US3486898A - Sensitivity of triarylmethane light sensitive systems - Google Patents

Description

United States Patent 3,486,898 SENSITIVITY 0F TRIARYLMETHANE LIGHT SENSITIVE SYSTEMS Eugene Wainer, Shaker Heights, Ohio, assignor to Horizons Research Incorporated, a corporation of Ohio No Drawing. Filed Sept. 7, 1965, Ser. No. 485,535 Int. Cl. C09b 23/16; G03c 1/72, 5/24 US. Cl. 96-90 24 Claims ABSTRACT OF THE DISCLOSURE This invention relates to a non-silver photographic system sensitive to both ultraviolet and visible light which may either printout directly, thus requiring no development, or which may produce a semi-latent image which maybe developed out by the application of infrared energy and which may be fixed by heating or by a solvent rinse and which has sufficient photographic speed to permit the use of a camera for the taking of pictures in a photographic speed representing a significant improvement over the teachings of the prior art.

The persent photosystem achieves a greatly improved sensitivity over that available from the teachings from US. Patent 3,102,810, by virtue of inclusion therein of a leuco base or a carbinol base of a simple, substituted, or pseudo-triarylmethane dye in which at least one of the aryls is fitted with specially selected substituents' which enhance the electron withdrawing or electrophilic characteristics of this single aryl group. I

United'StatesPatents 3,042,515; 3,042,516; 3,042,517;

3,042,518; 3,042,519; and 3,046,125 describe variously mixtures which may be designated slow photographically. In this group of materials exposure times of a 275 Watt G.E. Sunlamp of the reflector type at a distance of requires 5 to 25 seconds of exposure before a density of 1 in the colored image is produced.

United States Patent 3,102,810 describes compositions somewhat faster photographically speaking than those in the preceding patents. When exposed to a 275 watt G.E. Sunlamp of-the reflector type at a distance of 10" compositions of U.S.- Patent 3,102,810 required periods of 5 to 20 seconds to achieve a density'of 1. While images could be obtained at lesser exposures, down to'0.5 second, as described in the examples, the density of the'image thus obtained was very much less than 1.0 and in all cases no image was obtained under this light source at exposure times less than 0.5 second.

The compositions of the present invention yield densities of 1.0 for exposure times at least an order of magnitude less than those described in US. Patent 3,102,810. For all of the systems to be described hereinafter in this specification, exposure times of not more than 0.1 second yield a density of 1.0 and in many cases this density is achieved for exposure times as short as one hundredth of a second. Example 1 of US. Patent 3,102,810 reports that 30 seconds are required to give good images at F45 in bright sunlight, whereas Example 2 indicates that 6 minutes at P45 in bright sunlight are required to produce a good image. The compositions to be described in the following specification yield good images at 1 second ex- Patented Dec. 30, 1969 ice posure at F45 in bright sunlight in a camera and in certain cases exposure times of as short as 0.1 second yield the same density. Thus, the compositions of my invention are, photographically speaking, a factor of 30 to 100 times faster than the non-silver photographic compositions described in US. Patent 3,102,810.

The panchromatic photosystem of this invention is characterized by an enhanced speed due to a synergistic effect obtained by the use of a combination of (1) color dye bases or secondary or tertiary aryl, heterocyclic, arylheterocyclic amines unsubstituted in a para position on the ring structure, or with components having a reactive position for attachment of a methane carbon atom or mixtures of these in combination with (2) leuco bases 01' carbinol bases of triarylmethane dyes of both simple and substituted character in which at least one of the aryl or substituted aryl groups of the triarylmethane leuco bases is specially treated to increase strongly its electrophilic or electron withdrawing characteristics, in photosystems including organic halogen compounds which generate free radicals on exposure to radiation of a suitable Wavelength. Preferably the photosystem also includes a suitable base material in which the light sensitive material and the combination of synergistically acting agents are dispersed or on which they may be supported in the form of a thin film or coating, which coating may or may not contain a plastic binder.

In its simplest form the compositions of my invention may be described as comprising the following:

(a) An organic halogen compound;

(b) A dye base, a conjugated dye intermediate or mixtures of the above, each of which may be characterized by the description secondary or tertiary aromatic amines containing a ring structure unsubstituted in a para position, or with other components having a reactive position for attachment of a methane carbon atom;

(0) One or more leuco bases or carbinol bases of a triarylmethane compound having at least one aryl group specially substituted to increase its electrophilic or electron withdrawing characteristics; and

(d) A carrier which supports (a), (b), and (0) either as a dispersion or solution throughout the carrier or as an intimate admixture coated on the surface of the carrier material in which said coating may or may not contain a'plastic binder, and said carrier is a type which exhiibts little or no reactive hydrogen positions.

While useful results are available by disposition of the photosensitive system in or on carriers such as paper, coatedpaper, nitro-cellulose, cellulose acetate, polyvinyl acetate, ethyl cellulose, methyl cellulose, carboxy methyl cellulose, polystyrene, and the like, the preferred carrier which yields the maximum photographic speed is one in which positions normally available for hydrogen replacement or abstraction is blocked by another substituent, preferably Cl. Carriers which are preferred to the oxygen-containing bases such as the cellulose derivatives include polystyrene, polyvinylchloride, polyvinylidene chloride and copolymers of vinyl chloride and vinylidene respect to sensitivity and the development of color, it

appears that, either as a result of exposure to light or possibly simply as the result of the mixture of the organic halogen containing compound and the specialized leuco bases, a complex is formed which requires less energy to raise it to an excited state to permit the desired photolytic reaction to take place when such complexes do not form.

