PHOTOSENSITIVE COMPOSITIONS CONTAINING CARBONYLIC HALIDES AS ACTIVATORS

Abstract: Compositions containing a polymerizable, curable or crosslinkable component, a photoinitiator, a colorformer capable of changing color upon contact with a suitable activator and a latent activator containing an organic halide will become insoluble and change color under the influence of actinic radiation. The organic halide is a carbonylic compound such as an aliphatic or cycloalipathic ketone or an ester or amide of a dicarboxylic acid. The compositions are useful to make resists used in the electronics industry to manufacture printed circuits.

Description: CARBOLIC HALIDES AS ACTIVATORS FOR pHOTOTROpIC COMPOSTTONS Two techniques widely used in the fabrication of printed circuit boards are the additive process and the subtractive process. In the manufacture of tinted circuit boards by the subtractive process, there is adhered to the surface of a copper-clad laminate one surface of a dry, photoresist film; the other surface of the film is adhered to a filmsupport. The photoresist layer is thereafter exposed to light according to a predetermined pattern. The support film is thereafter removed and the copper layer is exposed by washina away the unexposed areas of the photoresist layer. The exposed copper layer is then etched away by chemical milling. In the additive process, there is adhered to the surface of a substrate (which may or may not be copper-clad) one surface of a dry photoresist film; the other surface is adhered to a film support. The dry photoresist layer is thereafter exposed to a predetermined light Pattern and the support film is thereafter removed. The substrate is exposed by washing away the unexposed areas of the photoresist layer. At this point, the substrate is treated with appropriate sensitizers and metalizing solutions, whereby a layer of metal, usually copper, is applied to the substrate. The dry photoresist films are typically formulated to contrast in color with the substrates with which they are used. Since they generally do not change color, it is extremely difficult to inspect the product after exposure to light but prior to removal of the unexposed areas of the photoresist film to insure that the light mask has been properly placed and to be sure that there are no imperfections or defects in the exposed photopolymerizable layer. It is extremely useful to have a dry photoresist film which visually indicates where the film has been exposed to light so that detection of defects can readily be made prior to developing the film and etching the copper-clad panels or building up a layer of metal on the exposed substrate. It would also be useful to have a liquid photopoler- izable system that is colorless or lightly colored in the unexposed state and which both crosslinks and becomes intensely colored upon exposure to actinic light. DESCRIPTION OF THE PRIOR ART Prior artisans who have worked on phototropic psot sensitive compositions have generally used the haldoenatet methanes and ethanes such as Cert, CCIS, CHEr3, Cho13, CI3 etc. While these materials work in a laboratory context, their volatility makes fabrication of products having a reasonable shelf-life virtually impossible. Further, the toxicity of these materials renders them dangerous to work with Work done by Toshio Yamazaki, Harriet J. Cook and rlelvin A. Lipson at Dynachem Corporation showed that stable phototropic photosensitive compositions could be obtained using the normally solid amideof a halogenated aliphatic carboxylic acid as an activator for the free base of an amino dyestuff. The general preference of the prior art in respect of organic halides used as activators is for there to be more than one halogen atom bound to a single carbon atom; particularly preferred are those compounds having three halogen atoms bound to a single carbon atom. Thus, such compounds as trichloroacetamide and tribromoacetamide are particularly preferred in the prior art. SUMMARY OF THE INVENTION It has now been found that carbonylic halides can be used to formulate stable, phototropic, photosensitive compositions. The carbonylic halide can be an aliphatic ketone, a cycloaliphatic ketone or an ester or amide of an aliphatic dicarboxylic acid. In one embodiment of the invention, there is provided a phototropic photosensitive composition which comprises 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, and d. a latent activator for the colorformer that is capable of activating the colorformer under the influence of actinic light, comprising a carbonylic halide. One aspect of this embodiment of the invention relates to the product obtained upon exposing the phototropic photosensitive composition to actinic radiation. Another embodiment of the invention relates. to a dry photoimagable compositlon,as described, in the form of a thin layer and especially to an assembly comprising a support sheet, a layer of a dry phototropic photosensitive composition as described, one surface of which is adhered to the support sheet, and a transparent sheet adhered to the other surface of said composition. In another embodiment, the invention relates to a phototropic photosensitive composition, as described, on a support. In one aspect of this embodiment, the support is a conductive metal layer, one surface of which can be in contact with a coextensive surface of an insulating layer. In another aspect of this embodiment, the support is non-conductive. In yet another aspect the invention relates to solvent-free liquid, actinic radiation curable coating or printing compositions which comprise 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 Illoro ill- tensely colored upon contact with a color activator, d. a latent activator for the colorformer that is capable of activating the fluoran colorformer under the influence of actinic light, comprising a carbonylic halide. These compositions can be applied as decorative or protective coatings to provide highly colored cured products upon exposure to actinic radiation. DETAILED DESCRIPTION As indicated above, the invention involves a phototropic photopolymerizable composition comprising: 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, d. a latent activator for the colorformer that is capable of activating the colorformer under the influence of actinic light, comprising a carbonylic halide. As used herein, the term "phototropic" is intended to identify the capability of a system, such as the composition described above, to darken in response to actinic light; the term is derived from "photo" - indicating light or radiant energy and "tropic" - changing or tending to change in a specified manner in response to a specified stimulus. As indicated, there is contemplated a photosensitive compound that contains at least one component capable of curing, crosslinking or polymerizing upon suitable initiation. In one aspect, this component contains at least one polymerizable ethylenically unsaturated group of structure EMI5.1 capable of curing, crosslinking or polymerizing under the influence of free radicals. Of these materials, one important class is characterized by the presence of at least one acrylyl or methacrylyl group of formula EMI5.2 where R is hydrogen or methyl. Monomers, polymers, oligomers and compositions whose functionality is attributable to the presence of acrylate and/or methacrylate groups include acrylic acid, methacrylic acid, acrylamide, methacrylamide, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, hexyl acrylate, cyclohexyl methacrylate, 2-ethylhexyl acrylate, butoxyethoxyethyl acrylate, bicyclo (2.2.1) hept-2-ylacrylate, dicyclopentenyl acrylate, isodecyl acrylate, ethylene diacrylate, diethylene glycol diacrylate, glycerol diacrylate, glycerol triacrylate, ethylene dimethacrylate; ethylene glycol diacrylate, ethylene glycol dimethacrylate, 1,2,4-butanetriol trimethacrylate, l,4-benzene- diol dimethacrylate, .1, 4-cyclohexanediol diacrylate, neopentyl glycol diacrylate, triethylene glycol diacrylate, tetraethyleneglycol diacrylate, pentaerythritol mono-, di-, tri-or tetraacrylate or mixtures thereof, pentaerythritol tri-or tetramethacrylate, 1,5-pentanediol dimethacrylate, trimethylol propane mono-, di, or triacrylate or mixtures thereof, 2 phenoxyethyl acrylate, glycidyl acrylate, 2-ethoxyethyl acrylate, 2-methoxyethyl acrylate, 2-(N,N-diethylamino) ethyl acrylate, omega-methoxyethyl (undecaoxyethylene) acrylate, omega-tridecoxyethyl (undecaoxyethylene) acrylate, trimethoxyallyloxymethyl acrylate, bicyclo (2.2.1) hept-2-en-5-ylmethyl acrylate, bicyclo (2.2.1) hept-2-en-5,6-diyl diacrylate, vinyl acrylate, 2-hydroxypropyl acrylate, 2-hydroxyethyl acrylate, (methyl carbamyl) ethyl acrylate, and the bisacrylates and methacrylate of polyethylene glycols of molecular weight 200-1500. One group of acrylyl and methacrylyl esters that are particularly useful have the general formula EMI6.1 Where the acrylyl compound has the formula EMI6.2 M is H or CH3 M' is cycloalkyl of 5 to 12 carbon atoms (such as cyclopentyl, dicyclopentyl, methyclyclopentyl, dimethylcyclopentyl, etc.) cycloalkenyl of 5 to 12 carbon atoms (such as cyclopentenyl, methylcyclopentenyl, dicyclopentenyl, bicyclo (2.2.1) hept-2-en-yl, etc.) CpH2pM" or (CqH2qO) 5 CqH2q+l; where p is an integer from 1 to 10 q is an integer from 2 to 4 s is an integer from 0 to 4 M" is hydrogen, hydroxyl, phenoxy, alkoxy of 1 to 8 carbon atoms; and where the acrylyl compound has the formula EMI6.3 G is a polyvalent alkylene group of formula CxH2x-y in which x is an integer from 2 to 8 y is an integer from 0 to 2 (for example, divalent alkylene when y=O such as -C2H4-, C3H6-iso-C3H6-,-C5H10-, neo-C6H12 etc; trivalent alkylene when y=l such as EMI7.1 or tetravalent alkylene when y is 2, such as EMI7.2 etc.) or G is a divalent ether or ester group of formula -(CqH2qO)tCqH2q- or -(CqH2qCOO)tCqH2qwhere t is an integer from 1 to 5 and q is an integer from 2 to 4 (such as oxyethylene, oxypropylene, oxybutylene, polyoxyethylene, polyoxypropylene, polyoxybutylene, etc.) and r is the valence of G and can be 2 to 4. Triethyleneglycol diacrylate, tetraethylene glycol diacrylate, pentaerythritol triacrylate, trimethylolpropane triacrylate and pentaerythritol tetraacrylate are especially useful. Acrylate or methacrylate functionality can be incorporated in polymers and oligomers having carboxyl, hydroxyl oxirane or isocyanate groups via reaction with acrylic monomers. Addition reactions of isocyanates to form urethanes or oxiranes to form esters are relatively straightforward. Other methods of acrylation involving condensation or ester interchange reactions are well known. Thus, there can be used epoxy acrylates obtained by reacting an epoxy resin with acrylic or methacrylic acid or obtained by reacting a hydroxyalkyl acrylate with an anhydride and reacting that product with a diepoxide. Oils, such as soybean oil and linseed oil, can be epoxidized and acrylated. Polyester resins, for example from a glycol-dibasic acid condensation, can be acrylated by using acrylic or methacrylic acid to complete the esterification. Another method uses the reaction of an anhydride with a mixture of propylene oxide and glycidyl acrylate to obtain an acrylated polyester. Acrylated alkyd resins are obtained by the reaction of, for example, a triol, dibasic acid, phthalic anhydride and a fatty acid such as hydrogenated castor oil. After reaction is complete acrylation is achieved by direct esterification with acrylic acid. Urethane acrylates can be prepared directly by the reaction of a diisocyanate with an hydroxyalkyl acrylate, such as 2-hydroxyethyl acrylate. Oligomers are obtained by using an isocyanate-terminated urethane prepolymer for reaction with the hydroxyalkyl acrylate. The urethane prepolymer can be of the polyether