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Publication numberUS3384487 A
Publication typeGrant
Publication dateMay 21, 1968
Filing dateSep 1, 1964
Priority dateSep 1, 1964
Also published asDE1472848A1
Publication numberUS 3384487 A, US 3384487A, US-A-3384487, US3384487 A, US3384487A
InventorsHeseltine Donald W, Jones Jean E, Lincoln Lewis L
Original AssigneeEastman Kodak Co
Export CitationBiBTeX, EndNote, RefMan
External Links: USPTO, USPTO Assignment, Espacenet
Butadienyl dyes for photography
US 3384487 A
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Description  (OCR text may contain errors)

y 21, 1968 D. w. HESELTINE ET AL 3,384,487

BUTADIENYL DYES FOR PHOTOGRAPHY Filed Sept. 1, 1964 Fi 9-1 l2 GELATIN CONTAIN/N6 BU 210/5 YL DYE '"N ASUPPORT LIGHT'SENSITIVE GELATINO SILVER HALIDE BLUE-SENSITIVE GELATINO SILVER HAL/DE GELATIN CONTAINING BUTAD/E/VYL DYE GREEN-SENSITIVE GELATINO SILVER HAL/DE RED-SENSITIVE GELATINO SILVER HA LIDE SUPPORT Fig.3

LIGHT-SENSITIVE GE LAT/N0 SILVER HAL/ DE l0 SUPPORT F N CONTfULNING BUTAD/E/VYL DYE 11 Hi 9 /-LIGHT-SENSITIVE GELATINO SILVER HAL/DE GE LAT'IN CONTAINING BU TAD/E N YL D YE L4 SUPPORT DonaldVHQSlfine JeanE. Jones incoln Lew's 'LINIEENTORS A'IIORNEYE AGENT United States Patent 3,384,487 BUTADIENYL DYES FOR PHOTOGRAPHY Donald W. Heseltine, Jean E. Jones, and Lewis L. Lincoln, Rochester, N.Y., assignors to Eastman Kodak Company, Rochester, N.Y., a corporation of New Jersey Filed Sept. 1, 1964, Ser. No. 393,684 Claims. (CI. 96-84) ABSTRACT OF THE DISCLOSURE Novel indolebutadienyl dyes prepared by reacting an indolium compound with a cinnamaldehyde compound have valuable light-absorbing characteristics which make them useful in light-sensitive photographic elements and are bleachable. Anhydro-2-(4-p-dimethylaminophenyl-1,1- dimethyl 1,3 butadienyl) 3 (4 sulfobutyl) 1H- benz[e]indolium hydroxide and 3-carboxyethyl-2-(4-pdimethylaminophenyl 1,3 butadienyl)-1,l-d-imethyl-1H- benz[e]indolium iodide, for example, are illustrative of the indolebutadienyl dyes.

This invention relates to photography and more particularly to butadienyl dyes and photographic elements containing them.

It is known that light-screening substances are often employed in photographic elements, for example (a) in overcoatings to protect the light-sensitive emulsion from ultraviolet light, especially with color materials, (b) in layers between differentially sensitized emulsions, e.g., to protect redand green-sensitized emulsions from the action of blue light, and (c) in anti'halation layers, on either side of a transparent support carrying the lightsensitive emulsion.

In most cases, and especially when the element contains a color-sensitized emulsion, it is desirable to employ lightscreening substances which do not react chemically to affect the general sensitivity or the color sensitivity of light-sensitive emulsions with which they come into contact. It is also desirable to employ light-screening substances which do not diffuse substantially from the layers in which they are incorporated, either during manufacture of the element or during storage. Finally, it is generally necessary to employ light-screening substances which can be decol-orized and/ or readily removed prior to or during photographic processing; for many purposes it is particularly convenient to employ light-screening substances which are rendered ineffective in one of the photographic processing baths. For example, in an element to be processed by chemical reversal, it may be convenient to employ a light-screening substance which is rendered ineffective =(bleached and/ or removed) in negative development in order to facilitate exposure of the residual silver halide.