As in US. Patent 3,102,810, as the result of exposure to light of these various systems with or without subsequent development by infrared energy or heat, a sharp difference in solubility in certain solvents exists between unexposed and exposed areas. While this finding is of exceptional importance in order to eliminate any residual color which may exist from the progenitor itself and which may mask the printout effects, more important than the elimination of such color-masking effects is the fact that such differences in solubility may be utilized for fixing and stabilization of the printed image, even though in the majority of cases fixing by simple heating is possible.

Further, the capability for taking advantage of the difference in solubility is that as the result of solvent extraction, as defined in US. Patent 3,102,810, hydrophilic-hydrophobic differentiation is available, depending on Whether or not the areas have been exposed to light. The developed out dye image appears to be ionic in character, and exhibits hydrophilic properties, and tends to be insoluble in non-polar solvents; whereas the unexposed progenitor Whether intermediate or dye base form, even in the presence of the organic halogen containing compound, is a covalent non-ionic compound, soluble in a variety of organic solvents, and tends to be hydrophobic in character. Such hydrophobic properties may be enhanced by placing the photosystem on a hydrophobic base, and as a consequence the system can be utilized as a foundation of photoetch processes and as a means for producing a lithographic plate.

Another aspect of the present invention is in the provision of a non-silver photographic system which by a proper combination of (1) ultraviolet and/or visible light and (2) infrared may be used for the production of ofiice copy by a flexographic technique hereinafter described.

Each of the components of this photosensitive system and the manner in which the photosensitive system is utilized will now be considered in greater detail.

(A) ORGANIC HALOGEN COMPOUNDS CBr (carbon tetrabromide) HCBr (bromoform) C Br (hexabromoethane) C H Cr (am-benzotribromide) HC Br (pentabromoethane) C H COCBr (am-tribromoacetophenone) HCI (iodoform) C Cl (hexachloroeth'ane) Cl CCONH (otaa-trichloracetamide) Each of the above compounds yields a halogen free radical when the bond joining a halogen atom to a polyhalogenated carbon atom is ruptured upon exposure to light. The presently preferred compounds for this invention are carbon tetrabromide and etaa-tribromoaceto phenone, both of which can be prepared readily in their requ1s1te purity.

4 (B) THE DYE BASES, SECONDARY AND TERTI- ARY RING AMINES HAVING AN UNSUBSTI- TUTED PARA POSITION ON AN ARYL RING OR WITH OTHER SUBSTITUENT HAVING A RE- ACTIVE POSITION FOR ATTACHMENT OF A METHANE CARBON The first of the several families of dye bases, dye progenitors or conjugated dye intermediates, which constitutes one of the synergists in the present photosystem, comprises the styryl'dye bases and their higher vinylene homologues, such as described in US. Patent 3,095,303, and whose photographic action is described in US. Patent 3,102,810, in a synergistic system. The various types of the styryl dye bases included in the above two aforementioned issued U.S. patents are included in this description by reference.

The second of the several families of dye bases, or dye progenitors or conjugated dye intermediates which constitutes one of the synergists in the present photosensitive system, comprises the cyanine dye bases such as those described in US. Patent 3,100,703.

The cyanine dye bases included in US. Patents 3,- 100,703 and 3,102,810, :are included herein by reference and include substantially all of those corresponding to all of the different classes of cyanine dyes, including symmetrical and unsymmetrical monomethine cyanines, carbocyanines, dicarbocyanines, tricarbocyanines, hemicyanines, pyrrolocyanines and azacyanines.

A further class of bases useful in my photo process are those related to the styryl dye bases and to the vinylene homologues described in US. Patent 3,102,810 and additionally containing nitrogen in the chain as set forth in column 7 of said patent.

A variety of dye intermediates may be utilized as substitutes for the above dye bases and as one of the synergists for the purposes of my invention. Typical compounds are listed in Table I and are primary, secondary or tertiary carbocyclic aryl amines containing an unsubstituted or open ring carbon para to the ring carbon to which the amine nitrogen is attached, i.e. compound which may be represented by the following general formula Ar-ITI-A B wherein Ar represents a carbocyclic nucleus such as phenyl or naphthyl aryl and wherein Ar may be unsubstituted or substituted provided that the ring carbon para to the carbon to which the amine nitrogen is attached is not substituted and A and B each represents H, lower alkyl (methyl, ethyl, etc.) or aryl.

In other words these amines may be represented by one of the following general formulas wherein A and B each represents H, alkyl, aryl or aralkyl and C represents substituents on the phenyl or naphthyl nucleus in any position other than that which the arrow points.

In addition to the heterocyclic compounds and/or dye bases described in. the above noted United States patents, particularly 3,102,810, a large number of other compounds are suitable for the present invention. Table II lists some representative compounds and is not intended to enumerate all of those which are suitable.

Of the compounds listed in'Table II, those preferred in the practice of the present invention are compounds in which the structure occurs in a 5 or, 6 membered heterocyclic ring and the reactive hydrogen, i.e. that which is most'easily replacable, is the hydrogen attached to the carbon indicated.

