MXPA98000278A - Photogeneration of amines from alpha-aminoacetophen - Google Patents

Abstract

The present invention relates to compounds of the formulas I, II or III (See Formula) wherein X is a divalent radical, Y is alkylene with 1 to 6 carbon atoms, cyclohexylene or a direct bond, Ar is an aromatic radical such as is defined in claim 1. R1 and R3 independently of each other, among other things are a radical of the formula R14 R15 (See Formula) R3 is, inter alia, hydrogen, alkyl with 1 to 12 carbon atoms, cycloalkyl with 5 to 12 atoms carbon or phenyl-alkyl with 1 to 3 carbon atoms, R4 is, inter alia, alkyl with 1 to 12 carbon atoms of cycloalkyl with 5 to 12 carbon atoms, phenyl-alkyl with 1 to 3 carbon atoms, or phenyl, or a salt of acid addition of a compound of the formula I, II or III, are useful as photosensitive base catalysts in entanglement compositions

Description

i PHOTOGBNERATION DB AMINES FROM OR-AMINOACETOPHENONES The application is directed to curable base-catalyzed compositions comprising a-amino ketone compounds as latent bases, as well as to a process for curing said compositions, inter alia in combination with polymerizable components by radicals. Among the thermosetting resins, epoxy resins have found extremely wide applications due to the variety of chemical reactions and materials that can be used to cure and the very different properties that result. More specifically, their excellent mechanical and chemical properties, high adhesive strength, good heat resistance, and high electrical resistance have made them extremely useful. They are widely used in applications such as adhesives, coatings, thermo-fixes or photoprotective layers (see for example CA May, Epoxy Resins, Chemistry and Technology, 2nd Ed. Marcel Dekker, New York, 1988) . The curing of epoxy resins can be affected by polyaddition reactions that result in coupling as well as entanglement. The most widely used agents for this purpose are active hydrogen compounds such as polyamines, polyacids, polymercaptans, polyphenols, anhydrides, isocyanates, etc. These reactions are in principle stoichiometric reactions between an active hydrogen in the curing agent and an epoxide group, such that the curing agent is usually present in relatively high concentrations. Of course, these polyaddition reactions can be catalyzed by appropriate catalysts. It is possible to use, for example dicyandiamide, benzoguanamine or imidazole derivatives as catalysts for the reaction of epoxides with carboxylic acids. The anionic and cationic polymerization of epoxides occurs with a variety of bases and Lewis acids, as well as with numerous salts and complex initiators. In the case of base catalyzed polymerization, amines such as benzyldimethylamine, or 2,4,6-tris (dimethylaminomethyl) phenol and imidazole derivatives, are the most useful initiators. Secondary amines, such as pepiridine, diethanolamine and imidazole derivatives, which are first subjected to addition to the epoxy group by their labile hydrogens and then function as initiators, have also been employed. In the case of cationic polymerization, strong Bronsted acids, such as trifluoroethane sulfonic acid and a wide variety of Lewis acids, the most useful of which are boron trifluoride complexes, can catalyze the cationic polymerization of epoxides.

The unique property of the epoxides can be employed in image photophering applications if suitable photosensitive compositions are available. In principle, epoxides can not be cured by typical free radical chemistry and therefore can only be used in radical photopolymerization systems if suitable reactive groups such as vinyl ethers or acrylates are also present. This is not always convenient. Photochemically initiated reactions of epoxy groups require photoinitiators that can generate the appropriate starter species. Cationic photoinitiators of the onium type, for example diaryliodonium salts or triarylsulfonium salts, are well known and can be used for the cationic photoinitiator polymerization of epoxides. Although the cationic photopolymerization mechanism has real advantages such as oxygen insensitivity, it can not be used if basic materials are present in the uv curable formulations. Therefore, there is a need for efficient photogenerated base catalysts which can be used to cure epoxy-containing photosensitive compositions. The purpose of the present invention is first to provide a new process for photochemically generating tertiary amine catalysts which can be used for the basic catalysis of epoxide polysubstances and second, corresponding compositions. The photogenerated base catalysts are already known in the art (for example Pure and Appl. Chem. (Pure and Applied Chemistry) 1992, 64, 1239) and have been applied to photoprotective layer technology (for example EP-A-599 571 , JP-A 4330444 and EP-A 555 749). Amines are the most useful photogenerated bases known to date. However, some known photo-generators of amines such as substituted benzylcarbamates (examples are described in J. Org. Chem. 1990, 55, 5919) suffer from or suffer from insufficient absorption in the near UV region, which is a severe restriction for many. Applications. Although the photocatalysts have been proposed, they generate amines with higher absorption in the region between 300 and 400 nm see, for example, Polym. Mat. Sci. Eng. 1991, 64, 55 or Macromol. 1995, 28 365, can not always be used, because the recombination of the free amine and the carbonyl by-product to form an imine, can occur depending on the acidity of the formulation. Furthermore, they can only generate primary or secondary amines, which are not very efficient catalysts for poloxides to epoxies or for anionic epoxide polymerization. It is well known that tertiary amines are efficient base catalysts that can be employed in epoxide reactions, but few attempts have been made to generate them photochemically. Photolysis of tetraalkyl ammonium salts has been proposed as a method for photochemically generating tertiary amines (Polym, Mat, Sci. Eng. 1995, 72, 201). These compounds require long radiation times, have an unfavorable absorption spectrum and their structure can only be varied with difficulty. According to this, there is a need for efficient photogenerators of tertiary amines. In order to be useful, these compounds must exhibit low reactivity with the formulation before exposure to UV light. In particular, the storage stability of photosensitive compositions containing them should be high, and should not be less revealable after the previous drying step which is usually necessary to remove the solvent. They will have to have high absorption in the near UV region in order to generate the free amine efficiently under exposure conditions commonly employed in the "photoformation" imaging industry Finally, after irradiation, the generated base should show high catalytic activity in the thermal curing reaction The photolytic breakdown of specific ce-amino ketone compounds in radicals and the photopolymerization process for oleic unsaturated monomers and oligomers employing ketone compounds is known and described inter alia in US Patent Nos. 4,582,862 , 4,992,547 and 5,077,402 European Patent Application 555 749 describes the use of latent bases in hybrid systems, ie systems with cationically and radically polymerizable compounds US Patent No. 4,943,516, describes hybrid systems comprising a photoinitiator for radically polymerizable components and among others a curing agent for the epoxy component, as well as a process for curing the compositions. (4-Methylthiobenzoyl) -1-methyl-1-morpholino-ethane is named as an example of a photoinitiator for the free-radically polymerizable components. It has now been found that specific compounds, already known as initiators for the curing of radically polymerizable compositions, are also suitable as base generating compounds, that is to say as compounds that generate bases before irradiation ("photobase generators") and thus can used in reactions catalyzed by base. Accordingly, this invention relates to a composition, comprising: (A) co or latent base catalyst, at least one compound of formula I, II or III ffl Ar.- - ° C-? CXC? ' - iC? -Ar. 1 l I 1 («) where ^ is an aromatic radical of formula IV, V, VI or VII • o- < SAW) X is a divalent radical of the formula -N (RX1) - or -NÍR.X- ^ -NÍR.J-; Y is alkylene with 1 to 6 carbon atoms, cyclohexylene or a direct bond; U is -0-, -S- or -N (R17) -; V has one of the meanings of U or is -CO-, -CH2-, -CH2CH, -, alkylidene with 2 to 6 carbon atoms or a direct bond, -W is alkylene with 7 carbon atoms or alkylidene with 2 to 6 carbon atoms unbranched or branched; x and R2 independently from each other (a) alkyl having 1 to 12 carbon atoms, which is unsubstituted or substituted by OH, alkoxy with 4 carbon atoms, SH, CN, -COO (alkyl with 8 carbon atoms), (alkyl with 4 carbon atoms) -COO-, phenoxy, halogen or phenyl, or are cyclopentyl or cyclohexyl R14R15 ii (b) a radical of the formula - (CHR13) pC = C-Rl6, where p is zero or , or (c) a radical of the formula / = \ wherein q is O, 1, 2 or 3, or I (d) a radical of the formula -CH-Ar2, (e) phenyl which is unsubstituted or substituted by halogen, alkyl with 12 carbon atoms or alkoxy with the 12 carbon atoms, (f) Rr and R2 together are alkylene with 2 to 9 carbon atoms or oxaalkylene with 3 to 9 carbon atoms without branching or branching, or form a radical of the formula AR2 is a phenyl, naphthyl, thienyl or furyl radical, each of which is unsubstituted or substituted by halogen, alkyl with 1 to 12 carbon atoms, or is substituted by alkyl with 1 to 4 carbon atoms, which is substituted by OH, halogen, alkoxy with 1 to 12 carbon atoms, -COO (alkyl with 1 to 18 carbon atoms), -CO (OCH2CH2) nOCH3 or -OCO (alkyl with 4 carbon atoms), or phenyl radicals , naphthyl, thienyl or furyl are substituted by alkoxy with 1 to 12 carbon atoms or by alkoxy with 4 carbon atoms, which is substituted by -COO (alkyl with 1 to 18 carbon atoms) 0 -CO (OCH2C? 2 ) nOCH, or the phenyl, naphthyl, thienyl, furyl or pyridyl radicals are substituted by - (OCH2CH2) nOH, - (OCH2CH2) nOCH3, alkylthio with 18 carbon atoms, phenoxy, -COO (alkyl with 18 carbon atoms) ), -CO (OCH2CH2) nOCH3, phenyl or benzoyl; n is 1-20; m is l or 2; R3 is alkyl with 1 to 12 carbon atoms, alkyl with 2 to 4 carbon atoms which is substituted by -OH-, alkoxy with 1 to 4 carbon atoms, -CN or -COO (alkyl with 1 to 4 carbon atoms), oP3 is alkenyl with 3 to 5 carbon atoms, cycloalkyl with 5 to 12 carbon atoms or phenyl alkyl with 1 to 3 carbon atoms; R 4 is alkyl with 1 to 12 carbon atoms, alkyl with 2 to 4 carbon atoms which is substituted by -OH, alkoxy with 4 carbon atoms, -CN or -COO (alkyl with 4 carbon atoms) or R 4 is alkenyl with 3 to 5 carbon atoms, cycloalkyl with 5 to 12 carbon atoms, phenylalkyl with 3 carbon atoms or phenyl which is unsubstituted or substituted by alkyl with 12 carbon atoms, alkoxy with 4 atoms of carbon or -COO (alkyl having 1 to 4 carbon atoms) or R 4 together with R 2 is alkylene with 1 to 7 carbon atoms, phenyl-alkylene with 4 carbon atoms, o-xylylene, 2-butenylene or oxaalkylene with 2 to 3 carbon atoms, or R3 and R4 together are alkylene with 4 to 7 carbon atoms, which may be interrupted by -0-, -S- or -CO-, or R3 and R4 together are alkylene with 3 to 7 carbon atoms which may be substituted by OH, alkoxy with 4 carbon atoms or -COO (alkyl with 4 carbon atoms); Rs # 6 17, R8 and > each independently of one another is hydrogen, halogen, alkyl having 1 to 12 carbon atoms, cyclopentyl, cyclohexyl, phenyl, benzyl, benzoyl or a group -0R17, -SR? a, -S0R? a, -S02R18, -N ( RJ0) (R19), -NH-S02R21 O Z is -0-, -S-, -N (RL1) -, -N (R11) -R12-N (R11) - R10 is hydrogen, alkyl having 1 to 12 carbon atoms, halogen or alkanoyl having 2 to 8 carbon atoms; RX1 is alkyl with 1 to 8 carbon atoms, alkenyl with 3 to 5 carbon atoms, phenyl-alkyl with 1 to 3 carbon atoms, hydroxyalkyl with 1 to 4 carbon atoms or phenyl; R 12 is alkylene with 2 to 16 carbon atoms without branching or branching, which may be interrupted by one or more of -0- OR -S-; R 13 is hydrogen, alkyl having 1 to 8 carbon atoms or phenyl; i4 Ris and R e each independently of one another are hydrogen or alkyl with 1 to 4 carbon atoms or R 14 and R 15 together are alkylene with 3 to 7 carbon atoms; R17 is hydrogen, alkyl having 12 carbon atoms, alkyl having 2 to 6 carbon atoms which is substituted by -SH, -CN, -OH, alkoxy with 4 carbon atoms, alkenoxy with 3 to 6 carbon atoms, -OCH2CH2CN, -OCH2CH2COO (alkyl having 4 carbon atoms), -COOH or -0-CO-alkyl having 4 carbon atoms, which is unsubstituted or substituted by SH, or R17 is -COO (alkyl with 4) carbon atoms), or R17 is alkyl with 1 to 6 carbon atoms, which is interrupted by one or more -0-, or R17 is - (CH2CH20) nH, alsanoyl with 2 to 8 carbon atoms, alkenyl with 3 to 12 carbon atoms, cyclohexyl, hydroxycyclohexyl, phenyl which is unsubstituted or substituted by halogen, alkyl with 12 carbon atoms or alkoxy with 4 carbon atoms or R 17 is phenyl-alkyl with 1 to 3 carbon atoms or Si (alkyl with 1 to 8 carbon atoms) r (phenyl) 3_r-; r is 1, 2 or 3; Rlß is hydrogen, alkyl with 12 carbon atoms, alkenyl with 3 to 12 carbon atoms, cyclohexyl, alkyl with 2 to 12 carbon atoms which is substituted by -SH, -OH, -CN, -COOH, -COO ( alkyl with 1 to 4 carbon atoms), alkoxy with 1 to 4 carbon atoms, -OCH2CH2CN or -0-CO-alkyl with the 4 carbon atoms which is unsubstituted or substituted by SH or Rlß is -OCH2CH2COO (alkyl with 1 to 4 carbon atoms), or R18 is alkyl with the 12 carbon atoms which is interrupted by -S- or -0-; or R 1 is phenyl which is unsubstituted or substituted by halogen SH, alkyl with 1 to 12 carbon atoms or alkoxy with 1 to 4 carbon atoms or R 18 is phenyl-alkyl with 1 to 3 carbon atoms; R19 and R30 each independently are alkyl with 12 carbon atoms, hydroxyalkyl with 2 to 4 carbon atoms, alkoxyalkyl with 2 to 10 carbon atoms, alkenyl with 3 to 5 carbon atoms, cycloalkyl with 5 to 12 carbon atoms, phenyl-C 1 -C 3 -alkyl, phenyl which is unsubstituted or substituted by halogen, C 1 -C 12 -alkyl or C 1 -C 4 -alkoxy or R 19 and R 20 are alkanoyl with 2 to 3 carbon atoms or benzoyl, or R19 and R20 together are alkylene with 2 to 8 carbon atoms which may be interrupted by -O- or -S-, or R19 and R20 together are alkylene with 2 to 8 carbon atoms which may be substituted by alkoxy hydroxy with 4 carbon atoms or -C000 (alkyl having 1 to 4 carbon atoms); and R21 is alkyl having 1 to 18 carbon atoms, phenyl which is unsubstituted or substituted by halogen, alkyl having 1 to 12 carbon atoms or alkoxy with 1 to 8 carbon atoms or R21 is naphthyl; or an acid addition salt of a compound of formula I, II or III; (B) at least one organic compound that is capable of reacting in a base catalyzed reaction; and (C) optionally a sensitizer. A further object of the invention is a process for photochemically generating bases in base-catalyzed polymerization reactions, characterized in that a compound of the formula I, II or III as defined above is added as a latent base to the mixture to be polymerized and irradiate with light of wavelength from 200 to 700 nm to generate the base. At least one compound of formula I, II or III is present in the composition of the invention. Accordingly, mixtures of compounds of the formulas I, II or III can be present in the composition, for example 1-4, preferably one or two compounds of the formula I, II or III are present. Alkyl with 1 to 4 carbon atoms, R 14, R 15 and R 16 can be, for example, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl or tert-butyl.