Numerous substances, including many well known dyes, have been employed for light-screening in the applications indicated above, but it has proved extremely difficult to find dyes having the combination of qualities desired. Many are not resistant to diffusion and wander from the layer in which they are coated; many adversely affect the sensitivity of light-sensitive emulsions with which they come into contact. Some are not sufliciently water soluble to enable incorporation into filter layers from aqueous solutions. Some are not bleached or destroyed readily by photographic processing and thus present stain problems in the processed photographic element.

The use of styryl dyes for antihalation protection in backing layers has been known for some time. For example, styryl dyes are disclosed for this purpose in US. Patent 1,845,404, issued Feb. 16, 1932. However, few

3,384,487 Patented May 21, 1968 ice styryl dyes have been found that absorb in the red spectral region, since the high deviations encountered in the dyes from highly basic nuclei reduce markedly the deepening of the color (that is, shift of spectral absorption to longer wave lengths) usually produced by increasing the chain length. Styryl dyes of the indole series are very unstable under even mildly alkaline conditions. Styryl dyes have been prepared previously as light-screening dyes that are soluble in organic solvents, do not wander and are bleachable in conventional processing baths. Many of the prior art dyes have a tendency to precipitate in aqueous solutions of hydrophilic colloids such as gelatin, polyvinyl alcohol, albumen, casein, etc. and the organic solvent, such as, acetone or alcohol allows the dyes to penetrate the support and render the dyes themselves very difiicult to bleach or destroy in conventional processing baths.

It is therefore an object of this invention to provide a novel class of butadienyl dyes which are useful in lightsensitive photographic elements.

Another object is to provide for use in filter layers and antihalation layers in photographic elements, a novel class of butadienyl dyes, which not only have valuable light-absorbing characteristics but are more water soluble in neutral or in slightly acid solution than prior art butadienyl dyes and thus are more easily incorporated in the filter layer.

Another object is to provide a novel class of butadienyl light-screening dyes which are less subject to diffusion from the filter layer than are the prior art dyes.

Another object is to provide a novel class of dyes which are bleachable by the photographic developer or fixing solutions during the processing of the photographic element.

Another object is to provide a photographic element having at least one light-sensitive silver halide emulsion layer and at least one light-absorbing filter layer containing a dye selected from the novel class of dyes of our invention.

Still other objects will become apparent from the following description of our invention in the specification and claims.

We have discovered that these and other objects are accomplished by the use of the novel dyes of our invention, which are included in the following formula:

wherein L represents the hydrogen atom, or a halogen atom, e.g., chlorine, bromine, fluorine, etc.; Y and Y each represent a member selected from the class consisting of the hydrogen atom and the nonmetallic atoms which together form a fused ring attached to the indolenine ring in the 4 and 5 positions, the 5 and 6 positions, or the 6 and 7 positions; R and R each represent a member selected from the class consisting of the hydrogen atom, an alkyl group, e.g., methyl, ethyl, propyl, butyl, etc., and together represent the nonmetallic atoms necessary to complete a cycloalkane group, e.g., cyclopentane, cyclohexane, e'tc.; R represents an alkyl group such as, a carboxyalkyl group (e.g. carboxymethyl, B-carboxyethyl, 'y-carboxypropyl, 6- carboxy'butyl, w-carboxypentyl, w-carboxyhexyl, etc.), a hydroxyalkyl group, (e.g., ,B-hydroxyethyl, e-hydr-oxybutyl, w-hydroxyhexyl, etc), a carboxyalkylcarbamoyloxyalkyl group (e.g., carboxymethylcarbamoyloxyethyl, fi-carboxyethylcarbamoyloxyethyl, 'y carboxypropylcarbamoyloxyethyl, w-carboxypentylcarbamoyloxyethy-l, ,B-carboxethylcarbamoyloxypropyl, etc.), an alkoxycarbonylalkyl-carbamoyloxyalkyl group (e.g., ethoxycarbonylmethylcarbamoy loxyethyl, methoxycarbonylethylca'rbamoyloxyethyl, ethoxycarbonylethylcarbamoyloxyethyl, etc.); a sulfoalkyl group (cg, fi-sulfoethyl, ysulfopropyl, fi-sulfobutyl, w-sulfohexyl, etc.); and methyl, ethyl, propyl, butyl, hexyl, etc.; X represents an acid anion, e.g., chloride, bromide, iodide, perchlorate, thiocyanate, benzenesulfonate, methylsulfate, ethylsulfate, p-toluenesulfonate, etc.; 12 represents an integer of from 1 :to 2 such that n is 1 only when R contains a carboxy group, and a sulfo group; and Z represents an aryl group (e.g., a phenyl, a tolyl, a propylphenyl, etc.) substituted with an amino group, such as, the amino group, a dialkylamino group, (e.g., N,N-dimethylamino, N,N-diethylamino, N,N-dip-ropylamino, N, N-dibutylamino, etc an alkylamino group (e.g., N- methylamino, N-propylamino, N-butylamino, etc.), a N- alkyl-N-ary'lamino group (e.g., N-methyl-N-phenylamino, N-bu-tyl-N-phenylamino, N-e thyl-N-phenylamino, etc.), an alkoxy group (e.g., methoxy, ethoxy, propoxy, butoxy, etc.) and the hydroxy group.