, TABLE 11 (The arrow marks the reactive position for attachment v fora methane carbon atom) (1) Benzofiavine base:

(3) Rosinduline:

(4) Indole:

(5) Carbazole:

(6) N-vinyl carbazole:

(7) B-carboline:

(8) Quinoline:

(9) Acridine:

(10) Phenanthridene v (3:4 benzoguinoline):

11 Quinoxa line (benzpyrazene):

. (12) Quinazoline 13 Phenoxazine: i F

7 (14) Phenothiazine (thiodiphenylamine) N SU 15) Carbazole indophenol:

( 16) Leuco carbazole indophenol:

(17) Carbazole thiazone:

(18) Carbazole oxazone:

(19) Indigo white:

(20) 2 indole 2' thionaphthene indigo white:

OH OH (21) 2,3'indo1e indigo white:

Ill H (22) 2 indole 2thionaphthene indigo white:

8 V (23) 4-[ 1-ethy1-2( 1H) -quin0lylidene) methyl] quinoline:

(24) 4 [2 methyl 3 (1 f ethyl v2(1H) quinolylidene)propenyl] quinoline:

C H C H5 (25) 4 [1 cyano 5 (3 methyl 2(3H) benzothia zolylidene) 1,3-pentadienyl] quinoline (26) 4 [3 ethyl 2(3H) benzothiazolylidene)methyl] quinoline (28) 4-( 1-ethy1-2( 1H) -quinolyideneamino quinoline:

l R C 2H5 (29) 4 [(3 ethyl 2(3H) -benzoxazolylidene)2 butenylidene1aminoquinoline:

30 4 [6 3 ethyl 2(3H) benzothiazolylidene)- 2,4 hexadienylidene] aminoquiholine:

7 (32) 4- (p-dimethylaminophenylazo quinoline:

(3 3) 4-p-dimethylaminostyrylquinoline:

(34) 4 [4 (p dimethylaminophenyl) 1,3-butadienyl] quinoline:

The substituted amines of Table I generally yield a deep color ranging from deep blue to deep violet. The simple heterocyclic bases of'Table II generally yield a color ranging from green to blue. The indigo type bases generally yield a deep blue black or green black. A range of colors varying from red to blue can be obtained from the simple heterocyclic bases by substituting the hydrogen most para to the position of the arrow with a chromophoric group such as paradimethyl amino phenyl azo. For example, in the case of quinoline such a compound would be 4-(p-dimethylamino phenyl azo)quinoline and the vinyl analogue would be 4-p-dimethyl amino styryl quinoline. Such chromophore substitution yields the styryl bases describedearlier in this specification.

In the case of carbazole, the indophenol and the leuco indophenol are important intermediates. Thionation of the leuco indophenol thiosulfate of carbazole yields the thiazone. These various carbazole derivatives containing chromophoric groups or groups which yield chromophores on oxidation are exemplified in Table II, as items 15 and 16.

Thus derivatives of the various heterocyclics may be utilized generally for preparation of dye bases for the purposes of my invention providing such dye bases have a position reactive with a methane type central carbon atom, or less preferably, an aryl ring having an open para position.

(C) LEUCO BASES OR CARBINOL BASES OF SIMPLE OR SUBSTITUTED TRIARYLMETHANE DYES TREATED PARTICULARLY TO IMPROVE THE ELECTROPHILIC OR ELECTRON WITH- DRAWING CHARACTERISTICS OF A SINGLE ARYL GROUP ON THE CENTRAL CARBON ATOM Simple or substituted leuco or carbinol bases of triarylmethane dyes are available from several classes. Class I has the general formula given below: wherein R R R and'R are each selected from the group consisting of H, alkyl, arylakyl and aryl groups and they may be the same or different and R represents a monovalent radical selected from the group consisting of H, and OCH where X is H for the leuco base and OH for the carbinol base, where A or B or both may be alpha naphthyl, beta naphthyl, o-anisyl, p-anisyl, p-biphenyl, p-alkylphenyl, p-chlorophenyl, phenyl, where A and B may be the same or different, where A and B may be combined together through an oxygen, a carbon, nitrogen, sulphur, selenium or tellurium bridge, where D is phenyl or naphthyl. The phenyl radicals in the above compounds may be substituted in the 2 and 6 positions taken with monovalent substituents from the class Cl, Br, CN, OCH CH COOH, SO H, OH and other monovalent substituents of the same nature. Other A and B ring entities may also be substituted in the 2 and 6 positions with monovalent substituents taken from the class Cl, Br, CN, OCH CH COOH, SO H, OH and other monovalent substituents of the same nature. Similar substituents may also be present in the 2 and 6 position on the D ring and the 3, 4 and 5 positions on the D ring are preferably unsubstituted. In the case of a-naphthyl, the naphthyl radicals may be substituted in the 2 and 8 positions with monovalent substituents taken from the class Cl, Br, CH, OCH CH COOH, SO H, OH, where the substituents are the same or different, providing all are in the foregoing class.