or polyester type. Acrylate functionality can be incorporated in a variety of polymer backbones by incorporating glycidyl methacrylate into the polymer chain and then reacting the pendant oxirane groups with acrylic or methacrylic acid. Other curable systems are based on unsaturated polyesters such as are obtained from fumaric acid, 4,4'stilbenedicarboxylic acid, maleic acid, and diallyl ether. Cinnamate ester groups are also useful, for example in a polyvinyl alcohol-cinnamate ester combination and in conjunction with a variety of polymer materials: polycarbonate cinnamate; polyurethane cinnamate; cinnamyl-modified poly (meth) acrylates; polyepichlorohydrin/cinnamate; poly (cinnamyl methacrylate); epoxy cinamylidene acetate; carboxycinnamate modified polyesters. Curable materials are also obtainable from the 2 phenylmaleimido group, allyl ester-maleimide combinations, allthioether polymers, aromatic polysulfone polymer, polysiloxanes, chalcones, sorbic acid derivatives, itaconic acid derivatives and mixtures containing itaconic acid; polyvinyl alcohol, polyvinyl acetate, polyvinyl butyral. Another polymerizable or curable polymer system is based on the free-radical addition of a thiol to an olefinic double bond: R-SH + CH2=CHRg 2 R-S-CH2-CH2-R' When a polyene and a polythiol are admixed and a stimulus that generates free-radicals is present, rapid curing occurs by simultaneous chain extending and crosslinking reactions. Other crosslinkable, polymerizable or curable materials include the nitriles such as acrylonitrile and methacrylonitrile; the olefins such as dodecene, styrene, 4-methylstryene, alphamethylstyrene, cyclopentadiene, dicyclopentadiene, butadiene, 1, 4-hexadiene, 4-methyl-1pentene, bicyclo(2.2.1) hept-2-ene, bicyclo(2.2.1) hept-2,5diene, cyclohexene; the vinyl halides such as vinyl chloride, vinylidene chloride; the vinyl esters such as vinyl acetate, vinyl butyrate, vinyl benzoate, vinyl butyral, vinyl methacrylate, vinyl crotonate; the vinyl ketones such as vinyl methyl ketone, vinyl phenyl ketone, isopropenyl methyl ketone, divinyl ketone, alpha-chloro-vinyl methyl ketone, vinyl phenyl ketone; acrolein and methacrolein; the vinyl ethers and thioethers such as methyl vinyl ether, ethyl vinyl ether, divinyl ether, isopropyl vinyl ether, the butyl vinyl ethers, 2-ethylhexyl vinyl ether, vinyl 2-chloro-ether, vinyl 2methoxyethyl ether, n-hexadecyl vinyl ether, vinyl methyl sulfide, vinyl ethylsulfide, divinyl sulfide, l-chloroethyl vinyl sulfide, vinyl octadecyl sulfide, vinyl 2-ethoxyethyl sulfide, vinyl phenyl sulfide, diallyl sulfide; the miscellaneous sulfur and nitrogen containing monomers such as divinyl sulfone, vinyl ethyl sulfone, vinyl sulfonic acid, vinyl ethyl sulfoxide, sodium vinyl sulfonate, vinyl sulfonamide, vinyl pyridine, N-vinyl pyrollidone, N-vinyl carbazole. Other curable materials are readily apparent to one skilled in the art of polymerization chemistry. The specific compounds mentioned are illustrative only and not all-inclusive. They can be polymerized alone or in mixtures of two or more thereof with the proportions thereof dependent upon the desire of the individual. They can also be blended with polymers. The component capable of curing, crosslinking or polymerizing upon suitable initiation can be used alone in mixtures and/or in conjunction with one or more preformed polymers. Among the polymers that can be used one can include, for example, the polyolefins and modified polyolefins, the vinyl polymers, the polyethers, the polyesters, the polylactones, the polyamides, the polyurethanes, the polyureas, the polysiloxanes, the polysulfides, the polysulfones, the polyformaldehydes, the phenolformaldehyde polymers, the natural and modified natural polymers, the heterocyclic polymers. The term preformed polymer as used herein includes the homopolymers and copolymers and includes the olefin polymers and copolymers such as polyethylene, poly(ethylene/ propylene), poly-(ethylene/norbornadiene), poly(ethylene/vinyl acetate), poly(ethylene/vinyl chloride), poly(ethylene/ethyl acrylate), po1ythylene/acry1onitri1e), poly(ethylene/acrylic acid), poly (ethylene/styrene), poly(ethylene/vinyl ethyl ether),poly(ethylene/vinyl methyl ketone), polybutadiene, poly (butadiene/styrene/acrylonitrile), poly(vinylchloride), poly (vinylidene chloride), poly(vinyl acetate), poly(vinyl methyl ether), poly(vinyl butyral), polystyrene, poly(N-vinylcarbazole), poly(acrylic acid), poly(methyl acrylate), poly (ethyl acrylate), polyacrylonitrile, polyacrylamide, poly (methacrylic acid), poly(methyl methacrylate), poly (ethyl methacrylate), poly(N,N-dimethyl acrylamide), poly (methacryl- amide), polycaprolactone, poly(caprolactone/vinyl chloride), poly(ethylene glycol terephthalate), poly(caprolactam), poly(ethylene oxide), poly(propylene oxide), copolymers of ethylene oxide and propylene oxide with starters containing reactivehydrogen atoms such as the mixed copolymer using ethylene glycol or glycerol or sucrose, etc., as starter, the natural and modified natural polymers such as gutta percha, cellulose, methyl cellulose, starch, silk, wool, and the siloxane polymers and copolymers, the polysulfides and polysulfones, the formaldehyde polymers such as polyformaldehyde, formaldehyde resins such as phenol-formaldehyde, melamineformaldehyde, urea-formaldehyde, aniline-formaldehyde and acetone-formaldehyde. Selection of the preformed polymer will usually depend on the properties desired of the ultimate, cured product. The materials utilized as curing, crosslinking or polymerization initiators are radiation-sensitive catalyst precursors that are potentiated by radiation to provide an effective initiator species. Ultraviolet light irradiation is the preferred mode of irradiation. The known photoinitiators include the azo compounds, organic dyes, sulfur containing compounds, metallic salts and complexes, oximes, amines, polynuclear compounds, peroxides, various halogen-containing compounds and organic carbonyl compounds; they can be used alone, in combination with each other or in combination with various synergistic agents. The aromatic carbonyl compounds are a quite important group of photoinitiators and include benzoin and the benzoin ethers, benzophenone and derivatives of benzophenone, the monoaryl ketones, the diketones, the xanthones, the thioxanthenones, the quinones, and the thioketones. In the group of benzoin and the benzoin ethers are included such ethers as benzoin methyl ether; benzoin ethyl ether; benzoin allyl ether; benzoin propyl ether; benzoin isopropyl ether; benzoin butyl ether; benzoin isobutyl ether; benzoin sec-butyl ether; benzoin thiophenyl ether; benzoin amyl ether; benzoin hexyl ether; benzoin octyl ether; benzoin 2-ethylhexyl ether; benzoin nonyl ether; benzoin trimethy hexyl ether; benzoin diethyl ether; benzoin phenyl ether; hydroxyethyl benzoin ether; ethylene glycol benzoin ether; 2-chloroethylbenzoin ether; benzoin isobutoxymethyl ether; and a-alkoxybenzoin ethers; benzoin carbamates. In the group of benzophenone and derivatives of benzophenone are the 4,4 '-di (loweralkyl) benzophenoncs; 4 , 4 '-di (lower alkoxy) benzophenones; 4,4'-diallylbenzophenone; 4,4' divinylbenzophenone; 4,4'-di(loweracryl)benzophenone; the alkylamino-benzophenones including 41 (dimethylamino) benzo phenone; 4-hydroxy-4 I- (dimethylamino) benzophenone; 4-hydroxy 4'- (diethylamino)benzophenone; 4-acryloxy-4'-(dimethylamino) benzophenone; 4-methoxy-4 I- (dimethylamino)benzophenone; 4,4' bis(diamino)benzophenone; 4,4'-bis-(dimethylamino)benzophenone; 4,4' -bis- (diethylamino) benzophenone; and p-dichloromethylbenzo phenone; 4-iodobenzophenone; p-chlorobenzophenone; 4,4 '-bis (bromomethyl)benzophenone; p-hydroxybenzophenone; 2-hydroxy-4 methoxybenzophenone-5-sulfonic acid; p-acryloxybenzophenone; o-methoxybenzophenone; p-methoxybenzophenone; glycidyl ethers of benzophenone; vinyl-substituted benzophenone; 2-isopropenyl benzophenone; monocarboxyl-substituted benzophenone; polycar boxyl-substituted benzophenone; p-nitrobenzophenone; m-benzo phenonesulfonyl chloride; p-p'-bis(dimethylamino) thio benzophenone; phenylthiomethylbenzophenone; benzylthiomethyl benzophenone; benzopinacolone; anthrone; benzanthrone; ben zanthronesulfonyl chloride; 9-fluorenone; hydroxyfluorenones; aminofluorenones; 2-bromoethyl-9-fluorenonesulfonl chloride; 2-methylfluorenone; 1-propylfluorenone; 2 ,7-dimethylfluorenoffie; 2-vinylfluorenone; 2-benzylfluorenone; 2-ethoxyfluorenone; 2,6-dimethoxyfluorenone; 2,4,5-trimethylfluorenone; 2-acetyl fluorenone; 2-chlorofluorenone; 2, 7-dichlorofluorenone; dibenzosuberone; 1-chloromethyl-6-chlorosulfonyl-2-naphthyl phenyl ketone; n-methylacridone; poly(vinyl benzophenone). The monoaryl ketones include acetophenone, propio phenone, butyrophenone, 3-methylacetophenone, 4-vinylaceto phenone, 4- (2-ethylhexyl) -acetophenone, 3-allylacetophenonc, 4-vinylacetophenone, 4-hexylpropiophenone, 3-butenylbutyrophenone, 4-tolylacetophenone, 3-benzylacetophenone, 3-xylylacetophenone, 3-methoxyacetophenone, 3-methoxybutyrophenone, 3-decoxyacetophenone, 4-heptoxypropiophenone, 3-bromoacetophenone, 4-chloroacetophenone, 3-chloropropiophenone, 4iodoacetophenone, 1,4-diacetylbenzene, 1,3-diacetylbenzene, 1,3,4-triacetylbenzene, 1,4-dipropionylbenzene, 1,4-dibutyrobenzene, 3 , 4-dimethylacetophenone, l-chloroacetophenone, l-bromoacetophenone, 1,1' -dichlorobenzophenone, l-cllloro- anthraquinone, l-bromoanthraquinone, l-chloroxanthane, l-chlorothioxanthone, 2-chlorothioxanthane, 2,2' -dipyridylketone, 2-benzoylpyridine, 3-benzoylpyridine, 4-benzoylpyridine, 3,4dihexylacetophenone, 3,4-diethylpropiophenone, 3-methyl-4 methoxyacetophenone, chloroalkylphenyl ketones; a-bromoacetophenone; ortho-bromoacetophenone; trichloroacetophenone; trichloroethylidineacetophenone; 2,2-dichloro-4'-tertiarybutylacetophenone; 2,2,2-trichloro-4'-tertiary-butylacetophenone; a-bromoisobutyrophenone; 2, 2-dibromo-2 (phenylsulfonyl) acetophenone; a,a-dialkoxyacetophenone; 2,2-dimethoxyacetophenone; 2,2-dimethoxy-2-phenylacetophenone; 2,2-diethoxyacetophenone;o-methoxyacetophenone; m-methoxyacetophenone; pmethoxyacetophenone; 2-butoxy-2-phenyl-acetophenone; 2-phenylthio-2-phenlacetophenone; ethyl benzoylacetate; para-aminophenyl ketones; cyclohexylphenyl ketone; pivalophenone; valerophenone; and acetonaphthone. The diketones include biacetyl; benzil dimethyl ketal; 2,3-dibenzoyl-2-norbornene; benzoylbenzal chloride; 2,2dibromo-2-(phenylsulfonyl) propanedione; a-naphthil; 2,3butanedione; benzil; pentanedione; l-aryl-1,2-propanediones; 2,3-bornanedione; phenylpyruvic acid; 2,4-pentanedione. The xanthones and thioxanthenones include xanthone, 2-methylxanthone, 3-pentylxanthone, 2,6-diethylxanthone, 2tolyxanthone, 2-methoxyxanthone, 4-methoxyxanthone, 2-acetylxanthone, 2,7,-diacetylxanthone, 3-chloroxanthone, 4-bromoxanthone, 2-chloroxanthone, 2,7-dichloroxanthone, 2-chloro-6nonylxanthone, 2-iodo-5-methoxyxanthone, thioxanthenone; 2 methylthioxanthenone; 3, 6-bis (dimethylamino) thioxanthenone; 2-chlorothioxanthenone. The quinones include p-benzoquinone; o-benzoquinonediazide; anthraquinone; alkylanthraquinones; 2-methylanthraquinone; 2-ethylanthraquinone; 2-tertiary-butylanthraquinone; 2, 6-dimethylanthraquinone; 1,5-diethylanthraquinone; 2-vinyllanthraquinone; 2-xylylanthraquinone; 2, 6-dimethoxyanthraquinone; 2,7-diethoxyanthraquinone; 2-acetylanthra(uinone; 2-clo- anthraquinone; 2,4,8-trichloranthraquinone; 2-bromoanthraquinone;aminoanthraquinone; 1,5-diaminoanthraquinone; piperidinoanthraquinones; anthraquinonesulfonyl chloride; benzanthraquinone; 1,4-napthoquinone derivatives; phenanthrenequinones; a-chloroanthraquinone; The thioketones include thiobenzophenone; p,p'dimethoxythiobenzophenone; p,p'-bis (dimethylamino) thiobenzophenone. The azo compounds that are useful