate for 120 seconds 140 DEG C and then developed for 30 seconds in propylene glycol methyl ether acetate (PGMEA), then rinsed for 10 seconds with 2-propanol and finally blown dry with compressed air.

   It is then determined the lowest transmission value at which the film under the corresponding transmission field of the mask is not yet dissolved away. This value characterizes the crosslinking reactivity and thus the photosensitivity of the photoinitiator used with the remaining composition remaining the same and under the same process conditions. Since the exposure energy is calculated using the following formula: Exposure energy = transmission x exposure time x radiation intensity [mJ / cm <2>] [s] [mW / cm <2>]



   For the same exposure time and constant radiation intensity, the minimum exposure dose required for cross-linking (photosensitivity) is directly proportional to the minimum transmission value at which the film is still sufficiently cross-linked so as not to be detached in the developer. The radiation intensity is constant 7.1 mW / cm in all experiments <2>, determined with an OAI 400 probe and an OAI power meter. Since the exposure in the sweet contact platesetter used is characterized in that virtually no heat acts on the substrate during the irradiation, the thermal activation of the epoxide crosslinking by the photochemically produced cations can be separated from the exposure, very reproducibly in a subsequent heating step on a temperature-controlled basis Heating plate done.

   At the same bake temperature and time, therefore, differences in the measured transmission level, at which the film is not yet detached from the substrate during development, are directly attributable to different photosensitivity or photoreactivities of the iodonium salts or sensitisers used.



   The transmission value can thus be used directly as a relative measure of the required exposure energy. A small value corresponds to a high photoreactivity (high photosensitivity) and a high level of low photoreactivity (low photosensitivity) of the photoinitiator (iodonium salt) or sensitizer system used.



   The transmission values for examples of the iodonium salts according to the invention which are minimally required for crosslinking are shown in Table 2 and for Comparative Examples in Table 2a in the column Example 17. Example 18



   Determination of photocrosslinking reactivity in an acid-catalytically curable melamine-phenolic resin composition



   A composition is prepared by dissolving 18.0 parts of poly (4-hydroxystyrene) (VP 8000, Nisso) 8.3 parts of hexamethoxymethylmelamine resin ( <RTM> Cymel 301, Dyno Cyanamid) 1.2 parts of an iodonium salt photoinitiator according to the invention and 0.3 part of a mixture of 2-isopropylthioxanthone and 4-isopropylthioxanthone ( <RTM> Quantacure ITX) in 72.2 parts of propylene glycol methyl ether acetate (PGMEA) and applied analogously to Example 17. The layer thickness with this composition after spin coating and drying of the layer is 5 micrometers. Before development, a post-exposure bake takes place at 140 ° C. on the hot plate for a period of 120 seconds. The layer is developed for 60 seconds in 2.38% aqueous tetramethylammonium hydroxide solution, rinsed in water for 10 seconds and blown dry with compressed air.

   The determination of the minimum transmittance values required for the crosslinking takes place as described in Example 17. The results are likewise listed in Table 2 for the compounds according to the invention and in Table 2a for Comparative Examples in each case in the column Example 18.



   The compositions of this invention combine high photosensitivity (low minimum transmission values) for effective crosslinking, in both epoxy curing and acid catalytic melamine resin curing, and do not produce harmful benzene upon exposure. Table 2



   In each case 4% of the photoinitiator according to the invention and 1% RTMQuantacure ITX were used



   
EMI72.1
 



   



   
EMI73.1
 Table 2a



   Comparative examples with non-inventive iodonium salts



   In each case 4% of the idonium photoinitiator and 1% Quantacure ITX were used



   
EMI73.2
 Example 19



   According to Example 17, a formulation with (4-isobutylphenyl) -p-tolyl-iodonium hexafluoroantimonate from Example 9 is prepared instead of the iodonium salt of Example 1. Application and evaluation are carried out as described in Example 17. The minimum transmission required for the crosslinking is only 1%. Example 20