When A and B are combined together a second class of triarylmethane dyes suitable for the purposes of my invention may possibly be described as pseudotriarylmethanes in which the combined A and B portions of the triarylmethane generic formula given above are substituted with 3,6 bisdimethyl or diethylamino anthracene, 3,6 bisdimethylamino xanthene, 3,6 bisdimethyl or diethyl aminoseleno xanthene, 3,6 bisdimethyl or diethylaminotelluroxanthene, 3,6 bisdimethylamino or diethylaminotoluoxanthene, or 3,6 bisdimethylamino or diethylaminoxanthene, p-pdimethylamino or diethylaminofluorene and modifications thereof Where methyl or ethyl in the para position on the A and B portions of the ring struction may be substituted for its opposite number of with hydrogen and where methyl, chloro, carboxyl, nitro, sulfonic and similar monovalent groups may be placed on ortho positions on the D ring structures, it being important, however, that both ortho positions on the or two prime or D ring be substituted as indicated with the same or both substituents, these positions being properly designated as the 2, 6 positions, and the 3, 4, 5 positions preferably being unsubstituted; and where the pseudotriarylmethanes substituted as described just above for the A and B portions may be further substituted in the parapara prime positions with ring structures as described previously for the general class of triarylmethanes; a further class of pseudotriarylmethanes representing combined bridge structures identified by the compound 5,9- dioxa-9,14-dihyrocoeranthyryl leuco base: chichibabins hydrocarbon: the benzoflavin nucleus as a replacement for the A and B substituents in accordance with the following formula in which the para aminogroups may contain hydrogen, alkyl, aryl, or aralkyl groups in which these positive substituents may be the same or different.

The foregoing description may be summarized by the generic description of a triarylmethyl or pseudotriarylmethyl compound in which a central carbon atom exists exhibiting the triarylmethyl bonding and capable of producing the hydrol or the hydrogen leuco base.

One important aspect of my invention is the nature of.

the substitution on the D constituent which improves the electrophilic or electron withdrawing characteristics of the composition. This improvement is developed invariably by substitution on the 2 and 6 positions on the D ring with substituents which accentuate the electron withdrawing characteristics of the entire ring. As indicated previously, the A and B rings may be phenyl or naphthyl and the substituents in the 2 and 6 positions in the case of phenyl and 2 and 8 in the case of naphthyl which accentuate electron withdrawing characteristics may be chlorine, bromine, cyanogen, methyl, methoxy, carboxyl, sulfo, hydroxyl or similar monovalent groups. The 3, 4 and 5 positions are preferably left unsubstituted.

The structures described above are illustrated Table III.

ll TABLE TIL-STRUCTURES ILLUSTRATING SUIT- ABLE TRIARYLMETHANE TYPE OF LUECO BASES 1) Generic formula, leuco malachite green type:

R R R R4=H, alkyl, arylalkyl or aryl X=H, OH, alkoxy, aroyl (ethers), halogen (C1 or Br),

or acetate (esters) A, B=phenyl, naphthyl, anisyl, biphenyl or substituted phenyl D phenyl or naphthyl Y'=Cl, Br, CN, OCH COOH, SO H, OH.

(2) Generic formula, closed ring type:

egy

(3) Generic formula, chichibabin type:

wherein A, B, D, R R R R X and Y have the same meanings as in (1) above.

12 (4) Generic formula, chichibabin closed ring type:

R1 R3 Z RZ A B Ri o Y Y \/X J A 1 N z 11 R4 wherein A, B, D, R,, R R R X and Y have the same meanings as in (1) above wherein Z and AZB have the same meanings as in (2) above.

(D) SPECTRAL SENSITIVITY The color sensitivity response or spectral sensitivity appears to bear a relationship to the color of the triarylmethane free radical and does not appear to be affected by the color of the dye base or substituted amine. Table IV gives the color of a number of triarylmethyl type radicals and the range of spectral sensitivity of the synergistic systems which are presumed to contain such radicals as a consequence of the presence of carbon tetrabromide and exposure to light.

This table illustrates another important aspect of my invention, namely, the extension of the spectral range by increasing the size of the ring structure attached to the central carbon atom.

TABLE IV.SPECTRAL SENSITIVITY DUE TO VARIOUS TRIARYLMETHYL COMPOUNDS Spectral sensitivity Radical (substituents on ring synergistic structures omitted) Color of radical system, A.

(1) Triphenylmethyl Yellow 3, 500-5, 200 (2) Tri-o-anisylmethyl Orange 3, 500-5, 400 (2131) 5,9-dioxa-9, 14-di-hydrocoeran- Red 3, 500-5, 600

r (4) D iphenyl-beta-napthyl methyl. WineBed. 3, 500-5, 700 (5) Diphenyl-alpha-napthyl methyl. Red-Brown 3, 500-6, 000 (6) Di-beta-napthyl phenyl methyl. Blue Red 3, 500-6, 800 (7) Chichibabin hydrocarbon Red Vio1et 3, 500-7, 000 (8) Tri-p-biphenylmethyl Deep Viole 3, 500-7, 000 Blue-Green-Red 3, 500-7, 200

(9) Di-alpha-napthyl biphenyl methyl.

(E) PROPORTIO'NS The preferred proportions of active ingredients in my novel photographic compositions are generally as follows: for each mole of the styryl or cyanine base, or open para position substituted amines as listed in Table I or heterocyclic nitrogen compounds as listed in Table II, 5 to 20 moles of the leuco bases or carbinol bases as described in Tables III and IV are used in combination with 50 to 300 moles of the source of halogen free radicals such as carbon tetrabrornide. A preferred composition comprises 1 mole of the dye base, substituted amine or heterocyclic nitrogen compound; 10 moles of the triarylmethane compound; and 200 moles of the halogen free radical source.