include azo compounds, azido compounds and diazonium salts. Azo and azido compounds include 2,2'-azobisisopropane; azobisisobutyronitrile; 2-phenylazobisisobutyronitrile; azobisisobutyramide; azobis (isobutyl acetate); di-(2,4,6-tribromophenyl)-4,4'-azobis (4-cyanovalerate); p-azidobenzaldehyde; b-naphthalenesulfonyl azide; diazomethane; bis(phenylsulfonyl) diazomethane; diazonaphthalenes; diazothioethers; quinone diazides; m,m'azoxystyrene. The sulfur containing compounds include n-dodecyl mercaptan; 2-mercaptobenzimidazole; diphenyl sulfide; cyclohexylphenylsulfide; benzoin thioethers; benzoin thiophenyl ether; phenylthiomethylbenzophenone; s,s'-diphenyl dithiocar- bonate; calcium sulfide; metallic tellurides; diaryl disulfidcs; diphenyl disulfide; dithiolane; dibenzoyldisulfide; dixanthate; benzothiazoles; 2,2'-dithiobis(benzothiazole); 2-mercaptobenzothiazole; thiazolines; thiocarbamates; dithiocarbamic esters;dithiocarbamic anhydrides; thiurams; toluene sulfonic acid; sulfonyl chlorides; m-(chlorosulfonyl)benzyl chloride; naphthalenesulfonyl chloride; 2-bromoethyl-9-fluorenonesulfonyl chloride; 2,2-dibromo-2 (phenylsulfonyl)acetophenone; 2,2dibromo-2(phenylsulfonyl) propanedione; benzophenonesulfonylchloride; diphenyl disulfone. The oximes include o-acyloximes; l-phenyl-l, 2propanedione-2-o-benzoyl oxime; oxido-oxazole; benzylmonooxime. The polynuclear compounds include napththalene; halogenated naphthalenes; 2,3,6-trimethylnaphthalene; a-naphthol; l-aminonaphthalene; l-methoxynaphthalene; 2 , 3-diphcnylquiioxa- line; anthracene; aminoanthraquinone; phenanthrene; naphthacene;fluorene; 9-fluorenone; stilbene; trinitrofluorenone; polynuclear quinones. The metal salts and complexes include zinc chloride; zinc bromide; zinc sulfide; ferric chloride; chromium chloride; nickel chloride; tin chloride; stannous chloride; vanadium tetrachloride; vanadium oxychloride; vanadium naphthenate; aluminum chloride; aluminum bromide; aluminum iodide; silver halides; gold salts; sodium chloraurate; mercury salts; mercury iodosulfide; titanium tetrachloride; cadmium sulfide; boron trifluoride; boron trichloride; ceric salts; thallium salts; uranyl salts; cobalt octoate; cobalt naphthenate; magnesium oxide; zinc oxide; titanium dioxide; alumina; cupric oxide; chromium oxide; silver oxide compounds; metal chelates; metal amine complexes; cobalt EDTA complexes; iron EDTA complexes; metal acetylacetonate; manganese tris (acetylacetonate); metal salt-saccharide complexes; metal oxalato complexes; p-benzoquinone complexes; copper (1) complexes; manganese carbonyl; rhenium carbonyl; osmium carbonyl; iron carbonyls; metal thiocarbonyls; trialkylaluminum; diethylaluminum chloride; triphenylmethyldiethyltitanium chloride; bis(2-chloroethyl) diethyltitanium; tetrabenzyltitanium; ferrocene; cyclopentadienylmanganese tricarbonyls. The peroxides include hydrogen peroxide; benzoyl peroxide; tertiary-butyl peroctoate; t-butyl a-cyanoperacetate; t-butyl hydroperoxide; di-t-butyl peroxide; cumene hydroperoxide; a-cumyl peroxide; ergosterol peroxide; fluorenone hydroperoxide; acetyl peroxide. The imidazoles include benzimidazoles; 2-methylbenzimidazole; 2-mercaptobenzimidazole; triphenyl-imidazolyl dimers. Ammonium salts include bipyridylium salt; benzyltrimethylammonium chloride. Organic dyes that are useful include acridines; benzacridine; benzidines; b-carotene; chlorophyll; crystal violet; eosin; erythrosine; fluorescein; indanthrene yellow; irgazin yellow; methyl violet; methylene blue; pyronine-G; rhodamines; riboflavin; rose bengal; thiazine dyes; thionine; xanthene dyes; xanthophyll; iodoeosine. Where the component capable of curing, crosslinking or polymerization contains an ethylenically unsaturated group, and notably an acrylyl or methacrylyl group, the preferred free radical photoinitiators are the benzoin ethers, benzophenone, the alkylamino benzophenones, the xanthones, the thioxanthones as well as combinations of said photoinitiators with each other and with chain transfer agents such as organic amines. As colorformer, there can, in one aspect, be used the free base of: (a) an amino derivative of a triarylmethane dye (b) an amino derivative of a xanthene dye (c) an amino derivative of an acridine dye (d) a methine or polymethine dye As ketone imine dyestuffs, there can be used the free bases of Auramine 0 and Auramine G, C.I. 4000B and 41005. The amino triarylmethane dyestuffs whose free bases can be used, can be generally represented by the formula EMI16.1 Where Ar1, Ar2 and Ar3 are carbocyclic aryl groups that are unsubstituted or substituted by one to three of: lower alkyl, lower alkoxy, lower acyl, carboxyl, carboloweralkoxy, sulfo, including the alkali, alkaline earth metal and amonium salts thereof, nitro, halo, hydroxyl and amino of formula EMI17.1 where R' and R" each independently is hydrogen, lower alkyl, phenylloweralkylene, phenyl, sulfoloweralkylene, lower acyl, naphthyl, and where said phenyl and naphthyl groups are optionally substituted by one to three of nitro, sulfo, hydroxyl, lower alkoxy, lower alkyl, amino, sulfamyl, carboxyl, carbamyl, phenylimino and halogen and provided that at least one of Arl, Ar2 and Ar3 contain at least one amino group of formula R' -N# R" and where Ar3 can additionally be indolyl that is optionally substituted. The triarylmethane dyes whose free bases are of particular interest herein can be more specifically represented by the following formula: EMI17.2 where R is carbocyclic or heterocyclic aryl of formula EMI18.1 where R1, R2, R3 and R4 each independently is hydrogen, hydroxyl, or amino of formula EMI18.2 where R' and R" each independently is hydrogen, lower alkyl, lower acyl, sulfoloweralkylene, phenylloweralkylene, phenyl or naphthyl, said phenyl or said naphthyl groups being unsubstituted or substituted by one to three of nitro, sulfo, hydroxyl, lower alkoxy, lower alkyl, amino, sulfamyl, carbamyl, carboxyl, lower acyl , carboloweralkoxy, halogen or phenylimino where said phenyl group may be substituted as described; and where at least one of R1, R2, R3 and R4 is amino of formula EMI18.3 and R10, R11, R12, R20, R21, R22, R30, R31, R32, R40, R41, R42, R50, R51 and R52, each independently is hydrogen, lower alkyl, hydroxyl, carboxyl, sulfo including the amonium, alkali or alkaline earth metal salt thereof, nitro, halo, phenylazo, loweralkoxy, lower acyl, carboloweralkoxy, or amino of formula EMI19.1 where R' and R" are as previously defined and R6 is lower alkyl or phenyl and R7 is hydrogen or lower alkyl. The free bases of triarylrnethane dyestuffs of the following formula are a preferred class of dyes EMI19.2 where the substituents are all as previously defined. Within the family of dyes described by the formula immediately preceding, preferred are those where R1, Rv and R3 are hydrogen or EMI19.3 where R' and R'' each independently is hydrogen, alkyl of one to four carbonatoms, benzyl, phenyl, sulfoethylene and where said phenyl and benzyl are unsubstituted or substituted in the aromatic moiety by one to three of nitro, sulfo, hydroxyl, alkyl of one to four carbonatoms, alkoxy of one to four car bonatoms, amino or chloro. Of the dyes set out immediately above, particularly preferred are those where R1 and R2 EMI19.4 and R3 is hydrogen, sodium sulfo EMI20.1 and where R' and R" each is hydrogen, methyl, ethyl, phenyl or sodium sulfo phenyl. Especially preferred are the free bases of the dyestuffs having the formula EMI20.2 where R3 is hydrogen or dimethyl amino. The xanthene dyestuffs, whose free bases are useful herein, can be represented bv the general formula: EMI20.3 where R8 is hydrogen or optionally substituted carbocyclic aryl R60 is oxo, lower alkoxy, hydroxyl EMI20.4 where R' and R" are as previously defined; m is an integer from one to three and R61 and R62 are selected from the same group as R10 and when m is two or three, the substituents can be the same or different. A is @wo preferred group of xanthene dyestuffs are represented by the following structural formula: EMI21.1 where R60 is EMI21.2 m is one or two and R30, R31 and R32 each independently is hydrogen, sulfamyl, sodium sulfo, halo, carboxyl, carboloweralkoxy, or hydroxyl. A particularly preferred subgroup of compounds have the formula EMI21.3 where R' and R" are hydrogen, lower alkyl, phenyl that is unsubstituted or substituted by lower alkyl or lower alkoxy R61 is lower alkyl m is one R32 is carboxyl or carboloweralkoxy R30 and R31 each independently is hydrogen, chloro, carboxyl or hydroxyl. Amino derivitives of acridine dyestuffs whose free bases can successfully be employed herein have the general formula: EMI22.1 where R70 is hydrogen or lower alkyl R71 is hydrogen, lower alkyl or phenyl that is unsubstituted or substituted by amino, carboxyl or di(loweralkyl)amino, m is one, two or three R72 and R73 each independently is hydrogen, lower alkyl or halogen R' and R" are hydrogen or lower alkyl. The methine and polymethine dyestuffs whose free bases can be used are those having Colour Index numbers C.I. 48010 through 48080. It should be noted that the dyestuffs described hereinabove are independently known to the art, for example, the amino derivatives of triarylmethane dyestuffs that are useful are those having the indicated formula and having a Color Index number between C. I. 42,000 and C. I. 4,520; useful amino derivatives of xanthene dyestuffs are those having the indicated formula and having a Colour Index number between C. I. 45,000 and C. I. 45,505; the acridine dyestuffs are those having a Colour Index number between C. I. 46,000 and C. I. 46,080. In the second aspect, the colorformer can be a fluoran compound. Fluoran colorformers contemplated herein are those having the following formula: EMI23.1 where Ra is hydrogen or an aliphatic group of one to 12 carbon atoms that is unsubstituted or optionally substituted and that may be interrupted by H - -or- O - and that is bound directly via carbon or oxygen; Rb 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 Rb is a heterocyclic group of 3 to 12 ring members bound via a ring nitrogen and containing in addition to nitro gen, one or more of oxygen and sulfur as hetero ring members or Ra and Rb together form a condensed aromatic nucleus ; ; R is hydrogen, halogen, an aliphatic group of one to 12 c carbon atoms that is unsubstituted or substi tuted and that may be interrupted by nitrogen or oxygen and that is bound directly via carbon or oxygen, or Rc is an amino group where one cr both hydrogen atoms are option ally replaced by unsubstituted or substituted aliphatic groups, cycloaliphatic groups, aromatic groups, mixed aliphatic-aromatic groups or where R is a heterocyclic group C with three to twelve ring members containing one or more of nitrogen, oxygen and sulfur as hetero ring members or R is all aromatic C group that is unsubstituted or optionally substituted or a mixed aliphatic-aromatic group or an aromatic ether or aliphatic-aromatic ether group; ; Rd 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 Rd is a heterocyclic group of 3 to 12 ring members containing one or more of nitrogen, oxygen and sulfur as hetero ring members; ; R and Rf each independently is hydrogen, unsubstituted or e f substituted aliphatic of one to 12 carbon atoms which may be interrupted by oxygen or nitrogen, and which is bound directly via carbon, cycloaliphatic groups, aromatic groups, mixed aliphatic-aromatic groups, or Re and Rf, together with the nitrogen atom form a heterocyclic group of 3 to 12 ring members, optionally containing, in addition to nitrogen, one or more of sulfur and oxygen as hetero ring members; (R ) represents one to 3, independently, of hydrogen, lower gm aliphatic bound directly via carbon or oxygen, or is halogen, acetamido or option ally substituted amino. Preferably, at