CA1286139C

CA1286139C - Filter dye for photographic element

Info

Publication number: CA1286139C
Application number: CA000553294A
Authority: CA
Inventors: Donald Richard Diehl; Ronda Ellen Factor
Original assignee: Eastman Kodak Co
Current assignee: Eastman Kodak Co
Priority date: 1986-12-23
Filing date: 1987-12-02
Publication date: 1991-07-16
Anticipated expiration: 2008-07-16
Also published as: JPS63197943A; EP0274723A1; EP0274723B1; DE3765921D1; JP2578146B2

Abstract

FILTER DYE FOR PHOTOGRAPHIC ELEMENT
Abstract of the Disclosure Dyes having the structure

Description

128~139 FILTER DYE FOR PHOTOGRAPHIC ELEMENT
Field of the Invention This invention relates to filter dyes and their use in photographic elements.
Back~round of the Inventio~
Filter dyes are widely used in photographic elements. Filter dyes may be located in several locations in an element. They may be in a radiation-sensitive layer, an overcoat layer, in a layer adja-cent to the radiation-sensitive layer, in an inter-layer of a multilayer element, in an undercoat layer adjacent to the support or in a backing layer on the side of the support opposite the radiation-sensitive layer.
When incorporated directly in the radiation-sensitive layer they can function to improve sharpnesæ by absorbing light scattered from one silver halide grain to another. Such dyes are referred to as absorber dyes. Filter dyes also func-tion to retard the sensitivity of one light sensitive layer relative to another in a multilayer element.
By absorbing some of the exposing radiation the fil-ter dye aids in balancing the sensitivities of all the light sensitive layers.
Filter dyes that function primarily to absorb unwanted radiation due to reflection or refraction from layer interfaces, the layer-support interface, and particularly from the back side of the support, are referred to as antihalation dyes. The layers that contain them are referred to as antihalation layers.

?
~ ~, 1~6139 There are other places and purposes for filter dyes and filter layers. For example, a filter layer may be used in or near the ouercoat layer to protect the light sensitiue layer against radiation from certain spectral regions. In multilayer films where there may be two or more light sensitiue layers, it is sometimes necessary to have filter dye interlayers. In duplitized materials, such as X-ray films, filter layers are used to reduce crossouer exposure of the light sensitiue layers.
Elimination of crossouer exposure is an ideal that is highly desirable but has not yet been fully attained.
~ number of problems are associated with filter dyes and filter layers. It is uery important that the dyes remain in the layer and not wander or diffuse into the adjacent layers. This often necessitates the presence of a mordant to hold the dye in the layer. It is equally important for the dyes to be completely decolorized andJor remoued from the element, usually during processing, after they haue performed their function. Dye stability, especially under high temperature and high humidity incubation is also important.
In some photographic elements, it is desir-able to absorb unwanted radiation across the entire uisible spectrum. In such elements it is not unusual to use up to fiue filter dyes in a single filter layer to accomplish this objectiue. Clearly, it is desirable to reduce the number of filter dyes used in the layers of such elements.
U.S. Patent 3,560,214 discloses dyes com-prising a carboxyl and phenyl substituted pyrazoline nucleus linked through a methine group to a dialkyl-aminophenyl group. Howeuer these dyes, according to the patent and our own experiments, are migratory.

12~613~

It is an objectiue of this inuention to pro-uide filter dyes for photographic elements which meet the foregoing requirements for filter dyes and do not cause post process dye stain or migrate from layer to layer.
Summarv of the Inuention The foregoing objectiues are achieued with a dye hauing the formula:

~_CtCH=CHtm-~ / --N~R2 ~ represents a substituted or unsubstituted nucleus hauing a carboxyphenyl or sulfonamidophenyl substituent selected from the group consisting of 2-pryazolin-5-ones free of any substituent bonded thereto through a carboxyl group, rhodanines, hydantoins, 2-thiohydantoins, 4-thiohydantoins, 2,4-oxazolidindiones, 2-thio-2,4-oxazolidindiones, isoxazolinones, barbiturics, 2-thiobarbiturics, and indandiones, R represents hydrogen, substituted or unsubsti-tuted alkyl of 1 to 4 carbon atoms, or benzyl, R1 and R2 each independently represents substituted or unsubstituted alkyl or aryl, or taken together with R , R , N, and the carbon atoms to which they are attached, represent the atoms needed to complete a julolydyl ring, R3 represents H, or substituted or unsubsti-tuted alkyl or aryl, R5 and R6 each independently represents H, or R taken together with Rl, or R6 taken to-gether with R2, represent the atoms necessary to complete a carbocyclic ring such as tetrahydro-quinoyl, and m is O or 1.