If this active composition is to be coated onto a surface such as paper, or a clear or pigmented plastic substrate, the photochemically active composition is generally dissolved in a solvent such that 1 gram of the photoactive composition may be dissolved in a volume varying from 2 to 10 ccs. of such solvent. If a plastic binder is 13 utilized for film forming characteristics an amount of such plastic binder is added to the solvent volume just recited so as to yield solutions in said solvent ranging between 1 percent plastic binder based on the solvent up to 10 percent.

(F) PREPARATION AND PHOTOGRAPHIC PROCESSING TECHNIQUE The photoactive composition, as described in the previous section, with or without the presence of film formers is coated on a suitable substrate such as paper, subbed paper, clear or pigmented plastic films, glass and the like by dipping, spraying, roller coating, doctor blading or any of the usual techniques utilized by those skilled in the art of applying photosensitive coatings of uniform thickness. These photosensitive compositions are mixed and applied in the dark and after application to the desired surface are allowed to dry in the dark in a drying chamber from which air and oxygen has been removed by purging with nitrogen or carbon dioxide. Drying is normally carried out at room temperature utilizing flowing nitrogen or carbon dioxide to facilitate the drying. Slightly elevated temperatures may be utilized for drying purposes but, preferably, not exceeding 45 C.

The dried film is then exposed in an appropriate device to a suitable light source such as daylight, ultraviolet lamps, floodlamps, or flashlamps and thereafter is developed for periods ranging between 30 seconds and 2 minutes with an infrared source fitted with an appropriate filter so that all visible and ultraviolet radiation below 7200 A. has been removed. The most effective infrared developing band of wavelengths is between 0.75 micron and 3 microns. A latent or semi-latent image is obtained on light exposure which develops out as a consequence of the infrared treatment. Some fixing is achieved in this step and in those systems where the background color of the original dyed base or secondary amine is not a disadvantage fixing may be completed by placing in an oven for 2 to 5 minutes at a temperature of 125 C. When the background color of the original starting materials is objectionable fixing may be accomplished after the infrared treatment by bathing in a solvent solution consisting of 3 parts of ethyl acetate and 17 parts of benzene (3:17) to remove the unreacted starting materials. Permanent and complete fixing results from such a procedure. The filter should cut off all radiation below 7 200 A. for compositions containing triphenyl leuco compounds but may have a cut off at 7500 A. when naphthyls and similar aryl groups replace the phenyl groups in such compounds.

It is also possible to utilize the compositions of this invention in a flexographic process in which the compositions are positioned above a subject to be reproduced and then given a blanket exposure to visible and/or UV. radiation after which they are subjected to infrared radiation alone.

(G) EXAMPLES Example 1 When 3 milligrams of the styryl base, 4-p-dimethylaminostyrylquinoline, and 25 milligrams of the leuco base, 4-4 bis (dimethylamino) 2"6" dichlorotriphenylmethane, were dissolved in 10 ccs. of ethyl acetate containing 700 milligrams of carbon tetrabromide, then coated on a clear or pigmented cellulose acetate substrate, excellent images were obtained on exposure in a camera for 1 second at P45 in bright sunlight after infrared treatment with radiation in a wavelength range between 0.75 and 3.0 microns for 2 minutes. The image obtained was background clarified and fixed by bathing in a solvent solution consisting of 3 parts of ethyl acetate and 17 parts of benzene which removed the unreacted starting materials.

Example 2 3 milligrams of the styryl base, 4-p-dimethylaminostyrylquinoline, and 25 milligrams of the leuco base, 4,4

bis(dimethylamino) 2",6" dihydroxytriphenylmethane, are dissolved in 10 ccs. of ethyl acetate containing 700 milligrams of carbon tetrabromide and coated on a clear cellulose acetate substrate. After drying, in a nitrogen atmosphere the film was exposed in a camera at P45 in bright sunlight for 1 second and then infrared developed as described in Example 1 for 1 /2 minutes. An excellent image was obtained which was fixed by bathing in solvent solution consisting of 3 parts of ethyl acetate and 17 parts of benzene as in Example 1.

Example 3 3 milligrams of the azacyanine dye base, 2-(3-ethyl-2 3H) -benzothiazolylidine) -ethylidine aninobenzothiazole, and 25 milligrams of the leuco base, 4,4 bis(dimethylamino) 2",6 di-cyanotriphenylmethane, were dissolved in a solution of 700 milligrams of carbon tetrabromide in 10 ccs. of a solution of 2 percent ethyl cellulose in toluene. The mixture was coated on white vinylite film in the darkroom and exposed under a negative through a light from a photoflood lamp. A full exposed print was obtained in 0.5 second of a neutral gray black color. A. similar mixture in which leuco crystal violet was substituted for the dicyanotriphenylmethane leuco base described above gave a barely perceptible image after similar exposure and infrared development indicating at least a 20 times increase in speed when these specially prepared leuco bases were substituted for the prior art leuco crystal violet.

