Photosensitive compositions containing carbonylic halides as activators

Claim 2

A phototropic photosensitive composition characterised in that it comprises the following ingredients a. at least one component capable of curing, crosslinking or polymerizing upon suitable initiation, b. an initiator for said component that is potentiated by actinic radiation, c. a colorformer capable of becoming more intensely colored upon contact with a color activator, said colorformer being selected from fluoran compounds and the free base of a dyestuff the halide salt of which is more intensely colored than the free base, and d. a latent activator capable of activating the colorformer under the influence of actinic radiation comprising a proton donor and a carbonylic halide.

Claim 3

A composition according to claim 1 further characterised in that the component capable of curing, crosslinking or polymerizing comprises an acrylyl or methacrylyl compound which has the general formula when the compound has the formula M is H or CH 3 M' is cycloalkyl of 5 to 12 carbon atoms, cycloalkenyl of 5 to 12 carbon atoms, or where p is an integer from 1 to 10 g is an integer from 2 to 4 s is 0 or an integer from 1 to 4 M" is hydrogen, hydroxyl, phenoxy, alkoxy of 1 to 8 carbon atoms; and where the compound has the formula G is a polyvalent alkylene group of the formula in which x is an integer from 2 to 8 y is an integer from 0 to 2 or G is a divalent ether or ester group of the formula or where t is an integer from 1 to 5, g is an integer from 2 to 4 and r is the valence of G and is an integer from 2 to 4.

Claim 4

A composition according to either of claims 1 or 2 further characterised in that the initiator comprises an aromatic carbonyl compound.

Claim 5

A composition according to any of claims 1 to 3 further characterised in that the fluoran compound has the general formula where R a is hydrogen or an aliphatic group having one to 12 carbon atoms that is either unsubstituted or optionally substituted and that may be interrupted by and that is bound directly via carbon or oxygen; R b is an amino group where one or both hydrogen atoms are optionally replaced by unsubstituted or substituted aliphatic groups, cycloaliphatic groups, aromatic groups or mixed aliphatic-aromatic groups or R b is a heterocyclic group having 3 to 12 ring members bound via a ring nitrogen and containing, in addition to nitrogen, one or more of oxygen and sulfur as hetero ring members or R a and R b together form a condensed aromatic nucleus; R is hydrogen, halogen, an aliphatic group having one to 12 carbon atoms that is unsubstituted or substituted and that may be interrupted by nitrogen or oxygen and that is bound directly via carbon or oxygen, or R is an amino group where one or both hydrogen atoms are optionally replaced by either unsubstituted or substituted aliphatic groups, cycloaliphatic groups, aromatic groups, mixed aliphatic-aromatic groups or where R c is a heterocyclic group with three to twelve ring members containing one or more of nitrogen, oxygen and sulfur as hetero ring members or R c is an aromatic group that is either unsubstituted or optionally substituted or a mixed aliphatic-aromatic group or an aromatic ether or aliphatic-aromatic ether group; R d is hydrogen, lower aliphatic or an amino group where one or both hydrogen atoms are optionally replaced by either unsubstituted or substituted aliphatic groups, cycloaliphatic groups, aromatic groups, mixed aliphatic-aromatic groups or R is a heterocyclic group having 3 to 12 ring members containing one or more of nitrogen, oxygen and sulfur as hetero ring members; R e and R each independently is hydrogen, unsubstituted or substituted aliphatic having 1 to 12 carbon atoms which may be interrupted by oxygen or nitrogen, and which is to be bound directly via carbon, cycloaliphatic groups, aromatic groups, mixed aliphatic-aromatic groups, or Re and R f , together with the nitrogen atom form a hetero cyclic group having 3 to 12 ring members, optionally containing, in addition to nitrogen, one or more of sulfur and oxygen as hetero ring members; (R ) represents 1 to 3, independently, of hydrogen, lower aliphatic bound directly via carbon or oxygen, or is halogen, acetamide or optionally substituted amino and provided that at least one or R b , R c and R d is an amino group, as defined.