1~613.9 .

In a preferred embodiment, the dyes of the inuention are merostyryl arylidenes ha~ing the formula: ~

( ~ x ~ ~ 4 CHt-n-~ T ~ -N~ 2 ~ wherein R represents hydrogen, substituted or unsubstituted alkyl of 1 to 4 carbon atoms, or benzyl, R and R each independently represents substituted or unsubstituted a kyl or aryl, or taken together with R5, R6, N, and the carbon atoms to whateuer they are at.tached, represent the atoms needed to complete a julolydyl ring, R and R each independently represents H, substituted or unsubstituted alkyl, aryl, alkoxy, hydrogen, or acetamido, R represents substituted or unsubstituted alkyl, alkoxycarbonyl, aryl, acyl, or amido, R and R each independently represents H, or R taken together with R , or R taken together with R2, represent the atoms necessary to complete a carbocyclic ring, R is C~2H or NHS02R wherein R
is substituted or unsubstituted alkyl or aryl, x is 1 or 2, and n is O or 1.
The carboxyphenyl or sulfonamidophenyl substituent on ~ is im- portant in immobilizing the dye at coating pH's of 5-7.
The acyl, alkyl and alkoxy groups may contain from one to twenty carbons. Examples of such groups include acetyl, benzoyl, methyl, ethyl, 613~

propyl, methoxy carboxyl, ethoxy carboxyl, butoxy-carboxyl, fluoroalkyl, dodecyl, and octadecyl. The aryl groups may contain from six to twenty carbons,~
which may be further substituted with a wide uariety of groups. Examples of such substituted and unsubstituted aryl groups including phenyl and napthyl with alkyl substituents as defined aboue.
Microcrystalline dispersions of the dyes of this invention leaue no residual post-processing stain in processed photographic elements. Polymeric mordants are not needed to immobilize the dyes, as immobilization is achieued without mordants.
Complete and irreuersible dye remoual during processing is achieued. Broadened and shifted ab-sorption is obtained which makes the compositions particularly suitable for filter or antihalation applications. Their broadened absorption bands are particularly useful in reducing the number of dyes needed in a single element to absorb unwanted radia-tion. ~nother aduantage is superior dye stability when subjected to high temperature and high humidity incubation.
DescriPtion of the_Preferred Embodiments Examples 1-3 below relate to the preparation of representatiue dyes of the inuention. Uariations on the procedures described to obtain other dyes of this inuention, such as those of the examples and Table I and II below are within the skill of the practicing synthetic chemist. Procedures for making such dyes are described in "The Cyanine Dyes and Related ComPounds", Frances Hamer, Interscience Publishers, 1984.

~3~9 ~ bbreuiations used in the examples are: NMR
= nuclear magnetic resonance, IR = infrared, HCl =
hydrochloric acid, EtOH = ethanol, MeOH = methanol,~
Et20 = ethyl ether, DMF = dimethylformamide, DMSO =
dimethylsulfoxide, NaOH = sodium hydroxide and mp =
melting point.
EX~MPLE 1 Preparation of Dye 6, Table I
Step 1 Preparation of Intermediate - 1-(3,5-Dicarboxvphenvl -3-methvl)-2-PYrazo-lin-5-one ~ solution of sodium nitrite (35.8 q, 0.52 mol) in water (75 ml) was added to a slurry of 5-aminoisophthalic acid (90.6 9, 0.50 mol) in 4.8 molar HCl (500 ml) at 0C o~er 15 minutes with stir-ring. Stirring was continued for one hour at 0-5C
and the slurry was then added to a solution of sodium sulfite (270 9, 2.2 mol) in water (1.21) all at one time, with stirring, at 2C. The resulting homogene-ous solution was heated at 50-60C for 45 minutes.
Concentrated HCl (60 ml) was added and the reaction mixture was heated further at 90C for one hour.
~fter cooling to room temperature, another portion of concentrated HCl (500 ml) was added. The solid was isolated by filtration and washed on a funnel with acidified water, EtOH and lignoin in succession. The off-white solid was dissolued in a solution of NaOH
(76 9, 1.85 mol in 600 ml water). This solution was subsequently acidified with glacial acetic acid (166 ml, 3.0 mol) to yield a thick slurry. This was isolated by filtration, washed on the funnel with water, EtOH, and lignoin in succession, and thoroughly dried in a uacuum ouen at 80C, and 10 mm Hg. The mp was aboue 300C. The NMR and IR
spectra were consistent with the structure for 5-hydrazino-1,3-benzenedicarboxylic acid. The 613~