   According to Example 17, a formulation with the iodonium salt of Example 1 is prepared, except that the sensitizer mixture of 2-isopropylthioxanthone and 4-isopropylthioxanthone ( <RTM> Quantacure ITX) in total by the same amount (1 part) of 1-chloro-4-propoxythioxanthen-9-one ( <RTM> Quantacure CPTX). Application and evaluation are carried out as described in Example 17. The measured minimum transmission required for the crosslinking is 12%. Example 21



   According to Example 17, a formulation with the iodonium salt of Example 1 is prepared, wherein the sensitizer mixture of 2-isopropylthioxanthone and 4-isopropylthioxanthone ( <RTM> Quantacure ITX) is replaced by the same amount (1 part) of 3,3'-carbonylbis (7-dimethylaminocoumarin). Application and evaluation are carried out as described in Example 17. The measured minimum transmission required for crosslinking is 10%. Example 22



   According to Example 17, a formulation with the iodonium salt of Example 1 is prepared, wherein the sensitizer mixture of 2-isopropylthioxanthone and 4-isopropylthioxanthone ( <RTM> Quantacure ITX) in total by the same amount (1 part) of 9,10-dimethoxy-2-ethylanthracene (Aldrich). Application and evaluation are carried out as described in Example 17. The measured transmission required for the crosslinking is 5%. Example 23



   Cationic clearcoat based on an epoxidized soybean oil



   To 100 parts of epoxidized soybean oil (Edenol D 81, Cognis) is added in each case 2% iodonium salt photoinitiator.



   The mixtures are applied to white melamine-coated chipboard with a 100 μm doctor blade and irradiated under 2 × 120 W / cm medium pressure mercury lamps at a belt speed of 3 × 5 m / min. The initiators used and the curing results are shown in the following Tables 3 (initiator according to the invention) and 3a (non-inventive iodonium salts). Table 3



   
EMI75.1
   Table 3a - Comparative Examples with non-inventive iodonium salts



   
EMI75.2
 Example 24



   A blue flexographic ink formulation is prepared by intimately triturating: 73.2 parts <RTM> Cyracure UVR-6105 (3,4-epoxycyclohexylmethyl carboxylate, Union Carbide) 10.5 parts <RTM> Cyracure UVR-6000 (3-ethyl-3-hydroxymethyl-oxetane, Union Carbide) 5.3 parts <RTM> TONE 0301 (epsilon -caprolactone-triol, Union Carbide) 0.5 parts <RTM> BYK 307 (polyether-modified dimethyl-polysiloxane copolymer, Byk) 10.5 parts Lrgalit Blue GLO (Cu phthalocyanine, Ciba Specialty Chemicals) and additionally 6% (4-isobutylphenyl) p-tolyl-iodonium hexafluorophosphate (compound from Example 1) and 0.5% of a mixture of 2-isopropylthioxanthone and 4- isopropylthioxanthone ( <RTM> Quantacure ITX).



   The cationic ink is applied to aluminum foil with a 4 bar K-bar coater and cured in an IST exposure machine equipped with a 120 W / cm mercury medium pressure lamp. Subsequently, the printed substrate is heated to 100 ° C. in the oven for 5 minutes, and thereafter the wipe resistance of the surface and resistivity of the cured ink layer is determined by the number of double-row tests with methyl ethyl ketone (MEK) -dipped pulp in which the ink is not yet removed ,



   In the present case, the ink is smear resistant at the cure speed of 100 m / min and withstands 12 double row trials with MEK. Example 25



   A flexographic ink is prepared and tested analogously to Example 24, but the photoinitiator from Example 1 is replaced by (4-isobutylphenyl) -p-ethylphenyl-iodonium hexafluorophosphate (compound from Example 8).



