CH649285A5 - 3,5-Disubstituted phthalic acids and phthalic anhydrides - Google Patents

Abstract

Compounds of the formula I <IMAGE> in which M1 and M2 are each -OH or together are -O-, X is -NO2, -OR', -SR' or -SO2R' and R' is C1-20-alkyl, C3-5-alkenyl, C3-5-alkynyl, C2-4-monohydroxyalkyl, C1-12-haloalkyl, benzyl, C5-12-cycloalkyl, phenyl, halophenyl, nitrophenyl, alkyl- or alkoxyphenyl each having 1-4 carbon atoms in the alkyl or alkoxy, or acetylaminophenyl, are described. The compounds (I) in which M1 and M2 together represent -O- are suitable as sensitisers for photocrosslinkable polymers or as initiators for the photopolymerisation of ethylenically unsaturated compounds or for the photochemical crosslinking of polyolefins.

Description

       

  
 

** WARNING ** beginning of DESC field could overlap end of CLMS **. 

 
EMI2. 1
 where X 'is -NO2 or -SR' and R and R 'are those of the formulas IIa and IIb or  I have the meaning given, and then the compounds of the formula Va by hydrolysis into a compound of the formula I, in which Ml and M2 each represent -OH, R 'has the meaning given under the formula I and X represents -NO2 or -SR', transferred. 



   8th.  A process for the preparation of compounds of the formula I according to claim 1, characterized in that compounds of the formula I according to claim 7 are prepared in which Ml and M2 each represent -OH, R 'has the meaning given under the formula I and X is -NO2 or -SR ', and these compounds thermally or with the addition of dehydrating agents in the corresponding compounds of formula I, wherein Ml and M2 together mean -0-. 



   9.  Use of compounds of the formula I according to claim 1, in which M1 and M2 represent -0-, as sensitizers for light-crosslinkable polymers. 



   10th  Use of compounds of formula I according to claim 1, wherein M1 and M2 together represent -0-, together with amine as initiators for the photopolymerization of ethylenically unsaturated compounds or for the photochemical crosslinking of polyolefins. 



   The present invention relates to new 3,5-disubstituted phthalic acids and phthalic anhydrides, processes for their preparation and the use of the new 3,5-disubstituted phthalic anhydrides as sensitizers for light-crosslinkable polymers or as initiators, in a mixture with amines, for the photopolymerization of ethylenically unsaturated compounds or for the photochemical crosslinking of polyolefins. 



   Optionally halogenated, especially chlorinated, thioxanthones are among the best known and most effective sensitizers for photo-induced crosslinking reactions. 



  A prerequisite for a successful application of this type is good compatibility of the sensitizer in the polymer, i.  H.  the sensitizer must be miscible with the polymer up to increased concentrations.  Furthermore, the sensitizers must be readily soluble in the solvents used in the processing of the polymers.  The aforementioned thioxanthones do not meet these requirements in every respect; in particular, they separate easily in the polymer, as a result of which the sensitizing effect is severely impaired. 



   It is also known that the photopolymerization of ethylenically unsaturated compounds can be initiated by aromatic ketones of the benzophenone, anthraquinone, xanthone and thioxanthone type.  It is also known from US Pat. No. 3,759,807 that the initiator action of such aromatic ketones can be accelerated by the addition of organic amines. 



  Since these amines usually do not have an initiator effect alone, they act in combination with aromatic ketones as activators or accelerators.  Technically, this is of great importance because the production speed of photochemically hardened coatings or printing inks depends primarily on the rate of polymerization of the unsaturated compound. 



   There have now been new phthalic acids and phthalic anhydrides of the formula I.
EMI2. 2nd
 found, where Ml and M2 each -OH or together -0-,
X -NO2, -OR ', -SR' or -SO2R 'and R Cl 20-alkyl, C ,, - alkenyl, CS-alkynyl, C2 4-mono-hydroxyalkyl, C112-haloalkyl, benzyl, C5 12-cycloalkyl, Phenyl, halophenyl, nitrophenyl, alkyl or alk oxyphenyl, each with 1-4 C atoms in the alkyl or  Alkoxy parts or acetylaminophenyl mean. 



   The phthalic anhydrides of the formula I (M, and M2 = together -0-) are outstandingly suitable for use as sensitizers for light-crosslinkable polymers. 



  They are particularly characterized by good compatibility with the polymer, good solubility in common organic solvents and high photosensitivity.  In addition, the UV absorption can be influenced in such a way that the phthalic anhydrides according to the invention can also be irradiated with long-wave UV light (up to approx.  450 nm) exert a sensitizing effect and thus bring about the crosslinking of the photosensitive polymers.  No photosensitizing phthalic anhydrides with donors in the 3-position were previously known. 



   The phthalic anhydrides according to the invention are also suitable, in a mixture with organic amines, as initiators for the photopolymerization of ethylenically unsaturated compounds or for the photochemical crosslinking of polyolefins. 



   The compounds of formula I can be prepared in a manner known per se, e.g.  B.  by either 3,5-dinitrophthalic anhydride with a compound of formula IIa
R-NH-Y (IIa) or 3,5-dinitrophthalic acid with a compound of the formula IIb
R-NH-Y '(IIb), wherein Y is hydrogen, -COH or -CO-NH-R and Y' -COH or -CO-NH-R, and R is hydrogen, C, 20-alkyl, C2 5-alkenyl , C} 5-alkynyl, C5, 2-cycloalkyl, benzyl, phenyl or toluyl represent a compound of formula III
EMI2. 3rd
  



  implements the compound of formula III with a compound of formula IVa
R'-SH (IVa), a salt of a compound of formula IVa or mixtures thereof to a compound of formula Va
EMI3. 1
 where X 'is -NO2 or -SR' and R and R 'are those of the formulas IIa and IIb or 

  I have the meaning given, compounds of the formula Va, in which X 'represents -NO2, if appropriate subsequently with a salt of a compound of the formula IVb or IVc
R'-OH (IVb) or R'-SO2H (IVc) to a compound of formula Vb
EMI3. 2nd
 implemented, where R and R 'have the meaning given above and X represents "-OR' or -SO2R ', and then the compounds of the formula Va or Vb by hydrolysis into a compound of the formula I, in which M1 and M2 each represent -OH , converted, and then optionally thermally or with the addition of dehydrating agents in a compound of formula I, wherein M and M2 together mean -0-. 



   By definition, alkyl, monohydroxyalkyl, haloalkyl, alkenyl and alkynyl groups R or R 'can be straight-chain or branched.  Haloalkyl groups R 'can be substituted by one or more halogen atoms, such as chlorine or bromine and in particular fluorine.  As examples by definition alkyl, monohydroxyalkyl, haloalkyl, alkenyl and alkynyl groups R or 

  R 'should be mentioned = methyl, ethyl, n-propyl, isopropyl, n-, secondary tert-butyl, n-pentyl, 2- or 3-pentyl, n-hexyl, n heptyl, 3-heptyl, n-octyl, n -Decyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-hexadecyl, n-octadecyl and eicosyl; 2-hydroxyethyl, 2- and 3-hydroxypropyl, 3- and 4-hydroxybutyl; Trifluoromethyl, 2-chloroethyl, 2-bromoethyl, 2,2,2-trifluoroethyl, -CH2CH2C4Fg, -CH2CH2CöF13, -CH2CH2C8FI7; Vinyl, allyl, methallyl, 2-butenyl, 4-pentenyl; 2-propynyl, 3-butynyl and 4-pentynyl. 



   Alkyl groups R are preferably straight-chain and have in particular 1-10 and especially 1-6 C atoms.  Methyl is very particularly preferred.  Preferred alkenyl and alkynyl groups R or  R 'are: vinyl (R), allyl, methallyl, 2-butenyl and propynyl.  Alkyl groups R 'preferably have 1-10 C atoms.  Straight-chain alkyl groups R 'with 1-10 and especially 1-4 C atoms are particularly preferred. 