product gaue a positiue test for hydrazine with Tollens' reagent.
~ slurry composed of the product 5-hydra-zino-1,3-benzenedicarboxylic acid (64.7 9, 0.33 mol), ethylacetoacetate (50.7 9, 0.39 mol) and glacial acetic acid (250 ml) was stirred and refluxed for 22 hours. The mixture was cooled to room temperature and the product that had precipitated was isolated by filtration, washed with water, EtOH, Et20, and lignoin in succession and thoroughly dried in a uacuum ouen at 80C and 10 mm Hg. The mp of the solid was aboue 310C. The NMR and IR spectra were consistent with the assigned structure. The product gaue a negatiue test with Tollens' reagent. The C,H, and N elemental analyses were in agreement with those calculated for the empirical formula.
Step 2 Preparation of 1-(3,5-Dicarboxv-phen~l)-4-(4-dimethylaminobenzyli-dene~-3-methyl-2-Pyrazolin-5-one (Dye 6, Table I) ~ slurry composed of 1-(3,5-dicarboxy-phenyl)-3-methyl-2-pyrazoline-5-one (44.6 grams, 0.17 mol), 4-dimethylamino-benzaldehyde (26.9 grams, 0.18 mol) and EtOH (500 mL) was heated at reflux for three hours. The reaction mixture was chilled in ice and the resulting crude orange product was isolated by filtration and washed with EtOH (200 mL). The pro-duct was purified by three repetitiue slurries of the solid in acetone (1.4 l) at reflux and filtering to recouer the dye. The mp of the product was aboue 310C. The NMR and IR spectra were consistent with the structure assigned. The C, H, and N elemental analyses were in agreement with those calculated for the empirical formula.

1~3613~

EX~MPLE 2 Preparation of DYe 1, Table I
(1--(4--Carboxvphenvl?-4-(4-dimethylamino-benzvlidene~-3-methyl-2-Pvrazolin-5-one ~ slurry composed of 1-(4-carboxyphenyl)-3-methyl-2-pyrazolin-5-one (21.8 9, 0.10 mol), 4-dimethylamino-benzaldehyde (14.9 9, 0.10 mol) and EtOH (250 ml) was heated at reflux for two hours.
The reaction mixture was cooled to room temperature, resulting in a crude orange product which was isolated by filtration. The product was then washed with ether and dried. The product was purified further by making a slurry of the solid in EtOH (700 ml) at refluxing temperature and filtering the slurry to recouer the dye. The treatment was repeated. The mp of the product was abo~e 310C. The NMR and IR
spectra were consistent with the structure assigned.
The C, H, and N elemental analyses were in agreement with those calculated for the empirical formula.
EX~MPLE 3 Preparation of Dve 11, Table I
1--(4--Carboxvphenvl)--4--(4-dimethyl--amino-cinnamvlidene)-3-methvl-2-Pvra-zolin-5-one 1-(4-Carboxyphenyl)-3-methyl-2-pyrazo-lin-5-one (2.18 9, 0.010 mol), 4-dimethylamino-cinnamaldehyde (1.75 9, 0.010 mol) and glacial acetic acid (10 ml) were mixed together to form a slurry.
It was heated to reflux with stirring, held at reflux for fiue minutes and then cooled to room tempera-ture. EtOH (20 ml) was added to the reaction mixture, which was heated again to reflux, held there for fi~e minutes, and cooled to room temperature.
The product was isolated by filtration, washed in succession with ethanol and lignoin, and dried. The reaction was repeated twice on the same scale and the ~3613~