Alkyl with 8 carbon atoms, R2, Rlx and R13 can also be, for example, pentyl, hexyl, heptyl, octyl, 2-ethylhexyl or 2,2,4,4-tetramethylbutyl, alkyl with 1 to 12 carbon atoms, R3 , R 4, Rs, R 6, R 7, R b, R 9, R 1 D, R 17, R 18, R 19 and R 20 can also be, for example, nonyl, decyl, isodecyl, undecyl or dodecyl. Alkenyl with 3 to 5 carbon atoms R3, R4, R?, Ri9 and 20 can for example be allyl, methallyl, crotyl or dimethylallyl, allyl is preferred. Alkenyl having 3 to 12 carbon atoms R 17 and R a can also be, for example, hexenyl, octenyl or decenyl. R., R5, R6, R- > 8 8 and 9 as cycloalkyl in particular are cyclohexyl, cycloalkyl with 5 to 12 carbon atoms R3, R ", R19 and R20 may also be for example cyclooctyl or cyclododecyl. Phenyl-alkyl having 1 to 3 carbon atoms R 3, R 4, R 17, R 8, R 19 and R 20, in particular is benzyl. Alkylene having 1 to 6 carbon atoms Y can be, for example, methylene, or di-, tri-, tetra-, penta- or hexamethylene. C 1 -C 7 -alkylene, for example, can be methylene, ethylene, 1,2-propylene or 1, 2-hexylene. Alkylidene are unbranched or branched alkyl chains having two free valencies on an alkyl atom! carbon -CH-. Accordingly, alkylidene having 2 to 6 carbon atoms V and W can for example be ethylidene, propylidene, isopropylidene, butylidene, isobutylidene or hexylidene. Examples of Ar2 are phenyl, 1-naphthyl groups, 2-naphthyl, 2-furyl, 2-thienyl, 4-chlorophenyl, tolyl, 4-isopropylphenyl, 4-octylphenyl, 3-methoxyphenyl, 4-phenoxyphenyl, 4-phenylphenyl, 4-benzoylphenyl and 4-chloro-1-naphyl . Examples of substituted alkyl R2 are 2-methoxyethyl, 3-butoxypropyl, 2-isopropoxyethyl, 4-phenoxybutyl, 2-chloroethyl, 3-chloropropyl, 2-phenylethyl or 3-phenyl-propyl groups. Examples of substituted phenyl R2 are the 4-chlorophenyl, 3-methoxyphenyl, 4-tolyl or 4-butylphenyl groups. Substituted alkyl R3 and R, for example, may be 2-hydroxyethyl, -hydroxypropyl, 2-hydroxyisobutyl, 2-ethoxyethyl, 2-methoxypropyl, 2-butoxyethyl, 2-cyanoethyl, 2-ethoxycarbonylethyl or 2-methoxycarbonylethyl. Substituted phenyl R 4 may for example be 3-chlorophenyl, 4-chlorophenyl, 4-tolyl, 4-tert-butylphenyl, 4-dodecylphenyl, 3-methoxyphenyl or 3-methoxycarbonyl nyl.

If R 4 together with R 2 is alkylene or phenylalkylene, they preferably form, together with the C atom and the linking N atom, a 5- or 6-membered heterocyclic ring. If R3 and R4 taken together are alkylene or interrupted alkylene, they preferably form together with the linking nitrogen atom, a 5- or 6-membered heterocyclic ring, for example a pyrrolidine, piperidine, morpholine, thiomorpholine or piperidone ring, which it may be substituted by one or more alkyl, hydroxyl, alkoxy or ester groups. Alkanoyl with 2 to 8 carbon atoms R 10 and R 17, for example, may be propionyl, butyryl, isobutyryl, hexanoyl or octanoyl, but preferably acetyl. Hydroxyalkyl with 1 to 4 carbon atoms or hydroxyalkyl with 2 to 4 carbon atoms Rlx, R19 and R2D for example can be 2-hydroxy-ethyl, 2-hydroxypropyl or 4-hydroxybutyl. Alkylene or interrupted alkylene R.sub.2, for example, may be ethylene, tri-, tetra-, penta-, hexa-, octa- or dodecamethylene, 2,2-dimethyltrimethylenes, 1,3,3-trimethyltetramethylene, 3-oxa-pentamethylene, 3- oxa-hept amet i 1 ene, 4-7-dioxadecamet i log, 4-9-dioxadodecamethylene, 3, 6, 9, 12-tetraoxatetradecamethylene or 4-thiaheptamethylene.

If alkyl with the 6 carbon atoms is interrupted by one or more atoms of 0, for example is interrupted by 1-3 or one or two atoms of 0. If R14 and R15 together are alkylene with 3 to 7 carbon atoms, particular are 1,3- or 1,4-alkylene for example 1, 3-propylene, 1,3-butylene, 2,4-pentylene, 1,3-hexylene, 1,4-butylene, 1,4-pentylene or 2,4-hexylene. Substituted phenyl R17, Rlβ, R19 and R20, for example, may be 4-chlorophenyl, 3-chlorophenyl, 4-tolyl, 4-tert-butylphenyl, 4-nonylphenyl, 4-dodecylphenyl, 3-methoxyphenyl or 4-ethoxyphenyl. A group -Si (alkyl with 8 carbon atoms) r (phenyl) 3 ^ r R17 can be in particular -Si (CH3) 3, -Si (phenyl) 2CH3, -Si (CH3) = phenyl, -Si ( CH3) 2- [C (CH3) 2CH (CH3) 2] or -Si (phenyl),. Alkyl with 1 to 6 carbon atoms substituted R17 can be, for example, 2-hydroxyethyl, 2-methoxyethyl or 2-allyloxyethyl. Alkyl with 1 to 6 carbon atoms Substituted Rlß for example can be 2-mercaptoethyl, 2-hydroxyethyl, 2-hydroxy-propyl, 2-methoxyethyl, -CH 2 CH 20 CH 2 CH 2 CN or -CH 2 CH 2-0 CH 2 CH 2 C00 CH 3. Alkoxyalkyl R19 and R2U can be, for example, methoxyethyl, ethoxyethyl, 2-ethoxypropyl, 2-butoxyethyl, 3-methoxypropyl or 2-hexyloxyethyl.

Alkanoyl with 2 to 3 carbon atoms R19 and R20 in particular are acetyl. Phenyl or substituted naphthyl R21 can be for example 4-tolyl, 4-bromophenyl, 3-chloro-phenyl, 4-butylphenyl, 4-octylphenyl, 4-decylphenyl, 4-dodecylphenyl, 3-methoxyphenyl, 4-isopropoxyphenyl, 4-butoxyphenyl , 4-octyloxyphenyl, chloronaphthyl, nonylnaphthyl or dodecylnaphthyl, Si Rl9 and R2Q together are alkylene or interrupted alkylene, together with the linking N atom, form a heterocyclic ring, preferably a 5- or 6-membered ring which may be substituted by alkyl, hydroxyl, alkoxy or ester groups. Examples of these rings are pyrrolidine, piperidine, 4-hydroxypiperidine, 3-ethoxycarbonylpiperidine, morpholine, or 2,6-di-methylmorpholine rings. All these compounds have at least one basic amino group and can therefore be converted into the corresponding salts, by adding acid. These acids can be inorganic or organic acids. Examples of these acids are HCl, HBr, H2S04, H3P04, mono- or polycarboxylic acids, for example acetic acid, oleic acid, succinic acid, sebasic acid, tartaric acid or CF3COOH, and sulfonic acids for example CH3S03H, C12H25S03H, p-Cj .2H25-C6H4-S03H, p-CH3-CbH-S03H or CF3S03H.

Preferred compounds of the formula I are those in which Arx is a group of the formula IV, R5 and R6 are hydrogen, halogen, alkyl with 12 carbon atoms or a group -OR17, -SR18, -S0R18, -S02-R18 , -N (R19) (R20), -NH-SO: R21 O wherein Z is -0-, -S-, -N (RX1) - or -N (R? n.) -R12-N (R1X) -, R, and R8 are hydrogen, R9 is hydrogen, halogen or alkyl with 1 to 12 carbon atoms and Rt, R3, R3, Rt1, R1S, R17, Rlt, R19, R20 and R31 are as defined above. Of the compounds of the formula I, wherein Ar, is a group of the formula IV, wherein R5 is a group -0R17, -SR18, -N (R19) (R20) or those compounds are preferred wherein R6 is hydrogen, halogen or alkyl having 4 carbon atoms or has one of the meanings given for R5, R7 and Rβ are hydrogen or halogen, Re is hydrogen or alkyl having 4 carbon atoms, z is -o-, -s- or -N (RX1) -, Rj. and R2 each independently of the other is any of (a) alkyl with i to 6 carbon atoms, Rl3 R14 R15 (b) a radical of the formula - C-C = C-Rl6 or (d) a radical of the formula -CH (R13) -Ar2; wherein Ar is a phenyl radical which is unsubstituted or substituted by halogen, alkyl having 1 to 4 carbon atoms, methylthio, methoxy or benzoyl; R3 and R4 each independently of the other are alkyl with 1 to 12 carbon atoms, alkyl with 2 to 4 carbon atoms, which is substituted by alkoxy with 4 carbon atoms, -CN or -COO (alkyl with 4 atoms) carbon) or R3 and R4 are allyl, cyclohexyl or benzyl or R3 and R4 together are alkylene with 4 to 6 carbon atoms which may be interrupted by -0-; RX1 is alkyl having 1 to 4 carbon atoms, allyl, benzyl or alkanoyl having 2 to 4 carbon atoms; Rl2 is alkylene with 2 to 6 carbon atoms; Ria, 14, Ris and Ris each independently is hydrogen or methyl; R17 is alkyl with 4 carbon atoms unsubstituted or substituted with SH, 2-hydroxyethyl, 2-methoxyethyl, 2-allyloxyethyl, allyl, cyclohexyl, phenyl, benzyl or -Si (CH a; Rlβ is hydrogen, alkyl with 1 to 12 carbon atoms in substitution or substituted with SH, 2-hydros-butyl, 2-methoxyethyl, phenyl unsubstituted or substituted with SH, or is p-tolyl or benzyl, and R19 and R0 each independently is alkyl with 12 atoms of carbon, alkoxyalkyl with 2 to 6 carbon atoms, acetyl, allyl or benzyl or R20 and R31 together are alkylene with 4 to 6 carbon atoms which may be interrupted by -0-. Particularly preferred compounds of formula I are those in where Arx is a group of the formula IV wherein R5 is a group -0Rj7, -SRlβ or -N (R19) (R20), Rb is hydrogen, chloro or alkyl having 1 to 4 carbon atoms, or has one of the meanings given for R5, R7 and R8 are hydrogen or chlorine, R9 is hydrogen or alkyl with 1 to 4 carbon atoms, Rj. is any of (a) a radical of the formula R14 R15 II-CH2-C = CH or (b) a radical of the formula -CH2-Ar2, wherein Ar2 is a phenyl radical which is unsubstituted or substituted by halogen, alkyl with the 4 carbon atoms, CH3S-, CH30- or benzyl, R2 has one of the meanings given for R? or is alkyl with 4 carbon atoms, R3 and R4 each independently of the other is alkyl with 6 carbon atoms, 2-methoxyethyl, allyl or benzyl, or R3 and R4 together are tetramethylene, pentamethylene or 3-oxapentamethylene, Ri And Ris are hydrogen or methyl, Rl7 is alkyl with 4 carbon atoms unsubstituted or substituted with SH, 2-hydroxyethyl, -methoxyethyl or phenyl, R18 is alkyl with 1 to 12 carbon atoms unsubstituted or substituted with SH, -hydroxyethyl, 2-methoxyethyl, unsubstituted or substituted phenyl with SH or is p-tolyl and R19 and R20 are hydrogen, C4 alkyl, 2-methoxyethyl, acetyl or allyl, or R19 and R20 together are alkylene with 4 to 5 carbon atoms that can be interrupted by -O-. The compound of the formula I (4-morpholin-benzoyl) -1-benzyl-1-dimethyl-amino propane is specifically preferred.