Example 4 5 milligrams of 3-ethoxy-4'-methyldiphenylamine was mixed with 40 milligrams of 4,4 bis(dimethylamino) 2",6" dicarboxyltriphenylmethane, in 10 ccs. of a 5 percent polystyrene solution containing 500 milligrams of carbon tetrabromide. This mixture was coated on baryta paper at a 1.5 mil wet thickness and allowed to dry in nitrogen. It was then exposed through a negative using the photofiood lamp utilized in Example 3 for 0.5 second. After infrared development, the sample was fixed by heating in an oven at C. for 3 minutes and an image of good density with clean background was achieved. When leuco crystal violet was substituted for the leuco base defined in this example, no image was visible after infrared development and the sample fogged completely on heating in the oven.

Example 5 4 milligrams of m-acetomidodiethylaniline was mixed with 30 milligrams of 4,4 bis(diethylamino) 2",6 dimethyltriphenylmethane in 10 ccs. of a 5 percent solution of polyvinylchloride in tetrahydrofuran containing 700 milligrams of carbon tetrabromide and the mixture was coated on subbed baryta paper and allowed to dry in the dark. It was thereafter exposed to the photoflood lamp utilized in Example 3, for 1 second through a negative yielding densities after infrared development and solvent leaching of 2.4 in the blacks.

Example 6 5 milligrams of N,N-dimethyl-m-toluidine and 35 milligrams of 4,4 bis(dimethylamino) 2",6" disulfotriphenylmethane were dissolved in 10 cos. of toluene containing 600 milligrams of carbon tetrabromide. The solution was coated on a clear cellulose acetate film and dried as described previously. It was then exposed in a camera at P45 in bright sunlight and images of excellent quality were obtained after infrared development and fixing as described in Example 1 utilizing an exposure time in the camera of 2 seconds.

Example 7 7 milligrams of p-ethoxyphenyl alpha naphthylamine and 40 milligrams of 4-4' bis(dimethylaminophenyl) 2",6" dichlorotriphenylmethane were dissolved in 10 ccs. of the solution containing 500 milligrams of carbon tetrabromide and 1 gram of polystyrene. This solution was coated on polyester subbed Mylar at a wet thickness of 2 mils and dried as before. Exposure to the photofiood lamp utilized in Example 3 for 0.5 second produced images in the blacks after infrared development and thermal fixing of densities about 2.0. Substitution of leuco crystal violet for the triphenylmethane leuco compound described in this example yielded no image under the described conditions and the sample fogged completely on thermal development.

Examples 8, 9, 10, 11 and 12 In five separate preparations, 4 milligrams each of N- vinylcarbazole, isorosinduline, indigo white, carbazole thiazone, and acridine (see Table II), and milligrams of the leuco base described in Example 1 were dissolved in 10 ccs. of a 1 percent ethyl cellulose solution comprising 4 ccs. of ethyl ether and 10 ccs. of toluene which contained 800 milligrams of carbon tetrabromide. These were spread on a clear cellulose acetate film, dried, exposed in a camera in bright sunlight at F45 for 2 seconds. After infrared development and solvent fixing as described in Example 1, excellent images With densities in each case exceeding 1.0 in image areas were obtained.

Example 13 3 milligrams of N-vinylcarbazole and 30 milligrams of 3,6 bis(dimethylamino)-9-2,6 dichlorophenylxanthene were dissolved in 10 ccs. of toluene containing 1 gram of polystyrene and 800 milligrams of carbon tetrabromide and spread in a wet thickness of 2 mils on baryta paper. Exposure followed by infrared development and solvent leaching as defined in Example 1, the exposure being made to a flodlamp for 0.6 second, yield an image exhibiting a density of 1.7 in 1 second.

Example 14 13 milligrams of 4-p-dimethylaminostyrylquinoline and milligrams of 3,6 bis(dimethylamino)-9-2,6 chlorophenylthioxanthene were dissolved in 10 ccs. of ethyl acetate containing 700 milligrams of carbon tetrabromide and coated in a 2 mil wet thickness on a clear acetate base. After drying and exposure as defined in Example 1, infrared development and fixing an excellent image was obtained with an exposure time of 0.5 second in the camera exposure as utilized in Example 1.

Example 15 5 milligrams of 4-p-dimethylaminostyrylquinoline and 50 milligrams of a leuco base in accordance with the generic formula given as item 3, Table III, as the leuco base in which all of the Rs are methyl groups, X=hydr0- gen, Y=Cl, and A, B and D are phenyl groups, Were dissolved in 15 ccs. of an equal part mixture of benzene and ethyl acetate containing 1 gram of carbon tetrabromide. This was spread in a 2 mil wet thickness on clear acetate in the dark as described before and after drying a go d density image (density 0.7) was otbained in a camera at F4.5 in bright sunlight at an exposure of 0.1 second, the image being developed out with infrared and solvent fixed as described in Example 1.

Example 16 The photosensitive composition described in Example 1 (including the carbon tetrabromide) was dissolved in a mixture of 8 ccs. of ethyl acetate and 8 ccs. of benzene and coated in 1.5 mil wet thickness on polypropylene filled paper. After drying and exposure to the photofiood lamp of Example 3 at a distance of 10" for 2 seconds, the infrared developed image was fixed by extraction with benzene, then sponged with water containing 0.01 grams of aerosol OT per 100 ccs. of water and then washed with water. When placed on a lithographic press, good reproductions were obtained, the dye image areas being ink repellent and the non-dye image areas being ink receptive.