products obtained were all combined. They were treated further by first slurrying in refluxing EtOH
(150 ml), isolating the solid by filtration while hot, and then slurrying in refluxing MeOH (200 ml) and isolating it again, while hot, by filtration.
The mp was 282-284C. The NMR and IR spectra were consistent for the structure assigned. The C,H, and N elemental analyses were in agreement with those calculated for the empirical formula of the dye.
The dyes prepared in Examples 1-3 and other dyes of the in~ention prepared with similar proper-ties are listed in Tables I and II along with their absorption maxima (in methanol solution with a sta-bilizing amount of triethylamine) and extinction coefficients.

361~

T~BLE I

(HOOC)x ~ C\R4 ~' R

l-Ph E-max Dye Rl R2 R3 4 Substni x n (nm~ ( 1 CH3 HCH3 1 4 0 466 3.73 2 5 HCH3 1 4 0 471 4.75 3 n-C4Hg HCH3 1 4 0 475 4.50 4 CH3 HCC2H5 1 4 508 5.20 i-C3H7C~H2 CH3C 3 1 4 0 430 3.34 6 CH3 HCH3 2 3,5 0 457 3.78 2 5 HCH3 2 3,5 0 475 4.55 8 n-C4H9 HCH3 2 3,5 0 477 4.92 9 i-C3H70C~H2 HCH3 2 3,5 0 420 3.62 3 7 ~o2 33 2 3,5 0 434 3.25 11 CH3 HCH3 1 4 1 516 4.62 12 iC3H70C CH2 H CH3 1 4 0 420 3.94 R

13 CH3 H C CH3 1 4 0 573 5.56 14 CH3 H COOEt 1 4 1 576 5.76 15 CH3 H CH3 2 3,5 1 506 3.90 16 CH3 H COOEt 1 4 0 502 4.83 T~BLE I - Cont'd 17 CH3 H COOEt 2 3,5 1 560 5.25 2 5 H COOEt 1 4 0 512 6.22 19 CH3 H CF3 1 4 0 507 4.58 CH3 H Ph 1 4 0 477 4.54 21 CH3 H C CH3 1 4 0 506 5.36 Table II

c~ ~'T'~
(HOOC)x C~R4 1-Ph Substn ~-max e-max Dve R- R-4 x position (nm~ (10-) 22 H CH3 1 4 500 5.82 23 H CH3 2 3,5 502 5.47 The aboue dyes in Tables I and II may also ha~e sulfonamido substituents instead of the carboxyl substituents, such as:

_ 2 ~ CH ~ CH2C2CH(CH ) CH3 CH2C02CH(cH3)2 or _ ~ 2 ~ ~. CH ~ ~, N~CH2C02CH(CH3)2 CH3 CH2C02CH(CH3)2 The dyes of this invention are useful in, for example, black and wh te, single color, multicolor, or duplitized X-ray photographic 1~36~3~

elements. They can be present in any layer of the element where it is desirable to include a filter dye, for example, in the siluer halide emulsion layer or a separate filter layer. The dyes of the inuention can be utilized in any amount that is useful to filter or absorb light, but it is particularly aduantageous to utilize them in an amount and in a location so that they will be solubilized and washed out during processing. In situations where it is desirable to absorb only a small amount of light, only a small amount of dye is needed. In situations where it is desirable to absorb a larger amount of light, larger amounts of dye can be used, as long as the stain leuel remains at a leuel that is acceptable for that particular photographic element. The dye is preferably present in the element of the inuention in an amount of from about 1 to 1000 mg/ft .
The dyes of the inuention are preferably in the form of a solid particle microcrystalline dispersion for incorporation into a layer such as a hydrophilic colloid layer coated on a photographic element. The microcrystalline dispersion can be formed by precipitating the dye in the form of a dispersion andJor by well-known milling techniques, e.g., ball-milling, sand-milling, or colloid-milling the dye in the presence of a dispersing agent. The dye particles in the dispersion preferably haue a mean diameter of less than about 10 ~m and more preferably of less than about 1 ~m. The dye particles can be conueniently prepared in sizes ranging down to about 0.01 ~m or less.
In the following discussion of suitable materials for use in the emulsions and elements of this inuention, reference will be made to Research Disclosur_, December 1978, Item 17643, published by 1~3613~