In addition, those compounds of the formula I, wherein A is a group of the formula IV are preferred, wherein R5 is a group -SR? E, Rt is a benzyl or allyl radical; R6 is hydrogen or methoxy; and R7, R "and R9 are hydrogen. Still further, compounds of formula I, wherein Ax is a group of formula IV, and Rx and R2 each independently of the other is alkyl having 1 to 8 carbon atoms, allyl or benzyl; and R5 is a group -0R17, -N (R20) (Rx9) or -SR18 are preferred, specifically (4-methylthiobenzoyl) -1-methyl-1-morpholinoethane. Preference is given to compounds of the formula I, wherein ArL is a group of formula IV, wherein R x and R 2 independently of each other is alkyl with 1 to 4 carbon atoms or benzyl; R3 and R4 each independently of the other is alkyl with 1 to 4 carbon atoms or together are morpholino; R5 is morpholino or alkylthio with 4 carbon atoms; and Rb, R7, Ra and R9 are hydrogen. Of the compounds of the formula I wherein rj is a group of the formula I, wherein R5 is a group N (R) L9) (R2Q), those compounds are preferred where R7 and R8 are hydrogen, and also those in which R6, R, Re and R9 are hydrogen, and those in which Rx is allyl or benzyl.

Preferred compounds of formula I are even more those in which Arx is a group of formula IV, wherein R5 is hydrogen, halogen or alkyl with 12 carbon atoms, and R6, R7, Rβ and R9 are hydrogen, RL is allyl or benzyl, R2 is alkyl having 1 to 6 carbon atoms, allyl or benzyl, R3 and R4 each one independently of the other is alkyl with 1 to 12 carbon atoms, alkyl with 2 to 4 carbon atoms substituted by alkoxy with 1 to 4 carbon atoms, -CN or -COO (alkyl with 1 to 4 carbon atoms) or R3 and R 4 are allyl, cyclohexyl or benzyl or R 3 and R 4 together are alkylene with 4 to 6 carbon atoms which can be interpolated by -0-. Examples of individual compounds of formula i are described in U.S. Pat. No. 5,077,402, column 7, line 65 to column 16, line 15 as well as Table 1 of this reference. The preparation of the compounds of the formulas i, II and ili is known and described among others in the patents of the U.S.A. Nos. 4,582,862, US 4,992,547 and US 5,077,402. According to this invention, the compounds of the formulas I, II and III can be used as latent base catalysts, ie as base generators, which are activated photochemically, in radiation curable systems. Systems which can be cured are those organic compounds which are capable of reacting in a base-catalyzed reaction, which may for example be a substitution reaction, an addition reaction or a condensation reaction. The base is only photogenerated in exposed areas of the composition and therefore, for example, thermosetting compositions for photophotography cured by the photobase catalyst, can be easily prepared without any need by an additional radical polymerization process. The process of the present invention is therefore useful for curing compositions that do not necessarily contain ethylenically unsaturated double bonds and provide novel thermoset compositions for photophotography cured by an anionic mechanism. The component (B) to be cured with the latent bases or in the process described respectively, is generally a compound containing at least one epoxide group and at least one group that is capable of reacting with epoxides in the presence of a base. Component (B) can also be a mixture of at least one epoxide compound and at least one compound that is capable of reacting with epoxides in the presence of a base. Compounds capable of reacting with epoxides in the presence of a base, in particular are carboxylic compounds such as carboxylic acids and anhydrides and thiols. Alcohols, amines and amides, in general compounds containing an "active" H atom are also suitable. Epoxide compounds that can be cured with the latent base compounds according to this inventionIn general, they are any compounds containing epoxide groups, monomeric or dimeric epoxides, as well as oligomeric compounds or polymeric compounds having epoxide groups. Typical examples are epoxidized acrylates, glycidyl ethers of bisphenol A, such as 2,2-bis [4- (2, 3-epoxypropoxy) phenyl] propane, phenol and cresol epoxy novolaks, glycidyl ethers of aliphatic diols, diglycidyl ether of bisphenol A hydrogenated, typically 2, 2-bis [4- (2, 3-epoxypropoxy) cyclohexyl] propane, 1,1,2,2-tetrakis [4- (2,3-epoxypropoxy) phenyl] ethane, triglycidyl isocyanurate and many others known to the person with skill in the specialty. Compounds with at least two epoxide groups are preferred. Epoxide compounds among others are described in the Ullma Xs Encyclopedia of Industrial Chemistry (Ullmann's Encyclopedia of Industrial Chemistry) 5th Edition, Vol. A9, Weinheim, New York, pages 547-553. In the context of the invention, it is possible to use any type of carboxylic acid having at least one carboxylic acid group, such as a compound that is susceptible or capable of reacting with the epoxide, such as for example dicarboxylic acids or polymeric acids . Specific examples are malonic acid, succinic acid, glutaric acid, adipic acid, sebasic acid, phthalic acid, terephthalic acid, maleic acid, cyclohexanedicarboxylic acid, polymeric acids such as partially saponified polyacrylates, for example Carboset resins available from Goodrich USA. Also copolymers of unsaturated compounds with or without acid functions can be used. Examples are partially esterified maleic anhydride-styrene copolymers, as sold under the trade name Scripset available from Monsanto. Also copolymers containing both epoxide and acid groups can be used in the context of the invention. Examples of suitable anhydrides in particular are dibasic anhydrides. Specific examples are phthalic anhydride, methyltetrahydrophthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, succinic anhydride, maleic anhydride, itaconic anhydride and nadic anhydride. Among others, they are described in U.S. Pat. No. 5,009,982 and JP-A 89-141904. Compounds with at least 2 acid groups are preferred in order to allow entanglement.

Typical thiols which are suitable are monomeric, oligomeric, aliphatic or aromatic thiols. Specific examples of these thiols are pentaerythritol tetra (mercaptoacetate, pentaerythritol tetra (mercaptopropionate), 4,4-thiobisbenzentiol, dithiothreitol, mercaptoethanol, dodecane thiol, thioglycolic acid, 3-mercato-propionic acid, or ethylene glycol dimercaptoacetate. systems which are suitable as component (B) in the present invention are described inter alia in EP 706,091, EP 747,770, WO 96/41240 and DE 196,22464 More examples for resins that can be cured with latent bases in accordance with invention among others are disclosed in U.S. Patent No. 4,943,516. Important compositions are those wherein component (B) is a curable or polymerizable organic material catalyzed by base.The organic material may be present in the form of monomers, oligomers or mono- or poly-functional polymers Preferred oligomeric / polymeric systems are as follows: Examples of these binder systems which can be catalysed by bases are: 1. Acrylate copolymers with alkoxysilane side groups or alkoxysilane side groups, for example the polymers described in US Pat. 4,772,672 or the US patent. 4,444,974; Two-component systems of polyacrylates containing hydroxyl groups, polyesters and / or polyethers and polyisocyanates, aliphatic or aromatic; Two-component systems of functional polyacrylates and a polyepoxide, the polyacrylate contains carboxyl groups, anhydride groups, thiol groups or amino groups; Two-component systems of polyacrylates modified by fluorine or modified by silicon, containing hydroxyl groups, polyesters and / or polyethers and aliphatic or aromatic polyisocyanates; Two-component systems of (poly) ketimines and aliphatic or aromatic polyisocyanates; Two-component systems of (poly) ketimines and unsaturated acrylate resins or acetoacetate or methyl-α-acrylamido-methyl glycolate resins; Two-component polyacrylate systems containing anhydride groups and polyamines; Two-component systems of (poly) oxazolidines and polyacrylates, containing anhydride groups or unsaturated acrylate resins or polyisocyanates; 9. Two-component systems of polyacrylates containing epoxy groups and polyacrylates which contain carboxyl groups or amino groups; 10. Polymers based on allyl / glycidyl ether; ll. Two-component systems of one (poly) alcohol and one (poly) isocyanate. Among these systems, points 1-3 are particularly preferred. Any mixtures or combinations of the compounds described above are also suitable. Catalyzed by the base, the components of the system react at room temperature or high and form an interlaced coating system that is suitable for many applications. The component (A) in the novel composition is usually present in an amount of 0.1-20% by weight, preferably 1-10% by weight, for example 1-5% by weight. The sensitivity of the photobase generating compound to the radiation can be further increased by combining the compounds with a suitable sensitizer (O. Examples of these sensitizers are in particular sensitizers of the group of carbonyl compounds having a triplet energy of 225-310 kj / mol.

Examples of suitable sensitizing compounds are also: xanthones, thioxanthones, phthalimides, anthraquinones, acetophenones, propiophenones, benzophenones, acylnaphthalenes, (acylmethylene) -thiazolines, 3-acylcoumarins and 3,3"-carbonyl-biscoumarins.Preferred sensitizers are thioxanthones, 3- acylcoumarins and 2 (aroylmethylene) -thiazoles, thioxanthones and 3-acyl-coumarins are particularly preferred Examples of individual compounds that can be used as component (C) according to the invention are described in U.S. Patent No. 4,992,547, column 16 line 58 to column 17 line 51 and are incorporated herein by reference.These sensitizers of component (C) increase the reactivity of the amine bases generated without shortening the shelf life or storage of the compositions. ) in the composition is from 0.01 to 5% by weight, preferably from 0.025 to 2% by weight. The fact that the photorupture of the latent base generating compounds of formulas I, II and III also generate radicals, is especially useful in dual curing systems (hybrid systems), where both a radical initiator and a base catalyst. Accordingly, the compounds of the formulas I, II and III can also be used as latent bases and at the same time as radical initiators in dual curing systems. The invention therefore also relates to systems that additionally contain radical polymerizable compounds (D) in addition to component (B). These compounds (D) are unsaturated compounds which may include one or more olefinic double bonds.

They can be of low molecular mass (monomeric) or high (oligomeric). Examples of monomers containing a double bond are alkyl or hydroxyalkyl acrylates or methacrylates, such as methyl, ethyl, benzyl, 2-ethylhexyl and 2-hydroxyethyl acrylate, isobornyl acrylate, methyl methacrylate and ethyl methacrylate. Silicone acrylates are also advantageous. Other examples are acrylonitrile, acrylamide, methacrylamide, N-substituted (meth) acrylamides, vinyl esters such as vinyl acetate, vinyl ethers, such as isobutyl vinyl ether, styrene, alkyl- and haloestyrenes, N-vinylpyrrolidone, vinyl chloride and sodium chloride. vini ideno Examples of monomers containing two or more double bonds are the diacrylates of ethylene glycol, propylene glycol, neopethyl glycol, hexamethylene glycol and bisphenol A, and 4,4"-bis (2-acryloxyethoxy) diphenylpropane, trimethylolpropane triacrylate, triacrylate or tetraacrylate pentaerythritol, vinyl acrylate, divinylbenzene, divinyl succinate, diallyl phthalate, triallyl phosphate, triallyl isocyanurate or tris (2-acrylethyl) isocyanurate Examples of relatively high molecular mass unsaturated compounds (oligomers) are acrylated epoxy resins, acrylated polyesters, polyesters containing vinyl ether or epoxy groups and also 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 which have molecular weights of about 500 to 3000. In addition, it is also possible to use monomers and oligomers of vinyl ether and also en olígómeros finished in maleato with main chains polyester, polyurethane, polyether, polyvinyl ether and epoxide. Particularly convenient are combinations of oligomers that carry vinyl ether groups and polymers as described in WO 90/01512. However, vinyl ether copolymers and monomers functionalized with maleic acid are also convenient. Unsaturated oligomers of this type can also be referred to as prepolymers. Particularly suitable examples are esters of ethylenically unsaturated carboxylic acids and polyols or polyepoxides and polymers having ethylenically unsaturated groups in the chain or in side or side groups, for example unsaturated polyesters, polyamides and polyurethanes and their copolymers, alkyd resins, copolymers of butadiene and polybutadiene, copolymers of isoprene and polyisoprene, polymers and copolymers containing (meth) acrylic groups in side chains and also mixtures of one or more of these polymers. Examples of unsaturated carboxylic acids are acrylic acid, methacrylic acid, crotonic acid, itaconic acid, cinnamic acid and unsaturated fatty acids such as linolenic acid or oleic acid. Acrylic and methacrylic acid are preferred. Suitable polyols are aromatic and in particular aliphatic and cycloaliphatic polyols. Examples of aromatic polyols are hydroquinone, 4,4"-dihydroxy-biphenyl, 2, -di (4-hydroxy-phenyl) -propane and also novolaks and cresols Examples of polyepoxides are those based on the aforementioned polyols, especially polyols Aromatics and Epichlorohydrin Other suitable polyols are polymers and copolymers containing hydroxyl groups in the polymer chain or in secondary groups, examples are polyvinyl alcohol and its copolymers, or polyhydroxy alkyl methacrylates or their copolymers Additional suitable polyols are oligoesters having hydroxyl end groups .