least one of Rb, Rc, and Rd is an amino group, as defined. Particularly useful are the 2-amino fluoran compounds of formula EMI25.1 where R1 is hydrogen, halogen, alkyl of one to 12 carbon atoms, alkoxy of one to 12 carbon atoms R2 and R each independently is hydrogen, alkyl of one to 12 3 carbon atoms, alkenyl of 2 to 12 carbon atoms, alkoxyalkyl of 2 to 8 carbon atoms, alkoxycarbonylalkyl of 3 to 9 carbon atoms; ; cycloalkyl of 5 or 6 carbon atoms, acyl of one to 12 carbon atoms, phenyl, naphthyl or benzyl that are unsubstituted or substituted in the aromatic nucleus by one to 3 of amino mono-or di-alkyl amino of one to 5 carbon atoms alkyl of one to 7 carbon atoms, alkoxy of one to 7 carbon atoms, carboxyl, alkoxycarbonyl of 2 to 7 carbon atoms, acyl or acylamino of one to 5 carbon atoms, or MeSO3- where Me is alkali metal or R2 and R3 together with the associated nitrogen atom form a heterocyclic radical of 3 to 12 ring mem bers selected from pyrrolidinyl, piperidyl, pipecolinyl, perhydroazepinyl, heptamethylene imino, octamethyleneimino, indolinyl, 1,2,3,4 tetrahydroquinolinyl, hexahydrocarbazolyl, morpholinyl, thiomorpholinyl, piperazinyl, N-alkyl piperazinyl where the alkyl group contains one to 4 carbon atoms, pyrazolinyl, or 3-methyl pyrazolinyl R4 is hydrogen, alkyl of one to 12 carbon atoms, alkoxy of one to 12 carbon atoms, halogen, amino that is unsubstituted or substituted by one or two of the substituents as defined for R2 and R3, or R4 is phenyl, phenoxy, benzyl or benzyloxy that is unsubstituted or substi tuted in the aromatic nucleus by one to 3 of amino, mono-or di-alkyl amino of one to 5 carbon atoms, lower alkyl, lower alkoxy carboxyl, alkoxy carbonyl of 2 to 7 carbon atoms, acyl of one to 5 carbon atoms or MeSO3 - where Me is alkali metal R5 is hydrogen, lower alkyl, lower alkoxy or amino that is unsubstituted or substituted by one or two of the substituents as defined for R2 and R3, including the heterocyclic members, R6 and R7, each independently is selected from the same group as defined for R2 and R3, including the heterocyclic members thereof; ; (R8)m represents one to 3 members independently selected from hydrogen, alkyl of one to 7 carbon atoms, alkoxy of one to 7 carbon atoms, halogen, acetamido, amino or mono-or di-alkyl amino of one to 7 carbon atems. Of the compounds described above, those wherein R1 R5 and R8 are hydrogen are of particular interest. These compounds have the general formula EMI27.1 where R2, R3, R4, R6 and R7 are all as previously defined. Of special interest are the compounds having the preceding formula wherein R2 is hydrogen, alkyl of one to 7 carbon atoms or acyl of one to 7 carbon atoms R3 is hydrogen, alkyl of one to 7 carbon atoms, acyl of one to 7 carbon atoms, phenyl, benzyl or naphthyl or where R2 and R3 together with the associated nitrogen atom form morpholinyl, piperazinyl, pyrrolidinyl or piperidinyl R4 is hydrogen, alkyl of one to 7 carbon atoms or alkoxy of one to 7 carbon atoms R6 and R7 is each alkyl of one to 5 carbon atoms or together with the associated nitrogen form morpholinyl, piperazinyl, pyrrolidinyl or piperidinyl. Especially preferred are the compounds of formula EMI27.2 where R3 is hydrogen or phenyl R4 is hydrogen, (C1-C3) alkyl or (C1-C3) alkoxy R6 and R7 is each (C1-C3) alkyl; the compounds found to be notably useful are these where R6 and R7 are both ethyl and where R4 is hydrogen, methyl or methoxy. Fluoran compounds as described herein are known in the art; they are prepared by reacting a sn-i LabJo benzophe- none with an appropriate phenol derivative in the presence of an acidic condensing agent according to the following general formula EMI28.1 where Rat Rb, Rc, Rd, R , Rf, and R are as previously defined g and R' and R" are hydrogen or lower alkyl, preferably hydrogen. The reaction is typically carried out at 100 to 100 0C in the presence of a condensing agent such as acetic anhydride, sulfuric acid, zinc chloride, phosphorous oxychloride and polyphosphoric acid for from 3 to 6 hours; after cooling, the solution is poured into ice water and the product is neutralized with suitable alkali such as an alkali metal hyoside solution. The crystals are then recovered and purified in known manner, as by recrystallization. The benzophenone compound can be prepared by reacting a phenol derivative with a phthalic anhydride in an organic solvent such as benzene, toluene, xylene and chlorobenzene, at reflux: EMI29.1 The general art of making fluoran compouncis use herein is described in U. S. Patents No. 4,007,195 3,997,561 3,929,831 3,681,392 3,514,310 3,501,331 and in British Patents No. 1,339,316 1,269,601 1,211,393 the compounds described in these patents are also useful herein. In describing the activators within the scope of this invention, it must be understood that the colorformers described herein are converted to dark-colored products by contact with an acidic substance. The acidic materials are those falling within the definition of a Lewis acid, that is, an electron acceptor. Thus the acLivaLor; iscflii herein will either generate a Lewis acid or will facilitate the production of a Lewis acid from some other source. The activators of this invention are the combination of a proton doner and a carbonylic halide in the presence of a free radical type photoinitiator. While not wishing to be bound to any theoretical explanation for the chemistry of this activator system, the perceived results may be explained as follows. The proton donor (PD), whether by the effect of the free radical initiator (In) or otherwise, provides protons that are effective to convert the colorformer to the dark colored reaction product. The carbonylic halide compound, functioning as an electron sink, pushes the reaction to the right, encouraging proton formation: EMI30.1 The proton donor can be an amine, an arsine or a phosphine and can be represented by the formula EMI30.2 where D is N, As or P R' and R", each independently is hydrogen, linear or branched alkyl of from 1 to about 12 carbon atoms, linear or branched alkenyl of from 2 to about 12 carbon atoms, cycloalkyl of from 3 to about 10 ring carbon atoms, cycloalkenyl of from 3 to about 30 ring carbon atoms, aryl of from 6 to 12 ring carbon atoms, alkaryl of from 6 to about 12 ring carbon atoms, aralkyl of from 6 to about 12 ring carbon atoms, R''' has the same meaning as R' and R" except that it cannot be hydrogen and cannot be aryl when both R' and R" are aryl; the aryl groups can be unsubstituted or substituted by one or more of amino, mono-or di- (lower alkyl) amino,loweralkylcarbonyl, loweralkoxy carbonyl, loweralkylcarbonyloxy, phenylcarbonyl or aminophenylenecarbonyl where the amino group is un substituted or substituted by lower alkyl. Additionally, flit and R''' together with D can form a heterocyclic group. Thus " and nX " together can ho cva?onL alkylene of 2 to 12 carbon ators, ivaIen all.enler.e of 3 to 12 carbon atoms, divalent alkadienylene of 5 to 1C carbon atoms, divalent alkatrienylene of from 5 to 10 carbon atoms, divalent alkyleneoxyalkylene having a total of from 4 to 12 carbon atoms or divalent alkyleneaminoalkylene having a total of from 4 to 12 carbon atoms. Because of ready availability, lower toxicity and stability, the amines are preferred; representative specific organic amines include methylamine, dimethylamine, trimethylamine, diethylamine, triethylamine, propylamine, isopropylamine, diisopropylamine, triisopropylamine, butylamine, tributylamine, t-butylamine, 2-methybutylamine, N-methyl-N-butylamine, di-2methylbutylamine, trihexylamine, tri-2-ethylhexylamine , do- decylamine, tridodecylamine, tri-2-chloroethylamine, di-2bromoethylamine, methanolamine, ethanolamine, diethanolamine, triethanolamine, N-methyldiethanolamine, N,N-dimethylethanolamine, N-methyldiethanolamine, isopropanolamine, propanolamine, diisopropanolamine, triisopropanolamine, N-butylethanolamine, dihexanolamine, 2-methoxyethylamine, di-2-ethoxyethylamine, tri-2-ethoxyethylamine, 2-hydroxyethyldiisopropylamine, 2aminoethylethanolamine, allylamine, butenylamine, dihexadienylamine, cyclohexylamine, tricyclohexylamine, trimethylcyclohexylamine, bis-methylcyclopentylamine, tricyclohexenylamine, tricyclohexadienylamine, tricyclopentadienylamine, N-methyl-N-cyclohexylamine, N-2-ethylhexyl-N-cyclohexylamine, phenyldimethylamine, p-acetylphenyldimethylamine, p-caprylyphenyl dimethylamine, methylphenylamine, ditolylamine, p-dimethylaminophenyl acetate, p-dimethylaminophenyl valerate, triphenethylamine, benzyldimethylamine, benzyldihexlamine, ethyl dimethylaminobenzoate, heptyl dimethylamiobnzoa Le, trischlorophenethyl- enimine, N-methylethylenimine, N-cyclohexylethylenimine, piperidine, N-ethylpiperidine, 2-methylpiperidine, 1,2,3,4tetrahydropyridine, 1,2,-dihydropyridine, 2-,3- and 4-picoline, morpholine, N-methylmorpholine, N-2-hydroxy ethylmorpholine, N-2-ethoxyethylmorpholine, piperazine, N-methylpiperazine, N,N'-dimethylpiperazine, 2,2-dimethyl-1,3- bis [ 3-(N-morpho- linyl)-propionyloxyl ] propane, 1,5-bis [ 3-(N-morpholinyl) - propionyloxy diethylj ether, N,N-dimethylbenzylamine, ethyldiethanolamine; triethanolamine; p-nitroaniline; n-acetyl-4nitro-l-naphthylamine; aminoanthraquinone. A preferred group of amines are the p-aminophenyl ketones of general formula EMI32.1 Where R' and R" are alkyl of one to 4 carbon atoms and R"" ' is alkyl of one to 12 carbon atoms, alkoxy of one to 12 carbon atoms, phenyl, loweralkyliminophenylene or di(loweralkyl) aminophenylene. Representative compounds include p- (dimethylamino) acetophenone; p-(dimethylamino) propiophenone; p-(dimethylamino) butyrophenone; p-(dimethylamino) valerophenone; p (dimethylamino) myristylphenone; the p-(diloweralkylamino) benzoic acid esters such as p-(dimethylamino) benzoic acid ethyl ester; p-(dimethylamino) benzoic acid butyl ester; p (dimethylamino) benzoic acid lauryl ester; p-(dimethylamino) benzoic acid myristyl ester; 4-dimethylaminobenzophenone; 4 dimethylamino-4' -propylaminobenzophenone; and 4,4'-bis(dimethylamino) benzophenone. As indicated, the compositions of this invention are formulated with carbonylic halides. These include the aliphatic ketones, the cycloaliphatic ketones and the esters and amides of aliphatic dicarboxylic acids. While all members of this class will be operative, particularly preferred results are obtained when the halogen atom is located adjacent to the carbonyl group. It may be hypothesized that the carbonyl group affects the alpha-halogen atoms in a manner analogous to the effect of the carbonyl group on the alphahydrogens; in any event the preferred carbonylic halides are those having at least one halogen atom on a carbon atom alphato a carbonyl group. Especially preferred are the carbonylic halides having two halogen atoms on an alpha-carbon atom. One group of halogenated aliphatic ketones has from 3 to about 13 carbon atoms and from one to 4 carbonyl groups; these compounds are represented by the general formula EMI33.1 where R is alkyl of one to eleven carbon atoms or aa said alkyl containing halogen atoms; Rbb is alkylene of one to ten carbon atoms, or said alkylene containing halogen atoms, or Rbb represents a covalent bond; fi is alkyl or alkoxy of one to eleven carbon cc atoms or said alkyl or alkoxy that contains halogen atoms; mm is a number from O to 3. These compounds are exemplified by : l,l-dichloroacetone l,l-dibromoacetone 1,3-dichloroacetone hexabromoacetone hexachloroacetone pentachloroacetone l,l,l-trichloroacetone 1,1,3,3-tetrachloroacetone iodoacetone 1,4-dichloro-2-butanone 3,4-dibromo-2-butanone 3,3-dibromo-2-butanone 2-iodo-3-pentanone 1, 3 , 5-trichloro-2-pentanone 4,4-dimethyl-3,3-dibromo-2-pentanone 3-iodo-2-hexanone 2,6-dimethyl-4,4-dibromo-3-heptanone 3,3-dibromo-2-heptanone 3,3-dichloro-4-heptanone 