Our dyes are produced to advantage by heating, preferably under refiux, a compound having the formula:

II R /Rt R2 with a compound having the formula:

III

II-OH=CH-Z dissolved in acetic anhydride. The groups, L, Y, Y R, R R X n and Z are as defined previously.

The butadienyl dyes of our invention absorb light of unexpectedly long wavelengths compared either with the corresponding styryl dyes or compared with other butadienyl dyes. Furthermore, our dyes are unexpectedly bleacha'ble in elonhydroquinone developer solutions compared to butadienyl dyes outside our invention. These properties make our dyes particularly valuable in redlight absorbing backing layers for photographic elements. The acid substituted dyes of our invention are particularly useful with basic vehicles, such as, the cellulose esters of dimethylamino acetic acid.

Among the dyes of our invention are the following typical examples which are intended to illustrate but not limit the scope of our invention.

Dye 1.Anhydro-2-(4-p-dimethylaminophenyl 1,1 dimethyl-1,3-butadienyl)-3-(4-sulfo'butyl)-1H benz[e] indolium hydroxide Anhydro-3-(4-sulfobutyl)-l,1,2-trirnethyl-1H benz[e] indolium hydroxide (1 mol., 6.9 g.) and p-dimethylaminocinnamaldehyde (l mol.+100%, 1 g.) Were dissolved in acetic anhydride ml.) and heated under reflux for five minutes. The reaction mixture was then chilled overnight and crystalline dye was filtered, washed on a Buchner funnel with acetone and dried. The yield of purified dye afte two recrystallizations from methyl alcohol Was 4.2 g. (44%), M.P. 220221 C.

Dye 2.-Anhydro-5-chloro-2-(4-p-dimethy-laminophenyl- 4 1,3-butadienyl)-3,3-dimethyl-l-(4-sulfobutyl)-3H indolium hydroxide Anhydro-5-chloro-2,3,3-trimethyl-1-(4-sulfobutyl) 3H- indolium hydroxide (1 mol., 3.3 g.) and p-dimethylaminocinnamaldehyde (1 mol.+100% excess, 3.5 g.) were dissolved in acetic anhydride ml.) and heated under reflux for twenty minutes. The reaction mixture was then chilled overnight and the crude dye thrown out of solution by the addition of an excess of ether with stirring. The ether was decanted from the sticky dye residue and the dye obtained in crystalline form by adding acetone with stirring. The crystalline dye was filtered, washed on the Buckner funnel with acetone and dried. After two recrystallizations from fifty percent methyl alcohol and water, the yield of purified dye was 1 g. (22%), M.P.

245 246 C. dec.