   The ink wipes at a cure speed of 20 m / min and resists> 50 MEK double row trials. Example 26



   Analogously to Example 24, a flexographic printing ink is prepared and tested, but the photoinitiator from Example 1 is replaced by 4-tert-butylphenyl-p-tolyl-iodonium hexafluorophosphate (compound from Example 2).



   The ink wipes at a cure speed of 70 m / min and resists 43 MEK double row trials. Example 27



   A flexographic ink is prepared and tested analogously to Example 24, but the photoinitiator from Example 1 is replaced by 4- [2- (2-methyl) -butyl) -phenyl] -p-tolyl-iodonium hexafluorophosphate (compound from Example 3) ,



   The ink is smear resistant at a cure speed of 20 m / min and withstands 48 MEK double row trials. Comparison with compound B



   Analogously to Example 24, a flexographic printing ink is prepared and tested, but the photoinitiator of Example 1 according to the invention is replaced by di (4-tert-butylphenyl) iodonium hexafluorophosphate (B).



   The ink is not smudge-resistant even at a reduced cure speed of 5 m / min and does not withstand a MEK double-batch test. Comparison with compound C



   Analogously to Example 24, a flexographic printing ink is prepared and tested, but the photoinitiator of Example 1 according to the invention is replaced by di- (4-isobutylphenyl) iodonium hexafluorophosphate (C).



   The ink is smear resistant at a cure speed of 20 m / min and withstands only 9 MEK double row trials. Comparison with compound E



   Analogous to Example 24, a flexographic ink is prepared and tested, but the inventive photoinitiator of Example 1 is replaced by n-decylphenyl-phenyl iodonium hexafluorophosphate (E).



   The ink is smear-resistant only at a cure speed of 30 m / min and withstands 2 MEK double-batch tests. Example 28



   Positive photoresist



   A composition is prepared by dissolving 37.5 parts of poly [(4-tetrahydropyranyloxystyrene) -co- (4-hydroxystyrene)] having a 4-tetrahydropyranyloxy-styrene moiety of 31 mol% and a 4-hydroxystyrene moiety of 69 mol% in 120 parts of propylene glycol methyl ether acetate (PGMEA) and subsequent dissolution of one of the below-designated iodonium salts in a concentration of 2.0%, based on the amount of polymer produced and spin-coated analogously to Example 17 in a layer thickness of 1 micron with 2000 revolutions per minute on aluminum sheet. After drying for 60 seconds on a hot plate at 110 ° C., a multidensity chromium mask in the contact method with a high-pressure mercury lamp is exposed to a Oriel Type 7800 deep UV exposure apparatus for 120 seconds, analogously to Example 17.

   The radiation intensity measured with an OAI 220 probe is 1.4 mW / cm <2> and with an OAI 400 probe 2.3 mW / cm <2>. Prior to development, a post-exposure bake is performed at 100 ° C. on a hot plate for 60 seconds. The layer is developed for 60 seconds in aqueous 2.38% tetramethylammonium hydroxide solution, rinsed in water for 10 seconds and blown dry with compressed air. The determination of the minimum relative exposure dose is carried out as described in Example 17, but the first transmission field is determined for which the positive resist in the developer has been completely removed.



   The following results are achieved:



     a) (4-isobutylphenyl) -p-tolyl-iodonium hexafluorophosphate, compound of Example 1, as iodonium salt:



   The minimum transmission value at which the resist is developed is 16%, corresponding to an exposure energy of 26.9 mJ / cm <2> with OAI 220 probe.



   b) (4-Isobutylphenyl) -m-tolyl-iodonium hexafluorophosphate, compound from Example 6, as iodonium salt:



   The minimum transmission value at which the resist is developed is also 16%, corresponding to an exposure energy of 26.9 mJ / cm <2> with OAI 220 probe.



   c) 4-isobutylphenyl) -p-tolyl-iodonium p-tosylate, compound of Example 11, as iodonium salt:



   The minimum transmission value at which the resist is developed is also 16%, corresponding to an exposure energy of 26.9 mJ / cm <2> with OAI 220 probe. Example 29