Kenneth Mason Publications, Ltd., The Old Harbour-master~s, 8 North Street, Emsworth, Hampshire P010 7DD, ENGLAND. This publication will be identified hereafter by the term "Research Digclosur~".
The radiation-sensitive layer of the element of the invention can contain any of the known radiation-sensitive materials, such as silver halide, diazo image-forming systems, light-sensitive tellurium-containing compounds, light-sensitive cobalt-containing compoundæ, and others described in, for example, J. Kosar, Light-Sensitive Systems:
Chemistry and Application of Nonsilver Halide Photographic Processes, J. Wiley & Sons, N.Y (1965).
Radiation-sensitive materials exhibiting sensitivity to blue light and especially those sensitive to blue light and at least some other wavelength of radiation are preferred, as the dyes according to the invention can be advantageously used to absorb some or all of the blue light.
Silver halide is especially preferred as a radiation-sensitive material. Silver halide emulsions can contain, for example, silver bromide, silver chloride, silver iodide, silver chlorobromide, silver chloroiodide, silver bromoiodide, or mixtures thereof. The emulsions can include coarse, medium, or fine silver halide grains bounded by 100, 111, or 110 crystal planes. Silver halide emulsions and their preparation are further described in Research Disclos~e, Section I. Also useful are tabular grain silver halide emulsions, as described in Research Disclosure, January, 1983, Item 22534 and U.S. Patent 4,425,426.
The radiation-sensitive materials described above can be sensitized to a particular wavelength r.~

1~61;~9 range of radiation, such as the red, blue, or green portions of the uisible spectrum, or to other wauelength ranges, such as ultrauiolet, infrared, X-ray, and the like. Sensitization of siluer halide can be accomplished with chemical sensitizers such as gold compounds, iridium compounds, or other group UIII metal compounds, or with spectral sensitizing dyes such as cyanine dyes, merocyanine dyes, styryls, or other known spectral sensitizers. ~dditional information on sensitization of siluer halide is described in Research Disclosure, Sections I~
Multicolor elements contain dye image-forming units sensitiue to each of the three primary regions of the spectrum. Each unit can be comprised of a single emulsion layer or of multiple emulsion layers sensitiue to a giuen region of the spectrum.
The layers of the element, including the l~yers of the image-forming units, can be arranged in uarious orders as known in the art. In an alternatiue for-mat, the emulsions sensitiue to each of the three primary regions of the spectrum can be disposed as a single segmented layer, e.g., as by the use of micro-uessels as described in Whitmore U.S. Patent 4,362,806, issued December 7, 1982.
~ typical multicolor photographic element would comprise a support bearing a cyan dye image-forming unit comprised of at least one red-sensitiue siluer halide emulsion layer hauing associated there-with at least one cyan dye-forming coupler, a magenta dye image-forming unit comprising at least one green-sensitiue siluer halide emulsion layer hauing associated therewith at least one magenta dye-forming coupler and a yellow dye image-forming unit compris-ing at least one blue-sensitiue siluer halide emul-sion layer hauing associated therewith at least one yellow dye-forming coupler. The element can contain 3613~9 additional layers, other filter layers, interlayers, ouercoat layers, subbing layers, and the like.
In addition to the couplers the elements can include additional couplers as described in Research Disclosure Section UII, paragraphs D, E, F and G and the publications cited therein. These couplers can be incorporated in the elements and emulsions as described in Research Disclosure Section UII, para-graph C and the publications cited therein.
The photographic elements or indiuidual layers thereof, can contain brighteners (see Research Disclosure Section U), antifoggants and stabilizers (see Research Disclosure Section UI), antistain agents and image dye stabilizer (see Research Disclosure Section UII, paragraphs I and J), light absorbing and scattering materials (see Research Disclosure Section UIII), hardeners (see Research Disclosure Section XI), plasticizers and lubricants (see Research Disclosure Section XII), antistatic agents (see Research Disclosure Section XIII), mat-ting agents (see Research Disclosure Section XUI) and deuelopment modifiers (see Research Disclosure Sec-tion XXI).
The photographic elements can be coated on a uariety of supports as described in Research Disclosure Section XUII and the references described therein.
Photographic elements can be exposed to ac-tinic radiation, typically in the uisible region of the spectrum, to form a latent image as described in Research Disclosure Section XUIII and then processed to form a uisible dye image as described in Research Disclosure Section XIX. Processing to form a uisible dye image includes the step of contacting the element with a color de~eloping agent to reduce deuelopable siluer halide and oxidize the color deueloping lX~3613~