Dye 3.--Anhydro-5-chloro-2-(4-p-methoxyphenyl 1,3-

butadienyl) -3 ,3 -dime thyll 4-sulfobutyl) -3 H-indolium hydroxide Dye 3 was made like Dye 2 but by using the reactants anhydro-5-chloro-2,3,3-'trimethyl-1-(4-sulfobuty l)-3H indolium hydroxide (1 mol., 3.3 g.) and p-methoxycinnamaldehyde (1 mol.+100% excess, 3.0 g.), and reducing the concentration of acetic anhy-dride to 20 ml. The yield of purified dye was 1.3 g. M.P. 297-298 C. dec.

Dye 4.-3-carboxymethylcarbamoyloxyethyl-Z-(4-p dimethylaminophenyl-1,3-butadienyl)-l,l-dimethyl 1H- benz[e]indo'lium iodide IIII 2):

1,1 dimethyl-2-(4-p-dimethylaminophenyl-1,3-butadienyl) 3 ethoxycarbonylmethylcarbamoxyethyl-lH-benz [e]indolium iodide (1 mol., 3.33 g.) and sodium hydroxide (1 mol.+100% excess, 0.4 g. in 2 ml. H 0) were dissolved in absolute ethyl alcohol (200 ml.) and the solution heated under reflux for ten minutes. The yellow precipitate that separated from the solution was then filtered, suspended in a small amount of water, the water suspension treated with acetic acid and the re-forrned dye filtered off, washed with a small amount of acetone and dried. After two recrystallizations from aqueous methyl alcohol the yield of pure dye was 2.0 g. (62%) M.P. 186-187 dec.

Dye 5.2 (4-p-dimethylaminophenyl-1,3 butadienyl)-3- ethoxycarbonylmethylcarbamoyloxyethyl 1,1-dimethyl-1H-benz[e]indolium iodide 1,1 dimethyl-2-(4-p-dimethylaminophenyl-1,3-butadienyl)-3-hydroxyethyl-1H-benz[e]indolium iodide (1 mol., 8 g.) and carbethoxymethylisocyanate (l mol.+300% excess, 5 g.) were mixed in dry pyridine ml.) and heated under reflux for one hour. The mixture was then chilled and the crystalline dye filtered oil and dried. After two recrystallizations from methyl alcohol the yield of pure dye was 0.5 g. (50%) M.P. 230-231 dec.

Dye 6.-2 (4-p-di'methylaminophenyl-1,3-butadienyl)-3- hydroxyethyl-1,1-dimethyl-1H-benz[e]indolium iodide 3 hydroxyethyl 1,1,2-trimethyl-1H-benz[e]indolium bromide (1 mol., 18 g.) and p-dimethylaminocinnamaldehyde (1 mol. plus excess, 10.3 g.) were mixed in absolute ethyl alcohol and the mixture heated under reflux for ten minutes. The mixture Was then chilled and the dye precipitated as the iodide by adding sodium iodide with good stirring. The dye was then filtered off, stirred in a water suspension, filtered off, washed with a small amount of acetone and dried. After two recrystallizations from methyl alcohol the yield of pure dye was 12 g. (42%) M.P. 250-250 dec.

Dye 7.--3 carboxyethyl-2-(4-p-dimethylaminophenyl-1, 3 butadienyl) 1,1 dimethyl-lH-benz [e]indolium iodide 3 carboxyethyl 1,1,2-trimethyl-lH-benz[e]indolium iodide (1 mol., 6.14 g.) and p-dimethylaminocinnamaldehyde were mixed in ethyl alcohol and the mixture heated under reflux for one hour. The mixture was then chilled and the crude dye filtered off, washed with a small amount of acetone and dried. After two recrystallizations from ethyl alcohol the yield of pure dye was 4.6 g. (54%), M.P.

174175 dec.