Examples of aliphatic and cycloaliphatic polyols are alkylene diols preferably having 2 to 12 carbon atoms, such as ethylene glycol, 1,2- or 1,3-propanediol, 1,2-, 1-3- or 1,4-butanediol. , pentanediol, hexandiol, octandiol, dodecanediol, diethylene glycol, triethylene glycol, polyethylene glycols having molecular weights preferably from 200 to 1500, 1,3-cyclopentanediol, 1,2-, 1,3-ol, 4-cyclohexylamino , 1,4-dihydroxymethylcyclohexane, glycerol, tris (d-hydroxyethyl) amine, trimethylolethane, trimethylolpropane, pentaerythritol, dipentaerythritol and sorbitol. The polyols can be partially or fully esterified with an unsaturated carboxylic acid or with several different unsaturated carboxylic acids and in partial esters the free hydroxyl groups can be modified, for example, esterified or etherified 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, triacrylate dipentaerythritol, dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, tripentaerythritol octaacrylate, pentaerythritol dimethacrylate, pentaerythritol trimethacrylate, dipentaerythritol dimethacrylate, dipentaerythritol tetramethacrylate, tripentaerythritol octamethacrylate, pentaerythritol diitaconate, dipentaerythritol trisitaconate, dipentaerythritol pentaitaconate, dipentaerythritol hexaitaconate, ethylene glycol diacrylate, l, 3-butanediol diacrylate, 1, 3- butanediol dimethacrylate, 1, -b-tandiol diitaconate, sorbitol triacrylate, sorbitol tetraacrylate, triacrylate modified with pentaer itritol, sorbitol tetramethacrylate, sorbitol pentaacrilate, sorbitol hexaacrylate, oligoester acrylates and methacrylates, glycerol diacrylate and triacrylate, 1,4-cyclohexanedrylate, bisacrylates and bis-methacrylates of polyethylene glycol having a molecular weight of 200 to 1500 or mixtures thereof. Suitable components (D) are also the amides of identical or different unsaturated carboxylic acids with aromatic, cycloaliphatic and aliphatic polyamines, which preferably have 2 to 6, especially 2 to 4, amino groups. Examples of these polyamines are ethylene diamine, 1,2- or 1,3-propylene diamine, 1,2-, 1,3-ol, 4-butylene diamine, 1,5-pentylenediamine, 1,6-hexylenediamine, octylenediamine, dodecylendi ina. , 1,4-diaminocyclohexane, isophorodiane, phenylenediamine, bisphenylenediamine, di - &; -aminoethyl ether, diethylenetriamine, triethylenetetraamine, di (β-aminoethoxy) - or di (S-a) inopropoxy) ethane. Other suitable polyamines are polymers and copolymers, which preferably contain additional amino groups in the side chain and oligoamides having amino end groups. Examples of these unsaturated amides are methylenebisacrylamide, 1,6-hexamethylene bisacrylamide, diethylenetriaminetris ethacrylamide, bis (methacrylamidopropoxy) ethane, β-methacrylamidoethyl methacrylate and N - [(β-hydroxyethoxy) ethyl] acrylamide. Suitable polyamides and unsaturated polyesters are derived, for example, from maleic acid, and from diols or diamines. Some of the maleic acid can be replaced by other dicarboxylic acids. They can be used together with ethylenically unsaturated comonomers, for example styrene. The polyesters and polyamides can also be derived from dicarboxylic acids and from ethylenically unsaturated diols or diamines, especially those having relatively long chains, for example from 6 to 20 carbon atoms. Examples of polyurethanes are those composed of saturated or unsaturated diisocyanates and of unsaturated or saturated diols, respectively. Polybutadiene and polyisoprene and their copolymers are known. Examples of suitable comonomers are olefins such as ethylene, propene, butene and hexene (meth) acrylates, acrylonitrile, styrene or vinyl chloride. Polymers with (meth) acrylate groups in the side chain are also known. For example, they can be reaction products of epoxy resins based on novolacs with (meth) acrylic acid or they can be homo- or copolymers of vinyl alcohol or its hydroxyalkyl derivatives which are esterified with (meth) acrylic acid or can be homo and copolymers of (meth) acrylates that are esterified with hydroxyalkyl (meth) acrylates. The photopolymerizable compounds can be used alone or in any desired mixture. It is preferred to use mixtures of poly (meth) acrylates. Binders can also be added to the novel compositions and this is particularly convenient when the photopolymerizable compounds are liquid or viscous substances. The amount of binder for example can be 5-95%, preferably 10-90% and especially 40-90% by weight, based on the total solids content. The selection of binder is made depending on the field of application and the properties required for this field, such as the capacity for development in solvent, aqueous and organic systems, adhesion to substrates and sensitivity to oxygen.

Examples of suitable binders are polymers having a molecular weight of about 5000 to 2000000, preferably 10000 to 1000000. Typical examples are: homo- and copolymers of acrylates and methacrylates, for example copolymers of methyl methacrylate / ethyl acrylate / methacrylic acid, poly (alkyl methacrylates), poly (alkyl acrylates); cellulose esters and cellulose ethers such as cellulose acetate, cellulose acetobutyrate, methyl cellulose, ethyl cellulose, polyvinyl butyral, polyvinyl formal, cyclized rubber, polyethers such as polyethylene oxide, polypropylene oxide and polytetrahydrofuran; polystyrene, polycarbonate, polyurethane, chlorinated polyolefins, polyvinyl chloride, vinyl chloride / vinylidene chloride copolymers, 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) and polyesters such as poly (ethylene glycol terephthalate) and poly (hexamethylene glycol succinate). The unsaturated compounds can also be used as a mixture with non-photopolymerizable film-forming components. They can, for example, be polymers or their typical drying solutions in organic solvents, for example nitrocellulose or cellulose acetobutyrate. However, they can also be chemically and / or thermally curable resins (thermo-curable), examples being polyisocyanates, polyepoxides and melamine resins. The use of thermo-curable resins is important concomitantly for use in these systems (also called hybrid systems), which are photopolymerized in a first stage and then interlaced by post-heat treatment in a second stage. In hybrid systems (as well as those comprising anionic and radical curable components as well as those comprising chemically and thermally curable components) the photopolymerizable mixtures in addition to the photoinitiator, may include various additives. Examples of these are thermal inhibitors which are used to prevent premature polymerization, examples being hydroquinone, hydroquinone derivatives, p-methoxyphenol, S-naphthol or sterically hindered phenols, such as 2,6-di-tert-butyl-p-cresol. In order to increase storage stability in the dark, it is possible for example to use copper compounds, such as copper naphthenate, stearate or octoate, phosphorus compounds, for example triphenylphosphine, triethyl phosphite, triphenyl phosphite or tribenzyl phosphite. To exclude atmospheric oxygen during polymerization in hybrid systems, it is possible to add paraffin or similar wax-like substances which, being of inadequate solubility in the polymer, migrate to the surface at the beginning of the polymerization and form a transparent surface layer that prevents the entry of air. It is also possible to apply an oxygen impermeable layer. Light stabilizers that can be added in a small amount are UV absorbers, for example those of the hydroxyphenylbenzotriazole, hydroxyphenebenzophenone, oxalamide or hydroxyphenyl-s-triazine type. These compounds can be used individually or in mixtures, with or without sterically hindered amines (HALS) with convenient (low) basicity, for example bis (? -octyloxy-2,, 6,6-tetramethylpiperidyl) succinate. Examples of these UV absorbers and light stabilizers are 1.2- (2"-hydroxyphenyl) benzotriazoles for example 2- (2" hydroxy-5"-methylphenyl) -benzotriazole, 2- (3", 5"-di-terbutil- 2"-hydroxyphenyl) benzotriazole, 2- (5" -tert-butyl-2"-hydroxyphenyl) benzothiole, 2- (2" -hydro? I-5"- (1,1,3,3-tetramethylbutyl ) phenyl) -benzotriazole, 2- (3", 5" -di-tert-butyl-2"-hydroxyphenyl) -5-chlorobenzotriazole, 2- (3" -tert-butyl-2"-hydroxy-5" -methylphenyl) ) -5-chlorobenzotriazole, 2- (3"-sec-butyl-5" -tert-butyl-2"-hydroxyphenyl) benzotriazole, 2- (2" -hydroxy-4"-octoxyphenyl) benzotriazole, 2- (3" -5"-di-ter-amyl-2" -hydroxyphenyl) benzotriazole, 2- (3", 5" -bis- (o ?, o'-dimethylbenzyl) -2"-hydroxyphenyl) -benzotriazole, mixture of 2- (3" -tert-butyl-2"-hydroxy-5) "- (2-octyloxycarbonylethyl) phenyl) -5-chlorobenzotrolyazole, 2- (3" -tert-butyl-5"- [2- (2-ethyl-hexxyloxy) carbonylethyl] -2" -hydroxyphenyl) -5-chlorobenzotriazole , 2- (3"-ter-butyl-2" -hydroxy-5"- (2-methoxy-carbonylythyl) phenyl) -5-chlorobenzotriazole, 2- (3" -tert-butyl-2"-hydroxy-5" - (2-methoxycarbonylethyl) phenyl) -benzotriazole, 2- (3"-tert-butyl-2" -hydroxy-5"- (octyloxycarbonylethyl) phenyl) -benzotriazole, 2- (3" -tert-butyl-5"- [2- (2-ethylhexyloxy) -carbonylethyl] -2"-hydroxy-phenyl) -benzotriazole, 2- (3" -dodecyl-2"-hydroxy-5" -methylphenyl) benzotriazole and 2- (3"-tert-butyl-2) "-hydroxy-5" - (2-isooctyloxycarbonylethyl) phenylbenzotriazole, 2,2"-methylenebis [4- (1,1,3,3-tetramethylbutyl) -6-benzotriazol-2-yl-phenol]; transesterification product of 2- [3"-ter-but i l-5 s - (2-methoxy-carboni let i l) -2" -hydroxyphenylbenzectriazole, with polyethylene glycol 300; [R-CH2CH2-COO (CH2) 3] 2- where R = 3"-tert-butyl-4" -hydroxy-5"-2H-benzotriazol-2-yl-f-enyl 2. -Hydroxybenzofenones, by example of 4-hydroxy-, 4-methoxy-, 4-octoxy-, 4-decyloxy-, 4-dodecyloxy-, 4-benzyloxy-, 4, 2", 4" -trihydroxy- and 2"-hydroxy derivative 4,4-dimethoxy 3 Esters of unsubstituted or substituted benzoic acids, for example 4-tert-butylphenyl salicylate, phenyl salicylate, octylphenyl salicylate, dibenzoylresorcinol, bis (4-tert-butylbenzoyl) resorcinol, benzoylresorcinol, , 4-di-tert-butylphenyl 3,5-di-tert-butyl-4-hydroxy-benzoate, hexadecyl-3, 5-di-tert-butyl-4-hydroxybenzoate, octadecyl-3, 5-di-tert-butyl- 4-hydroxybenzoate and 2-methyl-4,6-di-tert-butylphenyl 3,5-di-tert-butyl-yl-hydroxybenzoate 4. Acrylates, for example isooctyl or ethyl or β-cyano-β, β-diphenyl acrylate, methyl a-carbomexoticinamate, bifil or methyl o'-cyano-β-methyl-p-methoxycinnamate, methyl-carbomethoxy-p-methoxycinnamate and N- (β-carbomethoxy-β-cyanovinyl) -2-methyl-indole Ina 5. 2- (2-Hydr oxifenyl) -1,3,5-triazines, for example 2,4,6-tris (2-hydroxy-4-octyloxyfyl) -1,3,5-triazine, 2- (2-hydroxy) 4-octyloxyphenyl) -4,6-bis (2,4-dimethyl-ylphenyl) -1,3,5-triazine, 2- (2,4-dihydroxyphenyl) -4,6-bis (2,4-dimethylphenyl) ) - 1,3,5-triazine, 2,4-bis (2-hydroxy-4-propyloxy-phenyl) -6- (2,4-dimethyl-phenyl) -1,3,5-triazine, 2- ( 2-hydroxy-4-octyloxy phenyl) -4,6-bis (4-methylphenyl) -1,3,5-triazine, 2- (2-hydroxy-4-dodecyl oxy phenyl) -4,6-bis ( 2,4-dimethyl-f-enyl) -1,3,5-triazine, 2 [2-hydroxy-4- (2-hydroxy-3-butyloxy-propyloxy) phenyl] -4,6-bis (2,4) -dimethylphenyl) -l, 3, 5-triazine, 2- [2-hydroxy-4- (2-hydroxy-3-octyloxy-propyloxy) phenyl] -4,6-bis (2,4-dimethylphenyl) - 1,3,5-triazine, 2- [4-dodecyl / tridecyl-oxy- (2-hydroxypropyl) oxy-2-hydroxyphenyl] -4,6-bis (2,4-dimethylphenyl) -1,3,5- triazine. 6. Phosphites and phosphonites, for example triphenyl phosphite, diphenyl alkyl phosphites, phenyl dialkyl phosphites, tris (nonylphenyl) phosphite, trilauryl phosphite, trioctadecyl phosphite, distearyl pentaerythritol diphosphite, tris (2,4-di-tert-butylphenyl) phosphite, diisodecyl pentaerythritol diphosphite , bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite, bis-isodecyloxy pentaerythritol disphosphite, bis (2,4-di-ter) -butyl-6-methyl phenyl) pentaerythritol diphosphite, bis (2,4,6-tri-tert-butylphenyl) pentaerythritol diphosphite, tristearyl sorbitol? triphosphite, tetrakis (2,4-di-tert-butylphenyl) -4,4"-biphenylene diphosphite, 6-isooctyloxy-2, 4,8,10-tetra-tert-butyl-12H-dibenzo [d, g] - 1,3,2-dioxaphosphocin, 6-fluoro-, 3,8, 10-tetra-tert-butyl-12-methyl-dibenzo [d, g] -1, 3, 2-dioxaphosphocin, bis (2, 4- di-tert-butyl-6-methylphenyl) methyl phosphite and bis (2,4-di-tert-butyl-6-methylphenyl) ethyl phosphite Further customary additives for the compositions according to the invention, depending on the intended use, are fluorescent whitening agents, fillers, pigments, dyes, wetting agents, leveling assistants, flow improvers and adhesion promoters In order to cure thick and pigmented coatings, it is appropriate to add powdered glass beads or glass fibers, as described by example in U.S. Patent No. 5,013,768.In certain cases, especially for systems comprising components that are curable by different mechanisms, it may be advantageous to add one or more other photos. known ingredients (E) in addition to component (A), for example benzophenone, benzophenone derivatives, acetophenone, acetophenone derivatives, phenylglyoxalates, diketones (for example camphor quinone), anthraquinones, thioxanthones, acridines, electron transfer initiators (e.g. borate / dye systems), a-hydroxycycloalkyl phenyl ketones, dialkoxyacetophenones, a-hydroxyacetophenones, 4-aroyl-l, 3-dioxolanes, benzoin alkyl ethers and benzyl ketals, monoacyl phosphine oxides, bisacyl phosphine oxides, trisacylphosphine oxides, titanocenes or ferrocenium compounds, triazines and keto oximes. Examples of particularly suitable photoinitiators are: 1- (4-dodecylbenzoyl) -1-hydroxy-l-methyl ethane, 1- (4-isopropylbenzoyl) -1-hydroxy-1-methylethane, 1-benzoyl-1-hydroxy-1 - methane, l- [4- (2-hydroxyethoxy) enzoyl] -1-methylethane, 1- [4- (acryloyloxy-ethoxy) enzoyl] -l-hydroxy-1-methylethane, diphenyl ketone, phenyl-1-hydroxy cyclohexyl ketone, benzyl dimethyl ketal, bis (cyclopentadienyl) bis (2,6-difluoro-3-pyrril-phenyl) -titanium, complex salts of cyclopentadienyl arene iron (II) for example (€ - iso -propylbenzene) (? 5- cyclopentadienyl) -iron (II) hexafluorophosphate, trimethylbenzoyldiphenylphosphinoxide, bis- (2,6-dimethoxybenzoyl) - (2,4,4-trimethyl-pentyl) phosphinoxide, bis (2,4,6-trimethylbenzoyl) -2,4 -di-phenytophenylphosphino-oxide or bis (2,, 6-trimethylbenzoyl) phenyl-phosphinoxide. The invention therefore also provides compositions that in addition to the latent base photoinitiator (A) also provide at least one additional photoinitiator for radical polymerization (E) and / or other customary additives. The compounds of formulas i, II and III are suitable as photobase generators. Accordingly, they can be used in a process to carry out base catalyzed reactions. The process is characterized in that a composition as described above is irradiated with light having wavelengths from 200 to 700 nm. The invention therefore also relates to a process for photochemically generating bases in base-catalyzed polymerization reactions, characterized in that a compound of the formula I, II or III as defined above is added, as a latent base, to the mixture at polymerize and irradiate with light of wavelength from 200 to 700 nm, to generate the base. The process can be carried out in the presence of a sensitizer selected from the group of carbonyl compounds having a triplet energy of 225-310 kJ / mol. These sensitizing compounds are described above and are referred to as component (C) of the novel composition. In some cases, it is advantageous to heat the composition during or after irradiation. The entanglement reaction can often be accelerated, in this way in another of its aspects the invention therefore relates to a method for curing compositions comprising (A) a compound of the formula I, II or III as defined above, (B) at least one organic compound that is capable of reacting in a base catalyzed addition reaction or substitution reaction; and (C) optionally a sensitizer, wherein (1) the composition is irradiated with light having a wavelength of 200 to 700 nm to generate a base catalyst from the photosensitive precursor of formula I, II or III and ( 2) is subsequently cured in thermal form using as a catalyst the photogenerated base in step (1).

