Ciba-geigy Corporation

Ciba-geigy Ag

Louis Felder

Rudolf Kirchmayr

Vratislav Kvita

Hans Zweifel

Martin Roth

Rinaldo Husler

Walter Fischer

Daniel Bellus

Andreas Schmidt

Rinaldo Kusler

Husler

Thioxanthone carboxylic acid esters, thioesters and amides with reactive functional groups of the formula ##STR1## in which X, Y, Z, n and Q are as defined in the patent claim and Q is, for example, --OCH.dbd.CH.sub.2, --OCH.sub.2 CH.dbd.CH.sub.2, --SCH.sub.2 CH.dbd.CH.sub.2 or --NHCH.sub.2 CH.dbd.CH.sub.2 (n=1), --OH, --SH, --NH.sub.2, --COOH, --COCl or --OCO--C(R').dbd.CH.sub.2, in which R' is methyl or hydrogen (n=2), are suitable for the preparation of polymers with thioxanthone radicals in side chains. The compounds (I) and also the polymers which can be prepared therefrom can be employed as sensitizers for photocrosslinkable polymers or as initiators, if desired in a mixture with amines, for the photopolymerization of ethylenically unsaturated compounds or for the photochemical crosslinking of polyolefines.

Thioxanthonecarboxylic acids, esters thioesters and amides with reactive

Thioxanthonecarboxylic acid esters, thioesters or amides of the formula I ##STR1## in which X and Z are hydrogen or one of the substituents defined in more detail in claim 1 and Y is --OR.sub.1, --SR.sub.1 or --N(R.sub.1)(R.sub.2), in which R.sub.1 is C.sub.1-24 alkyl and R.sub.2 is H or R.sub.1, are suitable, if desired together with amines, as initiators for the photopolymerization of ethylenically unsaturated compounds or for photochemical crosslinking of polyolefines. They are also used as sensitizers for photocrosslinkable polymers. They can be prepared by methods known per se, for example by cyclization of phenylthio-phthalic, -isophthalic or -terephthalic acids, which can be correspondingly substituted, and subsequent reaction with suitable alcohols, thiols or amines.

Thioxanthonecarboxylic acid esters, thioesters and amides

Thioxanthonecarboxylic acid esters, thioesters or amides of the formula I ##STR1## in which X and Z are hydrogen or one of the substituents defined in more detail in claim 1 and Y is --OR.sub.1, --SR.sub.1 or --N(R.sub.1)(R.sub.2), in which R.sub.1 is C.sub.1-24 alkyl and R.sub.2 is H or R.sub.1, are suitable, if desired together with amines, as initiators for the photopolymerization of ethylenically unsaturated compounds or for photochemical crosslinking of polyolefines. They are also used an sensitizers for photocrosslinkable polymers. They can be prepared by methods known per se, for example by cyclization of phenylthio-phthalic, -isophthalic or -terephthalic acids, which can be correspondingly substituted, and subsequent reaction with suitable alcohols, thiols or amines.

Novel thioxanthonecarboxylic acids and thioxanthonecarboxylic acid derivatives of the formula I ##STR1## in which Y is --COOH, --CO-halogen, --CN or a carboxylic acid ester, thioester or amide group and X, Z and W are as defined in the patent claim, are described. The compounds of the formula I in which Y is other than --CO--halogen are suitable as sensitizers for photo-crosslinkable polymers or as initiators for photo-polymerization of ethylenically unsaturated compounds or for photo-chemical crosslinking of polyolefins. The acid halides of the formula I are starting materials for the preparation of the corresponding nitriles and carboxylic acid esters, thioesters and amides.