Dye 8.--Anhydro 1,1-dimethyl-2-(4-p-dimethylaminophenyl 1,3-butadienyl)-3-(3-sulfopropyl)-1H-benz[e] indolium hydroxide Anhydro-3-(3-sulfopropyl)-1,l,2-trimethy1-1H-benz[e] indolium hydroxide (1 mol., 66.2 g.) and p-dimethylaminocinnamaldehyde (1 mol. plus 50% excess, 47.5 g.) were mixed in absolute ethanol (500 ml.) and heated under reflux for one hour. The mixture was then chilled over night and the crystalline dye filtered off, washed on a Buchner funnel with acetone and dried. The yield of purified dye after two recrystallizations from methanol was 51g. (51%) M.P. 238239 C.

Dye 9.Anhydro-2-(4-p-methoxypheny1-1,3-butadienyl)- 3,3-dimethy1-1-(4-sulfobutyl) -3H-indolium hydroxide This dye was prepared by a method similar to that used for dye 2 but using the reactants anhydro-2,3,3-trimethyl- 1-(4-sulfobutyl)-3H-indolium hydroxide (1 mol.) and pmethoxycinnamaldehyde (1 mol.+100% excess), and reducing the concentration of acetic anhydride to ml.

( JHz 1,l,2-trimethyl-1H-benz[e] indole monosulfonated (1 mol., 5.78 g.) and 2,4-butanesultone (sufficient excess to form a mobile mixture) were mixed and heated over a free flame until the viscous mixture turned brownish-black in color. The mixture was then cooled and the anhydro- ,3 .(3 sulfobutyl)-1,1,2-1H-benz[e]indolium hydroxidem-onosulfonated precipitated as a grey solid by treating with an excess of acetone and stirring. At this point the hydroscopic grey solid was filtered off, dissolved in refluxing ethyl alcohol (100 ml.), p-dimethylaminocinnamaldehyde (1 mol., 3.5 g.) added and the mixture heated under reflux for fifteen minutes. The mixture was then chilled and the crude dye precipitated from solution by turning the mixture into acetone (300 ml.) with stirring. The solid dye was filtered off, washed with acetone and dried. After two recrystallizations from aqueous methyl alcohol and acetone the yield of pure dye was 3.5 g. (31%); melting point 289290 C. dec. Dye l2.Anhydr0-3-carboxyethyl 2-(4-p-dimethylaminophenyl 1,3-butadienyl)-1,1-dimethyl-lH-benz[e]indolium hydroxide, monosulfonated; pyridine salt 1,1,2-trimethyl-1H-benz[e]indole monosulfonated (1 mol., 5.78 g.) and propiolactone (suflicient excess to form a mobile mixture) were mixed and heated over a free flame until the solid went into solution and the solution turned amber in color. The mixture was then removed from heat and reaction took place causing the solution to turn dark in color with a vigorous evolution of heat. The dark viscous mass was cooled, stirred with an excess of ether, ether decanted and the sticky residue dissolved in refluxing ethyl alcohol (200 ml.). At this point p-dimethylaminocinnamaldehyde (1 mol., 3.5 g.) was added and the mixture heated under reflux for ten minutes. The solid dye was collected and after two recrystallizations from ethanol/ pyridine the yield of pure dye was 45 g. (43%), M.P. 226227 C. dec.

Dye 13.2-[4-p-dimethylaminophenyl-1,3-butadienyl]- l-ethyl-3,3-dimethyl-3H-indolium iodide This dye was prepared by a reaction similar to that used to prepare Dye 6 excepting that 1,1,2-trimethylindolenine ethiodide and p-dimethylaminocinnamaldehyde were used. The yield of purified dye was 32%, M.P. 238-239 C. with dec.

The preparation of typical intermediates used in making our dyes will further illustrate our invention.

3-hydroxyethyl-1,l-dimethyl-lH-benz[e] indolium bromide S-carboxyethyl-1,l,2-trimethyl-1H-benz[e] indolium iodide 1,1,2-trimethyl-1H-benz[e]indole (1 mol. plus 100% excess, 20.9 g.) and fl-iodopropionic acid (1 mol., 10 g.) were mixed and heated on a steam bath for 12 hours. The product was then washed with ether, refluxed in acetone, filtered and dried. The yield of light tan solid was 14 g. M.P. 181-182 dec.