The photosensitivity of the novel compositions generally ranges from about 200 nm to 700 nm. Suitable radiation is present, for example, in sunlight or light from artificial light sources. Consequently, a large number of very different types of light source are employed. Both point and joint sources ("lamp mats") are suitable. Examples are carbon arc lamps, xenon arc lamps, mercury lamps of medium, high and low pressure, possibly adulterated with metal halides (metal-halogen lamps), metal vapor lamps excited with microwaves, excimer lamps, super-actinic fluorescent tubes, fluorescent lamps, incandescent argon lamps, electronic flash lamps, photographic flood lamps, electron beams and X-rays produced by synchrotrons or laser plasma. The distance between the lamp and the substrate to be exposed according to the invention can vary depending on the intended application and the type and output of the lamp and for example can be laser light sources of 2 cm to 150 cm, for example excimer laser They are especially convenient. Laser in the visible region can also be used. In this case, the high sensitivity of the novel materials is very advantageous. By this method it is possible to produce printed circuits in the electronics industry, lithographic offset printing plates or relief printing plates and also materials for photographic image recording. The temperature for the treatment stage (2) can be in the range from room temperature (approximately 25 ° C) at 180 ° C. The preferred temperature range depends on the reaction catalyzed by particular base. For example, for acid / epoxy systems, the temperature range is from 70 ° C to 160 ° C, for epoxy / thiol reactions, the temperature range is from room temperature to 120 ° C. The invention also relates to a process as described above, wherein the thermal curing step (2) is followed by a developing step (3). The development means removing non-interlaced parts of the composition. The person with skill in the specialty is familiar with the appropriate development methods. It is also possible to conduct the above procedure such that the photochemical step (l) is followed by a development step (3), before the thermal cure step (2) or such that the steps (1), (2) ) and (3) are followed by a second stage of thermal curing (4). An additional base catalyst, other than a compound of the formulas I, II or III or a precursor of said catalyst, can of course be added to the composition as a co-catalyst for the thermal step (2). These catalysts, for example, are imidazole derivatives, triazine derivatives, guanidine derivatives. Specific examples are 2PHZ, 2E4MZ-CNS, (imidazole derivatives of Shikoku Chemicals), acetoguanamine, benzoguanamine, dicyandiamide. The use of these thermal catalysts is described, for example, in: U.S. Pat. No. 4,943,516, JP 7-278266, JP 1-141904, JP 3-71137, JP 6-138655, JP 5-140251, JP 6-67430, JP 3-172317, JP 6-161108), JP 7-26183) . Since the compounds of the formulas i, II and III are also useful as radical photoinitiators, as already mentioned above, the process can also be carried out in a hybrid system, ie a mixture of anion and radical curable components. Accordingly, in this process, the composition may additionally comprise a monomer, oligomer or radical polymerizable polymer (D). The photobase generators according to the present invention are especially useful in applications where high thermal stability and / or good solvent resistance, low electrical conductivity, good mechanical properties are required, as is the case for example in welding protective layers, conformal coatings, encapsulation of electrical devices, stereolithography, etc. In addition, they are useful for the photoformation of image compositions, using a base-catalyzed or dual-curing mechanism (by radical and anionic), wherein the ce-amino ketone compounds at the same time are photoinitiators of photobase radicals and generators (such compositions they are described previously). The invention also provides compositions additional to components (A) and (B) comprising at least one ethylenically unsaturated, photopolymerizable compound that is emulsified, dispersed or dissolved in water. Aqueous prepolymer dispersions, radiation curable of this type, are commercially available in numerous variations. This term is taken to mean a dispersion of water and at least one prepolymer there dispersed. The concentration of water in these systems is, for example, from 5 to 80% by weight, in particular from 30 to 60% by weight. The radiation-curable prepolymer or prepolymer mixture is present, for example, in concentrations of from 95 to 20% by weight, and in particular from 70 to 40% by weight. The total of the percentages indicated for water and prepolymers in these compositions in each case is 100, to which the additives and additives in various amounts are added depending on the intended application. The water-dispersible, radiation-curable film-forming prepolymers which frequently also dissolve are for dispersions of aqueous prepolymers, are monofunctional or polyfunctional ethylenically unsaturated prepolymers which are known per se, can be initiated by free radicals and contain, for example, 0.01 to 1.0 mole of polymerizable double bonds per 100 grams of prepolymer and have an average molecular weight for example of at least 400, in particular from 500 to 10,000. Depending on the intended application, however, prepolymers having higher molecular weights may also be suitable. For example, use is made of psylesters containing polymerizable CC double bonds and having a maximum acid number of 10, polyethers containing polymerizable CC double bonds, hydroxyl-containing products of the reaction of a polyepoxide containing at least two epoxide groups per molecule with at least one carboxylic acid or », ß-ethylenically unsaturated, polyurethane (meth) acrylates, and ac, ethylene-unsaturated acrylic copolymers containing acrylic radicals, as described in EP-A-12 339. Mixtures of these prepolymers can also be employed. Also suitable are the polymerizable prepolymers described in EP-A-33 896, which are the thioether adducts of polymerizable prepolymers having an average molecular weight of at least 600, a content of carboxyl groups from 0.2 to 15% and a content of from 0.01 to 0.8 mol of double polymerizable CC bonds per 100 g of prepolymer. Other suitable aqueous dispersions based on specific alkyl (meth) crylate prepolymers are described in EP-A-41 125; Suitable water-dispersible, radiation-curable prepolymers made from urethane acrylates are described in DE-A-2 936 039. Water-borne or water-soluble protective layer compositions are described, for example, in JP-A- 4-169985, JP-A 4-169986, JP-A 4-169987 and JP-A 4-31361. These aqueous radiation curable prepolymer dispersions can include additives, dispersion assists, emulsifiers, antioxidants, light stabilizers, colorants, pigments, fillers, for example talc, gypsum, silica, rutile, carbon black, zinc oxide. , and iron oxides, reaction accelerators, leveling agents, lubricants, wetting agents, thickeners, matting agents, defoamers and other assistants that are customary in coating technology. Suitable dispersion assistants are water-soluble organic compounds of high molecular mass containing polar groups, examples being polyvinyl alcohols, polyvinyl pyrrolidone and cellulose ethers. Emulsifiers can be used as nonionic emulsifiers and possibly also ionic emulsifiers. The compositions according to the invention can also be used for radiation curable powder coatings. The powder coatings can be based on the resin compositions described, including hybrid systems. A UV curable powder coating can be formulated by mixing polymers with carboxylic acid groups, with epoxides and adding the photobase generator (or mixtures thereof). Hybrid powder coatings can also be formulated by adding solid resins and monomers containing reactive double bonds to polymers containing carboxylic acid groups and epoxides and photobase generators (alone or in combination with radical initiators). Resins and monomers containing reactive double bonds, for example, are maleates, vinyl ethers, acrylates, acrylamides and mixtures thereof. The powder coatings may also comprise binders as described for example in DE-A-42 28 51 and in EP-A-636 669. The powder coatings may additionally comprise white or colored pigments. For example, titanium dioxide, preferably rutile titanium dioxide, may be used in concentrations of up to 50% by weight in order to give a cured powder coating of good hiding power. The process usually comprises electrostatic or tribostatic spraying of the powder onto the substrate, for example metal or wood, melting the powder by heating and after a smooth or uniform film has been formed, radiation coating the coating with ultraviolet and / or visible light , using for example medium pressure mercury lamps, metal halide lamps or xenon lamps. The irradiation can be carried out while the coated articles are still hot to accelerate the curing, but it is also possible to irradiate after cooling and a second heat treatment (at a different site after assembling different parts). A particular advantage of the radiation curable powder coatings against their thermosetting counterparts is that the flow time after fusing of the powder particles can be retarded if desired in order to ensure the formation of a high gloss coating., smooth or even. In contrast to thermo-curable systems, radiation curable powder coatings can be formulated to melt at lower temperatures without the undesired effect of shortening their useful life. For this reason, they are also suitable as coatings for thermosensitive substrates, for example wood or plastic. In addition, the powder coating formulations may also include UV absorbers and other additives. Appropriate examples were listed above. The photopolymerizable compositions can be used for various purposes, for example as printing inks, as a transparent finish, as a white finish, for example for wood or metal, as a coating material, inter alia for paper, wood, metal or plastic, as a powder coating, as a coating curable in daylight for marking roads and marking buildings, for photographic reproduction techniques, for holographic recording materials, for image recording techniques or for producing printing plates that can be developed with organic solvents or aqueous alkalis, to produce masks for screen printing or screen printing, as dental filling compositions, as adhesives, including pressure sensitive adhesives, such as laminating resins, as a permanent etch protective layer or protective layer; as welding masks and photoforming dielectrics for even image to electrical circuits, for electronic circuits, to produce three-dimensional articles by mass curing (UV curing in transparent molds) or by stereolithography technique, to produce composite materials and other thick-film compositions, to coat or seal electronic components or as coatings for optical fibers. When coating hybrid curing system materials, mixtures of a prepolymer with polyunsaturated monomers are often used, which may additionally include a mono-unsaturated monomer as well. It is the prepolymer here that primarily dictates the properties of the coating film and by varying it, the skilled in the specialty is able to influence the properties of the cured film. The functions of polyunsaturated monomer as an entanglement agent that makes the film insoluble. The monounsaturated monomer functions as a reactive diluent which is used to reduce the viscosity without the need for a solvent. The novel photocurable compositions are suitable, for example, as coating materials for substrates of all types, for example wood, textiles, paper, ceramics, glass, plastics such as polyesters, polyethylene terephthalate, polyolefins or cellulose acetate, especially in the form of films. and also metals such as Al, Cu, Ni, Fe, Zn, Mg or Co and GaAs, Si or Si02, to which it is intended to apply a protective layer or by means of image exposure to generate a reproduced image. The coating of the substrates can be carried out by applying a liquid composition, a solution or a suspension to the substrate. The selection of solvents and the concentration depend mainly on the type of composition and the coating technique. The solvent must be inert, ie it must not undergo a chemical reaction with the components and must be capable of being removed again after coating in the course of drying. Examples of suitable solvents are ketones, ethers and esters such as methyl ethyl ketone, isobutyl methyl ketone, cyclopentanone, cyclohexanone, dioxane, tetrahydrofuran, 2-methoethanol, 2-ethoxyethanol, α-methoxy-2-propanol, 1-2. dimethoxyethane, ethyl acetate, n-butyl acetate and ethyl 3-ethoxypropionate. The solution is applied uniformly to a substrate by means of known coating techniques, for example by spin coating, dip coating, spatula coating or knife, curtain coating, brushing, spraying, especially electrostatic spraying, and reverse roll coating, and also by electrophoretic deposition. It is also possible to apply the photosensitive layer to a temporary flexible support for coating the final substrate eg a copper-coated circuit board by transferring the layer by lamination. The amount applied (coating thickness) and the nature of the substrate (layer support) depend on the desired field of application. The range of coating thicknesses, in general, comprise values of approximately 0.1 μm to more than 100 μm. The novel radiation sensitive compositions find application as a negative protective layer, which have a very high sensitivity to light and are capable of being developed in an aqueous alkaline medium without bloating. They are suitable as protective photocaps for electronic components (electro-coating protective layer, etching protective layer, welding protective layer), the production of printing plates, such as offset printing plates, flexographic and relief plates or screen printing and / or production of dyes, for use in chemical milling or as a protective micro-layer in the production of integrated circuits. The possible layer supports and the processing conditions of the coated substrates are equally varied. The compounds according to the invention also find application for the production of single or multiple layer materials for image recording or image reproduction (copies, reprography) which can be mono- or polychromatic. In addition, the materials are suitable for color test systems. In these technologies, it is possible to apply formulations containing microcapsules and for the production of radiation curing image can be followed by a thermal treatment and / or depression. Substrates employed for recording photographic information include for example cellulose acetate or polyester films, or polymer coated papers; substrates for offset printing forms, are specially treated aluminum, substrates for producing printed circuits are laminated with copper cladding and substrates for producing integrated circuits are silicon wafers or wafers. The thicknesses of layers for photographic materials and forms of offset printing, in general are from approximately 0.5 μm to 10 μm, while for printed circuits they are from 0.1 μm to approximately 100 μm. After the substrates are coated, the solvent is removed, generally by drying, to leave a protective photo coating on the substrate. The temperature range depends on the particular base catalyst reaction and should be less than the start temperature of the uncatalyzed reaction.