4-iodo-3-octanone 4,4-dibromo-5-nonanone 3-bromo-4-ethoxy-2,4-butanedione i,l-dibromo-4-ethoxy-2,4-butanedione 1,4-dibromo-2,3-butanedione l-methoxy-2-chloro-l,3-butanedione l-methoxy-3-bromo-l , 2-butanedione 3-bromo-2,4-pentanedione 3,3-dibromo-2,4,-pentanedione 1,4-dibromo-2,3-hexanedione 4,4-dibromo-2,3-hexanedione Another group of carbonylic halides is formed by the cyclic ketones containing one or two ring carbonyl groups; preferred are the carbocyclic ketones of formula EMI34.1 where E is the halogenated residue of a carbocyclic ketone which, together with the bound carbonyl groups contains from 4 to about 8 carbon atons in the ring; A can be substituted, in addition to halogen, by lower alkyl, lower alkoxy of acyl or two to 6 carbon atoms; nn is 1 or 2. These compounds are illustrated by: perchloro-2-cyclobuten-l-one 2,2,4,4-tetrabromocyclobutanone 2-chlorocyclopentanone 2,2,5,5-tetrabromocyclopentanone 2-bromo-3-acetylcyclopentanone 2-chlorocyclohexanone 2,2,6,6-tetrabromocyclohexanone 3-ethoxy-2,3-dibromocyclohexanone 3,5-dimethyl-2,3-dibromocyclohexanone 2,2-dibromo-3-acetylcyclohexynone 3,3-dichloro-2,2-dihydroxycyclohexanone 3,6-dichloro-1,2-cyclohexanedione hexachloro-2,4-cyclohexanedione 3,6-dibromo-1,2-cyclohexanedione 3,3-dibromo-1,4-cyclohexanedione 2,3-dibromo-1,4-cyclohexanedione 2-iodo-1,3-cyclohexanedione 2-iodo-1,3-cyclopentanedione 2,2-dibromo-5,5-dimethyl-1,3-cyclohexanedione 2,2-dibromo-4,4-dimethyl-1,3-cyclohexanedione Another group of compounds useful herein are the esters and amides of formula: : EMI35.1 where R Raa, is amino that is unsubstituted or substituted by one or two of lower alkyl or halogenated lower alkyl, or Raa, is alkoxy or halogenated alkoxy of one to 4 carbon atoms, or Raa, is EMI35.2 where D is alkoxy or haloalkoxy of one to 4 carbon atoms and -A- is alkylene or haloalkylene of one to 4 carbon atoms; Rbb, is a covalent bond, alkylene or haloalkylene of one to 4 carbon atoms or the group: EMI36.1 where A and B each independently is alkylene or haloalkylene of one to 4 carbon atoms; RCc, is amino that is unsubstituted or substituted by one or two of lower alkyl or halogenated lower alkyl, or RCc, is alkoxy or haloalkoxy of one to 4 carbon atoms. These compounds will contain up to about 12 carbon atoms and are illustrated by: dimethyl dibromomalonate diethyl dibromomalonate diethyl iodomalonate dibromomalonamide iodomalonamide a dibromosuccinamide diethyl a,a'-dibromosuccinate methyl a-bromoglutarate a-iodoglutaramide dimethyl a, a' -dichloroglutarate 3-hromo-2-ketoglutaramide dimethyl-3-iodo-4-ketopimaleate diethyl-l , 3-dibromo-1, 3-acetonedicarboxylate diethyl-3,6-dibromo-1,4-cyclohexanedione-2,5-dicarboxylate From the foregoing, it is apparent that in one aspect the invention relates to a phototropic photosensitive composition comprising: : a. an ethylenically unsaturated component capable of free radical initiated curing, crosslinking or polyme¯zatio b. a free radical generator; c. a colorformer selected from (i) free bases of amino dyestuffs (ii) fluoran compounds; d. an activator for the colorformer (i) a hydrogen doner (ii) a halogenated carbonylic compound Where the free radical generator is a combination that includes a hydrogen doner, such as benzophenone, and an amine, such as an alkylamino benzophenone, another hydrogen doner need not be added. Thus an amine, if present, can perform two functions: as a chain transfer agent and as a proton donor in connection with activation of the fluoran colorformer. In the preferred embodiments the photosensivive phototropic composition comprises: a. an acrylyl or methacrylyl compound b. a photoinitiator c. a fluoran colorformer d.l. an amine 2. a carbonylic halide selected from aliphatic ketones of 3 to 13 carbon atoms, carbocyclic keto of 4 to 8 ring carbon atoms, esters and amides of dicarboxylic acids and esters and amides of keto acids. The particularly preferred embodiments are those where the photoinitiator is one or more of a benzoin ether, benzophenone, a derivative of benzophenone, a monoaryl ketone, a xanthone, a thioxanthone , or a quinone, the fluoran colorformer is a 2-amino fluoran and the amine is a tertiary amine and the carbonylic halide contains at least one alpha halogen. Thus, in the particularly preferred embodiments, the compositions comprise a. an acrylyl or methacrylyl compound b. a benzoin ether, benzophenone, a lower alkylamino benzophenone, a monoaryl ketone, a xanthone, a thioxanthone, a quinone or mixture thereof c. a 2-amino fluoran colorformer d.l. a tertiary amine 2. a carbonylic halide containing at least one alpha halogen, selected from halogenated aliphatic ketones.of 3 to 13 carbon atoms, halogenated carbocyclic ketones of 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. The compositions of the present invention may be used in relatively thick layers or may be cast as thin films having thicknesses of from about 0.25 to about 5 mils or even more. When prepared in the form of an assembly comprising a support, composition and transparent sheet, i.e., dry film photoresist, the composition will generally be from 0.5 to 5 mils thick. Suitable base or support materials include metals such as steel, aluminum, and copper in the form of plates, sheets and foils; film-forming synthetic resins or high polymers such as addition polymers and copolymers of vinyl chloride, vinylidinechloride, vinyl acetate, acrylonitrile, ethylene, propylene, etc.; and condensation polymers such as polyethylene terephthalate and polyamides and thermoset composites such as fiberglass-epoxy and paper-phenolic laminates. A typical useful dry film resist will contain: Component Broad Range Preferred Range (weight (weight %) (weight %? Preformed polymer binder 40 - 70% 50 - 702 Polymerizable, curable or crosslinkable component 30 - 50 > 30 - 40% Photoinitiator(s) 1 - 10 1 5 Fluoran Colorformer 0.01 - 2% 0.5 - 1.5% Carbonylic halide 0.1 - 5% 0.5 - 2% Amine 0.1 - 10% 0.2 - 5% The dry film phototropic photosensitive composition can additionally contain other conventional components such as thermal polymerization inhibitors, antioxidants, adhesion promoters and the like. In use, the photopolymerizable dry film is exposed to a source of actinic radiation which may be through a half tone image or a process transparency; e.g., a process negative or positive, stencil or a mask. Exposure may also be through a continuous tone, negative or positive image. The exposure can be by the contact or projection method, with or without a cover sheet over the photopolymerizable layer or by projection using a cover sheet. These procedures are well known to those skilled in the art. The photoresist compositions are generally used in conjunction wit ultraviolet licjIt ax tlle radiation source should furnish an effective amount of this radiation; point or broad radiation sources are effective. Such sources include carbon arcs, mercury-vapor arcs, fluorescent lamps with ultraviolet radiation emitting phosphors, argon glow lamps, electronic flash units and photographic flood lamps. Of these, the mercury vapor arcs, particularly the sun lamps, are most suitable. The dry film photoresist compositions after exposure can be developed in known manner, for example by impingement of spray jets, with agitated immersion, brushing or scrubbing to desirable images with an organic solvent or mixture thereof capable of washing away the unexposed portions of the resist film. Useful solvents include cellosolve acetate, ethyl acetate, methyl ethyl ketone, acetone, trichloroethylene, carbon tetrachloride, tetrachloroethylene, the alkanols of one to four carbon atoms, butyl cellosolve, chlorobenzene and dimethylformamide. Where the resist has been formulated to be developed by aqueous alkali, solutions of sodium carbonate, sodium hydroxide, trisodium phosphate and the like can be used, either alone or in admixture with each other or with one or more solvents. The phototropic compositions are also useful in ultraviolet-curable coating and printing compositions. One advantage that attends such compositions formulated with the phototropic dye systems is that thicker coatings can be employed than was previously the case since actinic light can penetrate through to the bottom of the coating before the color of the composition has intensified. Since color can now be obtained without pigments and the like which interfere with the penetration of actinic light, thicker, more resistant coatings are obtainable. The coating and printing compositions will generally contain from about .1 to about 2% of fluoran compound, from about .1 to about 5S of carbonylic halide from 0.1 to 109. of amine; the compositions will noncrsily contai'i from ZlbOL O 10% by weight of photoinitiator. The balance of the compositions will be monomeric (including reactive oligomers) compounds, polymeric binders, plasticizers, adhesion promoters, antioxidants, fillers, thixotropic agents and leveling agents. Pigments can be added if desired. These compositions can be applied by screen or other printing techniques or by brushing, roller coating, knife coating, curtain coating, etc. The acrylyl and methacrylyl compounds, notably the acrylyl oligomers and esters, as described above, are particularly useful. One useful class of oligomers is obtained by reacting an organic polyether or polyester polyol with a diisocyanate to provide an isocyanate-terminated prepolymer. This product can be reacted with an unsaturated alcohol, such as a hydroxy alkyl acrylate to provide, either alone or in combination with other unsaturated monomers, a material that will polymerize under the influence of free radicals to form a hard, tough, adherent film. In a variation of the foregoing, a polymercaptoester such as trimethylolpropane-tris-(thioglycolate); trimethylolpropane tris-(mercaptopropionate); pentaerythritol tetrakis (thioglycolate); pentaerythritol tetrakis-(mercaptopropionate); and the like are reacted with a diisocyanate to provide a polythiourethane intermediate which can be reacted with an unsaturated alcohol, such as a hydroxy acrylate to provide, either alone or in combination with other unsaturated monomers, a free radical polymerizable material having excellent film properties after crosslinking. Another illustration of a useful oligomer is an acrylate-capped polycaprolactone polyurethane, obtained by reacting a hydroxy-terminated polycaprolactone with a diisocyanate and thereafter reacting the isocyanate-terminated intermediate with an unsaturated alcohol such as a hydroxyalkyl acrylate. Still another useful class of oligomers is obtained by reacting an epoxy resin with acrylic acid to obtain an epoxy diacrylate. For example, an epichlorohydrin/bisphenol A-type epoxy resin can be reacted with a stoichiometric amount of acrylic acid. Such products are available commercially as under the trademark "Epocryl" from Shell Chemical Company. Such materials can be combined with a variety of acrylic esters including neopentyl glycol diacrylate, hydroxyethyl acrylate and dicyclopentenyl acrylate and other unsaturated esters of polyols including such esters of methylene carboxylic acid such as, ethylene glycol diacrylate; diethylene glycol diacrylate; glycerol diacrylate; glycerol triacrylate; ethylene glycol dimethacrylate; 1,3-propylene glycol dimethacrylate; 1,2,4butanetriol trimethacrylate; 1,4-benzenediol dimethacrylate; pentaerythritol tetramethacrylate; 1,3-propanediol diacrylate; 1,6-hexanediol diacrylate; the bis-acrylates and methacrylates of polyethylene glycols of molecular weight 200-500; trimethylolpropane triacrylate; pentaerythritol triacrylate; and other ethylenically unsaturated compounds, to polymerize under the influence of free radicals to form films of excellent adhesion and toughness. Another composition comprises a combination