Anhydro-3 (4-sulfobutyl) 1,1,2 trimethyl lH-benz [e]indolium hydroxide, and anhydro 3 (3 sulfopropyl) 1,1,2 trimethyl 1H benz[e]indolium hy droxide were prepared by the methods described in Heseltine and Brooker, US. Patent 2,895,955, issued July 21, 1959. Anhydro 2,3,3 trimethyl 1 (4-sulfobutyl)- 3H-indolium hydroxide was prepared from 1,1,2-trimethylindole by reaction described in US. Patent 2,895,955. The corresponding 5-chloro derivative was prepared in the same manner but starting with 5-chloro- 2,3,3-trimethyl-3H-indole.

Our dyes have light-absorbing characteristics that make them valuable for use in filter and antihalation layers of photographic elements. These characteristics are illustrated in Table I below.

TABLE I Maximum light absorption by dye Dye Number: occurs at a wavelength in mg of TABLE II.-ADSORPTION MAXIMA OF P-DIMETHYL- AMINOSTYRYL AND P-DIMETIIYLAMINOBU'IENYL- IDENE DYES Increase in Depth Styryl Dye Butadienyl of Color With Heterocyclie Nucleus (my) Dye (m Introduction of One Vinylene Group (m CaHs X A 525. 0 556. 0 31. 0 K/\ C1115 X CH CH 1 (CH2) is 03 Cg: /CH3 557. 0 633.0 76. 0 a

(o in ,s 03

These data show that of the higher vinylogs only the immediate dyes absorb at wavelengths longer than 600 m It is-unexpected that the immediate dyes would have shifts inthe spectral absorption as high as m from the corresponding styry-l (lower vinylog) dye when the shift in spectral absorption of butadienyl dyes outside our invention and their lower vinylogs is only about 31 mp.

Our dyes are readily soluble in water because of their ionic nature and are thus readily incorporated in hydrophilic colloids such as gelatin, polyvinyl alcohols, albumen, and casein which are usually used 'for filter and antihalation layers of photographic materials. A stock solution may be made of the dye to be used and this can be added to the hydrophilic colloid solution before it is coated.

The concentration of dye in the hydrophilic colloid may be varied considerably depending upon the product in which the filter or antihalation layer is to be used. The

proper amount of dye to be used for a given product can 7 be determined by methods well known in the art.

In the accompanying drawing, FIGURES 1 and 2 are enlarged sectional views of photographic elements having filter layers or antihalation layers made according to our invention. As shown in FIGURE 1, a support 10 of any suitable material such as cellulose acetate, cellulose nitrate, synthetic resin materials or opaque materials such as paper, is coated with an emulsion layer 11 and an overcoating layer 12 comprising a hydrophilic colloid such as gelatin and a butadienyl dye of our invention.

FIGURE 2 illustrates a multilayer photographic element for color photography in which the support 10 is coated with sensitive layers 13, 14 and 15 which record light of the red, green and blue regions of the spectrum respectively. Between the emulsion layers 14 and 15 there is a filter layer 16 containing gelatin and a yellow butadienyl dye. This filter layer serves .a purpose well known in color photography of preventing exposure of a lower layer of the element by light which the filter layer absorbs. The dye may also absorb light in other regions such as the ultraviolet region on the spectrum.

FIGURE 3 represents a film having an antihalation layer containing a dye of our invention. As shown therein, the support 10 carries an emulsion layer 11 on one side and an antihalation layer 17 containing a butadienyl dye on the oppositeside.

FIGURE 4 represents a fil-m having under the emulsion an antihalation layer containing a dye of our invention. As shown, the support 10 carries an antihalation layer 18 which has been overcoated with emulsion layer 11. This antihalation layer serves the well-known purpose of absorbing light passing through the layer and its reflection from the surface of the support back to the emulsion layer.

These dyes can be advantageously used in the preparation of photographic light screening layers by dissolving the dyes in water, or a mixture of alcohol and water, and adding the resulting solution to an aqueous hydrophilic colloidal solution, or to a hydrophobic colloidal solution, e.g., cellulose acetate phthalate or the cellulose ester of dimethylaminoa-cetic acid before coating.