1 6 Example 17 When 5 milligrams of the azacyanine base, 4-(1-ethyl-2 (1H)-quinolylideneamino)quinoline, and 30 milligrams of the leuco base, 4-4bis(dimethylamino) 2"6dichloro triphenylmethane, were dissolved in a mixture of 8 ccs. of ethyl acetate and 2 ccs. of toluene containing 500 milligrams of iodoform, then coated on a pigmented (TiO cellulose acetate substrate, excellent images were obtained on exposure in a camera for 0.5 seconde at P45 in bright sunlight after infrared treatment with radiation and wavelength range between 0.75 and 3.0 microns for 5 minutes. The image obtained was background clarified and fixed by bathing in a solvent solution consisting of 3 parts of ethyl acetate and 17 parts of benzene which removed the unreacted starting materials. The color of the image was greenish-blue.

Example 18 3 milligrams of the azo base, 4-(p-dimethylaminophenyl-azo)quinoline, and 45 milligrams of the leuco base, 4-4 bis(dimethylamino) 2"6" dichloro 4"methoxytriphenylmethane, were dissolved in 200 ccs. of a 50/50 mixture of ethyl acetate and benzene containing 1000 milligrams of hexachlorethane, then coated on a clear cellulose acetate substrate, excellent images were obtained on exposure in a camera for 2 seconds at P45 in bright sunlight after infrared treatment with radiation in a wavelength range between 0.75 and 3.0 microns for 5 minutes. The image obtained was background clarified and fixed by bathing in a solvent solution consisting of 3 parts of ethyl acetate and 17 parts of benzene which removed the unreacted starting materials. The image was blue in color.

Example 19 When 5 milligrams of the dye base, 4-[4-(p-dimethylaminophenyl)-1,3-butadieneyl]quinoline, and 30 milligrams of a leuco base, 4-4'bis(dimethylaminonaphthyl) 26dichloro diphenylmethane, were dissolved in 10 ccs. of a solution comprising 8 ccs. of ethyl acetate and 2 ccs. of benzene containing 500 milligrams of carbon tetrabromide, then coated on a titanium dioxide pigmented cellulose acetate substrate, excellent images were obtained on exposure in a camera for 1 second a P45 in bright sunlight. After infrared treatment of radiation in a Wavelength range between 0.75 and 3.0 microns for 7 minutes, the image otbained with background clarified and fixed by bathing in a solvent solution consisting of 3 parts of ethyl acetate and 17 parts of benzene which removed the unreacted starting materials.

Examples 21, 22 and 23 Same as in Example 1 except that in place of the 25 milligrams of the leuco base described in Example 1, the following triphenylmethyl compounds are used respectively.

(1)4-4bis(dimethylamino) 2"6" dichlorotriphenylmethylethylether (2) 4-4bis(dimethylamino) 2"6" dichlorotriphenylmethylbromide (3) 4-4bis(dimethylamino) 2"6" dichlorotriphenylmethacetate Example 24 Same as in Example 1 except that composition included 50 mg. of triphenylstibine (between 25 and mg. could be used.) Similar results were obtained.

Example 25 Same as Example 24 except that reflexographic technique was utilized for exposure. Using clear cellulose acetate as the film the coated film was laid on a subject to be duplicated, sensitive side of the film being up, and passed under a battery of illuminating and heating lamps, first being exposed to the illumination from a visible plus U.V. source and then to I.R. lamps equipped with filters which removed all radiation to which the film might be sensi- Examples 26 and 27 The process of Example 1 was repeated using 3 mg. of compounds having the formula:

in place of the 3 mg. styril base compound and in each instance a permanent black image was obtained.

I claim:

1. In a non-silver photosensitive composition comprising a mixture of the following:

(a) photolytically active organic halogen containing compounds represented by the general formula A-C-X wherein A represents a member of the group consisting of H, Cl, Br, I, alkyl, aryl and aroyl and each Xrepresents a halogen atom -selected from the group consisting of Cl, Br and I;

(b) at least one constituent selected from the group consisting of dye bases;

(c) at least one base selected from the group consisting of leuco bases and carbinol bases of triarylmethane compounds; and

(d) a carrier which supports the mixture of (a), (b) and the improvements which comprise:

providing as constituent (b) a conjugated dye intermediate or heterocyclic compound having a reactive position for attachment of a methane carbon atom or a mixture thereof with a dye base; and

providing as constituent compounds having at least one aryl group substituted to increase its electrophilic characteristics and represented by one of the following formulas: (l) generic formula, leuco malachite green type:

Y=Cl, Br, CN, 0on cooH, so,H, 0H.

18 (2) generic formula, closed ring type:

A, B, D, R1, R2, R3, R4, R5, X and Y have the same meaning as in (1) above Z=C (anthracene), O (xanthene), S (thioxanthene),

N (benzoflavine or acridine or merely a bond between A and B (fluorene) AZB=5,9, dioxa-9, 14 dihydroceranthryl.