of a terminally unsaturated urethane composition (polyene) and a polythiol which are polymerizable under the influence of free radicals generated by the action of actinic light on a photoinitiator. The coating and printing ink compositions will contain a predominant amount of film-forming materials and photosensitizer and a relatively minor amount of fluoran compound halogen compound and amine. For example, a typical composition will contain from 15 to 70% by weight of an ethylenically unsaturated compound as described above, 10-50% of one or more unsaturated monomers or of a preformed polymeric binder, 0.1 to 10% by weight of a photoinitiator; 0.01 to 2E by weight of fluoran compound as described above, 0.1 to about 5% of carbonylic halide and 0.1 to 10% of amine. A more narrow range is from about 40 to about 55 by weight of ethylenically unsaturated compound, from 30-459 of monomer or of polymeric binder from 1 to 5% of initiator, from 0.5 to 1.5% of fluoran compound, from 0.5 to 2% of halogen compound and from 0.2 to 5% of amine. The invention is further illustrated by the following examples. Examples A through H illustrate the preparation of a variety of useful fluoran colorformers. EXAMPLE A 2-anilino-6-diethylaminofluoran EMI43.1 Heat together 2.2 parts by weight of 2-carboxy-4'-diethylamino2'-hydroxybenzophenone, 1 part by weight of p-nitrophenol and 40 parts by weight of 90 weight percent H2 SO4 for about 1 hour at 1500C. Thereafter pour the mixture into about 225 parts by weight of ice and raise the pH to about 8 by addition of dilute NH OH. Extract this solution with benzene and thereafter wash the benzene with 10 percent by weight aqueous NaOH and then with water. Purify the washed benzene extracted by passage through an activated alumina chromatograph column. Concentrate the resulting solution by evaporation, add petroleum ether and recrystallize. Reduce the product with stannous chloride solution, extract with benzene and recrystallize to obtain 2-amino-6-diethylaminofluoran. Reflux 7.8 parts by weight of this product, 4 parts by weight of o-bromobenzoic acid, 2.8 parts by weight of potassium carbonate, 0.1 part by weight of copper powder and 40 parts by weight of amyl alcohol for about 3 hours. Cool and add petroleum ether to separate the crude reaction product. Heat the crude reaction product to 250 - 2600C to decarboxylate, then dissolve in benzene and wash twice with 1 weight percent aqueous sodium carbonate and once with water. Concentrate the benzene solution by evaporation and precipitate with petroleum ether. Dissolve the product in benzene, purify over activated alumina, recrystallize using petroleum ether and recover the product. EXAMPLE B 2- (2' -methoxycarbonyl anilino)-6-diethylamino fluoran EMI44.1 The crude reaction product of Example A is methylated by refluxing 1 part by weight of said reaction product with 0.3 parts by weight of dimethylsulfate, 0.5 parts by weight of dicyclohexylamine and 12 parts by weight of acetone for about 15 minutes. Evaporate the solvent and then heat over a steam bath for an additional 15 minutes. Extract with benzene and purify through activated alumina. Concentrate by evaporation and add petroleum ether to crystallize the reaction product. EXAMPLE C 2-(2'-methOxyCarbonyl-anilino)-3-methyl-6-diethylaminofluoran EMI45.1 Following the procedure of Example A, but using 3-methyl-4nitrophenol in place of p-nitrophenol, there is obtained 2amino-3-methyl-6-diethylaminofluoran. Reacting this product with o-bromobenzoic acid in the manner described in Example A provides the carboxylic acid-containing crude reaction product. Methylating this crude reaction product according to Example B provides the desired product. EXAMPLE D 2-anilino-3-methyl-6-diethylaminofluoran EMI46.1 Decarboxylation of the carboxylic acid-containing crude reaction product of Example C as described in Example A provides the desired product. By an alternate route, one gram of 2'-carboxy-4diethylamino-2-hydroxybenzophenone can be dissolved in a mixture of 4 ml. of concentrated sulfuric acid and an equal volume of fuming sulfuric acid at an SO3 content of 20% with mechanical stirring, and externally cooled to about. 150C Add 1.9 grams of 4-amino-3-methylphenol gradually and continue stirring over 16 hours at about 200C. Thereafter, pour the reaction mixture into about 200 grams of ice-water, raise the pH to about 8 with a 10 percent by weight aqueous solution of NaOH and extract with benzene. Wash the benzene successively with 10% NaOH, 2% NaCl and then water. Concentrate by evaporation, purify over activated alumina, elute with a 3:3:1 mixture of benzene:ether:ethyl acetate, evaporate and recover the product. EXAMPLE E 2-anilino-6-diethylamino-3-methoxyfluoran EMI47.1 Following the alternate procedure described in Example D but using 4-amino-3-methoxyphenol instead of 4-amino-3methylphenol, there is obtained the indicated product. EXAMPLE F 2- (N-benzylamino) -6-N-pyrrolidinylfluoran EMI48.1 Stir a mixture of 77.75 grams of 2'-carboxy-2-hydroxy-4-Npyrrolidinylbenzophenone 75.6 grams N-benzyl-p-anisidine and 250 ml of 98% H2SO4 at 60 C for 5 hours and then quench into 2,750 ml. ice water. Filter the solid, wash with water and add the solid to a mixture of 500 ml. water, 250 ml. methanol and 26.8 grams NaOH at 700C. Boil this mixture for 2 hours and cool to 850C. Filter the solid product, wash with hot water, recrystallize from methanol/acetone and dry. The starting benzophenone compound can be prepared by heating a mixture of 74 grams phthalic anhydride 81.5 grams 1-(3'-hydroxyphenyl) pyrrolidine and 335 ml. xylene for 6 hours at 1250C. Cool to 25 0C., filter the precipitate, wash with methanol and recrystallize from ethanol. EXAMPLE G 2,6-di-(N-pyrrolidinyl) fluoran EMI49.1 Following the procedure of Example F, but condensing the 2'carboxy-2-hydroxy-4-N-pyrrolidinylbenzophenone with 1 (4'-hydroxyphenyl) pyrrolidine, instead of N-benzyl-p-anisidine, there is obtained the indicated product. EXAMPLE H 2-methyl-4-amino-6-diethylaminofluoran EMI50.1 React 2'-carboxy-2-hydroxy-4-diethylamino benzophenone with 4-methyl-2-nitrophenol according to the procedure of Example A and then reduce the product by suspending one part by weight of product in a solution of 2.5 parts by weight of stannous chloride, 2 parts by weight of HC1 having a specific gravity of 1.15 and about .6 parts by weight of water; warm and stir the suspension until a solution forms. Cool the solution to room temperature, dilute with about 2 parts by weight of water and raise the pH to about 12 with a 10 weight percent aqueous NaOH solution. Recover and purify the precipitate by washing, extraction and recrystallization, as indicated in the previous examples. EXAMPLE 1 Colorformers are evaluated with respect to phototropic capacity in the following composition: Parts by wt. Acryloid A-101(a) 60.3 (solids basis) Trimethylolpropane triacrylate 19.6 Tetraethylene glycol diacrylate 9.8 2-Chlorothioxanthenone 3.4 2,2'-methylene bis (4-ethyl-6 t-butyl) phenol .18 Nodaflow (b) .15 Tricresyl phosphate 4.31 4,4'-bis (dimethylamino)benzophenone 0.45 Halide ( ) 1.51 Colorformer 0.3 ¯¯¯¯¯¯¯¯ 100.0 Methyl ethyl ketone 195 (a) an acrylic ester polymer in organic solvent from Rohm & Haas Company. (b) a hydrocarbon flow control agent from Monsanto Chemical Co. (c) TBCY= 2,2,6,6-tetrabromocyclohexanone DDB = dimethyldibromomalonate The composition is coated onto a l-mil thick polyester film and dried in air. The dry thickness of the photosensitive composition is 1-2 mils. The dried layer is covered with a l-mil thick polyethylene film. The phototropic capacity is determined visually by removing the polyethylene film, laminating the photopolymerzable composition to a copper-clad panel, placing a light mask over the assembly and exposing this combination to a mercury vapor lamp for 30 seconds. The image is read immediately. Zero means no image, a negative rating indicates the dye system is photofugitive (i.e., fades) while a positive rating indicates the system has darkened in response to the light and is phototropic. Fluoran compounds, color and phototropic capacity are indicated below: EMI52.1 EMI52.2 <tb> <SEP> Color <SEP> Cni'asit7 <tb> <SEP> Lolot <tb> R <SEP> J <SEP> R <SEP> R <SEP> lie <SEP> Pt <tb> a <SEP> b <SEP> d <SEP> e1 <SEP> e <tb> <SEP> LII <tb> Ii <SEP> --N <SEP> l <SEP> II <SEP> II <SEP> L'2II9 <SEP> C2 <SEP> (;re'jn <SEP> + <tb> <SEP> C112COC2115 <tb> <SEP> 5 <tb> <SEP> 0 <tb> <SEP> Nil2 <tb> - <SEP> CH <SEP> H <SEP> t <tb> <SEP> H <SEP> - <SEP> N- <SEP> C2H5 <SEP> c2il5 <SEP> c2ii5 <SEP> Ptir?le <tb> <SEP> C1I3 <SEP> Hick <SEP> A <tb> <SEP> 3 <tb> <SEP> ii <tb> H <SEP> - <SEP> N-O <SEP> H <SEP> II <SEP> C2115 <SEP> C2H5 <SEP> Plack <SEP> + <tb> <SEP> vC112-f3 <tb> Ii <SEP> --NCII2 <SEP> 11 <SEP> C2 <SEP> 115 <SEP> C2 <SEP> H5 <SEP> Dark <SEP> Green <SEP> 4 <tb> <SEP> co) <tb> H <SEP> N <SEP> -&commat; <SEP> <SEP> H <SEP> H <SEP> C2l;5 <SEP> C2 <SEP> 115 <SEP> black <tb> II <SEP> - <SEP> ND <SEP> II <SEP> 11 <SEP> C2115 <SEP> C2115 <SEP> (5rye <tb> <SEP> 5 <tb> <SEP> COOCE13 <tb> H <SEP> - <SEP> NE <SEP> H <SEP> H <SEP> C2I15 <SEP> C21Ij <SEP> Black <SEP> + <tb> <SEP> Ii <tb> H <SEP> ¯ <SEP> N <SEP> C!!3 <SEP> 3 <SEP> C2ll5 <SEP> C2lI5 <SEP> 131.Ck <SEP> + <tb> EMI53.1 <tb> <SEP> I)(^v(lopeel <SEP> l'hot <SEP> iXi <SEP> c <tb> <SEP> Color <SEP> Capaci <SEP> t <SEP> y <tb> <SEP> p <tb> <SEP> a <SEP> b <SEP> c <SEP> Rd <SEP> R <SEP> R <tb> <SEP> ¯¯ <SEP> . <SEP> . <SEP> . <SEP> e <tb> <SEP> CII <tb> <SEP> II <SEP> N <SEP> il <SEP> II <SEP> ( <SEP> 14 <SEP> <tb> <SEP> C1I2\j) <tb> <SEP> II <SEP> I <SEP> Ii <SEP> N <SEP> 11 <SEP> c <SEP> II <SEP> II <tb> <SEP> 2 <SEP> , <SEP> 2 <SEP> 5 <tb> <SEP> II <SEP> -NIl2 <SEP> CII <SEP> C21 <SEP> 211) <SEP> C <SEP> 211 <SEP> j <SEP> P <SEP> rtMr <SEP> '' <SEP> I <tb> 5 <SEP> 1 <SEP> ) <SEP> OC113 <SEP> II <SEP> II <SEP> 131elclt <tb> <SEP> C2Il5 <SEP> C2 <SEP> <tb> <SEP> II <SEP> Cl <SEP> Cli3 <SEP> II <SEP> C <SEP> 2115 <SEP> C2 <SEP> 115 <SEP> Bed <SEP> + <tb> <SEP> II <SEP> IJ <SEP> Cl <SEP> II <SEP> II <SEP> ( <SEP> 'e} <SEP> lo.v- <SEP> F <tb> <SEP> Oran <SEP> g(t <tb> <SEP> II <SEP> II <SEP> c2lis <SEP> C2 <SEP> 115 <SEP> vil <SEP> k <tb> <SEP> Q <SEP> H <SEP> li <SEP> C26ìS <SEP> C2115 <SEP> Blue <SEP> + <tb> <SEP> 'N(C2H5)2 <tb> 10 <SEP> Ii <SEP> -jD <SEP> r; <SEP> II <SEP> NN <SEP> ,rQ <tb> <SEP> 3 <SEP> II <SEP> II <SEP> (r; <SEP> 1a(-k <tb> <SEP> 11 <SEP> -S-CI13 <SEP> II <SEP> II <SEP> C2115 <SEP> C2 <SEP> 115 <SEP> tod <tb> Dye base, color and phototropic capacity are indicated below: Rhodamine B Base red + + Malachite Green Base blue-green + + C.I. Solvent Blue 2 red-blue + + C.I. Solvent Blue 5 red-blue + + C.I. Solvent Red 49 red-violet + + C.I. Solvent Violet 10 red-vio1?t I C.I. 42510B red violet + + C.I. 42535B blue-violet + + C.I. 42600 blue-violet + + C.I. 44520 violet + + C.I. 45006 red + + C.I. 45015 red + + C.I. 46025 yellow + + C.I. 46055 orange + + C.I. 48013 red-violet + + EXAMPLE 2 A photoresist composition useful to evaluate various combinations of colorformers and carbonylic halides is prepared from the following ingredients: Parts by wt. poly(methyl methacrylate) (1) 60.0 pentaerythritol triacrylate 32.0 benzophenone 3.2 2,2'-methylene-bis- (4-ethyl-6-t-butylphenol) .9 Colorformer .9 Carbonylic halide 2.2 4,4'-bis(dimethylamino)benzophenone .8 methyl ethyl ketone 150.0 (1) a medium molecular weight product available from E.I. duPont de Nemours & Co., Inc., Wilmington, Delaware under the trademark Elvacite 2010. The composition is made by dissolving the methyl methacrylate polymer in the solvent, using conventional equipment at low to medium speeds, then adding the monomer and then adding the remaining ingredients. The solution is coated onto a 1 mil thick polyester film and dried in air. The