Examples of the use of the dyes of our inventions are illustrated as follows:

One mg. of Dye l was dissolved in 5 ml. of methanol and diluted to 20 ml. with water. This solution was added to 10 ml. of a 10 percent photographic gelatin solution containing 0.5 ml. of 15% saponin solution. The mixture was coated on a suitable support at a thickness that contained from ten to twenty mg. of dye per square foot.

A layer of alkali-removable cellulose acetate phthalate coated over cellulose tr-iacetate sheeting was followed by an overcoat of the following composition: 1.0% of Dye 2 in a mixture of alcohol and 5% water.

A layer of alkali-removable cellulose acetate phthalate was coated over cellulose triacetate followed by a dye 9 coat of the following composition: 0.4% anhydro-S- chloro Z-p-dimethylaminostyryl 3,3 dimethyl-1-(4- sulfo butyl)-3H-indolium hydroxide, 1.0% of Dye 2 from alcohol-water.

The following examples will illustrate more fully how our dyes may be used in preparing light absorbing filter layers.

Example 1 1.5 grams of Dye 1 were dissolved in 37.5 ml. of water and this solution was added to 4.5 liters of 5% aqueous gelatin. This mixture was then coated as an antihalation backing on the reverse side of a support which has been coated with a photographic silver halide emulsion layer.

After exposure of the photographic element in the usual manner, development of the exposed material in a developer having the following composition:

N-methyl-p-aminophenol sulfate grams 2 Sodium sulfite (desiccated) do 90 Hydroquin-one do 8 Sodium carbonate monohy-drate do 52.2 Potassium bromide -do 5 Water to make liter 1 followed by fixation in a conventional sodium thiosulfate fixing bath resulted in complete removal of the dye from the photographic element.

Example 2 A photographic element made as in Example 1, but using Dye 4 in place of Dye 1 was exposed. No dye color was evident in this element after development, and fixing with the solutions used in Example 1.

Example 3 A mixture of Dye 1 and aqueous gelatin solution as prepared in Example 1 was coated over a light sensitive silver halide emulsion layer on a conventional support.

After exposure of the photographic element in the usual manner, development and fixing of the exposed material in the solutions of Example 1 resulted in a complete removal of the dye color from the light filtering layer over the developed image.

Example 4 Similarly, the other dyes of our invention can be used in light filtering layers as in Example 3.

The above examples show the use of our dyes in antihalati-on layers and in layers overcoating the light sensitive silver halide emulsion layer; they can also be coated between light sensitive silver halide layers in multilayer photographic elements.

The novel dyes of our invention are characterized by being readily water soluble and readily bleachable by ordinary photographic developers and processing solutions. These properties make our dyes valuable for use in making light sensitive photographic elements. Our dyes are particularly valuable in light absorbing filter layers either coated over the silver halide emulsion layers, or coated between light sensitive silver halide layers, or coated on either side of the support on which the light sensitive silver halide emulsion layers are coated.

The invention has been described in detail with particular reference to preferred embodiments thereof, but it will be understood that variations and modifications can be efiected within the spirit and scope of the invention as described hereinabove and as defined in the appended claims.

We claim:

1. A photographic element comprising a support having coated thereon at least one light-sensitive silver halide emulsion layer, said element having a light-absorbing layer containing a dye having the formula:

wherein L represents a group selected from the class consisting of the hydrogen atom, and a halogen atom; Y and Y each represent a member selected from the class consisting of a hydrogen atom, the non-metallic atoms which when taken together form a fused ring attached to the indolenine ring; R and R each represent a member selected from the class consisting of the hydrogen atom, an alkyl group, and R and R together represent the non-metallic atoms necessary to complete a cycloalkane group; R represents an alkyl group; X represents an acid anion; n represents an integer of from 1 to 2 such that n represents the integer 1 only when R; contains a group selected from the class consisting of the carboxy group, and the sulfo group; and Z represents a member selected from the class consisting of an aminoaryl group, an alkoxyaryl group and a hydroxyaryl group.