Thioxanthonecarboxylic acids and thioxanthonecarboxylic acid derivatives

Thioxanthone carboxylic acid esters, thioesters and amides with reactive functional groups of the formula ##STR1## in which X, Y, Z, n and Q are as defined in the patent claim and Q is, for example, --OCH.dbd.CH.sub.2, --OCH.sub.2 CH.dbd.CH.sub.2, --SCH.sub.2 CH.dbd.CH.sub.2 or --NHCH.sub.2 CH.dbd.CH.sub.2 (n=1), --OH, --SH, --NH.sub.2, --COOH, --COCl or --OCO--C(R').dbd.CH.sub.2, in which R' is methyl or hydrogen (n=2), are suitable for the preparation of polymers with thioxanthone radicals in side chains. The compounds (I) and also the polymers which can be prepared therefrom can be employed as sensitisers for photocrosslinkable polymers or as initiators, if desired in a mixture with amines, for the photopolymerisation of ethylenically unsaturated compounds or for the photochemical crosslinking of polyolefines.

Thioxanthonecarboxylic acids, esters, thioesters and amides with

Aromatic-aliphatic ketones of the formulae I, II, III or IV ##STR1## wherein n is 1 or 2, Ar is an aryl radical, R.sup.1 and R.sup.2 are monovalent aliphatic, cycloaliphatic or araliphatic radicals, R.sup.3 is a direct bond or a divalent organic radical, X is a hydroxyl or amino group or the monovalent etherification or silylation products thereof, and X' is a divalent amino, ether or silyloxy group, Y is a direct bond or CH.sub.2 and Z is O, S, SO.sub.2, CH.sub.2 or C(CH.sub.3).sub.2, are suitable sensitizers for the photopolymerization of unsaturated compounds and for the photochemical crosslinking of polyolefins. Some of these compounds are novel and can be obtained by methods analogous to those for obtaining the known compounds of this type.

Bis benzoyl sensitizers for photopolymerization or photo cross linking

Use of aromatic-aliphatic ketones as photo sensitizers

Sensitizers for photopolymerization

Aromatic-aliphatic ketones of the formulae I, II, III or IV ##STR1## wherein n is 1 or 2, Ar is an aryl radical, R.sup.1 and R.sup.2 are monvalent aliphatic, cycloaliphatic or araliphatic radicals, R.sup.3 is a direct bond or a divalent organic radical, X is a hydroxyl or amino group or the monovalent etherification or silylation products thereof, and X' is a divalent amino, ether or silyloxy group, Y is a direct bond or CH.sub.2 and Z is O, S, SO.sub.2, CH.sub.2 or C(CH.sub.3).sub.2, are suitable sensitizers for the photopolymerization of unsaturated compounds and for the photochemical crosslinking of polyolefins. Some of these compounds are novel and can be obtained by methods analogous to those for obtaining the known compounds of this type.

Benzophenone thioethers of the general formula I or Ia ##STR1## in which X is hydrogen, alkyl, alkoxy or --COO-alkyl and X.sub.1 is hydrogen, Cl, Br or --SR, R is an unbranched or branched alkyl radical having 1-20 C atoms, which is unsubstituted or substituted by --OH, --OR.sup.1, --O--C(O)--R.sup.2, --COOR.sup.3, --C(O)-phenyl. --CN, --SR.sup.1, --NH.sub.2, --NHR.sup.4, --NR.sup.4 R.sup.5 or phenyl, in which R.sup.1, R.sup.2, R.sup.3, R.sup.4 and R.sup.5 are monovalent hydrocarbon radicals, R.sub.a is an alkylene radical having 2-10 C atoms, which is unsubstituted or substituted by --OH. --OR.sup.1 or --O--C(O)--R.sup.2 and/or is interrupted by --O--, --NR.sup.4, --O--C(O)--R.sup.6 --C(O)--O--, --C(O)--O--R.sup.7 --O--C(O)-- or phenylene and R.sup.6 and R.sup.7 are divalent hydrocarbon radicals, can be prepared by reacting a mono- or di-halogenobenzophenone of the general formula II ##STR2## in which X.sub.2 is Cl or Br and X.sub.3 is H, Cl or Br, in a polar solvent with a mercapto compound of the formula RSH or R.sub.a (SH).sub.2 in the presence of a base in an amount equivalent to the amount of halogen to be reacted.