agent. Oxidized color deueloping agent in turn reacts with the coupler to yield a dye.
The following examples illustrate the use of the dyes of the inuention in filter layers of photo-graphic elements.
EX~MPLES 4-23 Procedure for Preparation of the Microcrvstalline Dve Dispersions The dyes were subjected to ball-milling according to the following procedure. Water (21.7 ml) and a 6.7~ solution of Triton X-200~ surfactant (TX-200~) (2.65 9) (a~ailable from Rohm ~ Haas) were placed in a 60 ml screw-capped bottle. ~ 1.00 9 sample of dye was added to this solution. Zirconium oxide (ZrO) beads (40 ml) (2 mm diameter) were added and the container with the cap tightly secured was placed in a mill and the contents were milled for four days. The container was remoued and the contents added to a 12.5X aqueous gelatin (8.0 9).
The new mixture was placed on a roller mill for 10 minutes to reduce foaming and the resulting mixture was then filtered to remo~e the ZrO beads.
Coatin~ Procedure ~ spreading agent, surfactant 10G~, and a hardener (bis(uinyl-sulfonylmethyl)ether) were added to the dye-gelatin melt prepared as described in the preparation of the microcrystalline dye dispersions.
melt prepared from the latter mixture was then coated on polyethylene terephthalate support to achie~e a dye co~erage of 0.32 g/m , gelatin couerage of 1.60 g/m2, a spreading agent leuel of 0.096 9/m2 and a hardener level of 0.016 g/m .
Spectral data were obtained from an analysis of the coatings on a spectrophotometer interfaced with a computer. ~ summary of the data obtained is in Table III where the dye numbers correspond to those of ~36~3!9 Tables I and II. ~ll absorption maxima and half band width (HeW) data are expressed in nanometers (nm).
Three sets of absorption data are presented: ~-max .
and HBW of the coating containing the ball-milled dispersion of the dye, ~-max and HBW of the same coating at pH 10, the pH at which the merostyryl chromophore is fully ionized, and ~-max and HBW of the dye in methanol solution.
In addition to the data in Table III, ab-sorption spectra of the coatings for dyes 1, 2, 3, 6, 10 and 11 were made. Comparison of the curues of coatings containing microcrystalline dispersion of a particular dye with the same dye in a coating at pH
10 showed the microcrystalline dispersion absorbance maximum was shifted compared to the solution spec-tra. This prouides an unexpected aduantage for use as a filter dye.
Referring to Table III, it is clear that the absorption spectra of the coatings containing the microcrystalline dye dispersion are broader than for the same dyes in solution or in coatings at pH 10.
Thus, microcrystalline dispersions of the dyes of the inuention are suitable for filter applications where broad uisible light filtration is required. This broad absorption also serues to reduce the number of dyes needed for a particular filter application.

613~9 Table III

Microcrystalline Coating Table ICoatinq (pH 10~ Solution Dve~-max HBW ~-max HBW ~-max HBW

EX~MPLES 24-29 Dve Immobilization in Coatinq and Remo~al Durinq Processinq The coated microcrystalline dye dispersions prepared as described in the preuious examples were eualuated for dye mobility. Samples of the coatings were giuen a fiue minute distilled water wash. The results for four of the dyes, 1, 2, 3 and 5, are shown in Table I~. The coatings were also eualuated ~6~3~9 for post processing stain following processing in the Kodak Prostar~ processor used commercially to process microfilm, subjecting the elements to a development step at a pH of 11.4 for 30 seconds.
These results are also included in Table IU.

