Phototropic photosensitive compositions containing a fluoran colorformer

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 fluoran compound capable of becoming more intensel; colored upon contact with a color activator, and d. a latent activator for the fluoran dyestuff that is capable of activating the fluoran dye under the influence of actinic light.

Claim 3

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

Claim 4

A composition according to claim 1 or claim 2 further characterised in that the fluoran compound is a 2-amino fluoran of the general formula: where R 1 is hydrogen, halogen, alkyl having one to 12 carbor atoms, alkoxy having one to 12 carbon atoms R 2 and R 3 each independently is hydrogen, alkyl having one to 12 carbon atoms, alkenyl having 2 to 12 carbon atome alkoxyalkyl having 2 to 8 carbon atoms, alkoxycarbonylalkyl having 3 to 9 carbon atoms, cycloalkyl having 5 or 6 carbon atoms, acyl having one to 12 carbon atoms, phenyl, naphthyl or benzyl that are either unsubstituted or are substituted in the aromatic nucleus by one to 3 of amino, mono- or di-alkyl amino having one to 5 carbon atoms, alkyl having one to 7 carbon atoms, alkoxy having one to 7 carbon atoms, carboxyl, alkoxycarbonyl having 2 to 7 carbon atoms, acyl having acylamino of one to 5 carbon atoms, or MeS0 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 one to 4 carbon atoms, pyrazolinyl, or 3-methylpyrazolinyl group R 4 is hydrogen, alkyl having one to 12 carbon atoms, alkoxy having one to 12 carbon atoms, halogen, amino which is either unsubstituted or is substituted by one or two of the substituents as defined for R 2 and R 3 9 or R 4 is phenyl, phenoxy, benzyl or benzyloxy that is either unsubstituted or substituted in the aromatic nucleus by one to 3 of amino, mono-or di-alkylamino having one to 5 carbon atoms, lower alkyl, lower alkoxy, carboxyl, alkoxycarbonyl having 2 to 7 carbon atoms, acyl having one to 5 carbon atoms or MeS0 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 3 9 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; and (R 8 ) m represents from one to 3 members independently selected from hydrogen, alkyl having one to 7 carbon atoms, alkoxy having one to 7 carbon atoms, halogen, acetamido, amino or mono- or di-alkyl amino having one to 7 carbon atoms.

Claim 5

A composition according to any of claims 1 to 3 further characterised in that the component capable of curing, crosslinking of polymerizing contains at least one ethylenically unsaturated group capable of curing, crosslinking or polymerizing under the influence of free radicals, or at least one epoxide group capable of curing, crosslinking or polymerizing under the influence of a Lewis acid.

Claim 6

A composition according to claim 4 further characterised in that the component capable of curing, crosslinking or polymerizing comprises an acrylyl or methacrylyl compound.

Claim 7

A composition according to any of the preceding claims further characterised in that the initiator comprises a photoinitiator or a mixture thereof.

Claim 8

A composition according to claim 4 further characterised in that the latent activator generates a Lewis acid under the influence of actinic light.

Claim 9

A composition according to any of claims 1 to 3 further characterised in that in which the latent activator comprises a proton donor and a halogenated compound.

Claim 10

A composition according to claim 8 further characterised in that the proton doncrcomprises a p-aminophenyl ketone of the general formula in which R' and R" are alkyl having one to 4 carbon atoms and R '''' is alkyl having one to 12 carbon atoms, alkoxy having one to 12 carbon atoms, phenyl, loweralkyliminophenylene or di(lower-alkyl) aminophenylene.

Claim 11

A composition according to claim 8 further characterised in that the halogenated compound comprises a compound of the where X is C1, Br or I a is an integer from 1 to 4 A is alkyl or alkenyl of 1 to 7 carbon atoms G is -OA' or A' is alkyl or haloalkyl having 1 to 15 carbon atoms and halo is C1, Br or I; A" is hydrogen, alkyl or haloalkyl having 1 to 4 carbon atoms and halo is C1, Br or I; and b is 1 or 2.

Claim 12

A composition according to any of claims 1 to 3 further characterised in that it comprises: (a) 40 to 70 percent by weight of a preformed polymer binder; .% (b) 30 to 50 percent by weight of curable, crosslinking or polymerizable component; (c) 1 to 10 percent by weight of photoinitiator; (d) 0.01 to 2 percent by weight of fluoran compound; (e) 0.1 to 5 percent by weight of halogenated compound, and (f) 0.1 to 10 percent by weight of amine.

Claim 13

A composition according to any of claims 1 to 3 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 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 photoinitiator, (d) 0.01 to 2 percent by weight of fluoran compound, (e) 0.1 to 5 percent by weight of a halogen compound, and (f) 0.1 to 10 percent by weight of a tertiary amine.

Claim 14

A composition according to claim 11 further characterised in that it is in the form of a thin film.