Process for the preparation of benzophenone thioethers

Mixtures of (A) a mercaptophenyl ketone of the formula I ##STR1## in which n is 1 or 2, Ar is an unsubstituted or substituted aryl radical or a hetero-aromatic radical, R.sup.1 is hydrogen, alkyl or, if n is 1, also --SCH.sub.2 X and X, if n is 1, is one of the groups --CH(R.sup.2)--OH, --CH(R.sup.2)--O--CO--R.sup.5, --CH.sub.2 SH or --(CH.sub.2).sub.1-3 --NR.sup.3 R.sup.4, in which R.sup.2 is hydrogen, methyl, phenyl or one of the groups --CH.sub.2 OH, --CH.sub.2 --NR.sup.3 R.sup.4 or --CH.sub.2 --OR.sup.6, R.sup.3 and R.sup.4 independently of one another are hydrogen, alkyl or hydroxyalkyl, or R.sup.3 and R.sup.4 together are 1,4-butylene, 1,5-pentylene or 3-oxa-1,5-pentylene, and R.sup.5 and R.sup.6 are monovalent hydrocarbon radicals, and X, if n is 2, is alkylene, vinylene, phenylene or one of the divalent groups --CH.sub.2 S--SCH.sub.2 --, --CH(R.sup.2)--O--CO--O--CH(R.sup.2)--, --CH(R.sup.2)--O--CO--R.sup.7 --CO-- OCH(R.sup.2)--, --CO--O--R.sup.8 --O--CO--, --CH.sub.2 COO--R.sup.8 --OOCCH.sub.2 -- or --CH(OH)--CH.sub.2 --O--R.sup.8 --O--CH.sub.2 --CH(OH)--, in which R.sup.7 is a divalent hydrocarbon radical or --NH--R.sup.9 --NH--and R.sup.8 and R.sup.9 are divalent hydrocarbon radicals, and (B) an organic amine are effective initiators for the photopolymerization of ethylenically unsaturated compounds or for the photochemical crosslinking of polyolefins.

Mercaptophenyl ketones as initiators for the photopolymerization of

Compounds of the formula I ##STR1## wherein Ar.sup.1 and Ar.sup.2 represent unsubstituted or substituted phenyl, R.sup.1 represents hydrogen, alkyl, alkoxy, hydroxyalkyl, allyl, benzyl or a group --O--R.sup.2 -NR.sup.3 R.sup.4, R.sup.2 represents alkylene and --NR.sup.3 R.sup.4 is an open chain or cyclic organic amino group, are effective initiators for the photopolymerization of unsaturated compounds or for the photocrosslinking of polyolefins. They can be obtained by different methods which are in themselves known, in particular by reaction of the corresponding haloalkyl ethers or haloalkyl ketals with primary or secondary amines.

Aminoalkoxy derivatives of aromatic ketones

Dialkoxy-acetyl derivatives of aromatic compounds are photosensitizers for the curing of photopolymerisable systems. They can be synthesized from aromatic acetyl compounds(aryl methyl ketones) by reaction with nitrosyl chloride and the corresponding alkanol. Examples of photopolymerizable systems are coatings or printing inks on the basis of unsaturated polyesters or acrylic compounds.

Photoinitiators for UV-curable systems

Anthrone derivatives having hydroxy, ether or hydrocarbyl groups in 10-position, for example 10,10-dimethoxyanthrone, are excellent photoinitiators for the UV-curing of unsaturated systems. Preferable systems are monomeric or oligomeric acrylates and their mixtures. The systems may be used in thin layers as for instance for coatings or printing inks.

Photopolymerizable composition containing anthrones

Monoketals of esters and amides of aromatic .alpha.,.beta.-dioxocarboxylic acids having the formula

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Basel, Switzerland

Louis Felder