2. A photographic element of claim 1 in which the said light-absorbing layer is coated over the said lightsensitive layer.

3. A photographic element of claim 1 in which the said light-absorbing layer is coated between the said support and the said light-sensitive layer.

4. A photographic element of claim 1 in which the said light-absorbing layer is coated on one side of the said support and the said light-sensitive layer is coated on the other side of the said support.

5. A photographic element of claim 1 in which the said light-absorbing layer is coated between two lightsensitive layers.

6. A photographic element of claim 1 containing anhydro 2 (4 p dimethylaminophenyl 1,1 dimethyl- 1,3 butadienyl) 3 (4 sulfobutyl) 1H benzo [e]indolium hydroxide.

7. A photographic element of claim 1 containing 3- carboxyethyl 2 (4 p dimethylaminophenyl 1,3- butadienyl) 1,1 dimethyl 1H benz[e]indolium iodide.

8. A photographic element of claim 1 containing anhydro 5 chloro 2 (4 p dimethylaminophenyl 1,3- butadienyl) 3,3 dimethyl 1 (4 sulfobutyl) 3H- indolium hydroxide.

9. A photographic element of claim 1 containing anhydro 3 carboxyethyl 2 (4 p dimethylaminophenyl 1,3 butadienyl) 1,1 dimethyl 1H benz[e] indolium hydroxide; monosulfonated pyridine salt.

10. A photographic element of claim 1 containing 3- car-boxymethylcarbamoyloxyethyl 2 (4 p dimethylaminophenyl 1,3 butadienyl) 1,1 dimethyl 1H- benz[e]indolium iodide.

References Cited UNITED STATES PATENTS 3,095,303 6/1963 Sprague et al. 96-33 3,102,810 9/1963 Sprague et al. 96-33 OTHER REFERENCES P. Ruggli, and P. Jensen, Helv. Chim. Acta. 18, pp. 632, 633, 1935.

NORMIN G. TORCHIN, Primary Examiner.

R. H. SMITH, Assistant Examiner.

Patent Citations
Cited PatentFiling datePublication dateApplicantTitle
US3095303 *Jul 12, 1960Jun 25, 1963Horizons IncStyryl dye base composition and photographic processes for producing lithographic surfaces photoresists and prints therewith
US3102810 *Apr 5, 1961Sep 3, 1963Horizons IncPrint-out cyanine and styryl dye bases and process of producing litho masters and the like therewith
Referenced by
Citing PatentFiling datePublication dateApplicantTitle
US3955984 *Apr 18, 1975May 11, 1976Fuji Photo Film Co., Ltd.Styryl dyes
US3972877 *Jan 7, 1974Aug 3, 1976Hoechst AktiengesellschaftButadiene derivatives, process for their preparation and their use as optical brighteners
US4268622 *Dec 19, 1979May 19, 1981Fuji Photo Film Co., Ltd.Photographic light-sensitive materials having dyed layers
US4839265 *Jan 19, 1988Jun 13, 1989Fuji Photo Film Co., Ltd.Silver halide photosensitive material containing an infrared absorption dye
US5258274 *May 22, 1992Nov 2, 1993Minnesota Mining And Manufacturing CompanyAlkoxystyryl substituted indolinium dye and thermal nucleophile-generating agent; photography
US5401620 *Mar 18, 1993Mar 28, 1995Fuji Photo Film Co., Ltd.Silver halide photographic material for laser exposure
US5561028 *Jun 2, 1995Oct 1, 1996Mitsubishi Paper Mills LimitedStable photographic films for high speed development
EP0772080A2Oct 22, 1996May 7, 1997Eastman Kodak CompanyPhotographic element useful as a motion picture print film
Classifications
U.S. Classification430/507, 548/511, 430/522, 548/427
International ClassificationC09B23/00, G03C1/83, C09B23/10, B05B9/00, B05B9/01
Cooperative ClassificationC09B23/107, G03C1/832, B05B9/01
European ClassificationG03C1/83C, B05B9/01, C09B23/10D