1 (3) generic formula, chichibabin type:

/N N/ R: A \R| t X R1 A 0 R3 N/ R: \R4

wherein A, B, D, R R R R X and Y have the same meanings as in (1) above. (4) generic formula, chichibabin closed ring type:

wherein A, B, D, R R R R X and Y have the same meanings as in (1) above wherein Z and AZB have the same meanings as in (2) above.

2. The composition of claim 1 wherein the ACX constituent is a compound in which at least three bromine atoms are attached to a single carbon atom. 3. The composition of claim 1 wherein the AC-X constituent is CBr RI! RI wherein R and R each represents monovalent radicals selected from the group consisting of lower alkyl and benzyl; R" represents a monovalent radical selected from the group consisting of H and CN, d and n each represent a positive integer of from 1 to 2; m is a positive integer not greater than 4; and the sum of n-1 and m1 is not greater than 4; and Q represents the non-metallic atoms selected from the group consisting of C, O, S, Se, N, necessary to complete a heterocyclic ring with not more than 6 atoms in the ring.

6. The composition of claim 1 wherein the constituent (b) is a cyanine dye base represented by the general formula )d1 b )n1=- (CH CH)el=N wherein d and e each represents a positive integer of from of from 1 to 2; n represents a positive integer of from 1 to 4; R represents an organic radical selected from the group consisting of alkyl, aralkyl and aryl groups; R represents a member of the group consisting of hydrogen and cyano groups; and Z and Q each represents the nonmetallic atoms necessary to complete a heterocyclic organic nucleus containing from 5 to 6 carbon atoms in the ring, and a preferred R is 7. The composition of claim 1 wherein the constituent (b) is a cyanine dye base represented by the general formula wherein d and e each represents a positive integer of from 1 to 2; n represents a positive integer of from 1 to 4; R represents an organic radical selected from the group consisting of alkyl, aralkyl and aryl groups; R represents a member of the group consisting of hydrogen and cyano groups; each L represents a member selected from the group consisting of CH and N, at least one L being a nitrogen atom; and Q and Z each represents the nonmetallic atoms necessary to complete a heterocyclic organic nucleus containing from 5 to 6 carbon atoms in the ring, and a preferred R is 8. The composition of claim 1 wherein the constituent (b) is a styryl dye base represented by the general formula wherein R and R' each represents monovalent radicals selected from the group consisting of lower alkyl and benzyl; a represents a positive integer from 1 to 2; n represents a positive integer from 1 to 4; L represents a member selected from the group consisting of CH and N, at least one L being a nitrogen atom and Q represents the nonmetallic atoms selected from the group consisting of C, O, S, Se, N, necessary to complete a heterocyclic ring with not more than 6 atoms in the ring.

9. The composition of claim 1 wherein the constituent (b) is an amine represented by the general formula Ar-N wherein Ar represents phenyl or naphthyl and each of E and F represents a member selected from the group consisting of H, alkyl, aryl, substituted alkyl and substituted aryl and the carbon para to the ring carbon to which the N is attached is not substituted.

10. The composition of claim 1 in which the (a), (b), (c) mixture is dispersed in the support (d).

11. The composition of claim 1 in which the (a), (b), v(c) mixture is supported as a thin film on the support ((1).

12. The composition of claim 1 including a plastic binder for the mixture.

13. The composition of claim 1 in which the support is a polymer of a vinylidene halide selected from the group consisting of vinyl chloride and vinylidene chloride and mixtures thereof.

14. The composition of claim 1 dispersed in a clear transparent solid film forming plastic.

15. The composition of claim 1 wherein the relative proportions of the several constituents are as follows: for each mole of (b) there are between 5 and 20 moles of (c) and 50 to 300 moles of (a).

16. The composition of claim 1 wherein the relative proportions of the several constituents are as follows: for each mole of (b) there are about 10 moles of (c) and about 200 moles of (a).

17. A process for producing colored photographic prints which comprises preparing the composition of claim 1; exposing the composition to a colored subject, thereby producing an image of said subject.

18. The process of claim 17 wherein the resulting image is intensified by heating for between 30 and seconds.

19. The process of claim 18 wherein the resulting print is treated with a solvent to wash away any undecomposed dye base, remaining after exposure and heat intensification.

20. The composition of claim 1 wherein the triarylmethane compound is a triphenylmethyl compound.

21. The composition of claim 1 wherein the triarylmethane compound is a tri-o-anisylmethyl compound.

22. The composition of claim 1 wherein the triarylmethane compound is 5,9-dioxa-9,l4-dihydrocoeranthryl.

23. The composition of claim 1 wherein the triarylmethane compound is diphenyl-beta-naphthyl methyl compound.

24. A process of producing colored photographic prints in which a transparent layer including the composition of claim 1 is disposed between a subject to be reproduced and source of visible and/or ultraviolet radia tion, and while so positioned is exposed to such radiation and thereafter to infrared radiation for a time suflicient to develop a visible image of said subject.

References Cited UNITED STATES PATENTS 3,102,810 9/1963 Sprague et al. 9633 OTHER REFERENCES Gould, Edwin: Mechanism and Structure in Organic Chemistry Holt, Rinehart & Winston, 1959, p. 208. QD 251 66.

Hine: Physical Organic Chemistry, McGraw Hill, 1962, p. 405. QD 476 H5.

NORMAN G. TORCHIN, Primary Examiner R. E. FIGHTER, Assistant Examiner US. Cl. X.R. 9648; 260240.1