The term "in the form of image formation" includes both exposure through a photomask which comprises a predetermined pattern, for example a slide, exposure by a light beam (e.g. a laser beam), which for example moves under computer control over the surface of the coated substrate, producing an image in this manner, and irradiation with electron beams controlled by computer. Following the exposure as an image of the material and before development, it may be advantageous to carry out heat treatment for a short time. In this case, only the exposed sections are thermally cured. The temperatures for this post-exposure baking are in the range from room temperature (approximately 25 ° C) up to 200 ° C and depending on the reaction catalyzed with particular base. Preferred temperatures for the reaction with epoxide acid are 100-160 ° C and for the thiol epoxide reaction from room temperature to 120 ° C. The period of thermal treatment in general is from 0.25 to 10 minutes. The photocurable composition can additionally be employed in a process for producing protective plates or protective photo-layers similar to those described for example in DE-A-40 13 358. After exposure and if implemented, heat treatment, the unexposed areas of the photosensitive coating they are removed with a developer in a way known per se. As already mentioned, novel compositions can be developed, inter alia, with aqueous alkalis. Particularly suitable aqueous alkaline developer solutions are aqueous solutions of tetralkyl ammonium hydroxides or alkali metal silicates, phosphates, hydroxides and carbonates. If desired, minor amounts of wetting agents and / or organic solvents can also be added to these solutions. Examples of typical organic solvents that can be added to developer liquids in small amounts are cyclohexanone, 2-ethoxyethanol, toluene, acetone and mixtures of these solvents. Another field where photocoating is employed is for coating metals, such as coating metal plates and tubes, cans and bottle caps, and light curing polymer coatings, for example floor or wall coverings with a PVC base. Examples of the curing of paper coatings are the colorless finishes of labels, disc covers and book covers.

The compositions and compounds according to the invention can be used for the production of optical switches and waveguides, where the development of a difference in the refractive index between irradiated and non-irradiated areas is used. The use of photocurable compositions for imaging techniques and for the optical production of information carriers is also important. In these applications, as already described above, the layer (wet or dry) applied to the support is irradiated through a photomask with UV or visible light, and the unexposed areas of the layer are removed by treatment with a solvent (= revealing). The application of the photo-stable layer to the metal can also be carried out by electrodeposition. The exposed areas are polymeric through interlacing and therefore insoluble and remain in the support. Proper coloring produces visible images. When the support is a metallized layer, the metal can, following exposure and development, mordentate in non-exposed areas or be reinforced by electrocoating. In this way it is possible to produce printed electronic circuits and protective photocaps. The invention further provides the use of the composition described above, for preparing pigmented and non-pigmented paints and varnishes, printing inks, powder coatings, printing plates, adhesives, dental compositions, waveguides, optical switches, systems for testing color, composite compositions, fiberglass cable coatings, stencils for screen printing, protective layer materials, for photographic reproductions, for encapsulating electronic and electrical components, for producing magnetic recording materials, for producing three-dimensional objects by stereolithography and as material for image recording, especially for holographic recordings. The preferred composition is used for the production of protective layer materials, welding masks, conformal coatings, protective coatings, powder coatings, overprint varnishes, glass fiber coatings, wave guides, printing plates, adhesives, inks, stencils for screen printing, reinforced composite materials, optical switches, color test systems, magnetic recording media, dental materials, or a procedure conducted as a stereolithographic or holographic process. The compounds of formulas I, II and III are base generators that can be photochemically activated and exhibit surprisingly excellent latency before exposure to UV light. In addition, they have high absorption in the near UV region and high catalytic activity after photorupture of the substituted benzoyl portion of the molecule. The following examples illustrate the invention in more detail. Parts and percentages as in the remainder of the description and in the claims, are by weight unless otherwise indicated. When alkyl radicals having more than three carbon atoms are mentioned without mention of specific isomers, the n-isomers are intended in each case. Example 1: Photobase activity. Testing the latency of ce-amino ketones before irradiation and catalytic activity after irradiation 1. (a) A formulation is prepared by mixing 20 <0 parts of a polyacrylate with 3-5% carboxylic function (MRCarboset 525, which is provided by Goodrich, USA) and 100 parts of epoxyphenol novolac (GY 1180, provided by Ciba Specialty Chemicals). A sample of this formulation is subjected to Differential Scanning Calorimetry (CED = DSC = Differntial Scanning Calorimetry). The DSC curve (heating rate 10 ° C / minute) shows a peak temperature of 242 ° C. l. (b) A formulation is prepared by mixing 200 parts of a polyacrylate with 3-5% carboxylic function (MRCarboset 525, which is provided by «Goodrich, USA) and 100 parts of novolac epoxyphenol (GY 1180, provided by Ciba Specialty Chemicals) 6 parts of 4- (methylthiobenzoyl) -1-methyl-l-morpholinoethane (MRIrgacure 907, which is provided by Ciba Specialty Chemicals) A sample of this formulation is subjected to DSC (heating rate, 10 ° C / minute). The DSC curve shows a peak temperature of 243 ° C. A second sample is irradiated for 40 s, with a metal halide lamp (ORC SMX3000, 3 kW), the peak shown at 169 ° C. 1. (c) A formulation is prepared by mixing 200 parts of a polyacrylate with 3-5% carboxylic function (MRCarboset 525, which is provided by Goodrich, USA) and 100 parts of epoxyfenol novolak (GY 1180, provided by Ciba Specialty Chemicals) 6 parts of 4- (methylthiobenzoyl) -1-benzyl-1-dimethyl-aminopropane (MRIrgacure 369, which is provided by Ciba Specialty Chemicals).

A sample of this formulation is subjected to DSC (heating rate 10 ° C / minute). The DSC curve shows a peak temperature of 212 ° C. A second sample is irradiated for 40 s, with a metal halide lamp (ORC SMX3000, 3 kW), the peak is displayed at 152 ° C. Example 2: 2. (a) A formulation is prepared by mixing 200 parts of a polyacrylate with 3-5% carboxylic function (MRCarboset 525, which is provided by Goodrich, USA) and 100 parts of epoxyphenol novolac (GY 1180, provided by Ciba Specialty Chemicals) 9 parts of 4- (methylthiobenzoyl) -1-methyl-1-morpholine ethane (MttIrgacure 907, which is provided by Ciba Specialty Chemicals), 450 parts of acetone. 2 (b) A formulation is prepared by mixing 200 parts of a polyacrylate with 3-5% carboxylic function (MRCarboset 525, which is provided by Goodrich, USA) and 100 parts of epoxyphenol novolac (GY 1180, provided by Ciba Specialty Chemicals 9 parts of (4-morpholinbenzoyl) -1-benzyl-1-dimethyl-aminopropane (MRIrgacure 369, which is provided by Ciba Specialty Chemicals), 450 parts of acetone. Samples of the formulations are applied to an aluminum plate using a wire-coated applicator with 100 μm wire and air-dried at 50 ° C for 15 minutes. The resulting protective layers, which are approximately 25 μm thick, are covered firmly with a thin sheet of polyester and this is covered with a standardized test negative with 21 stages of different optical density (Stouffer wedge), and finally covered over with a second polyester film and the resulting laminate is fixed on a metal plate. The sample is irradiated with a 3 kW metal halide lamp (ORC SMX3000) at a distance of 60 cm by 80 seconds in a first series of tests, by 160 seconds in a second series of tests and by 320 seconds in a third series of tests. After irradiation, the samples are heated for 5 minutes at 150 ° C in the case of the formulation (a) and at 130 ° C in the case of the formulation (b). Then, the samples are revealed in ethanol in an ultrasonic bath for 5 minutes. The highest tack-free stage of the protective layer is determined as a measure for the sensitivity of the protective layer. The greater the number of stages, the more reactive is the formulation of protective layer. The results are summarized in Table 1.

Table i Number of stages that are achieved after irradiation by Formulation 80 s 160 s 32Q g 2. (a) 6 8 10 2. (b) 6 8 10 Example 3: (Photobase activity: ce-amino ketone latency test before irradiation and catalytic activity after irradiation) Formulation 3. (a): 200 parts of an epoxyphenol novolac (GY 1180, provided by Asahi CIBA, Japan) 50 parts of 4, 4"-thiobisbenzentiol (which is provided by Sigma- Aldrich, Japan) The DSC curve (heating speed ° C / minute) shows a peak temperature of 175 ° C. Formulation 3. (b): 200 parts of a Novslaca epsxyphenol (GY 1180, provided by Asahi CIBA, Japan) 50 parts of 4, 4"-thiobisbenzentiol (provided by Sigma-Aldrich, Japan) 6 parts of 4- ( methylthiobenzoyl) -l-methyl-1-morpholin ethane (MRIrgacure 907, provided by Ciba Specialty Chemicals).