   Chemically amplified positive resist



   A chemically amplified positive resist formulation is prepared by mixing the following components: 100.00 parts of a binder component (copolymer of 22 mole percent styrene, 69 mole percent p-hydroxystyrene, and 9 mole percent t-butyl acrylate, with a Mw of 9850 ; <RTM> Maruzen MARUKA LYNCUR PHS / STY / TBA, Maruzen Oil Company, Japan) 0.48 parts of a flow control agent (FC-430, 3M) 475.00 parts of propylene glycol methyl ether acetate (PGMEA) (Tokyo Kasei, Japan) 4.0 parts of the photoinitiator of Example 14.



   The resist formulation is applied to a silicon wafer treated with hexamethyldimethylsilane for 45 seconds by spinning at 3000 rpm and heated on a hot plate at 140 ° C. for 90 seconds to obtain a film thickness of 800 nm. The resist is then exposed to UV radiation of 254 nm wavelength through an interference filter and a multi-density quartz mask, using a Ushio high pressure mercury lamp, UXM-501MD, and a mask aligner Canon PLA-521. The samples are then heated and developed for 90 seconds at 140 ° C. on a hot plate. Radiation intensity is determined using a Ushio UIT-150 Unimeter.

   The "Dose to Clear (E 0)", i. the intensity sufficient to completely remove the resist film after 60 seconds of development in 1.79% aqueous tetramethylammonium hydroxide developer is determined from the measured contrast curve. The "Dose to Clear (E 0)" is 0.68 mJ / cm <2>.


    

Claims (12)