dry thickness of the sensitized layer is 1-2 mils. The dried layer is covered with a 1 mil thick polyethylene film. The following table indicates the phototropic capacity of six representative colorformers in the presence of a variety of carbonylic halides; phototropic capacity is determined as described in Example 1. A = 2-anilino-3-methoxy-6-diethylaminofluoran B = 2-anilino-6-diethylaminofluoran C = 2-piperidino-6-diethylaminofluoran D = 2-(N,N-dibenzylamino) -6-pyrrolidinofluoran E = Rhoadamine B Base F = Malachite Green Base Halogenated Compound A B C D E F hexabromoacetone + + + + + + 3,4-diiodo -2-butanone + + + + + + 3,3-dibromo-2-butanone + + + + + + 3,3-dibromo-2-heptanone + + + + + + 1,1-dibromo-4-ethoxy-2,4-butanedione + + + + + + 1,4-diiodo -2,3-butanedione + + + + + + 4,4-dibromo-2,3-hexanedione + + + + + + 3,3-dibromo-2,4-hexanedione + + + + + + perchloro-2-cyclobuten-l-one + + + + + + 2,2,6,6-tetrabromocyclohexanone + + + + + + 3,6- diiodo- 1,2-cyclohexanedione + + + + + + hexachloro-2,4-cyclohexanedione + + + + + + 2-iodo-1,3-cyclohexanedione + + + + + + 2,2-dibromo-5,5-dimethyl-1,3-cyclo- + + + + + + hexanedione dibromomalonamide + + + + + + 2-iodobutyramide + + + + + + iodomalonamide + + + + + + dimethyl dibromomalonate + + + + + + diethyl iodomalonate + + + + + + 3-iodo -2-ketoglutaramide + + + + + + dimethyl 3-iodo-4-ketopimaleate + + + + + + diethyl-1,3-diido -1,3-acetone- + + + + + + dicarboxylate diethyl-3,6- diiodo-1,4-cyclohexane- + + + + + + dione-2,5-dicarboxylate EXAMPLE 3 When the procedure of Example2 isrepeated using colorformers A, B, C, D, E and F and dimethyl dibromomalonate, dibromomalonamide, diethyl-1,3-dibromo-1,3-acetone dicarboxylate and tetrabromocyclohexanone as the carbonylic halide with a variety of amines as hydrogen donors, the systems display phototropic capacity: EMI58.1 <SEP> Carbonylic <SEP> Halide <SEP> I <SEP> II <SEP> III <SEP> IV <tb> ------------------------------------------------------------------------------------------------------ <SEP> Colorformer <SEP> A <SEP> B <SEP> C <SEP> D <SEP> E <SEP> F <SEP> A <SEP> B <SEP> C <SEP> D <SEP> E <SEP> F <SEP> A <SEP> B <SEP> C <SEP> D <SEP> E <SEP> F <SEP> A <SEP> B <SEP> C <SEP> D <SEP> E <SEP> F <tb> ------------------------------------------------------------------------------------------------------propylamine <SEP> + <SEP> + <SEP> + <SEP> + <SEP> + <SEP> + <SEP> + <SEP> + <SEP> + <SEP> + <SEP> + <SEP> + <SEP> + <SEP> + <SEP> + <SEP> + <SEP> + <SEP> + <SEP> + <SEP> + <SEP> + <SEP> + <SEP> + <SEP> + <tb> ------------------------------------------------------------------------------------------------------diisopropanolamine <SEP> + <SEP> + <SEP> + <SEP> + <SEP> + <SEP> + <SEP> + <SEP> + <SEP> + <SEP> + <SEP> + <SEP> + <SEP> + <SEP> + <SEP> + <SEP> + <SEP> + <SEP> + <SEP> + <SEP> + <SEP> + <SEP> + <SEP> + <SEP> + <tb> ------------------------------------------------------------------------------------------------------triethylamine <SEP> + <SEP> + <SEP> + <SEP> + <SEP> + <SEP> + <SEP> + <SEP> + <SEP> + <SEP> + <SEP> + <SEP> + <SEP> + <SEP> + <SEP> + <SEP> + <SEP> + <SEP> + <SEP> + <SEP> + <SEP> + <SEP> + <SEP> + <SEP> + <tb> ------------------------------------------------------------------------------------------------------dimethylethanolamine <SEP> + <SEP> + <SEP> + <SEP> + <SEP> + <SEP> + <SEP> + <SEP> + <SEP> + <SEP> + <SEP> + <SEP> + <SEP> + <SEP> + <SEP> + <SEP> + <SEP> + <SEP> + <SEP> + <SEP> + <SEP> + <SEP> + <SEP> + <SEP> + <tb> ------------------------------------------------------------------------------------------------------ N,N-dimethyl <SEP> butylamine <SEP> + <SEP> + <SEP> + <SEP> + <SEP> + <SEP> + <SEP> + <SEP> + <SEP> + <SEP> + <SEP> + <SEP> + <SEP> + <SEP> + <SEP> + <SEP> + <SEP> + <SEP> + <SEP> + <SEP> + <SEP> + <SEP> + <SEP> + <SEP> + <tb> ------------------------------------------------------------------------------------------------------p-acetylphenyl <SEP> dimethylamine <SEP> + <SEP> + <SEP> + <SEP> + <SEP> + <SEP> + <SEP> + <SEP> + <SEP> + <SEP> + <SEP> + <SEP> + <SEP> + <SEP> + <SEP> + <SEP> + <SEP> + <SEP> + <SEP> + <SEP> + <SEP> + <SEP> + <SEP> + <SEP> + <tb> ------------------------------------------------------------------------------------------------------p-caprylphenyl <SEP> dimethylamine <SEP> + <SEP> + <SEP> + <SEP> + <SEP> + <SEP> + <SEP> + <SEP> + <SEP> + <SEP> + <SEP> + <SEP> + <SEP> + <SEP> + <SEP> + <SEP> + <SEP> + <SEP> + <SEP> + <SEP> + <SEP> + <SEP> + <SEP> + <SEP> + <tb> -------------------------------------------------------------------------------------------------------p-dimethylaminophenyl <SEP> acetate <SEP> + <SEP> + <SEP> + <SEP> + <SEP> + <SEP> + <SEP> + <SEP> + <SEP> + <SEP> + <SEP> + <SEP> + <SEP> + <SEP> + <SEP> + <SEP> + <SEP> + <SEP> + <SEP> + <SEP> + <SEP> + <SEP> + <SEP> + <SEP> + <tb> -------------------------------------------------------------------------------------------------------p-dimethylaminophenyl <SEP> valerate <SEP> + <SEP> + <SEP> + <SEP> + <SEP> + <SEP> + <SEP> + <SEP> + <SEP> + <SEP> + <SEP> + <SEP> + <SEP> + <SEP> + <SEP> + <SEP> + <SEP> + <SEP> + <SEP> + <SEP> + <SEP> + <SEP> + <SEP> + <SEP> + <tb> -------------------------------------------------------------------------------------------------------ethyl <SEP> dimethylamnobenzoate <SEP> + <SEP> + <SEP> + <SEP> + <SEP> + <SEP> + <SEP> + <SEP> + <SEP> + <SEP> + <SEP> + <SEP> + <SEP> + <SEP> + <SEP> + <SEP> + <SEP> + <SEP> + <SEP> + <SEP> + <SEP> + <SEP> + <SEP> + <SEP> + <tb> --------------------------------------------------------------------------------------------------------amyl <SEP> dimethylaminobenzoate <SEP> + <SEP> + <SEP> + <SEP> + <SEP> + <SEP> + <SEP> + <SEP> + <SEP> + <SEP> + <SEP> + <SEP> + <SEP> + <SEP> + <SEP> + <SEP> + <SEP> + <SEP> + <SEP> + <SEP> + <SEP> + <SEP> + <SEP> + <SEP> + <tb> ---------------------------------------------------------------------------------------------------------p-dimethylamino <SEP> acetophenone <SEP> + <SEP> + <SEP> + <SEP> + <SEP> + <SEP> + <SEP> + <SEP> + <SEP> + <SEP> + <SEP> + <SEP> + <SEP> + <SEP> + <SEP> + <SEP> + <SEP> + <SEP> + <SEP> + <SEP> + <SEP> + <SEP> + <SEP> + <SEP> + <tb> ---------------------------------------------------------------------------------------------------------4-dimethylamino <SEP> benzophenone <SEP> + <SEP> + <SEP> + <SEP> + <SEP> + <SEP> + <SEP> + <SEP> + <SEP> + <SEP> + <SEP> + <SEP> + <SEP> + <SEP> + <SEP> + <SEP> + <SEP> + <SEP> + <SEP> + <SEP> + <SEP> + <SEP> + <SEP> + <SEP> + <tb> ----------------------------------------------------------------------------------------------------------4-4'-bis-(dimethylamino-benzophenone <SEP> + <SEP> + <SEP> + <SEP> + <SEP> + <SEP> + <SEP> + <SEP> + <SEP> + <SEP> + <SEP> + <SEP> + <SEP> + <SEP> + <SEP> + <SEP> + <SEP> + <SEP> + <SEP> + <SEP> + <SEP> + <SEP> + <SEP> + <SEP> + <tb> ---------------------------------------------------------------------------------------------------------- I = dimethyl dibromomalonate II = dibromomalonamide III = diethyl-1-3-dibromo-1,3-acetonedicarboxylate IV = tetrabromccclohexanone EXAMPLE 4 Combinations of photoinitiators and amines can be evaluated using the following composition and the procedures described in Examples 2 and 3. Parts by wt. poly (methyl methacrylate) ) 60.0 pentaerythritol triacrylate 30.0 photoinitiator 3.2 2,2' -methylene-bis- (4-ethyl-6-t-butylphenol) .9 colorformer .9 2,2,6,6-tetrabromocyclohexanone 2.2 amine 2.8 methyl ethyl ketone 150.0 (1) Elvacite 2010 from Du Pont. The following table indicates phototropic capacity of representative colorformers A and B of Example 2 with a variety of photointiators and amines. Photoinitiator 1. thioxanthone 2. 2-chlorothioxanthone 3. fluorenone 4. benzil Photo initiator 1 2 3 4 Colorformer AB AB AB AB dimethylethanolamine + + + + + + + + N,N-dimethyl butylamine + + + + + + + + p-acetylphenyl dimethylamine + + + + + + + + p-caprylylphenyl dimethylamine + + + + + + + + p-dimethylaminophenyl acetate + + + + + + + + p-dimethylaminophenyl valerate + + + + + + + + ethyl dimethylamino benzoate + + + + + + + + amyl dimethylamino benzoate + + + + + + + + p-dimethylamino acetophenone + + + + + + + + 4-dimethylamino benzophenone + + + + + + + + 4,4'-bis (dimethylamino) benzophenone + + + + + + + + EXAMPLE S The following solution is coated onto a 1 mil thick polyester film to provide a dry thickness of about 0.001 inch, and dried in air. The dried film is covered with a 1 mil thick polyethylene film. Ingredients Parts by wt. copolymer of 758 styrene and 25% methacrylic acid; viscosity of a 40% solution in MEK is 10,360 cps 57.0 trimethylolpropane triacrylate 24.0 tetraethyleneglycol diacrylate 12.2 benzophenone 4.0 4,4'-bis-(dimethylamino)-benzophenone 0.6 2-anilino-3-methoxy-6-diethylaminofluoran 0.3 diethyliodomalonate 1.5 benzotriazole .4 methyl ethyl ketone 16.0.0 A piece of copper clad, epoxy-fiberglass board is cleaned by scouring with an abrasive cleaner, swabbing and thoroughly rinsing in water. It is given a 20 second dip in dilute hydrochloric acid solution (2 volumes water plus 1 volume concentrate hydrochloric acid), a second rinse with water and then dried with air jets. The polyethylene cover film is removed from a section of the sandwiched photoresist dry film described above. the bared resist coating with its polyester support is laminated to the clean copper with the surface of the photoresist in contact with the copper surface. The lamination is carried out with the aid of rubber covered rollers operating at 2500F (121 0C) with a pressure of 3 pounds per lineal inch at the nip at a rate of 2 feet per minute; The resulting sensitized copper clad board protected as it is by the polyester film can be held for later use if desired. Exposure to light is had through a high contrast transparency image in which the conducting pattern appears as transparent areas on an opaque background. Exposure is carried out by placing the sensitized copper clad board (with polyester film still intact) and the transparency into a photographic printing frame. Exposure is maintained for a period of 90 seconds to a 400 watt, 50 ampere vapor lamp at a distance of 12 inches. it is seen that the areas of the resist that have been exposed to light have darkened in color considerably, to a black color which contrasts substantially with the unexposed portions of the resist. The polyethylene terephthalate support film is peeled off and the exposed resist layer developed by agitating the board in a tray containing 2% trisodium phosphate in water for 2 minutes followed by a water rinse. The resulting board which contained a deeply colored resist pattern of the clear areas of the exposing transparency is then etched in ferric chloride slution, rinsed and dried. The resist is removed from the remaining copper by dipping for 2 minutes in a 3% solution of sodium hydroxide in water at -700C. The result is a high quality printed circuit board. In an alternative embodiment, the surface of the exposed copper obtained after developing is further cleaned by dipping the board into a 20% ammonium persulfate bath for 30 seconds, washing copiously with water, dipping for 30 seconds in a 20% solution of hydrochloric acid in water, rinsing with water, then drying the board with jets of air. This cleaned board is then plated for 45 minutes at 30 amperes per square foot in a copper pyrophosphate plating bath at 550C EXAMPLE 6 A copper clad piece of epoxy-fiberglass board is cleaned as described in Example 5 above. The cleaned, dried board was sensitized by flowing the following solution over the surfaceof the board. Ingredients Parts by wt. Copolymer of 379. styrene and 63% mollobutyl maleate, average mol. wt. 20,000, viscosity of 10% aqueous solution of ammonium 60.0 salt = 150 cps. Pentaerythritol tetraacrylate 34.2 Benzophenone 2.5 4,4'-bis-(dimethylamino)-benzophenone 0.3 Benzotriazole 0.2 2,2'-methylene-bis- (4-ethyl-6-tert-butylphenol) 0.9 2-anilino-3-methoxy-6-diethylaminofluoran 0.4 2,2,6,6-tetrabromocyclohexanone 1.5 ethyl Ethyl Ketone 150.0 The excess solution is drained off the board at room temperature for 2 minutes. The coating is further dried by heating in a forced air oven at 600C for 5 minutes. After cooling, the coated board is exposed as described in Example 5 above, and it is seen that where the board is exposed to light, a dark color that dramatically contrasts with the unexposed portions is visible. The resist is developed by agitating the board in a solution of 290 trisodium phosphate in water for one minute, followed by a water rinse. The board is etched in ferric chloride as described in Example 5, and after etching, the exposed resist is stripped from the protected copper by immersing the board in a 3% solution of sodium hydroxide in water at 500C. for 2 minutes. The result is a high quality printed circuit board. EXAMPLE 7 Coating compositions are prepared from the following amounts of components: Components Composition, Parts by t. I II III IV V PCP(a) 36.2 - - - EPOA(b) 4.8 4.5 E.D.