The DSC curve (heating rate 10 ° C / minute) shows a peak temperature of 167 ° C without exposure. After irradiating a sample for 40 s with a metal halide lamp (ORC SMX3000, 3 kW), the DSC curve shows a peak at 7 ° C-Formulation 3. (c): 200 parts of an epoxyphenol novolac (GY 1180) , supplied by Asahi CIBA, Japan) 50 parts of 4, 4"-thiobisbenzentiol (which is provided by Sigma-Aldrich, Japan) 6 parts of (4-morpholinbenzoyl) -1-benzyl-1-dimethylaminopropane (MRIrgacure 369, provided by Ciba Specialty Chemicals) The DSC curve (heating rate 10 ° C / minute) shows a peak temperature of 172 ° C without exposure, after irradiating a sample for 40 s with a metal halide lamp (ORC SMX3000, 3). kW), the DSC curve shows a peak at 44 ° C. Example 4: (Photobase activity: ce-amino ketone latency test before irradiation and catalytic activity after irradiation.) Formulation 4. (a): 200 parts of cresolnovolac epoxy (ECN1299, which is provided by Asahi CIBA, Japan) 50 parts of 4, 4"-thio bisbenzentiol (provided by Sigma-Aldrich, Japan) The DSC curve (heating rate 10 ° C / minute) shows a peak temperature of 148 ° C. Formulation 4. (b): 200 parts of epoxyresol novolac (ECN1299, which is provided by Asahi CIBA, Japan) 50 parts of 4, 4"-thiobisbenzentiol (provided by Sigma-Aldrich Japan) 6 parts of 4- (methylthiobenzoyl) - ? -methyl-l-morpholine ethane. {"" Irgacure 907, which is provided by Ciba Specialty Chemicals) The DSC curve (heating rate 10 ° C / minute) shows a peak temperature of 149 ° C (start temperature 105 ° C) without exposure and after irradiating a sample for 40s, with a metal halide lamp (ORC SMX3000, 3 kW), the DSC curve shows a peak of 135 ° C (start temperature 50 ° C). (c): 200 parts of cresolnovolac epoxy (ECN1299, which is provided by Asahi CIBA, Japan) 50 parts of 4, 4"-thiobisbenzentiol (provided by Sigma-Aldrich Japan) 6 parts of (4-morpholinbenzoyl) -l- benzyl-l-dimethyl-aminopropane (RIrgacure 369, which is provided by Ciba Specialty Chemicals) The DSC curve (heating rate) to 10 ° C / minute) shows a peak temperature of 145 ° C without exposure. After irradiating a sample for 40s, the DSC curve shows a peak at 87 ° C. Example 5: (Photobase activity: latency test of ce-amino ketones before irradiation and catalytic activity after irradiation). Formulation 5. (a): 200 parts of an epoxyphenol novolac (GY 1180, which is provided by Asahi CIBA, Japan) 50 parts of DL-dithiothreitol (provided by Tokyo Kasei, Japan) The DSC curve (heating rate l0 ° C / minute) shows a peak temperature of 121 ° C. Formulation 5. (b): 200 parts of an epoxyphenol novolac (GY 1180, which is provided by Asahi CIBA, Japan) 50 parts of DL-dithiothreitol (which is provided by Tokyo Kasei, Japan) 6 parts of (4- morpholinbenzoyl) -1-benzyl-l-dimethyl-aminopropane (NRIrgacure 369, which is provided by Ciba Specialty Chemicals) The DSC curve (heating rate 10 ° C / minute) shows a peak temperature of 121 ° C without exposure. After irradiating a sample for 40s, the DSC curve shows a peak at 69 ° C. Example 6: (Photobase activity: ce-amino ketone latency test before irradiation and catalytic activity after irradiation). Formulation 6. (a): 200 parts of epoxylesol novolac (ECN1299, which is provided by Asahi CIBA, Japan) 50 parts of DL-dithiothreitol (provided by Tokyo Kasei, Japan) The DSC curve (heating rate 10 ° C / minute) shows a peak temperature of 138 ° C. Formulation 6. (b): 200 parts of epoxyresol novolac (ECN1299, which is provided by Asahi CIBA, Japan) 50 parts of DL-dithiothreitol (provided by Tokyo Kasel, Japan) 6 parts of (4-morpholin-benzoyl) -1 -benzyl-l-dimethyl-aminopropane (MRIrgacure 369, which is provided by Ciba Specialty Chemicals) The DSC curve (heating rate 10 ° C / minute) shows a peak temperature of 135 ° C without exposure. After irradiating a sample for 40 s, the DSC peak is displayed at 9l ° C. Example 7: (Photobase activity: ce-aminocetsen latency test before irradiation and catalytic activity after irradiation) Formulation 7. (a): 200 parts of an epoxyphenol novolac (GY 1180, which is provided by Asahi CIBA, Japan 100 parts of pentaerythritol tetra (mercaptoacetate) (which is provided by Tokyo Kasei, Japan) The DSC curve (heating rate 10 ° C / minute) shows a peak temperature of 240 ° C. Formulation 7. (b): 200 parts of an epoxyphenol novolac (GY 1180, which is provided by Asahi CIBA, Japan) 100 parts of pentaerythritol tetra (mercaptoacetate) (which is provided by Tokyo Kasei, Japan) 6 parts of 4- ( methylthiobenzoyl) -i-methyl-l-morpholine ethane (MRIrgacure 907, which is provided by Ciba Specialty Chemicals) The DSC curve (heating rate ° C / minute) shows a peak temperature of 243 ° C without exposure. After irradiating a 40s sample with a metal halide lamp (ORC SMX3000, 3 kW) the DSC peak is displayed at 161 ° C.

Formulation 7. (c): 200 parts of an epoxyphenol novolac (GY 1180, which is provided by Asahi CIBA, Japan) 100 parts of pentaerythritol tetra. { mercaptoacetate) (which is provided by Tokyo Kasei, Japan) 6 parts of 4- (methylthiobenzoyl) -1-benzyl-1-dimethyl-aminopropane (KRIrgacure 369, which is provided by Ciba Specialty Chemicals) The DSC curve (heating rate 10 ° C / minute) shows a peak temperature of 242 ° C without exposure. After irradiating a sample by 40e, the DSC peak is displayed at 124 ° C. Example 8: photobase: ce-amino ketone latency test before irradiation and catalytic activity after irradiation Formulation 8. (a): 200 part? of epoxylesol novolac (ECN 1299, which is provided by Asahi CIBA, Japan) 50 parts of pentaerythritol tetra (mercaptoacetate) (which is provided by Tokyo Kasei, Japan) The DSC curve (heating rate 10 ° C / minute) shows a temperature peak of 199 ° C. Formulation 8. (b): 200 parts of epoxyresol novolac (ECN 1299, which is provided by Asahi CIBA, Japan) 50 parts of pentaerythritol tetra (mercaptoacetate) (which is provided by Tokyo Kasei, Japan) 6 parts of 4- (methylthiobenzoyl ) -l-methyl-1-morpholin ethane (MRlgagacure 907, which is provided by Ciba Specialty Chemicals). The DSC curve (heating rate 10 ° C / minute) shows a peak temperature of 212 ° C without exposure. After irradiating a sample for 40 s with a metal halide lamp (ORC SMX3000, 3 kW) the peak is displayed at 167 ° C. Formulation 8. (c): 200 parts of epoxyresol novolac (ECN 1299, which is provided by Asahi CIBA, Japan) 50 parts of pentaerythritol tetra (mercaptoacetate) (which is provided by Tokyo Kasei, Japan) 6 parts of (4-morpholinbenzoyl) ) -1-benzyl-1-dimethyl-aminopropane (MRIrgacure 369, which is provided by Ciba Specialty Chemicals). The DSC curve (heating rate 10 ° C / minute) shows a peak temperature of 20 ° C without exposure. After irradiating a sample for 40 s with a metal halide lamp (ORC SMX3000, 3 kW) the peak is displayed at 124 ° C.

Example 9: (Test that thermosetting compositions for photoforming of image cured by an ionic mechanism, can be obtained with the process of the invention) The following formulations are prepared by mixing (parts by weight): Formulation 9. (a): 200 parts of epoxylesol novolac (ECN 1299, which is provided by Asahi CIBA, Japan) 50 parts of 4, 4"-thiobisbenzentiol (which is provided by Sigma-Aldrich, Japan) 6 parts of (4-morpholin-benzoyl) -l-benzyl-1 -dimethyl aminopropane (MRIrgacure 369, which is provided by Ciba Specialty Chemicals) 250 parts of tetrahydrofuran Formulation 9. (b): 200 parts of epoxyresol novolac (ECN 1299, which is provided by Asahi CIBA, Japan) 50 parts of DL-dithiothreitol (which is provided by Tokyo Kasei, Japan) 6 parts of (4-morpholinbenzoyl) -1-benzyl-1-dimethyl-to inopropane (MRIrgacure 369, which is provided by Ciba Specialty Chemicals) 250 parts of hydro-furan. Formulation 9. (c): 200 parts of epoxyphenol novolac { ECN 1299, which is provided by Asahi CIBA, Japan) 50 parts of pentaerythritol tetra (mercaptoacerate) (which is provided by Tokyo Kasei, Japan) 6 parts of (4-morpholinbenzoyl) -i-benzyl-1-dimethyl-aminopropane (MRIrgacure 369, which is provided by Ciba Specialty Chemicals) 250 parts of Hydrofuran. Formulation 9. (d): 200 parts of epoxyphenol novolac (GY 1180, which is provided by Asahi CIBA, Japan) 50 parts of 4, 4"-thiobisbenzentiol (which is provided by Sima-Aldrich, Japan) 6 parts of (4-morpholinbenzoyl) -1-benzyl-1-dimethyl-aminopropane (MRIrgacure 369, which is provided by Ciba Specialty Chemicals) 150 parts of tetrahydrofuran. Formulation 9. (e): 200 parts of epoxyphenol novolac (GY 1180, which is provided by Asahi CIBA, Japan) 50 parts of 4, 4"-thiobisbenzentiol (which is provided by Sigma-Aldrich, Japan) 6 parts of 4- (methylthiobenzoyl) -l-methyl-l-morpholinoethane (MRIrgacure 907 , which is provided by Ciba Specialty Chemicals) 150 parts of tetrahydrofuran Formulation 9. (f): 200 parts of epoxyphenol novolak (GY 1180, which is provided by Asahi CIBA, Japan) 50 parts of DL-dithiothreitol (which is provided by Tokyo Kasei, Japan) 6 parts of (4-morpholinbenzoyl) -1-benzyl-i-dimethyl-aminopropane (MRIrgacure 369, which is provided by Ciba Specialty Chemicals) 150 parts of tetrahydrofuran Formulations 9. (a) -9. (f) are coated on an aluminum plate with a coating applicator with coiled wire rod (wet thickness of 50 μm for formulations (ac) and wet thickness of 36 μm for formulations (df)) and air-dried at 45 ° C for 10 minutes.

The resulting protective layers, with a thickness of approximately 23 μm and thickness of 18 μm for the formulations (a-c) and (d-f), respectively, are firmly covered with a thin sheet of polyester, and radiate for 320 seconds with a metal halide lamp of 3 kW (ORC SMX3000), which is placed at a distance of 60 cm. The samples are irradiated through a wedge with a 21-stage density (Stouffer Graphic Arts) and a thin sheet under vacuum at 30 ° C. After irradiation, the samples are heated under various post-exposure baking conditions (collected in Table 2). The samples are revealed by a mixture of ethanol and methyl ethyl ketone (1: 1) in an ultrasonic bath. The highest tack free stage is used as a measure of the sensitivity of the protective layer. The higher the number of stages, the better the cure effectiveness of the formulation. The sensitivities obtained are listed in the following Table 2. Table 2 Stepwise wedge sensitivity evaluation after 320 seconds of irradiation Number of stages achieved Revealed Baking conditions after exposure f ° Cl Formu- Time r.t. r.t. r.t. r.t. r.t. 50 70 80 100 120 tion rseg.1 0 15 30 60 120 5 5 5 5 5 a 120 3 6 8 10 13 7 9 nt nt nt b 60 X 4 8 10 13 6 11 nt nt nt nt c 120 XXXXX nt nt x 6 11 d 10 8 11 12 13 14 11 12 nt nt nt nt e t 10 - 4 5 7 9 4 6 nt 7 nt f 10 - 8 11 14 16 9 14 nt nt nt nt -: slightly polymerized, x: without polymerization, nt: not tested, r.t .: 22-23 ° C.

Claims (17)

CLAIMS 1. A composition, characterized in that it comprises (A) as a latent base catalyst, at least one compound of the formulas i, II or III
1. Ar.-? C- fC-X-C? 1-? C-Ar. 1 i? 1 (ll) wherein Arx is an aromatic radical of formulas IV, V, VI or VII
2. X is a divalent radical of the formula
3. -N (R1L) - or -NYR ^) -R12-N (RX1) -; Y is alkylene with 1 to 6 carbon atoms, cyclohexylene or a direct bond; U is -O-, -S- or -N (Rl7) -; V has one of the meanings of U or is -CO-, -CH2-, -CH2CH2-, alkylidene with 2 to 6 carbon atoms or a direct bond; w is alkylene with 7 carbon atoms or alkylidene with 2 to 6 carbon atoms, unbranched or branched; Rx and R2 each independently of each other, are: (a) alkyl with 12 carbon atoms, which is unsubstituted or substituted by OH, alkoxy with 4 carbon atoms, SH, CN, -COO (alkyl with 8 atoms) carbon), (alkyl with 4 carbon atoms) -COO-, phenoxy, halogen or phenyl or are cyclopentyl or cyclohexyl, (b) a radical of the formula i I (CHR13) P-C = C-R16 in where p is zero ol, or (c) a radical of the formula / ^ N where q is 0, 1, 2 or 3, or (d) a radical of the formula
4. - CH - Ar2, (e) phenyl which is unsubstituted or substituted by halogen, alkyl with 1 to 12 carbon atoms or alkoxy with 1 to 12 carbon atoms, (f) Rx and R2 together are alkylene with 2 to 9 atoms carbon or oxaalkylene with 3 to 9 carbon atoms, unbranched or branched, or form a radical of the formula
5. Ar 2 is a phenyl, naphthyl, thienyl or furyl radical, each of which is unsubstituted or substituted by halogen, OH, alkyl having 1 to 12 carbon atoms, or is substituted by alkyl with 4 carbon atoms, which is substituted by OH, halogen, alkoxy with 1 to 12 carbon atoms, -COO (alkyl with 1 to 18 carbon atoms), -CO (OCH2CH2) nOCH3 or -OCO (alkyl with 1 to 4 carbon atoms), or Phenyl, naphthyl, thienyl or furyl radicals are substituted by 12-carbon alkoxy or the phenyl, naphthyl, thienyl, furyl or pyridyl radicals are substituted by - (OCH 2 CH 2) nOH, - (OCH 2 CH 2) nOCH 3, alkylthio with 8 atoms carbon, phenoxy, -COO (alkyl having 1 to 18 carbon atoms), -CO (OCH 2 CH,) nOCH 3, phenyl or benzoyl; n is 1-20; m is 1 or 2; R3 is alkyl with 1 to 12 carbon atoms, alkyl with 2 to 4 carbon atoms which is substituted by -OH, -alkoxy with 1 to 4 carbon atoms, -CN or -COO (alkyl with 4 carbon atoms) , or R3 is alkenyl with 3 to 5 carbon atoms, cycloalkyl with 5 to 12 carbon atoms or phenyl-alkyl with 1 to 3 carbon atoms; R 4 is alkyl with 1 to 12 carbon atoms, alkyl with 2 to 4 carbon atoms which is substituted by -OH, alkoxy with 1 to 4 carbon atoms, -CN or -COO. { alkyl with 1 to 4 carbon atoms), or R 4 is alkenyl with 3 to 5 carbon atoms, cycloalkyl with 1 to 12 carbon atoms, phenyl-alkyl with 3 carbon atoms or phenyl which is unsubstituted or substituted by alkyl with the 12 carbon atoms, alkoxy with 4 carbon atoms or -COO (alkyl with 4 carbon atoms), or R4 together with R2, is alkylene with 1 to 7 carbon atoms, phenyl-alkylene with 1 to 4 carbon atoms, o-xylylene, 2-butenylene or oxaalkylene with 2 to 3 carbon atoms, or R3 and R4 together are alkylene with 4 to 7 carbon atoms, which may be interrupted by -O-, -S- or - CO-, or R3 and R4 together are alkylene with 3 to 7 carbon atoms which may be substituted by OH, alkoxy with 4 carbon atoms or -COO (alkyl with 4 carbon atoms); R5, R6, RT, Rs and s each independently are hydrogen, halogen, alkyl with 1 to 12 carbon atoms, cyclopentyl, cyclohexyl, phenyl, benzyl, benzoyl or a group -OR17, -SR18, -S0Rx
6. -S02R18, -N (R2Q) (R19), -NH-S02R21 O z is -O-, -S-, -N (RX1) -, -NÍRJX- ^ -NÍR ,,) or -N N-
7. R10 is hydrogen, alkyl having 1 to 12 carbon atoms, halogen or alkanoyl with 2 to 8 carbon atoms; Rxl is alkyl of 1 to 8 carbon atoms, alkenyl of 3 to 5 carbon atoms, phenyl-alkyl of 1 to 3 carbon atoms, hydroxyalkyl of 1 to 4 carbon atoms, hydroxyalkyl of 1 to 4 carbon atoms or phenyl; R12 is alkylene with 2 to 16 carbon atoms, unbranched or branched, which may be interrupted by one or more of -0- or -S-; R 13 is hydrogen, alkyl having 1 to 8 carbon atoms or phenyl; R14, R15 and R16 each independently are hydrogen or alkyl with 1 to 4 carbon atoms, or R14 and Rlt together are alkylene with 3 to 7 carbon atoms; R17 is hydrogen, alkyl with 12 carbon atoms, alkyl having 2 to 6 carbon atoms which is substituted by -SH, -CN, -OH, alkoxy with 4 carbon atoms, alkenoxy with 3 to 6 carbon atoms, -OCH2CH2CN, -OCH2CH2COO (alkyl having 1 to 4 carbon atoms), -COOH or -0-CO-alky or with 1 to 4 carbon atoms which is unsubstituted or substituted by SH, or R17 ee -COO (alkyl with the 4 carbon atoms), or R17 is alkyl with the 6 carbon atoms which is interrupted by one or more -0-, or R17 is - (CH2CH20) nH, alkanoyl with 2 to 8 carbon atoms, alkenyl with 3 a 12 carbon atoms, cyclohexyl, hydroxycyclohexyl, phenyl which is substituted or substituted by halogen, alkyl with 1 to 12 carbon atoms or alkoxy with 4 carbon atoms or R17 is phenyl-alkyl with 3 carbon atoms or -Si (alkyl with 8 carbon atoms) r (phenyl) 3 r; r is 1, 2 or 3; R18 is hydrogen, alkyl having 1 to 12 carbon atoms, alkenyl having 3 to 12 carbon atoms, cyclohexyl, alkyl having 2 to 12 carbon atoms which is substituted by -SH, -OH, -CN, -COOH, -COO (alkyl with 4 carbon atoms), alkoxy with 4 carbon atoms, -OCH2CH2COO (alkyl with 1 to 4 carbon atoms) or Rx8 is alkyl with the 12 carbon atoms which is interrupted by -s- or -0 -, or R18 is phenyl which is unsubstituted or substituted by halogen, SH, alkyl with 12 carbon atoms or alkoxy with 1 to 4 carbon atoms, or R18 is phenyl-alkyl with 3 carbon atoms; R19 and Rs0 each independently of one another, is alkyl with 12 carbon atoms, hydroxyalkyl with 2 to 4 carbon atoms, alkoxyalkyl with 2 to 10 carbon atoms, alkenyl with 3 to 5 carbon atoms, cycloalkyl with 5 to 12 carbon atoms, phenyl-alkyl with 3 carbon atoms, phenyl which is unsubstituted or substituted by halogen, alkyl with 12 carbon atoms, alkoxy with 4 carbon atoms or R 19 and R 20 are alkanoyl with 2 to 3 atoms of carbon or benzoyl, or R19 and R20 together are alkylene with 2 to 8 carbon atoms, which may be interrupted by -O- or -S-, or R19 and R20 together are alkylene with 2 to 8 carbon atoms which may be substituted by hydroxyl, alkoxy with 1 to 4 carbon atoms or -COO (alkyl with ia 4 carbon atoms); and R31 is alkyl with 1 to 18 carbon atoms, phenyl which is unsubstituted or substituted by halogen, alkyl with 1 to 12 carbon atoms or alkoxy with 1 to 8 carbon atoms or R21 is naphthyl; (B) at least one organic compound that is capable of reacting in a base catalyzed reaction; and (C) optionally a sensitizer. 2. A composition according to claim 1, characterized in that the component (B) comprises a mixture of at least one epoxide compound and at least one compound that is capable of reacting with epoxides in the presence of a base. 3. A composition according to claim 2, characterized in that the compound capable of reacting with epoxides in the presence of a base is a carboxylic compound or a thiol. 4. A composition according to claim 1, characterized in that the component (A) is a compound of the formula I wherein Arx is a group of the formula IV, wherein R5 is a group -0R17, -SRxa, -N (R19) (RJ0) OR those compounds are preferred wherein R6 is hydrogen, halogen, or alkyl having 1 to 4 carbon atoms or has one of the meanings given for Rs, R7 and Rβ are hydrogen or halogen, R9 is hydrogen or alkyl having 1 to 4 carbon atoms. carbon, Z is -0-, -S- or -N (Rxl) -, Rx and R2 each independently are (a) alkyl with 1 to 6 carbon atoms, R13 R14 R15 III (b) a radical of the formula - C-C = C-R1 £, or (d) a radical of the formula -CH (Rl3) -Ar2; wherein Ar 2 is a phenyl radical which is unsubstituted or substituted by halogen, alkyl having 1 to 4 carbon atoms, methylthio, methoxy or benzoyl; R3 and R4 independently of each other is alkyl having 1 to 12 carbon atoms, alkyl having 2 to 4 carbon atoms which is substituted by alkoxy with 1 to 4 carbon atoms, -CN or -COO (alkyl having 1 to 4 carbon atoms), or R3 and R4 are allyl, cyclohexyl or benzyl, or R3 and R4 together are alkylene with 4 to 6 carbon atoms which can be interrupted by -0-; Rlx is alkyl having 1 to 4 carbon atoms, allyl, benzyl or alkanoyl having 2 to 4 carbon atoms; R12 is alkylene with 2 to 6 carbon atoms; R13, R14, R15 and R16 each independently of each other are hydrogen or methyl; R17 is alkyl with 4 carbon atoms unsubstituted or substituted by SH, alkyl with 4 carbon atoms, 2-hydroxyethyl, 2-methoxyethyl, 2-allyloxyethyl, allyl, cyclohexyl, phenyl, benzyl or -Si (CH3) 3; R18 is hydrogen, alkyl with 12 carbon atoms unsubstituted or substituted with SH, 2-hydroxyethyl, 2-methoxyethyl, phenyl unsubstituted or substituted by SH or is p-tolyl or benzyl; and R19 and R20 each independently of the other are alkyl with 1 to 12 carbon atoms, alkoxyalkyl with 2 to 6 carbon atoms, acetyl, allyl or benzyl or R20 and 2? together they are alkylene with 4 to 6 carbon atoms which may be interrupted by -0-. 5. A composition according to claim 1, characterized in that the component (A) is a compound of the formula I, wherein Arx is a group of the formula IV, wherein R5 is a group -0R17, -SR18 or - N. { R19) (R20), Re is hydrogen, chloro or alkyl with 4 carbon atoms or has one of the signifiers given for R5, R7 and Re with hydrogen or chlorine, R9 is hydrogen or alkyl with 4 carbon atoms, RL is any of (a) | | a radical of the formula -CH2-C = CH or (b) a radical of the formula -CH2-Ar2, wherein Ar2 is a phenyl group which is unsubstituted or substituted by halogen, alkyl with 4 carbon atoms, CH3S -, CH30- or benzyl, R2 has one of the given meanings for Rx or is alkyl with 4 carbon atoms, R3 and R4, each independently of the other is alkyl with 6 carbon atoms, 2-methoxyethyl, allyl or benzyl, or R3 and R4 together are tetramethylene, pentamethylene or 3-oxapentamethylene, R14 and R15 are hydrogen or methyl, R17 is unsubstituted or substituted with SH, alkyl with 4 carbon atoms, 2-hydroxyethyl, 2-methoxyethyl or phenyl, R18 is alkyl with 1 to 12 carbon atoms, unsubstituted or substituted with SH, 2-hydroxyethyl, 2-methoxyethyl, phenyl unsubstituted or substituted with SH or is p-tolyl, RI9 and R20 are hydrogen, alkyl with the 4 carbon atoms, 2-methoxyethyl, acetyl or allyl, or R19 and R20 together are alkylene with 4 to 5 carbon atoms arbono, which may be interrupted by -0-. 6. A composition according to claim 1, characterized in that the component (A) is a compound of the formula I, wherein Arx is a group of the formula IV, wherein Rx and R2 each independently of the other is alkyl with the 4 carbon atoms or benzyl; R3 and R "each independently of the other is alkyl with 1 to 4 carbon atoms or together are morpholino; R5 is morpholino or alkylthio with 1 to 4 carbon atoms; and R6, R7, R8 and R9 are hydrogen. 7. A process for photochemically generating bases in polymerization reaction catalysed by bae, characterized in that a compound of the formulas I, II or III according to claim 1 is added as a latent base to the mixture to be polymerized and irradiated with light. of wavelength from 200 to 700 nm, to generate the base.
8. 8. A process according to claim 7, characterized in that a triplet energy enhancer selected from the carbonyl compound group having a triplet energy of 225-310 kJ / mol is added to the latent bath.
9. 9. A process for curing compositions comprising (A) a compound of formula I, II or III according to claim 1, (B) at least one organic compound that is capable of reacting in a base-catalyzed addition reaction. or substitution reaction; and (C) optionally a sensitizer, wherein (l) the composition is irradiated with light having a wavelength of 200 to 700 nm, to generate a base catalyst from the photosenetable precursor of formula I, II or III and (2) is subsequently thermally cured, using as a catalyst the photogenerated base in step (l).
10. 10. A method according to claim 9, characterized in that the step of thermal curing (2) is followed by a development step (3).
11. 11. A process according to claim 9, characterized in that an additional base catalyst or its precursor is added to the composition as a co-catalyst for the thermal step (2).
12. 12. A method according to claim 9, characterized in that the photochemical step (l) is followed by a development stage (3) before the thermal curing step (2).
13. 13. A method according to claim 10, characterized in that steps (l), (2) and (3) are followed by a second thermal curing step (4).
14. 14. A process according to claim 9, characterized in that the composition additionally comprises a monomer, oligomer or radical polymerizable polymer (D).
15. 15. A process according to claim 9, characterized for the production of protective layer materials, welding masks, conformal coatings, protective coatings, powder coatings, overprint varnishes, glass fiber coating, waveguides. , printing plates, adhesives, inks, silkscreen printers, reinforced composite materials, optical switches, color test systems, magnetic recording media, dental materials or a process performed as a stereolithographic or holographic process.
16. 16. Use of a composition according to claim 1, for the production of protective layer materials, welding masks, conformal coating, protective coatings, powder coatings, overprint varnishes, glass fiber coatings, wave guides, printing plates, adhesives, inks, screen printing stencils, reinforced composite materials, optical switches, color test systems, magnetic recording media, dental materials, in a stereolithographic or holographic process.
17. 17. Use of the compounds of formula I, II and III as described in claim 1, as photobase generators in radiation curable systems. SUMMARY OF THE INVENTION The present invention relates to compounds of the formulas I, II or III wherein X is a divalent radical; Y is alkylene with 1 to 6 carbon atoms, cyclohexylene or a direct bond; Arx is an aromatic radical as defined in claim 1, Rj. and R2 independently from each other, among other coeae are a radical of the formula R14 R15 20 | | (CHRx3) p - C = C - Rlß, I - CH - Ar,, R3 is among other things, hydrogen, alkyl with 12 carbon atoms, cycloalkyl with 5 to 12 carbon atoms or phenyl - alkyl with 3 atoms of carbon; R 4 is, inter alia, alkyl with 12 carbon atoms, cycloalkyl with 5 to 12 carbon atoms, phenylalkyl with 1 to 3 carbon atoms, or phenyl; or an acid addition salt of a compound of formula I, II or III; they are useful as photosensitive base catalysts in base entanglement compositions.