A radiation-sensitive composition comprising (a1) a cationically or acid-catalytically polymerizable or crosslinkable compound or (a2) a compound which increases its solubility under the action of acid in a developer; and (b) at least one diaryliodonium salt of formula I EMI79.1      X is branched C 3 -C 20 alkyl or C 3 -C 8 cycloalkyl; X 1 is hydrogen, linear C 1 -C 2 0 alkyl, branched C 3 -C 2 0 alkyl or C 3 -C 8 cycloalkyl; with the proviso that the sum of the carbon atoms in X and X 1 is at least 4; Y is linear C 1 -C 10 alkyl, branched C 3 -C 10 alkyl or C 3 -C 8 cycloalkyl;      A 'is a non-nucleophilic anion selected from the group (BF 4)', (SbF 6) ', (PF 6)', (B (C 6 F 5)) 4 ', C 1 -C 20 -alkyl sulfonate, C 2 C 20 haloalkyl sulfonate, unsubstituted C 6 -C 10 aryl sulfonate, camphorsulfonate, C 1 -C 20 perfluoroalkylsulfonyl methide, C 1 -C 20 perfluoroalkylsulfonyl imide, and, with halogen, NO 2, C 1 -C 12 alkyl, C C 1 -C 12 haloalkyl, C 1 -C 12 alkoxy or COOR 1 substituted C 6 -C 10 arylsulfonate; and R 1 is C 1 -C 20 alkyl, phenyl, benzyl; or denotes mono- or polysubstituted by C 1 -C 12 -alkyl, C 1 -C 12 -alkoxy or halogen-substituted phenyl; with the proviso that the two phenyl rings on the iodine atom are not the same substituted. Second  A radiation-sensitive composition according to claim 1, wherein in the compounds of the formula IA 'a non-nucleophilic anion selected from the group (PF 6)', (B (C 6 F 5)) 4 ', C 1 -C 12 -alkyl sulfonate, C 2 C 12 haloalkyl sulfonate, unsubstituted phenyl sulfonate, camphorsulfonate, C 1 -C 20 perfluoroalkylsulfonyl methide, C 1 -C 20 perfluoroalkylsulfonyl imide, and, with halogen, NO 2, C 1 -C 12 alkyl, C 1 -C 12 haloalkyl C 1 -C 12 -alkoxy or COOR 1-substituted phenylsulfonate. Third  A radiation-sensitive composition according to claim 1, wherein in the compounds of formula I X is branched C 4 -C 6 -alkyl or cyclohexyl; X 1 is hydrogen or branched C 4 -C 6 alkyl; Y is linear C 1 -C 4 alkyl, branched C 3 -C 4 alkyl or cyclohexyl; A 'is a non-nucleophilic anion selected from the group consisting of (PF 6)', camphorsulfonate, and C 1 -C 4 alkyl-substituted phenylsulfonate. A radiation-sensitive composition according to claim 1, wherein the component (a1) is at least one compound selected from the group of cycloaliphatic epoxy compounds, glycidyl ethers, oxetane compounds, vinyl ethers, acid-crosslinkable melamine resins, acid-crosslinkable hydroxymethylene compounds and acid-crosslinkable alkoxymethylene compounds. 5th  A radiation-sensitive composition according to claim 1, wherein component (a2) is at least one compound selected from the group consisting of cycloaliphatic copolymers, 4-hydroxyphenyl group-containing copolymers, maleic anhydride-containing copolymers, and copolymers containing acrylic acid, acrylic acid ester and methacrylic acid ester In that these copolymers carry functional groups that increase the solubility of the polymer upon reaction with an acid in an alkaline developer. 6. A radiation-sensitive composition according to claim 1, comprising in addition to the components (a1) or (a2) and (b) at least one sensitizer compound (d), in particular benzophenone, thioxanthone, anthracene or derivatives thereof. 7th  Use of compounds of the formula I according to claim 1 as photolatent acid donors for the polymerization or crosslinking of cationic or acid-catalytically polymerizable or crosslinkable compounds or for increasing the solubility of compounds which increase their solubility under the action of acid in a developer. A coated substrate coated on at least one surface with a composition according to claim 1. 9. Use of a radiation-sensitive composition according to claim 1 for the production of relief images, characterized in that a radiation-sensitive composition according to claim 1 is applied to a substrate and then imagewise exposed. 10th  Diaryliodonium salt Compound of formula I EMI81.1      X is branched C 3 -C 20 -alkyl or C 3 -C 8 -cycloalkyl; X 1 is hydrogen, linear C 1 -C 20 alkyl, branched C 3 -C 20 alkyl or C 3 -C 8 cycloalkyl; with the proviso that the sum of the carbon atoms in X and X 1 is at least 4; Y is linear C 1 -C 10 alkyl, branched C 3 -C 10 alkyl or C 3 -C 8 cycloalkyl;  A 'is a non-nucleophilic anion selected from the group (BF 4)', (SbF 6) ', (PF 6)', (B (C 6 F 5)) 4 'C 1 -C 2 0 alkyl sulfonate, C 2 -C 2 0 -haloalkylsulfonate, unsubstituted C 6 -C 10 -arylsulfonate, camphorsulfonate, C 1 -C 2 0 -perfluoroalkylsulfonylmethide, C 1 -C 20 perfluoroalkylsulfonylimide, and, with halogen, NO 2, C 1 -C 12 -alkyl C 1 -C 12 haloalkyl, C 1 -C 12 alkoxy or COOR 1 substituted C 6 -C 10 arylsulfonate; and R 1 is C 1 -C 20 alkyl, phenyl, benzyl; or phenyl which is mono- or polysubstituted by C 1 -C 12 -alkyl, C 1 -C 12 -alkoxy or halogen; with the proviso that the two phenyl rings on the iodine atom are not the same substituted. 11th   Use of diaryliodonium salt compounds of the formula I according to claim 10 as a radiation-sensitive acid donor in the production of paints, powder coatings, printing inks, printing plates, dental compositions, stereolithography resins, adhesives, non-stick coatings, color filters, resist materials or image recording materials. 12. A photoresist comprising, as a radiation-sensitive acid donor, a diaryliodonium salt compound of the formula I as claimed in claim 10.