(C) 16.2 57.0 54.5 59.5 47.G NPGDA (d) 14.2 18.1 17.3 19.0 19.0 EHA (e) 14.2 9.0 8.7 9.5 9.5 DCPA( 9.6 6.9 15.2 7.2 19.0 Benzophenone 4.8 4.5 4.3 4.8 4.9 Colorformer(g) 0.9 0.9 0,g o.9(h) 0.9(i) Dibromomalonamide 1.5 1.5 1.5 1.5 1.5 4,4'-bis(dimethylamino) benzophenone .5 .5 .5 .5 .5 (a) 80% solution of Union Carbide PCP-0300 polycaprolactone/toluene diisocyanate oligomer in 20% hydroxyethyl acrylate (b) polyacrylate of epoxidized soya bean oil available from Union Carbide (c) Epocryl (epoxy diacrylate) (d) neopentyl glycol diacrylate (e) 2-ethylhexyl acrylate (f) dicyclopentenyl acrylate (g) 2-anilino-3-methoxy-6-diethylaminofluoran (h) 2-anilino-6 diethylaminofluoran (i) 2-piperidino-6-diethylaminofluoran The compositions are prepared by combining the monomers and mixing in conventional equipment at low to medium speeds until dissolved. The photoinitiator is added and the other ingredients are incorporated. The coatings are applied to a cellulosic substrate (hardboard) by direct roller coating. The wet coated substrate is then exposed to UV radiation by being placed on a chain link conveyor and passed under a 200 watt/lineal inch Hanovia quartz ultraviolet lamp at a distance of about two inches at a speed of approximately 12 feet per minute. Tough, resistant, deeply colored coatings are obtained. EXAMPLE 8 An ink composition is prepared as follows by mixing together the following components in conventional manner. Epoxy Acrylate 60.0 Ultraflex Microcrystalline Wax 3.3 Pentaerythritol Tetraacrylate 29.2 Benzophenone 4.5 4,4'-bis (dimethylamino) benzophenone .50 2-anilino-3-methoxy-6-diethylaminofluoran 1.0 Dibromomalonamide 1. 50 When this ink is silk screened onto a paper substrate and exposed to light using a 200 watt/linear inch medium pressure mercury vapor lamp at a distance of 4 inches for about 5 seconds, there is obtained a dry, tack-free darkprinted substrate having good gloss and adhesion. When the color former is replaced by the colorformers described in Example 1, there is obtained an ink that cures to a dry, tack-free, deeply colored product. EXAMPLE 9 An acrylated urethane modified polyester can be prepared as follows: To a reaction vessel equipped with stirrer, reflux condenser, thermometer and heating means charge Parts by weight 1,3-butylene glycol 12.68 1,6-hexanediol 66.64 adipic acid 20.58 dibutyl Tin Oxide .10 using a nitrogen sparge. Heat to a reflux and react to an acid value less than 3. The product will have an equivalent weight of about 501 and a molecular weight of about 1000. To a reaction vessel equipped with a stirrer, thermometer and nitrogen sparge charge 15.22 parts by weight of 2,4-tolylene diisocyanate and heat to 500C. Add a mixture of 10.13 parts by weight of 2-ethylhexyl acrylate and 0.0035 parts by weight of phenothiaxine over a two hour period, maintaining the temperature at 60 C during this period. Hold at 600C for an additional three hours. Cool to 500C and add 43.83 parts by weight of the polyester previously prepared over a one hour period, maintaning the temperature at 60 C ; thereafter hold the temperature al 70 C for 3 hours. Cool to 60 C ; add 0,35 parts by weight of methanol to obtain zero free isocyanate and hold an additional 1/2 hour at 600C Cool and store the product. A. A UV curable composition can be prepared having the following composition: Parts by Weight Acrylated polyester 66.6 1,6-hexanediol diacrylate 14.5 Pentaerythritol triacrylate 4.6 Methyl ethyl ketone 1.9 2-ethylhexyl acrylate 4.7 Dibromomalonamide 2.0 2-Chlorothioxantheonone 3.0 2-anilino-3-methoxy-6-diethyl- .7 aminofluoran dimethylamino ethanol 2.0 The composition is mixed until homogeneous. The photopolymerizable composition is applied to a wooden test piece, having a smooth surface, at the rate of 100 grams per square meter and the coated surface is covered with a 30 mm. thick untreated polyethylene film exercising care to ensure that no air bubbles are entrained. This is then exposed to actinic rays with a 2-KW high pressure mercury-vapor lamp for 30 seconds at a radiation distance of 30 mm. When the polyethylene film is stripped, it is seen that a smooth cured coating is obtained having good hardness, good adhesion to the wood and that is black in color. B. A second UV-curable system can be prepared having the following composition: Parts by Weight Acrylated polyester 65.3 Pentaerythritol tetrakis 26.0 (ss -mercaptopropionate) Benzophenone 3.0 2-anilino-3-methoxy-6-diethylaminofluoran .7 4,4'-bis(dimethylamino) benzophenone 3.0 Dibromomalonamide 2.0 When coated on a wood test specimen and treated as in part A above, there is obtained a cured coating having a black color.

Claims: CLAIMS 1. 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. 2. 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 EMI69.1 when the compound has the formula EMI69.2 M is H or CH3 is is cycloalkyl of 5 to 12 carbon atoms, cycloalkenyl of 5 to 12 carbon atoms, -c H N" or p 2p (CqH2qO) s qHq+ where P is an integer from 1 to 10 g is an integer from 2 to 4 s is O or an integer from 1 to 4 N" is hydrogen, hydroxyl, phenoxy, alkoxy of 1 to 8 carbon atoms; ; and where the compound has the formula EMI70.1 G is a polyvalent alkylene group of the formula -CXH2X-Yin 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 -(CqH2qO)tCqH2q- or -(CqH2qCOO)tCqH2qwhere 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. 3. A composition according to either of claims 1 or 2 further characterised in that the initiator comprises an aromatic carbonyl compound. 4. A composition according to any of claims 7 to 3 further characterised in that the fluoran compound has the general formula EMI70.2 where II is hydrogen or an aliphatic group having one a to 12 carbon atoms that is either unsubstituted or optionally substituted and that may be interrupted by EMI71.1 and that is bound directly via carbon or oxygen; Rb 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 Rb 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 Ra and Rb together form a condensed aromatic nucleus ; ; R is hydrogen, halogen, an aliphatic group having one C 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 IC is an C 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 is a heterocyclic c group with three to twelve ring members containing one or more of nitrogen, oxygen and sulfur as hetero ring members or 1t is an aromatic group that is either unsub C stituted or optionally substituted or a mixed aliphaticaromatic group or an aromatic ether or aliphatic-aromatic ether group; Rd 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 Hd is a heterocyclic group having 3 to 12 ring members containing one or more of nitrogen, oxygen and sulfur as hetero ring members; ; IC and Rf each independently is hydrogen, unsubstituted e 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 R and ltf, 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 ; (Rg)m 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 Rb, Rc and lld is an amino group, as defined. 5. A composition according to claim 4 further characterised in that the fluoran compound is a 2-amino fluoran of the general formula: EMI72.1 where A1 is hydrogen, halogen, alkyl having 1 to 12 carbon atoms or alkoxy having 1 to 12 carbon atoms; R2 and R3 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, alkoxycarbonyl having 2 to 7 carbon atoms, acyl or acylamino having 1 to 5 carbon atoms, or MeSO - where Me is 3 alkali metal or R2 and R3 together with the associated nitrogen atom form a pyrrolidinyl, piperidyl, pipocolinyl, 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, R4 is 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 off the substituents as defined for 112 and R3, or it4 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 MeSO3 - where Me is alkali metal; R5 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 R2 and IC including the heterocyclic members; 96 and R7 each o 7 independently is the same as defined for 92 and R3, including the heterocyclic members thereof; (tig) 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 dialkyl amino having 1 to 7 carbon atoms. 6. A composition according to any of claims 1 to 5 characterised in that the carbonylic halide is an ali phatic ketone, a cycloalkphatic ketone, an ester of an aliphatic dicarboxylic acid or an amide of an aliphatic dicarboxylic acid. 7. 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. 8. A composition according to any of claims 1 to 5 further characterised in that the carbonylic halide contains at least one alpha C1, 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. 9. A composition according to any of claims 1 to 5 further characterised in that the carbonylic halide has the formula EMI74.1 where IC is alkyl having 1 to 11 carbon atoms or said aa alkyl containing halogen atoms; Rbb is alkylene having 1 to 10 carbon atoms, or said alkylene containing halo gen atoms, or Abb represents a covalent bond; It is cc alkyl or alkoxy having 1 to 11 carbon atoms or said alkyl or alkoxy that contains halogen atoms ; mm is O or an integer from 1 to 3. 10. 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 EMI74.2 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. 11. 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 EMI75.1 where R , is amino that is unsubstituted or substituted by one or two of lower alkyl or halogenated lower alkyl, or It at is alkoxy or halogenated alkoxy group having aa' 1 to 4 carbon atoms, or 1taat is EMI75.2 where D is alkoxy or haloalkoxy having 7 to 4 carbon atoms and -A- is alkylene or haloalkylene having 1 to 4 carbon atoms; Ilbb is a covalent bond, alkylene or haloalkylene having 1 to 4 carbon atoms or the group; EMI75.3 where A and B each independently is alkylene or haloalkylene having 1 to 4 carbon atoms; ; Rcc, is amino that is either unsubstituted or substituted by one or two of lower alkyl or halogenated lower alkyl, or Rcc' is alkoxy or haloalkoxy having 1 to 4 carbon atoms. 12. 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. 13. 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 et11ylen- ically 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) O.1 to 10 percent by weight of a photoinitia tor; (d) 0.01 to 2 percent by weight of fluoran com pound; (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 C1, Br or I. 14. A composition according to any of the preceding claims further characterised in that it is in the form of a thin film.

Inventors: LIPSON, MELVIN A., REARDON, EDWARD JOSEPH JR.
Applicants: DYNACHEM CORPORATION
Application year: 1979
Main classification: G03C1
IPC codes: C08F2, G03F7, G03C1, C09B11, G01N23, C09K9