Table I~
Optical Densitv ~fter ~fter Dye 5efore H20 WashProstar 1 2.255 2.292 0.007 2 1.782 1.795 0.010 3 1.440 1.451 0.007 1.403 1.383 0.013 24 1.43 0.01 0.01 Dye 24 is a comparison dye of the structure:

3 ~ C=CH~ -N~ 3 which exhibited a ~-max of 450 nm and a bandwidth of 117 nm before any washing or processing.
Table IU shows that no dye density was lost by the dyes dispersed and coated as described in the preuious examples due to the distilled water wash.
This shows that there was no dye wandering from layer to layer. The comparison dye, on the other hand, exhibited se~ere washout, indicating a high degree of dye wandering.
Table I~ also demonstrates dramatically the complete remo~al of the microcrystalline dispersion dyes on ProstarO processing at room temperature.
No residual stain is left. The same results were obser~ed when the coatings were processed with Kodak X-OmatO processing, which is used commercially to l~a6~

process x-ray film, subjecting the elements to a de~elopment step at a pH of 10.3 for 30 seconds.
This is an improuement ouer other known latex imbibed yellow filter dyes which are incompletely remo~ed by these processing conditions.
For Examples 28 and 29, microcrystalline dispersions of dyes of the formula:
~- S0 NH~ ~ CH ~ ~.-N~ 2 CH3 CH2C02CH(CH3)2 were coated as with Examples 24-27, and subjected to a 5-minute distilled water wash and processed with Kodak E-6 processing, as described in British Journal of Photograp~ ~nnual 1977 pp. 194-97. The results are presented in Table U.

Table U
O~
~fter ~fter R Before H 0 Wash E-6-2 -- _ 25 H 1.04 1.26 Q.01 26CH3 1.72 1.66 0.01 24 - 1.43 0.01 0.01 Dye 25 had a ~-max of 449 nm and a bandwidth of 121 nm before washing or processing. Dye 26 had a ~-max of 453 nm and a bandwidth of 97 nm before washing or processing. The results in Table U indicate that the photographic compositions of the in~ention containing Dyes 25 and 26 do not wander during the water wash, but decolorize completely after photographic processing. The comparison Dye 24, howeuer, washes out during the water wash, indicating seuere wandering.

Example 30 Eualuation of D~es of the Inuention in ~ntihalation Lavers in Combination With Other D~es The utility of microcrystalline dyes of this inuention, in combination of other dyes, is illustrated with dyes 1 and 5 of Table I. The dispersions were prepared as in examples 5-19. These dispersions were each coated as a component of an antihalation layer in a multilayer format, along with a cyan filter dye, bis[1-(4-carboxyphenyl)-3-methyl-2-pyrazolin-5-one-(4)]pentamethineoxonol. The coatings, 1 to 4 in Table UI, were eualuated for dye stain after processing. The emulsion layer was a chemically and spectrally sensitized 0.25 micron cubic siluer bromoiodide (3% iodide) emulsion layer coated to achieue siluer couerage of 1.45 9/m2 and gelatin couerage of 1.56 g/m . The gelatin couerage in the antihalation layer was 1.88 g/m . The leuels of dyes 1 and 5 and of the cyan dye are indicated in Table ~I. The gelatin couerage in the ouercoat layer was 1.56 g/m . The coatings were exposed to a tungsten light source in a sensitometer, deueloped, fixed and washed in the Kodak Prostar~ process and dried.

Table_~I
Leue2 Cyan Coatinq No. Dye q/m Leuel 0.11 0.11 2 1 0.16 0.16 3 5 0.11 0.11 4 5 0.16 0.16 The coatings containing microcrystalline dispersions of dyes 1 and 5 and the cyan filter dye, at the levels shown in Table I, exhibited no residual dye stain and provided significantly high light ab-sorption.