   Haloalkyl groups R 'are preferably also straight-chain and have 1-10 C atoms.  Trifluoromethyl, -CH2CF3 and -CH2CH2CnF with n = 4.6 or 8 are particularly preferred.    



   Examples of cycloalkyl groups R or  R 'are cyclopentyl, cyclohexyl, cyclooctyl and cyclododecyl.  Cyclohexyl is preferred.  As toluyl group R, p toluyl is particularly suitable. 



   Halophenyl, nitrophenyl, alkylphenyl and alkoxyphenyl groups R 'can be substituted one or more times.  Phenyl groups with one or two of the substituents mentioned are preferred.  As halogen atoms come e.g.  B.  Fluorine, bromine and especially chlorine into consideration. 



  Examples of such groups are: 3-chloro- or 3-bromophenyl, 3,4-dichlorophenyl, 2,5-dichlorophenyl, 3,4-dibromophenyl, 4-chloro-, 4-bromo- or 4-fluorophenyl; 3- or 4-nitrophenyl, 3,5-dinitrophenyl; o-, m- and p-toluyl, 3,4-dimethylphenyl, 4-ethylphenyl, 4-n-butylphenyl; 2-, 3- or 4 methoxyphenyl, 3- and 4-ethoxyphenyl, 2,5-dimethoxyphenyl, 3,4-diethoxyphenyl, 4-n-propoxyphenyl, 4-isopropoxyphenyl and 4-n-butoxyphenyl.     Preferred halophenyl, alkylphenyl and alkoxyphenyl groups R 'are 3,4 dichlorophenyl, p-toluyl and 4-methoxyphenyl. 



   Preference is given to compounds of the formula 1 in which M and M2 together represent +, X is -NO2, alkyl having 1-4 C atoms, especially methoxy, -SO2-phenyl or -SR 'and R' Cl to-alkyl, C140-haloalkyl , Phenyl, p methoxyphenyl, p-toluyl or 3,4-dichlorophenyl. 



   Compounds of the formula I in which M1 and M2 together are -0-, X -NO2 and R 'C "are 0-n-alkyl or phenyl are particularly preferred. 



   The starting compounds (3,5-dinitrophthalic acid, 3.5 dinitrophthalimide, 3,5-dinitrophthalic anhydride, compounds of the formulas IIa, IIb, IVa and salts of compounds of the formulas IV, IVb and IVc) are known or can be prepared by methods known per se will. 



   The above reactions can be carried out in a manner known per se.  The reaction of the 3,5-dinitrophthalic anhydride or  the 3,5-dinitrophthalic acid with the compounds of the formula Ha or IIb can, with or without the addition of a suitable inert organic solvent, such as N, N-dimethylformamide or aromatic hydrocarbons, e.g.  B.  Toluene or xylenes can be made. 

  If the reaction is carried out in the presence of an inert organic solvent, the reaction is generally carried out at the reflux temperature.     For working in the melt (without the addition of solvent), the reaction temperatures are preferably between about 160 and 220 C.     In the above-mentioned reaction, the corresponding amic acids can be formed as intermediates, which in general pass into the imides simply by heating.  As compounds of the formula IIa or  IIb, in which Y or  Y '-CO-NH-R means, N, N-dimethylurea is preferred.  The reaction of 3,5-dinitrophthalic anhydride with a compound of the formula IIa, in which Y is -COH and especially hydrogen, is particularly preferred. 

 

   The reaction of the 3,5-dinitrophthalimides of the formula III with the mercaptans of the formula IVa or  their salts and the possible further reaction of compounds of the formula Va with X '= -NO2 with salts of compounds of the formula IVb or IVc is advantageously in the presence of an inert organic solvent at temperatures between about 0 and reflux temperature, preferably between about 20 and 50 "C for mercaptans of the formula IVa or their salts and salts of compounds of the formula IVb, and about 50-150" C for the reaction with salts of the formula IVc.  Suitable inert organic solvents are e.g. 

  B.  optionally chlorinated aliphatic hydrocarbons, such as methylene chloride or chloroform; aliphatic or cyclic ethers, such as diethyl ether, diisopropyl ether, dimethoxyethane, tetrahydrofuran and dioxane; Alkyl esters of aliphatic monocarboxylic acids with a total of 2-8 C atoms, such as methyl, ethyl and n-butyl acetate, ethyl butyrate and n-butyl ester; N, N dialkylamides of aliphatic monocarboxylic acids with 1-3 C atoms in the acid part, such as N, N-dimethylformamide and N, N-dimethylacetamide; Dialkyl sulfoxides such as dimethyl sulfoxide and diethyl sulfoxide; Alkyl nitriles with 2-5 C atoms, such as acetonitrile and propionitrile; Phosphoric acid amides such as hexamethylphosphoric triamide; cyclic amides, such as N methylpyrrolidone. 



   Suitable salts of compounds of the formulas IVa, IVb and IVc are both salts with organic and inorganic bases.  Alkali metal and quaternary ammonium salts such as the Na, K, tetramethyl, tetraethyl, benzyltrimethyl and benzyltriethylammonium salts are preferred.  The salts mentioned can be used as such or can be formed in situ in a manner known per se.  In the latter case, alkali metal acetates or carbonates are advantageously used as bases.  The compounds of the formula Va are preferably used in the form of salts.  Sodium and potassium phenates, alcoholates or sulfinates are particularly preferred. 



   The hydrolysis of the compounds of formula Va or Vb to phthalic acids of formula I and their cyclization to the corresponding anhydrides can also be carried out in a manner known per se.  Hydrolysis to the
Phthalic acids are expediently carried out in an aqueous medium by adding suitable bases, such as NaOH or KOH, at the reflux temperature, the corresponding ones initially
Amidic acids are formed, and then acidifying the reaction mixture, preferably with a strong acid, such as HCl.  The phthalic acids obtained can be customary
Be cyclized thermally or with the addition of dehydrating agents to the anhydrides.  The phthalic acids of formula I are thus intermediates for the production of the corresponding anhydrides. 



   Suitable dehydrating agents are, for.  B.  Anhydrides of aliphatic C2 5 monocarboxylic acids optionally substituted by halogen atoms or C14-alkyl groups, such as acetic, propionic, butyric, trifluoro and trichloro, trimethyl and triethyl acetic anhydride; optionally halogenated acetyl halides, such as acetyl chloride, chloroacetyl chloride and dichloroacetyl chloride; Carbodiimides such as N, N'-diisopropylcarbodiimide and N, N'-dicyclohexylcarbodiimide.  The preferred dehydrating agent is acetic anhydride. 



   The above reactions can also be carried out without intermediate isolation of the compounds of the formulas III, Va or Vb or of the 3,5-dinitrophthalic acids of the formula I.  The preparation of compounds of the formula Va, in which X is' -SR ', is generally carried out in two stages by first moving the -SR' group to the 3-position and then an identical or different one
Introduces group -SR 'in 5-position. 



   The phthalic anhydrides of the formula I (Ml and M2 together -0-) can be used as sensitizers for various types of light-crosslinkable polymers. 



   Such polymers are e.g.  B.  for production of
Printing plates for the offset printing process, for the production of photo offset lacquers, for unconventional photography, z.  B.  used for the production of photographic images by means of photopolymerization or photocrosslinking.  Such polymers are used in particular as so-called photoresists for the production of printed
Circuits according to known methods.  The side of the printed circuit board provided with the light-sensitive layer is exposed through a slide negative having the conductive pattern and then developed, whereupon the unexposed areas of the layer are removed by developing liquid. 



   Any materials per se can be used as polymers whose sensitivity to light (sensitivity to actinic rays) can be increased by using the sensitizers according to the invention. 



  The anhydrides of the formula I are particularly suitable as sensitizers for polymers of the type described in German Offenlegungsschrift 2,626,769, i.e.  H.  Polymers which are photosensitive groups of those of the formula VI
EMI4. 1
 have, in which G1 and G2 independently of one another alkyl with 1-4 C atoms, especially methyl, or G1 and G2 together mean the addition to a five- to six-membered carboxyclic ring. 



   The phthalic anhydrides of the formula I can be incorporated into the light-crosslinkable polymers in a manner known per se.  The level of sensitizer in the polymer can vary widely depending on the application and the number of light-crosslinkable groups present in the polymer, but is generally between about 0.1 and 20%, based on the weight of the polymer. 



   Finally, the phthalic anhydrides of the formula I are also used as photoinitiators.  The invention therefore also relates to the use of the compounds mentioned together with amines as initiators for the photopolymerization of ethylenically unsaturated compounds or for the photochemical crosslinking of polyolefins. 



   The organic amines used can be aliphatic, aromatic, araliphatic, cycloaliphatic or heterocyclic amines.  They can be primary, secondary or tertiary amines.  Examples include: butylamine, dibutylamine, tributylamine, cyclohexylamine, benzyldimethylamine, dicyclohexylamine, triethylamine, phenyl-di-ethanolamine, piperidine, piperazine, morpholine, pyridine, quinoline, p-dimethylaminobenzoic acid ethyl ester or Michler's ketone (4,4'-bis-bis-methyl benzophenone). 



   Mixtures of are preferred
A) an anhydride of formula I, wherein X and R 'have the preferred meanings given above, and
B) an aliphatic tertiary amine, a p-dimethylaminobenzoic acid alkyl ester or Michler's ketone. 

 

   Examples of aliphatic tertiary amines are trimethylamine, triethylamine, tri-isopropylamine, tributylamine, dodecyldimethylamine, octyldimethylamine, triethanolamine, tris (hydroxypropyl) amine, N-methyldiethanolamine or N butyldiethanolamine. 



   Mixtures of are particularly preferred
A) an anhydride of formula I, wherein X and R 'have the preferred meanings given above, and
B) triethanolamine or a Cl 4-alkyldiethanolamine.    



   The preferred mixtures mentioned contain the anhydrides of the formula I and the organic amines preferably in a weight ratio of 4: 1 to 1: 4.      



   Examples of photopolymerizable compounds are unsaturated monomers such as esters of acrylic or methacrylic acid, e.g. B.  Methyl, ethyl, n- or tert. Butyl, isooctyl or hydroxyethyl acrylate, methyl or ethyl methacrylate, ethylene diacrylate, butanediol diacrylate, hexanediol diacrylate, neopentyl diacrylate, trimethylolpropane trisacrylate, pentaerythritol tetraacrylate or pentaerythritol; Acrylonitrile, methacrylonitrile, acrylamide, methacrylamide, N-substituted (meth) acrylamides; Vinyl esters such as  B. 

  Vinyl acetate, propionate, acrylate or succinate; other vinyl compounds, such as vinyl ethers, vinyl ketones, vinyl sulfones, styrene, alkylstyrenes, halostyrenes, divinylbenzene, N, N'-divinylurea, vinylnaphthalene, N-vinylpyrrolidone, vinyl chloride or vinylidene chloride; Allyl compounds such as diallyl phthalate, diallyl maleate, triallyl isocyanurate, triallyl phosphate or ethylene glycol diallyl ether and the mixtures of such unsaturated monomers. 



   Such mixtures are particularly suitable for the photopolymerization of acrylic acid esters and their mixtures. 



   Other examples are unsaturated acrylic resins.  These include, for example, reaction products of polyepoxides (epoxy resins) with acrylic acid or methacrylic acid or reaction products of polyisocyanates with hydroxyalkyl acrylates, and the reaction products of hydroxyl-containing polyesters or polyethers with acrylic or methacrylic acid.  These unsaturated acrylic resins are usually mixed with one or more acrylates of a mono-, di- or polyalcohol, such as.  B.    Ethyl, butyl, benzyl, 2-ethylhexyl or 2-hydroxypropyl acrylate, ethylene glycol diacrylate, propylene glycol diacrylate, butanediol diacrylate, hexanediol diacrylate, trimethylolpropane trisacrylate or pentaerythritol tetraacrylate are used. 



   The phthalic anhydrides of the formula I can also be used in photopolymerizable systems.  Such systems consist of a) at least one ethylenically unsaturated compound, b) a defined mixture of A) and B) and optionally c) other additives, such as inhibitors, stabilizers, UV absorbers, fillers, pigments, dyes, thixotropy agents and leveling agents, for . B.  Silicone oil. 



   For example, hydroquinone, hydroquinone derivatives, p-methoxyphenyl or ss-naphthols are used as inhibitors, which are intended to protect against premature polymerization, especially during the production of the systems, by mixing the components.  As UV absorbers, for.  B.  those of the benzotriazole or benzophenone type are used.  As fillers such.  B.  Silica, talc or gypsum. 



   Such photopolymerizable systems in the quantitative ratios of 99.980% are preferred. -% of a) and c) and 0,> 20 wt. % of b), component A) preferably consisting of an anhydride of the formula I, in which X and R 'are the preferred ones indicated above
Have meanings. 



   An acrylic acid ester or a mixture of several acrylic acid esters is preferably used as component a). 



   Combinations with known photoinitiators which form free radicals by photofragmentation, such as, for. B.  Benzoin ethers, dialkoxyacetophenones or benzil ketals can be used. 



   Such initiator mixtures are of great importance for the
Photocuring of printing inks and white pigmented ones
Layers, because the drying time of the binder is a significant factor for the production speed of graphic products and in the order of
Should be a fraction of a second.  The initiators according to the invention are also very suitable for photocurable systems for the production of printing plates. 



   Another area of application is the UV curing of metal coatings, for example in the coating of sheet metal for tubes, cans or bottle closures, as well as the UV curing of plastic coatings, for example floor or wall coverings based on PVC. 



   Examples of the UV curing of paper coatings are the colorless coating of labels, record sleeves or book covers. 



   The mixtures mentioned can also be used as initiators for the photochemical crosslinking of polyolefins.  For this come z.  B.    Polypropylene, polybutene, polyisobutylene and copolymers such.  B.  Ethylene-propylene copolymers in question, but preferably low, medium or high density polyethylene. 



   The photoinitiators are generally added to the photopolymerizable systems simply by stirring in, since most of these systems are liquid or readily soluble.  The initiators are usually dissolved, which ensures their uniform distribution and the transparency of the polymers. 



   The polymerization is carried out according to the known methods of photopolymerization by irradiation with light which is rich in short-wave radiation.  As light sources such.  B.  Medium-pressure, high-pressure and low-pressure mercury lamps, as well as superactinic fluorescent tubes, whose emission maxima lie in the range between 250 and 450 nm. 



   In the photochemical crosslinking of polyolefins, the photoinitiator is added to the polyolefin before or during shaping processing, for example by powdery mixing or by mixing with the plasticized polyolefin.  Crosslinking takes place by irradiation of the shaped object in solid form, for example in the form of foils or fibers. 



   Compounds of the formula I, in which X is the nitro group and R 'phenyl, halophenyl, nitrophenyl, alkyl or alkoxyphenyl, each having 1-4 C atoms in the alkyl or  Alkoxy or acetylaminophenyl mean are also suitable for the preparation of thioxanthones, which in turn are valuable sensitizers for light-crosslinkable polymers.  Such thioxanthones can be obtained by cyclizing the compounds mentioned in a manner known per se in the presence of a protonic acid or a Lewis acid and, if appropriate, subsequently converting the obtained nitrothioxanthone-1-carbon acids into other thioxanthone derivatives, such as esters or amides. 



   A) Manufacturing examples
Example 1: 3-n-Butylthio-5-nitrophthalic anhydride
883 mg (3 mmol) of 3-n-butylthio-5-nitrophthalic acid-Nmethylimide are refluxed overnight in 9 ml of 1N sodium hydroxide solution, acidified with 10 ml of 2N hydrochloric acid and cooled to reflux after 5 minutes.  The mixture is extracted with tetrahydrofuran / toluene, and the extracts are washed with saturated NaCl solution, dried over sodium sulfate and evaporated.  The acid obtained is converted into the anhydride with 1 ml of acetic anhydride and 10 ml of toluene by heating and evaporation.  After recrystallization from cyclohexane, 790 mg (94% of theory  Th. ) the above anhydride as a yellow product; M.p. 

 

     9997 C.    



  Analysis for Cl2HllNO5S (molecular weight 281.28): calculated
C 51.24% H 3.94% N 4.98% S 11.40% found
C 51.55% H 3.91% N 5.14% S 11.12%.   



   The 3-n-butylthio-5-nitrophthalic acid-N-methylimide is prepared as follows:
25.1 g (100 mmol) of 3,5-dinitrophthalic acid-N-methylimide, 19.8 g (220 mmol) of n-butyl mercaptan, 41.5 g (300 mmol) of anhydrous potassium carbonate and 250 ml of absolute tetrahydrofuran are overnight held at reflux.  The reaction mixture is filtered, the filtrate is evaporated and the residue is taken up in methylene chloride / 2N HCl.  The extracts are washed with saturated NaCl solution, dried over sodium sulfate and evaporated.  After recrystallization from cyclohexane, 11.96 g (41% of theory Th. ) of the above imide; M.p. 



     106-108 C.    



  Analysis for C1 3H14N2O4S (molecular weight 294.33): calculated
C 53.05% H 4.80% N 9.52% S 10.90% found
C 53.30% H 4.90% N 9.01% S 11.29%. 



   The 3,5-dinitrophthalic acid-N-methylimide is prepared as follows: a) 51.22 g (0.2 mol) of 3,5-dinitrophthalic acid and 8.81 g (0.1 mol) of N, N'-dimethylurea finely ground together and carefully heated to 180 "C in an open flask.  The dark, clear melt formed after the foaming subsided is kept at 180 ° C. for 6 hours and at 200 ° C. for 1 hour.  After cooling, the residue is dissolved in tetrahydrofuran / methylene chloride (volume ratio 1: 1), filtered and evaporated. 

  After recrystallization from tetrahydrofuran / cyclohexane, 42.37 g (84% of theory. Th. ) 3,5-dinitrophthalic acid-N-methylimide of mp.    174-6 C.     After further recrystallization, the product has an mp.  from 178-180 "C. 



   b) 238.11 g (1 mol) of 3,5-dinitrophthalic anhydride are dissolved in 1 liter of xylene under reflux.  62.02 g (1.05 mol) of N-methylformamide are added dropwise over 30 minutes at reflux.  After 18 hours of reflux, the water and formic acid formed are distilled off together with a little xylene (total 140 ml), the boiling point rising to 137 ° C.  The solution is filtered hot.  After slow cooling and concentration of the mother liquor, 209.42 g (83% of theory Th. ) 3,5-dinitrophthalic acid-N-methylimide; M.p. 174-6 C.    



  Analysis for C9H5N306 (molecular weight 251.15): calculated C 43.04% H 2.01% N 16.73% found C 43.40% H 2.00% N 16.5%. 



   Example 2: 3,5-bis (n-C8F17 (CH2) 2) thiophthalic anhydride
266.05 g (0.223 mol) of 3,5-bis- (n-C8F17 (CH2) 2) -thio-phthalic acid-Np-toluylimide are refluxed in 1.2 1 20% NaOH with stirring for one day, whereupon the reaction mixture is cooled and filtered.  The residue is ground, stirred with 2N HC1 solution and filtered off. 



  The amic acid thus obtained is concentrated with 1.8 1.  HCl heated to 120 ° C. for 5 hours, the mixture is cooled and the precipitate is filtered off, washed with water and dried.  The mixture of acid and anhydride obtained is completely converted into the anhydride by heating with acetic anhydride and evaporation.  Recrystallized from ethyl acetate gives 201 g (81% of theory  Th. ) of the above anhydride of mp.    151-154 "C.    



  Analysis for C28H10F34O3S2 (molecular weight 1104.44): calculated
C 30.45% H 0.91% F 58.49% S 5.81% found
C 30.1% H 0.7% F 58.1% S 6.2%. 



   The 3,5-bis- (n-C8FI7 (CH2) 2) -thiophthalic acid-N-p-toluylimide is prepared as follows:
184.6 g (0.243 mol) 5-nitro-3-n-C8F17 (CH2) 2-thiophthalic acid-Np-toluylimide, 116.6 g (0.243 mol) n C8F7 (CH2) 2-5H, 100.75 g (0.729 mol) of potassium carbonate and 1.8 liters of N, N-dimethylformamide (DMF) are stirred at 25 ° C. for 30 minutes.  The reaction mixture is evaporated in portions (foams strongly), the residue is extracted in CH2Cl2lacetone / water, and the organic phase is washed with water, dried over sodium sulfate and evaporated.  After recrystallization from ethyl acetate, 266 g (91% of theory Th. ) of the above imide; M.p.    144-6 C.    



  Analysis for C3 5H1 7F34NO2S2 (molecular weight 1193.58): calculated
C 35.22% H 1.44% F 54.12% N 1.17% S 5.37% found
C 35.0% H 1.5% F 54.2% N 1.2% S 5.5%. 



   The 3-n-C8F1 7-CH2CH2-thio-5-nitrophthalic acid-N-p-toluylimide is prepared as follows:
20 g (0.06 mol) of 3,5-dinitrophthalic acid-Np-toluylimide, 32.3 g (0.0673 mol) of n-C8F17 (CH2) 2-SH, 12.7 g (0.092 mol) of potassium carbonate and 250 ml absolute dioxane are stirred at 25 "C for 42 hours.  The reaction mixture is concentrated, the residue is taken up in water and extracted three times with CH2Cl2.  The extracts are washed with water, dried over sodium sulfate and concentrated.  Recrystallized from toluene gives 44.7 g (98% of theory  Th. ) the above imide in the form of yellowish leaflets; M.p. 



     169-171 C.    



  Analysis for C25H13F17N2O4S (molecular weight 760.42): calculated
C 39.49% H 1.72% F 42.47% N 3.68% S 4.22% found
C 39.55% H 1.65% F 42.50% N 3.80% S 4.40%. 



   The 3,5-dinitrophthalic acid-N-p-toluylimide is prepared as follows:
2 kg (8.4 mol) of 3,5-dinitrophthalic anhydride and 897 g (8.4 mol) of p-toluidine are refluxed in 6.21 glacial acetic acid for 3 hours.  After cooling, the mixture is filtered, washed with 21 water, and the residue is suspended in 25 l of water, filtered off and dried at 100 ° C. in vacuo.  Yield 2339 g (85% of theory Th. ); M.p. 



  182-3 "C.    



  Analysis for C1 sHoN3Oö (molecular weight 327.25): calculated C 55.05% H 2.77% N 12.84% found C 55.05% H 3.02% N 12.91%. 



   Example 3: 5-n-Decylthio-3-n-C8F1 7 (CH2) 2-thiophthalic anhydride
0.50 g (0.564 mmol) of 5-n-decylthio-3-n-C8F17 (CH2) 2-thiophthalic acid-N-p-toluylimide and 6 ml of 20% NaOH are stirred at 120 ° C. overnight.  After cooling, the mixture is filtered and the precipitate is concentrated in 5 ml.  HCI heated to reflux for 3.5 hours.  After cooling, the mixture is filtered, the precipitate is washed with water and recrystallized from isopropanol and n-hexane. 

 

  Yield of (directly formed) anhydride = 260 mg (60% of theory Th. ); M.p.  110-111 0C.    



  Analysis for C28H27F17O3S2 (molecular weight 798.61): calculated
C 42.11% H 3.40% F 40.44% S 8.03% found
C 42.45% H 3.45% F 40.75% S 7.75%. 



   The 5-n-decylthio-3-n-C8F17 (CH2) 2-thiophthalic acid-N-p-toluylimide is prepared as follows:
3 g (3.95 mmol) of 5-nitro-3-n-C8F17 (CH2) 2-thiophthalic acid-Np-toluylimide, (prepared according to Example 2) 0.70 g (4.34 mmol) of n-decanethiol, 1.60 g (11.85 mmol) of potassium carbonate and 35 ml of DMF are stirred at 25 ° C. for 17 hours.   



  The mixture is evaporated, the residue is taken up in water / CH2Cl2, and the organic phase is washed with water, dried over Na2SO4 and evaporated.  After recrystallization from ethyl acetate, 3.0 g (86% of theory Th. ) of the above Imid vomSmp.    117-119 C.    



  Analysis calculated for C35H34F17NO2S2 (molecular weight 887.75)
C 47.35% H 3.86% F 36.38% N 1.58% S 7.22% found
C 47.4% H 3.7% F 36.6% N 1.6% S 7.1%. 



   Example 4:
3-n-decylthio-5-n-C8F17 (CH2) 2-thiophthalic anhydride
3.0 g (3.3 mmol) of 3-n-decylthio-5-n-C8FI 7 (CH2) 2-thiophthalic acid-N-methylimide are stirred vigorously in 40 ml of 2N NaOH for 18 hours at reflux, after which the mixture is added 0 "C with 50 ml conc.  Acidified hydrochloric acid.  After 5 hours of stirring at reflux, the mixture is cooled and extracted with tetrahydrofuran / toluene (volume ratio 1: 3).    



  The extracts are dried over sodium sulfate and evaporated.  The residue is refluxed with 10 mmol acetic anhydride in toluene and the solution is filtered and concentrated.  After recrystallization from hot n-hexane, 1.68 g (64% of theory  Th. ) the above anhydride; M.p.    116-7 C.    



  Analysis for C28H27F17O352 (molecular weight 798.608): calculated
C 42.11% H 3.40% F 40.44% S 8.03% found
C 42.36% H 3.36% F 40.91% S 8.12%. 



   The 3-n-decylthio-5-n-C8 F17 (CH2) 2-thiophthalic acid-N-methylimide is prepared as follows:
13.07 g (34.6 mmol) of 3-n-decylthio-5-nitrophthalic acid N-methylimide, 18.35 g (38.2 mmol) of n-C8Fl7 (CH2) 2-SH, 14.3 g of ground, anhydrous Potassium carbonate and 450 ml of N, N-dimethylformamide are stirred at 25 ° C. for 18 hours, and the reaction mixture is evaporated.  The residue is taken up in methylene chloride / dilute hydrochloric acid.  The organic phase is washed with saturated NaCl solution, dried over sodium sulfate and evaporated.  After recrystallization from toluene, 25.04 g (89% of theory Th. ) of the above imide from mp. 



     117-8 "C.    



  Analysis for C29H30F17NO2S2 (molecular weight 811.65): calculated
C 42.91% H 3.73% N 1.73% S 7.90% F 39.79% found
C 42.44% H 3.53% N 1.73% S 8.08% F 40.52%. 



   The 3-n-decylthio-5-nitrophthalic acid-N-methylimide is prepared as follows:
20 g (79.6 mmol) of 3,5-dinitrophthalic acid-N-methylimide (prepared according to Example 1) and 21 g (107 mmol) of sodium n-dodecyl mercaptide are stirred for 2 hours at 40 ° C. in 100 ml of ethyl acetate.  After evaporation, the residue is extracted into methylene chloride / dilute hydrochloric acid, and the organic phase is washed with saturated NaCl solution, dried over sodium sulfate and evaporated.  After recrystallization from methanol / diethyl ether, 23.24 g (77% of theory  Th. ) of the above imide (yellow product) of mp.  85-86 "C.    



  Analysis for ClgH26N204S (molecular weight 378.49): calculated
C 60.29% H 6.92% N 7.40% S 8.47% found
C 60.28% H 6.71% N 7.39% S 8.19%. 



   Example 5:
5-nitro-3-phenylthiophthalic acid a) 160 g (0.41 mol) of 5-nitro-3-phenylthiophthalic acid-N-p-toluylimide are kept under reflux in 1590 ml of 20% sodium hydroxide solution with stirring overnight.  The mixture is concentrated under good cooling with conc.  Acidified hydrochloric acid (10-15 C), the amic acid is filtered off and concentrated with 1070 ml.  Hydrochloric acid stirred at reflux for 3 hours.  After cooling, the mixture is filtered off, the residue is stirred in 650 ml of 5% Na2CO3 solution, filtered and the filtrate is acidified.  After cooling, filtering off and drying in vacuo over phosphorus pentoxide, 116.2 g (89% of theory) are obtained. Th. ) 5-nitro-3-phenylthiophthalic acid; M.p. 



     183-5 "C.    



   b) 3.0 g (10 mmol) of 5-nitro-3-phenylthiophthalimide are held in 30 ml of 1N sodium hydroxide solution for 8 hours under reflux, cooled, with 3 ml of conc.  Acidified hydrochloric acid, extracted with tetrahydrofuran / toluene, washed with saturated NaCl solution, dried over sodium sulfate and evaporated.  After drying, 3.13 g (98% of theory Th. ) 5-nitro-3-phenylthiophthalic acid; M.p. 



     182-4 "C.    



  Analysis for Cl4HgNO6S (molecular weight 319.29): calculated
C 52.67% H 2.84% N 4.39% S 10.04% found
C 52.90% H 3.20% N 4.30% S 9.80%. 



   The 5-nitro-3-phenylthiophthalimide is prepared as follows:
9.48 g (40 mmol) of 3,5-dinitrophthalimide are suspended in 150 ml of ethyl acetate, and 5.55 g (42 mmol) of sodium thiophenolate are added.  After stirring for 18 hours at 25 "C, the reaction mixture is evaporated, taken up in a mixture of methylene chloride and ethyl acetate, and the organic phase is washed with saturated NaHCO3 and saturated NaC1 solution, dried over sodium sulfate and evaporated. 



  After recrystallization from methylene chloride / hexane, 10.54 g (88% of theory Th. ) 5-nitro-3-phenylthiophthalimide of mp.  207-209 "C.    



  Analysis for C14H8N204S (molecular weight 300.29): calculated
C 56.00% H 2.69% N 9.33% S 10.68% 0 21.31% found
C 55.49% H 2.88% N 9.56% S 10.45% 0 21.42%. 



   The 5-nitro-3-phenylthiophthalic acid-Np-toluylimide is prepared as follows: a) 820 mg (2.5 mmol) of 3,5-dinitrophthalic acid-Np-toluylimide [prepared according to Example 2], 0.33 g (3 mmol ) Thiophenol and 29 mg (0.125 mmol; 5 wt. -%) Benzyltri äthylammoniumchlorid are dissolved in 15 ml of CH2CI2, whereupon a solution of 0.492 g (6 mmol) of anhydrous sodium acetate in 4 ml of water is added.  After 20 minutes of vigorous stirring at 25 ° C., the mixture is diluted with water, adjusted to pH 9-10, and the organic phase is separated off, washed with 2N NaOH, dried over sodium sulfate and evaporated.  After recrystallization from toluene, 930 mg (95% of theory Th. ) 5-nitro-3-phenylthiophthalic acid-N-p-toluylimide of mp.  207-209 C.    

 

   b) 49 g (0.15 mol) of 3,5-dinitrophthalic acid-N-p-toluylimide are placed in 500 ml of dimethyl sulfoxide.  While cooling gently, 22.5 g (0.204 mol) of thiophenol are added dropwise at 22-23 ° C. over the course of 10 minutes, resulting in nitrous gases.  After 30 minutes at 25 ° C., the mixture is kept at 45 ° C. for 4 hours, poured onto one liter of ice water, and the precipitate is filtered off, washed with water and dried.  After recrystallization from toluene, 52.5 g (90% of theory) are obtained. Th. ) 5-nitro-3-phenylthiophthalic acid-N-p-toluylimide of mp.  208-9 "C.    



  Analysis for C2lHl4N204S (molecular weight 390.40): calculated
C 64.61% H 3.62% N 7.18% S 8.21% found
C 64.30% H 3.81% N 7.32% S 8.45%. 



   Example 6:
5-nitro-3-phenylthiophthalic anhydride a) 4.3 g (13.5 mmol) 5-nitro-3-phenylthiophthalic acid [prepared according to Example 5] are mixed with 4.1 g (40.2 mmol) acetic anhydride in 100 ml toluene 1 Held at reflux for one hour.  After evaporation and recrystallization from methylene chloride / n-pentane, 3.97 g (98% of theory) are obtained.  Th. ) 5 nitro-3-phenylthiophthalic anhydride; M.p.  167-169 "C.    



   b) 5 g (21 mmol) of 3,5-dinitrophthalic anhydride are dissolved in 17 ml of tetrahydrofuran; then 2.78 g (25.2 mmol) of thiophenol and 4.3 g (42 mmol) of acetic anhydride are added.  This solution is added dropwise with vigorous stirring to a mixture of 22.4 g of 30% sodium hydroxide solution, 47.8 mg (0.21 mmol) of benzyltriethylammonium chloride and 100 ml of methylene chloride. 



   After stirring for 2 hours, the mixture is diluted with water.  Neutral impurities are extracted with methylene chloride, then the aqueous phase is acidified, extracted with methylene chloride, and the extracts are dried over sodium sulfate and evaporated.  The residue is heated with acetic anhydride and toluene and, after evaporation and recrystallization from methylene chloride / n-pentane, gives 2.57 g (41% of theory Th. ) 5-nitro-3-phenylthiophthalic anhydride; M.p.    167-169 C.    



  Analysis for Cl4H7NOsS (molecular weight 301.27): calculated
C 55.82% H 2.34% N 4.65% S 10.64% found
C 55.8% H 2.4% N 4.7% S 10.5%. 



   Example 7: 3- (3,4-dichlorophenylthio) -5-nitrophthalic anhydride
18.84 g (75 mmol) of 3,5-dinitrophthalic acid-N-methylimide [prepared according to Example 1] are placed in 250 ml of ethyl acetate and mixed with 30.4 g (220 mmol) of ground, anhydrous potassium carbonate, whereupon 14 g (78 mmol) of 3,4-dichlorothiophenol was added dropwise.  After adding 95 ml of tetrahydrofuran, the mixture is stirred overnight and then evaporated to dryness.  The residue is refluxed with 100 ml of water overnight, the mixture is extracted with petroleum ether at 25 C and filtered, and the aqueous filtrate is acidified with 300 ml of 2N HCl and heated to reflux.  After 2.5 hours, the mixture is cooled, extracted with tetrahydrofuran / toluene, washed with saturated NaCl solution, dried over sodium sulfate and evaporated. 

  The residue is heated to reflux with 100 ml of toluene and 7.66 g (75 mmol) of acetic anhydride and, after cooling, evaporated.  After recrystallization from methylene chloride / n-pentane, 22.2 g (80% of theory Th. ) 3- (3,4-dichlorophenylthio) -5-nitrophthalic anhydride; M.p.    154-7 C.    



  Analysis for C1 4Hs Cl2NO5S (molecular weight 370.16): calculated C 45.43% H 1.36% N 3.78% found C 45.39% H 1.28% N 3.93%. 



   Example 8:
3- (p-methylphenylthio) -5-nitrophthalic anhydride
46.05 g (0.180 mol) of 3,5-dinitrophthalic acid are refluxed with 26 g (0.25 mol) of acetic anhydride in 210 ml of toluene for one hour.  The mixture is filtered hot and the filtrate is evaporated.  The residue is dissolved together with 27.4 g (0.221 mol) of p-thiocresol and 34.7 g (0.34 mol) of acetic anhydride in 4.6 liters of methylene chloride at reflux.  This solution is added dropwise with vigorous stirring at 20-27 "C to a solution of 1.9 g (8.5 mmol) of benzyltriethylammonium chloride in 190.4 g of 50% potassium hydroxide solution (1.7 mol).  After the dropping (135 minutes), the mixture is stirred for 90 minutes and cooled with conc.  Acidified hydrochloric acid. 

  The mixture is converted into two clear phases with the addition of water and acetone; the organic phase is separated off, dried over sodium sulfate and evaporated.  The residue is refluxed with 36.7 g acetic anhydride in 200 ml toluene, filtered hot, and the filtrate is evaporated.  The above reaction is repeated with the residue using 21.8 g (0.214 mol) acetic anhydride, 19.9 g (0.161 mol) p-thiocresol, 2.4 g benzyltriethylammonium chloride and 285 g 30% NaOH solution.  After stirring, the mixture is acidified, the organic phase is separated off, dried over sodium sulfate and evaporated.  The residue is converted into the anhydride with 52.1 g of acetic anhydride and 250 ml of toluene.  After recrystallization from methylene chloride-pentane, 20.83 g (39% of theory  Th. ) 3- (p-methylphenylthio) -5-nitrophthalic anhydride; M.p. 



  180-2 "C.    



  Analysis for C15H0NO55 (molecular weight 315.30): calculated
C 57.14% H 2.88% N 4.44% S 10.17% found
C 57.3% H 3.0% N 4.5% S 10.1%. 



   Example 9:
3- (p-methoxyphenylthio) -5-nitrophthalic anhydride
12.17 g (51.1 mmol) of 3,5-dinitrophthalic anhydride are dissolved in 1350 ml of methylene chloride, after which 10.7 g (76.6 mmol) of 4-methoxythiophenol and 10.2 g (100 mmol) of acetic anhydride are added.  This solution is added dropwise with vigorous stirring at 2> 24 C to a mixture of 1.2 g of benzyltriethylammonium chloride, 68.6 g of 33% KOH solution (408 mmol) and 50 ml of methylene chloride. 



   After 2 hours it is acidified with hydrochloric acid, extracted with methylene chloride, dried over sodium sulfate and evaporated.  The residue is refluxed with 5.3 g of acetic anhydride in 100 ml of toluene.  The solution is filtered hot and the mother liquor is evaporated.  The dark residue is boiled out several times with cyclohexane.  After evaporation, 5.15 g (31% of theory  Th. ) 3- (p-methoxyphenylthio) -5-nitrophthalic anhydride; M.p.  143-48 0C.    

 

  Analysis for CISH9NOsS (molecular weight 331.30): calculated
C 54.38% H 2.74% N 4.23% S 9.68% found
C 54.40% H 2.90% N 4.30% S 9.50%. 



   B) Examples of use
Example I:
Production of thioxanthone A) Production of thioxanthone a) 12.7 g (40.3 mmol) of 3- (p-methylphenylthio) -5-nitrophthalic anhydride and 16.1 g (121 mmol) of aluminum trichloride in 120 ml of 1.1, 2 , 2-tetrachloroethane slowly heated to 120 "C.  After cooling, evaporate, stir in dilute hydrochloric acid, and the product is filtered off and dried.  After recrystallization from isopropanol, 7.37 g (58% of theory Th. ) 7-methyl-3-nitrothioxanthone-l-carboxylic acid; M.p.   > 250 "C.      



   b) 3.2 g (10.15 mmol) of 7-methyl-3-nitrothioxanthone-1-carboxylic acid are kept under reflux with 20 ml of oxalyl chloride for 5 hours.  After evaporation, 20 ml of n-butanol are added dropwise with ice cooling, and the mixture is heated under reflux for 30 minutes.  After concentration from toluene / cyclohexane, 2.7 g (72% of theory Th. ) 7-methyl-3-nitrothioxanthone-1-carboxylic acid n-butyl ester; M.p.    164-7 C.    



   c) 1 g (3.17 mmol) of 7-methyl-3-nitrothioxanthone-1-carboxylic acid is suspended in 15 ml of methylene chloride. 



  Then 2 drops of pyridine are added and 0.56 g (4.76 mmol) of thionyl chloride are added dropwise.  After 2 hours at reflux, the clear solution is concentrated and 5 ml of benzene are added.  A solution of 0.7 g (951 mmol) of n-butylamine in benzene is then added dropwise.  After stirring for 30 minutes at 25 ° C., the mixture is concentrated, the residue is taken up in methylene chloride / water, and the organic phase is dried over sodium sulfate and evaporated. 



  After recrystallization from methylene chloride / n-pentane, 0.68 g of 7-methyl-3-nitrothioxanthone-1-carboxylic acid-N-n-butylamide (58% of theory Th. ); M.p.     > 250 "C.    



   Example II a) Preparation of Polymers
Polymers with the following structure and composition are produced:
EMI9. 1
 m = 0.8 m + n. 



   n = 0.2 m + n
465.5 g (1.963 mol) of dimethylmaleinimidyl-ss- (methacryloyl-oxy) ethyl ester [prepared according to German Offenlegungsschrift 2,626,769] together with 49.15 g (0.49 mol) of ethyl acrylate under nitrogen in 960 ml of l- Acetoxy-2-ethoxyethane dissolved.  A solution of 3.86 g of azoisobutyronitrile in 25 ml of 1-acetoxy-2-ethoxyethane is run in at 80 ° C. under a nitrogen atmosphere and the mixture is then polymerized for 6 hours.  The still hot solution is stabilized with 2.57 g of 2,6-di-tert-butyl-p-cresol. 

  The average molecular weight of the polymers thus obtained (determined by scattered light measurement in CHCl3) and their intrinsic viscosity nlimit: average.  limit
Molecular weight (scattered light measurement in CHCI3) dl / g (CHCl3) polymer no.  1 3 x 106 0.8 20 "C polymer no.  2 4.36 x 105 0.29 20 "C b) Creation of images
To each 10 g of the polymer solutions described above in 1 acetoxy-2-ethoxyethane, diluted with N, N-dimethylformamide, the amounts of sensitizer given in Tables I and II below are added, the amount (concentration) being based on the solids content. 

  The polymer solutions with the dissolved sensitizer are applied by spin-coating (500 revolutions / minute for 1 minute) onto copper-clad epoxy plates in such a way that, after drying (15 minutes at 80 ° C.), a 1-3 liter thick polymer layer is formed on the copper.  The coated plates are exposed through a negative template (step wedge: Stouffer 21-Step Sensitivity Guide) with a 400 watt high-pressure mercury lamp at a distance of 55 cm from the vacuum table.  Vacuum table with upstream Pyrex glass filter of 8 mm thickness; For exposure times, see Tables I and II). 



   After the exposure, the image is developed in a l, l, l trichloroethane bath for 2 minutes, the uncrosslinked portions being removed.  The resulting relief image of the step wedge shown is made visible by etching the bare copper parts with a 50% FeCl3 solution.  In Tables I and II below, S means relative sensitivity.  It is a factor that specifies by how much longer or shorter than 3 minutes the exposure has to be carried out in order to image level 7 (optical density of the step wedge = 1).  The following relationship applies:
EMI9. 2nd
 where X is the level actually shown after 3 minutes of exposure. 

  The determination of Srel is based on that of W. S.     De Forest (Photoresist, Mc Graw Hill Book Company, New York, 1975, pages 1 13ff) described method for determining photosensitivity.    Table I: Polymer 1, exposed to a 400 watt high pressure mercury lamp
EMI10. 1


 <tb> sensitizer <SEP> photosensitivity
 <tb> <SEP> concentration <SEP> last one <SEP> pictured <SEP> level <SEP> after
 <tb> <SEP> Xmax. <SEP> Emax.

   <SEP>% by weight <SEP> mol% <SEP> 10 " <SEP> 30 " <SEP> 1 ' <SEP> 3 ' <SEP> 6 ' <SEP> S,
 <tb> 0 <SEP> N <SEP>. \ <SEP>, R,
 <tb> <SEP> 1 <SEP> II <SEP> o <SEP> 410 <SEP> 3000 <SEP> 1.41 <SEP> 0.005 <SEP> 3 <SEP> 5 <SEP> 7 <SEP> 11 <SEP> 4.0
 <tb> <SEP> \\
 <tb> <SEP> (r <SEP> ei2) 3
 <tb> <SEP> 23
 <tb> <SEP> cfl
 <tb> <SEP> 3
 <tb> H3C (CH2) <SEP> v <SEP> \ <SEP> / <SEP> \
 <tb> <SEP>! <SEP> II <SEP> <SEP> 335 <SEP> 7300 <SEP> 3.99 <SEP> 0.005 <SEP> 6 <SEP> 9 <SEP> 11 <SEP> 13 <SEP> 4.0
 <tb> <SEP> \\ / <SEP> \ / <SEP> 275 <SEP> 18800
 <tb> <SEP> F17C8 <SEP> (CH2) <SEP> 2µ
 <tb> F17C8- <SEP> (CH2) <SEP> -S <SEP>> <SEP> 380 <SEP> 4100 <SEP> 3.99 <SEP> 0.005 <SEP> 4 <SEP> 6 <SEP> 8 <SEP> 12 <SEP> 5.66
 <tb> 2 <SEP> \ // <SEP> 380 <SEP> 4100 <SEP> 3.99 <SEP> 0.005 <SEP> 4
 <tb> <SEP>; no
 <tb> <SEP> \\ / <SEP> \ /
 <tb> <SEP> (& 2) <SEP> 9-CH3
 <tb> Table II:

  Polymer 2, exposed with 400 watt high pressure mercury lamp
EMI10.2


 <tb> sensitizer <SEP> sensitizer <SEP> photosensitivity <SEP> last one
 <tb> <SEP> concentration <SEP> pictured <SEP> level <SEP> after
 <tb> <SEP> hmax. <SEP> Emax. <SEP>% by weight <SEP> mol% <SEP> 1 ' <SEP> 3 ' <SEP> 6 ' <SEP> 12 ' <SEP> 5 ,,
 <tb> H <SEP> C, <SEP> 9 <SEP> \\ 00H <SEP> 420 <SEP> 4000 <SEP> 1.58 <SEP> 0.005 <SEP> 3 <SEP> 6 <SEP> 8 <SEP> 0.71
 <tb> <SEP> 420 <SEP> 420
 <tb> <SEP> I <SEP> II <SEP> II <SEP>
 <tb> <SEP> 0 <SEP> 0 <SEP> 2
 <tb> R <SEP> 2 <SEP> i - <SEP> (C112) <SEP> 3CH3
 <tb> <SEP> 3 <SEP> \ o / 0 \ o / <SEP> tv <SEP> t <SEP> 420 <SEP> 4150 <SEP> 1.86 <SEP> 0.005 <SEP> 4 <SEP> 8 <SEP> 10 <SEP> 1.41
 <tb> <SEP> II <SEP> II
 <tb> <SEP> \ s <SEP> \
 <tb> <SEP> N02
 <tb>


    

Claims (10)

 PATENT CLAIMS 1. Compounds of Formula I EMI1.1  wherein M1 and M2 each -OH or together -0-, X -NO2, -OR ', -SR' or -SO2R 'and R 'C120-alkyl, C3-4-alkenyl, C3-5-alkynyl, C2-4-mono-hydroxyalkyl, C112-haloalkyl, benzyl, C5-12-cycloalkyl, phenyl, halophenyl, nitrophenyl, alkyl- or alkoxyphenyl, each with 1-4 carbon atoms in the alkyl or alkoxy parts or acetylaminophenyl mean.  2. Compounds of formula I according to claim 1, wherein M1 and M2 together represent -O-.  3. Compounds of formula I according to claim 1, wherein M1 and M2 together -0-, X -NO2, -Oalkyl with 1-4 C atoms, -SO2-phenyl or SR 'and R' C110-alkyl, C110-haloalkyl, Phenyl, p-methoxyphenyl, p-toluyl or 3,4 dichlorophenyl mean.  4. Compounds of formula I according to claim 1, wherein M2 and M2 together mean -0-, X -NO2 and lt 'C1-10n-alkyl or phenyl.  5. A process for the preparation of compounds of formula I according to claim 1, characterized in that either 3,5-dinitrophthalic anhydride with a compound of formulas IIa R-NH-Y aIa) or 3,5-dinitrophthalic acid with a compound of the formula IIb R-NH-Y '(IIb), in which Y is hydrogen, -COH or -CO-NH-R and Y' -COH or -CO-NH-R, and R is hydrogen, C20-alkyl, C25-alkenyl, C3-5-alkynyl, C5-12-cycloalkyl, benzyl, phenyl or toluyl, to a compound of formula III EMI1.2  implements the compound of formula III with a compound of formula IVa R'-SH (IVa), a salt of a compound of formula IVa or mixtures thereof to a compound of formula Va EMI1.3  implements  wherein X 'is -NO2 or -SR' and R and R 'have the meaning given under the formulas IIa and IIb or I, compounds of the formula Va, in which X' is -NO2, then with a salt of a compound of the formula IVb or IVc R'-OH (IVb) or R'-SO2H (IVc) to a compound of formula Vb EMI1.4  is implemented, wherein R and R 'have the meaning given under the formulas IIa and IIb or I and X represents "-OR' or -SO2R ', and then the compounds of the formula Vb by hydrolysis into a compound of the formula I, in which M1 and M2 each represent -OH, R 'has the meaning given under the formula I and X represents -OR' or -SO2R '.  6. A process for the preparation of compounds of the formula I according to claim 1, characterized in that compounds of the formula I according to claim 5 are prepared in which M1 and M2 each represent -OH, R 'has the meaning given under formula I and X - OR 'or -SO2R', and these compounds thermally or with the addition of dehydrating agents in the corresponding compounds of formula I, wherein M1 and M2 together mean -O-, converted.  7. A process for the preparation of compounds of formula I according to claim 1, characterized in that either 3, 5-dinitrophthalic anhydride with a compound of formulas IIa R-NH-Y (IIa) or 3,5-dinitrophthalic acid with a compound of the formula IIb R-NH-Y '(IIb), in which Y is hydrogen, -COH or -CO-NH-R and Y' -COH or -CO-NH-R and R is hydrogen, C120-alkyl, C2-alkenyl, C5- Represent alkynyl, C5-12-cycloalkyl, benzyl, phenyl or toluyl, to a compound of formula III EMI1.5  implements the compound of formula III with a compound of formula IVa R'-SH (IVa) a salt of a compound of formula IVa or mixtures thereof to a compound of formula Va EMI2.1  implements  wherein X 'is -NO2 or -SR' and R and R 'have the meaning given under the formulas IIa and IIb or I, and then the compounds of the formula Va by hydrolysis into a compound of the formula I, in which Ml and M2 each Mean -OH, R 'has the meaning given under the formula I and X represents -NO2 or -SR'.  8. A process for the preparation of compounds of the formula I according to claim 1, characterized in that compounds of the formula I according to claim 7 are prepared in which Ml and M2 each represent -OH, R 'has the meaning given under the formula I and X - NO2 or -SR ', and these compounds thermally or with the addition of dehydrating agents in the corresponding compounds of formula I, wherein Ml and M2 together mean -0-, converted.  9. Use of compounds of formula I according to claim 1, wherein M1 and M2 represent -0-, as sensitizers for light-crosslinkable polymers.  10. Use of compounds of formula I according to claim 1, wherein M1 and M2 together represent -0-, together with amine as initiators for the photopolymerization of ethylenically unsaturated compounds or for the photochemical crosslinking of polyolefins.  The present invention relates to new 3,5-disubstituted phthalic acids and phthalic anhydrides, processes for their preparation and the use of the new 3,5-disubstituted phthalic anhydrides as sensitizers for light-crosslinkable polymers or as initiators, in a mixture with amines, for the photopolymerization of ethylenically unsaturated compounds or for the photochemical crosslinking of polyolefins.  Optionally halogenated, especially chlorinated, thioxanthones are among the best known and most effective sensitizers for photo-induced crosslinking reactions. A prerequisite for a successful application of this type is good compatibility of the sensitizer in the polymer, i. H. the sensitizer must be miscible with the polymer up to increased concentrations. Furthermore, the sensitizers must be readily soluble in the solvents used in the processing of the polymers. The aforementioned thioxanthones do not meet these requirements in every respect; in particular, they separate easily in the polymer, as a result of which the sensitizing effect is severely impaired.  It is also known that the photopolymerization of ethylenically unsaturated compounds can be initiated by aromatic ketones of the benzophenone, anthraquinone, xanthone and thioxanthone type. It is also known from US Pat. No. 3,759,807 that the initiator action of such aromatic ketones can be accelerated by the addition of organic amines. Since these amines usually do not have an initiator effect alone, they act in combination with aromatic ketones as activators or accelerators. Technically, this is of great importance because the production speed of photochemically hardened coatings or printing inks depends primarily on the rate of polymerization of the unsaturated compound.  There have now been new phthalic acids and phthalic anhydrides of the formula I. EMI2.2  found, where Ml and M2 each -OH or together -0-, X -NO2, -OR ', -SR' or -SO2R 'and R Cl 20-alkyl, C ,, - alkenyl, CS-alkynyl, C2 4-mono-hydroxyalkyl, C112-haloalkyl, benzyl, C5 12-cycloalkyl, Phenyl, halophenyl, nitrophenyl, alkyl or alk oxyphenyl each with 1-4 carbon atoms in the alkyl or alkoxy parts or acetylaminophenyl mean.  The phthalic anhydrides of the formula I (M, and M2 = together -0-) are outstandingly suitable for use as sensitizers for light-crosslinkable polymers. They are particularly characterized by good compatibility with the polymer, good solubility in common organic solvents and high photosensitivity. In addition, the UV absorption can be influenced in such a way that the phthalic anhydrides according to the invention have a sensitizing effect even when irradiated with long-wave UV light (up to approx. 450 nm) and thus bring about the crosslinking of the photosensitive polymers. No photosensitizing phthalic anhydrides with donors in the 3-position were previously known.  The phthalic anhydrides according to the invention are also suitable, in a mixture with organic amines, as initiators for the photopolymerization of ethylenically unsaturated compounds or for the photochemical crosslinking of polyolefins.    The compounds of formula I can be prepared in a manner known per se, e.g. B. by either 3,5-dinitrophthalic anhydride with a compound of formula IIa R-NH-Y (IIa) or 3,5-dinitrophthalic acid with a compound of the formula IIb R-NH-Y '(IIb), wherein Y is hydrogen, -COH or -CO-NH-R and Y' -COH or -CO-NH-R, and R is hydrogen, C, 20-alkyl, C2 5-alkenyl , C} 5-alkynyl, C5, 2-cycloalkyl, benzyl, phenyl or toluyl represent a compound of formula III EMI2.3   ** WARNING ** End of CLMS field could overlap beginning of DESC **.