Claim 6

A composition according to claim 4 further characterised in that the fluoran compound is a 2-amino fluoran of the general formula: where R 1 is hydrogen, halogen, alkyl having 1 to 12 carbon atoms or alkoxy having 1 to 12 carbon atoms; R 2 and R 3 each independently is hydrogen, alkyl having 1 to 12 carbon atoms, alkenyl having 2 to 12 carbon atoms , alkoxyalkyl having 2 to 8 carbon atoms, alkoxycarbonylalkyl having 3 to 9 carbon atoms, cycloalkyl having 5 or 6 carbon atoms, acyl having 1 to 12 carbon atoms, phenyl, naphthyl or benzyl that are either unsubstituted or are substituted in the aromatic nucleus by 1 to 3 of amino, mono- or di- alkyl amino having 1 to 5 carbon atoms, alkyl having 1 to 7 carbon atoms, alkoxy having 1 to 7 carbon atoms, carboxyl, alkoxy- carbonyl having 2 to 7 carbon atoms, acyl or acylamino having 1 to 5 carbon atoms, or MeSO 3 - where Me is alkali metal or R 2 and R 3 together with the associated nitrogen atom form a pyrrolidinyl, piperidyl, pipecolinyl, perhydroazepinyl, heptamethyleneimino, octamethyleneimino, indolinyl, 1,2,3,4-tetrahydroquinolinyl, hexahydrocarbazolyl, morpholinyl, thiomorpholinyl, piperazinyl, N-alkylpiperazinyl where the alkyl group contains 1 to 4 carbon atoms, pyrazolinyl, or 3-methylpyrazolinyl group, R4is hydrogen, alkyl having 1 to 12 carbon atoms, alkoxy having 1 to 12 carbon atoms, halogen, amino that is either unsubstituted or is substituted by one or two of the substituents as defined for R 2 and R , or R 4 is phenyl, phenoxy, benzyl or benzyloxy that is either unsubstituted or substituted in the aromatic nucleus by one to three of amino, mono- or di- alkyl amino having 1 to 5 carbon atoms, lower alkyl, lower alkoxy, carboxyl, alkoxy-carbonyl having 2 to 7 carbon atoms, acyl having 1 to 5 carbon atoms or MeSO 3 - where Me is alkali metal; R 5 is hydrogen, lower alkyl, lower alkoxy or amino which is either unsubstituted or is substituted by one or two of the substituents as defined for R 2 and R 39 including the heterocyclic members; R 6 and R 7 each independently is the same as defined for R 2 and R 3 , including the heterocyclic members thereof; (R 8 ) m represents 1 to 3 members independently selected from hydrogen, alkyl having 1 to 7 carbon atoms, alkoxy having 1 to 7 carbon atoms, halogen, acetamido, amino or mono- or di-alkyl amino having 1 to 7 carbon atoms.

Claim 7

A composition according to any of claims 1 to 5 characterised in that the carbonylic halide is an aliphatic ketone, a cycloalkphatic ketone, an ester of an aliphatic dicarboxylic acid or an amide of an aliphatic dicarboxylic acid.

Claim 8

A composition according to claim 6 further characterised in that at least one halogen is located on a carbon atom alpha- to a carbonyl group.

Claim 9

A composition according to any of claims 1 to 5 further characterised in that the carbonylic halide contains at least one alpha Cl, Br or I atom and is selected from halogenated aliphatic ketones having 3 to 13 carbon atoms, halogenated carbocyclic ketones having 4 to 8 ring carbon atoms, esters and amides of halogenated dicarboxylic acids containing up to 12 carbon atoms and esters and amides of halogenated keto acids containing up to 12 carbon atoms.

Claim 10

A composition according to any of claims 1 to 5 further characterised in that the carbonylic halide has the formula where R aa is alkyl having 1 to 11 carbon atoms or said alkyl containing halogen atoms; R bb is alkylene having 1 to 10 carbon atoms, or said alkylene containing halogen atoms, or R bb represents a covalent bond; R cc is alkyl or alkoxy having 1 to 11 carbon atoms or said alkyl or alkoxy that contains halogen atoms; mm is 0 or an integer from 1 to 3.

Claim 11

A composition according to any of claims 1 to 5 further characterised in that the carbonylic halide is a carbocyclic ketone having the general formula where E is the halogenated residue of a carbocyclic ketone which, together with the bound carbonyl groups contains from 4 to 8 carbon atoms in the ring; E can be substituted, in addition to halogen, by lower alkyl, lower alkoxy or acyl having 2 to 6 carbon atoms; nn is 1 or 2.

Claim 12

A composition according to any of claims 1 to 5 further characterised in that the carbonylic halide is an ester or amide of the general formula where R aa , is amino that is unsubstituted or substituted by one or two of lower alkyl or halogenated lower alkyl, or R aa , is alkoxy or halogenated alkoxy group having 1 to 4 carbon atoms, or R aa , is where D is alkoxy or haloalkoxy having 1 to 4 carbon atoms and -A- is alkylene or haloalkylene having 1 to 4 carbon atoms; R bb , is a covalent bond, alkylene or haloalkylene having 1 to 4 carbon atoms or the group; where A and B each independently is alkylene or haloalkylene having 1 to 4 carbon atoms; R cc , is amino that is either unsubstituted or substituted by one or two of lower alkyl or halogenated lower alkyl, or R cc , is alkoxy or haloalkoxy having 1 to 4 carbon atoms.

Claim 13

A composition according to any of the preceding claims further characterised in that it comprises: 40 to 70 percent by weight of said preformed polymer binder; 30 to 50 percent by weight of said curable crosslinkable or polymerizable component; 1 to 10 percent by weight of said photoinitiator; 0.01 to 2 percent by weight of said fluoran compound; 0.1 to 5 percent by weight of carbonylic halide and 0.1 to 10 percent by weight of amine.

Claim 14

A composition according to any of claims 1 to 11 further characterised in that it comprises: (a) 15 to 70 percent by weight of an ethylenically unsaturated component capable of curing crosslinking or polymerizing under the influence of free radicals; (b) 10 to 50 percent by weight of a preformed polymeric binder or of a compound capable of curing, crosslinking or polymerizing with said ethylenically unsaturated component under the influence of free radicals; (c) 0.1 to 10 percent by weight of a photoinitiator; (d) 0.01 to 2 percent by weight of fluoran compound; (e) 0.1 to 10 percent by weight of a tertiary amine, and (f) 0.1 to 5 percent by weight of an amide or lower alkyl ester of malonic, succinic or glutaric acid containing at least one alpha-halogen which is Cl, Br or I.

Claim 15

A composition according to any of the preceding claims further characterised in that it is in the form of a thin film.