Claims

1. A photographic element comprising a support, and a radiation-sensitive layer and a layer comprising a solid particle dispersion of a dye having the formula:

, wherein A represents a substituted or unsubstituted acidic nucleus having a carboxyphenyl or sulfonamidophenyl substituent selected from the group consisting of 2-pryazolin-5-ones free of any substituent bonded thereto through a carboxyl group, rhodanines, hydantoins, 2-thiohydantoins, 4-thiohydantoins, 2,4-oxazolidindiones,

2-thio-2,4-oxazolidindiones, isoxazolinones, barbiturics, 2-thiobarbiturics, and indandiones, R represents hydrogen, substituted or unsubstituted alkyl of 1 to 4 carbon atoms, or benzyl, R1 and R2 each independently represents substituted or unsubstituted alkyl or aryl, or taken together with R5, R6, N, and the carbon atoms to which they are attached, represent the atoms needed to complete a julolydyl ring, R3 represents H, or substituted or unsubstituted alkyl, or aryl, R5 and R6 each independently represents H, or R5 taken together with R1, or R6 taken together with R2, may each represent the atoms necessary to complete a carbocyclic ring, and m is 0 or 1.

2. A photographic element according to claim 1 wherein the dye layer is located on the opposite side of the support from the radiation-sensitive layer.

3. A photographic element according to claim 1 wherein the silver halide layer is on one side of the support, and further comprising a second radiation-sensitive layer on the other side of the support, and wherein the dye layer is located between one of the radiation-sensitive layers and the support.

4. A photographic element comprising a support and a radiation-sensitive layer comprising a dye having the formula:

, wherein A represents a substituted or unsubstituted acidic nucleus having a carboxyphenyl or sulfonamidophenyl substituent selected from the group consisting of 2-pryazolin-5-ones free of any substituent bonded thereto through a carboxyl group, rhodanines, hydantoins, 2-thiohydantoins, 4-thiohydantoins, 2,4-oxazolidindiones, 2-thio-2,4-oxazolidindiones, isoxazolinones, barbiturics, 2-thiobarbiturics, and indandiones, R represents hydrogen, substituted or unsubstituted alkyl of 1 to 4 carbon atoms, or benzyl, R1 and R2 each independently represents substituted or unsubstituted alkyl or aryl, or taken together with R5, R6, N, and the carbon atoms to which they are attached, represent the atoms needed to complete a julolydyl ring, R3 represents H, or substituted or unsubstituted alkyl, or aryl, R5 and R6 each independently represents H, or R5 taken together with R1, or R6 taken together with R2, may each represent the atoms necessary to complete a carbocyclic ring, and m is 0 or 1.

5. A photographic element according to any one of claims 1-4 wherein the dye is merostyryl arylidene dye having the formula:

, wherein R represents hydrogen, substituted or unsubstituted alkyl of 1 to 4 carbon atoms or benzyl, R1 and R , each independently, repre-sents substituted or unsubstituted alkyl or aryl, or taken together with R5, R6, N and the carbon atoms to which they are attached represent the atoms needed to complete a julolydyl ring, R3 and R7 each independently represents H, substituted or unsubstituted alkyl, aryl, alkoxy, hydrogen or acetamido, R4 represents substituted or unsubstituted alkyl, alkoxycarbonyl, aryl, acyl and amido, R5 and R6 each independently represents H, or R5 taken together with R1, or R6 taken together with R2, represent the atoms necessary to complete a carbocyclic ring, R8 represents CO2H or NHSO2R9 wherein R is substituted or unsubstituted alkyl or aryl, and x is 1 or 2, and n is 0 or 1.

6. A photographic element according claim 5 wherein R1 and R2, each independently represents CH3, C2H5, n-C4H9, or i-C3H1O?CCH2, R3 represents H, CH3, or OH, R4 represents CH3, COOC2H5, or COOH, R5, R6 and R7 each represent H, or R5, R6, R1 and R2, together with the atoms to which they are attached, form a julolydyl ring.

7. A photographic element according to claim 5 wherein the dye is in the form of a microcrystalline dispersion.

8. A photographic element according to claim 1 or 4 wherein the layer containing said dye comprises a mixture of bis[1-(4-carboxyphenyl)-3-methyl-2-pyrazolin-5-one-(4)]
pentamethine oxonol and a dye selected from the group consisting of: